EP1377974A1

EP1377974A1 - Optical data carrier containing a xanthene dye in the information layer thereof as a light-absorbing compound

Info

Publication number: EP1377974A1
Application number: EP02724250A
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: JP2004523395A; CN1516872A; US20030096192A1; TWI223252B; WO2002077984A1

Abstract

The invention relates to an optical data carrier containing a preferably transparent substrate which has optionally been coated with at least one reflection layer. An information layer which can be written with light, optionally at least one reflection layer and optionally a protective layer or another substrate or a covering layer can be applied to the surface of said substrate. Said data carrier can be written and read with blue or red light, preferably laser light. The information layer contains a light-absorbing compound and optionally a binding agent, and is characterised in that at least one xanthene dye containing at least two anionic groups and having, as a counterion, at least one cation containing at least one conjugated pi -system having at least 6 pi -electrons is used as a light-absorbing compound. Said cation cannot be benzyltrimethylammonium, benzyltriethylammonium, tetraphenylphosphonium, butyltriphenylphosphonium and ethyltriphenylphosphonium.

Description

Optical data carrier containing a xanthene dye in the information layer as a light-absorbing compound

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

Information layer as a light-absorbing compound contains a xanthene dye, and a process for their preparation.

The write-once optical data carriers using special light-absorbing substances or their mixtures 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

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-A-08191171 or Second Harmonie Generation SHG JP-A-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 storage density that can be achieved depends on the focus of the laser spot in the information level. The spot size scales with the laser wavelength λ / NA. 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 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 to the 450 nm range Working wavelength extended 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 light-absorbing information layer by sputtering or vapor deposition, are diffused by diffusion

Form interfaces and thus adversely affect reflectivity. About that In addition, a light-absorbing substance with too low heat resistance at the interface to a polymer carrier can diffuse into it 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 340 to 680 nm.

A high capacity optical storage medium containing xanthene dyes is known from EP-A-0 805 441. The claimed xanthene dyes can have up to four positive or negative excess charges and corresponding counterions. A proton or a metal, ammonium or phosphonium cation are described as cationic counterions.

Surprisingly, it was found that light-absorbing compounds from the group of xanthene dyes, which contain at least two anionic groups and have at least one cation as counterion, which contains at least one specific conjugated π system with at least 6 π electrons, meet the requirement profile mentioned above can meet particularly well.

The invention therefore relates to an optical data carrier, comprising a preferably transparent substrate, possibly already coated with one or more reflection layers, on the surface of which a surface can be written on with light Information layer, optionally one or more reflection layers and optionally a protective layer or another substrate or a cover layer are applied, which can be written and read with blue or red light, preferably laser light, the information layer containing a light-absorbing compound and optionally a binder, thereby characterized in that at least one xanthene dye is used as the light-absorbing compound, which contains at least two anionic groups and has at least one cation as the counter ion, which contains at least one conjugated π system with at least 6 π electrons, with the proviso that the cation is not a benzyl tri methylammonium, benzyltriethylammonium, tetraphenylphosphomum,

Butyltriphenylphosphonium or Ethyltriphenylphosphomum is.

The light-absorbing compound should preferably be thermally changeable. The thermal change preferably takes place at a temperature <600 ° C., particularly preferably at a temperature <400 ° C., very particularly preferably at one

Temperature <300 ° C, especially <200 ° C. Such a change can be, for example, a decomposition or chemical change in the chromophoric center of the light-absorbing compound.

A xanthene dye of the formula (I) is preferred

wherein

R ¹ to R ⁴ independently of one another for hydrogen, Ci to C ₁₆ alkyl, C ₃ to C ₆ -

Alkenyl, C ₅ to C ₇ cycloalkyl, C ₇ to C ₁₆ aralkyl, C ₆ to C ₁₀ aryl or are a heterocyclic radical which can be substituted by nonionic radicals or an anionic group X ^' or

NR'R ² or NR ³ R ⁴ independently of one another represent a five- or six-membered saturated ring which is attached via N and which may additionally contain an N or O and / or may be substituted by nonionic radicals,

R ⁵ to R ¹⁰ independently of one another are hydrogen, halogen, C ₁ -C ₁₆ -alkyl, C 1 -C ₆ -alkoxy, C 1 -C ₆ -alkylthio, cyano or nitro or

R; R, R; R, R; R or R; R independently of one another represent a two- or three-membered bridge which may contain an N or O and / or which may be substituted by nonionic radicals,

R ^{11 represents} hydrogen, d to C ₆ alkyl, C ₅ to C ₇ cycloalkyl, C ₆ to C ₀ aryl or a heterocyclic radical which can be substituted by nonionic radicals or an anionic group X ^" ,

X ^"represents an anionic group of the formulas -COO ^" , -SO ^" or -O-SO ₃ ^" or an equivalent of the di-anionic groups of the formulas -PO ₃ ^{2 "} or -O-PO ₃ ^2" ,

M ^{+ stands} for a cation or an equivalent of a polycation which contains at least one conjugated π system with at least 6 π electrons, and

represents an integer from 1 to 3,

with the proviso that M ⁺ does not represent benzyltrimethylammonium, benzyltriethylammonium, tetraphenylphosphonium, butyltriphenylphosphonium or ethyltriphenylphosphonium. Examples of nonionic radicals are Ci to C ₄ alkyl, Ci to C alkoxy, halogen, cyano, nitro, Ci to C alkoxycarbonyl, Ci to C ₄ alkylthio, C to C ₄ alkanoylamino, benzoylamino, Mono- or di-Ci to C ₄ alkylamino in question.

Alkyl radicals, including those in alkoxy, alkylthio or aralkyl, also those that later in

Text mentioned can be straight or branched.

Heterocyclic radicals are furyl, thienyl, pyridyl or a radical of the formula

Alkyl, alkoxy, aryl and heterocyclic radicals, even those mentioned later in the text, can optionally carry further radicals, such as alkyl, halogen, nitro, cyano, CO-NH ₂ , alkoxy, trialkylsilyl, trialkylsiloxy or phenyl, which 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 ethoxylated or propoxylated or silylated, adjacent alkyl and / or alkoxy radicals on aryl or heterocyclic radicals can together form a three- or four-membered radical Form a bridge and the heterocyclic radicals can be benzannelated and / or quaternized.

A cation or an equivalent of a polycation which contains at least one conjugated π system with at least 6 π electrons is preferably to be understood

a) an aromatic or heteroaromatic substituted ammonium, sulfonium or iodonium salt, b) a cyclic onium salt, c) a redox system in its oxidized cationic or radical-cationic form or d) a cationic dye system.

Examples for this are:

a) anilinium salts, diphenyliodonium, thien-2-yl-trimethylammonium, b) pyridinium salts, quinolinium salts, benzothiazolium salts, dithiolium salts, c) bipyridinium salts, Chinodiimmoniumsalze, Metallocenyle as ferrocenyl (Fe ^m (C ₅ H ₅₎ ₂ ^+), Manganocenyl ^{(Mn, II} (CO) ₃ C ₅ H ₅ ⁺ ), d) cationic organic dyes.

Aromatic and heteroaromatic substituents mean, for example: phenyl, tolyl, anisyl, chlorophenyl, naphthyl, furyl, thienyl, pyridyl, quinolyl.

Cationic organic dyes can, for example, come from the classes of cyanines, streptocyanines, hemicyanines, diazahemicyanines, zero methines, enamine dyes, hydrazone dyes, di- or tri (het) arylmethane dyes, xanthene dyes, azine dyes (phenazines, oxazines, thiazines) or, for example, the

Classes of azo dyes, anthraquinone dyes, neutrocyanines, porphyrins or phthalocyanines come from if they carry at least one localized positive charge. Such dyes are disclosed, for example H. Berneth, Cationic Dyes in Ullmann's Encyclopedia of Industrial Chemistry, VCH, ^th edition sixth

Preferred are cationic organic dyes whose λ _max differs from the λ _ma χ _{2 of} the xanthene dyes by no more than 50 nm, preferably no more than 30 nm, very particularly preferably no more than 10 nm.

Redox systems are known for example from S. Hünig, H. Berneth, Topics in

Current Chemistry, vol. 92, 1, 1980 and K. Deuchert, S. Hünig, Angew. Chem. 1978, 90, 927. For the purposes of the invention, the oxidation stage OX and the radical stage SEM are suitable as cations M ⁺ , provided they are cationic.

Xanthene dyes of the formula (I), in which

R ¹ to R ⁴ independently of one another are hydrogen, methyl, ethyl, propyl, butyl, chloroethyl, cyanoethyl, hydroxyethyl, hydroxypropyl, -CH ₂ CH ₂ COO \ -CH ₂ CH ₂ CH ₂ COO \ -CH ₂ CH ₂ CH ₂ CH ₂ COO \ -CH ₂ CH ₂ SO ₃ ^" ,

-CH ₂ CH ₂ CH ₂ SO ₃ \ -CH ₂ CH ₂ CH ₂ CH ₂ SO ₃ -, -CH ₂ CH ₂ OSO ₃ ^" , allyl, cyclopentyl, cyclohexyl, benzyl, phenethyl, phenyl, tolyl, anisyl, -C ₆ H ₄ -SO ₃ ^" ,

Pyridyl or furyl or

NR'R ² or NR ³ R ⁴ independently of one another represent pyrrolidino, piperidino, morpholino, piperazino or N-methylpiperazino,

R ⁵ to R ¹⁰ independently of one another represent hydrogen, chlorine, methyl or methoxy or

R '; R ⁵ , R ² ; R ⁶ , R ³ ; R ⁸ or R ⁴ ; R ⁹ independently of one another for a -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ - or -CH ₂ CH ₂ -O - stand bridge,

R ¹¹ for hydrogen, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ CH ₂ COO \

-CH ₂ CH ₂ CH ₂ CH ₂ COO-, -CH ₂ CH ₂ SO ₃ ^" , -CH ₂ CH ₂ CH ₂ SO ₃ \

-CH ₂ CH ₂ CH ₂ CH ₂ SO ₃ ^" , -CH ₂ CH ₂ OSO ₃ ^" , phenyl, naphthyl or pyridyl, which are substituted by up to two radicals -COO ^" , -SO ₃ ^" , CN, -COO-methyl -Butyl are substituted,

where the radicals R ¹ to R ⁴ and R ¹¹ contain a total of at least two -COO ^" or -SO ₃ ^" groups, represents a cation or an equivalent of a polycation of one of the following formulas,

(XNIII)

(XXIII)

(XXNII)

(XXVIII), where

R ²¹ to R ²³ , R ³⁶ , R ³⁷ , R ³⁹ to R ⁴² , R ⁵¹ to R ⁵⁴ , R ⁵⁷ , R ⁶¹ to R ⁶⁶ , R ⁷² , R ⁷³ , R ^{72 '} , R ^73' , R ⁷⁶ , R ⁷⁷ , R ⁸⁰ and R ⁸¹ independently of one another for hydrogen, d- to C ₁₆ - Alkyl, C - to C ₆ -alkenyl, C ₅ - to C ₇ -cycloalkyl, C ₇ - to -CC ₆ aralkyl or C ₆ - to Cio-aryl, which can be substituted by nonionic radicals or

two adjacent radicals together with the nitrogen atom connecting them independently represent a five- or six-membered saturated ring which is bonded via N and which may additionally contain an N or O and / or may be substituted by nonionic radicals,

R ²⁵ to R ²⁷ , R ³² , R ³³ and R ⁷⁸ independently of one another for d- to C ₁₆ -alkyl, C ₃ - bis

C ₆ alkenyl, C ₅ to C ₇ cycloalkyl, C ₇ to C ₆ aralkyl or C ₆ to C ₁₀ aryl, which can be substituted by nonionic radicals,

R ²⁸ for hydrogen, chlorine, amino, Ci to C ₁₆ alkyl, C ₃ to C ₆ alkenyl, C ₅ to C ₇ cycloalkyl, C ₇ to C _{] 6} aralkyl or C ₆ to Cio -Aryl stands,

R ²⁴ , R ^{24 '} , R ²⁹ to R ³¹ , R ³⁴ , R ³⁵ and R ⁷⁹ independently of one another for hydrogen, halogen, Ci to C ₈ alkyl, C _\ to C ₈ alkoxy, Ci to C ₄ -Alkylthio, Cyano or Nitro stand or

two adjacent radicals R ²⁴ , R ²⁹ , R ³⁴ and R ³⁵ stand for a -CH = CH-CH = CH- bridge,

R ³⁸ , R ⁵⁵ and R ⁵⁶ independently of one another are hydrogen, halogen, Ci to C ₄ alkyl, d to C ₄ alkoxy, cyano, nitro, d to C ₄ alkoxycarbonyl, Ci to C ₄

Are alkanoylamino or Ci to C ₄ -alkanesulfonylamino and R can form a - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ bridge with R,

R ⁴³ to R ⁴⁸ , R ⁶⁰ , R ⁶⁷ , R ⁶⁸ and R ⁸² independently of one another represent hydrogen, halogen, Ci to C ₈ alkyl, d to C ₈ alkoxy or Ci to C ₄ alkylthio and R ⁴³ with R ³⁹ , R ⁴⁴ with R ⁴⁰ , R ⁴⁶ with R ⁴¹ , R ⁴⁷ with R ⁴¹ , R ⁶⁷ with R ⁶³ , R ⁶⁸ with R ⁶⁵ and R ⁸² with R ⁸⁰ a - (CH ₂ ) ₂ - or - ( CH ₂ ) ₃ bridge can form

R ⁴⁹ , R ⁷⁴ and R ⁷⁴ independently of one another are hydrogen, Ci to C ₁₆ alkyl, C to C ₇ cycloalkyl or C ₆ to C ₀ aryl, which by nonionic

Residues can be substituted,

Y ¹ to Y ³ independently represent O, S, NR ⁵⁷ , CR ⁵⁸ R ⁵⁹ or -CH = CH-,

represents CR, 6 ^o 0 ^υ or N,

Y ⁵ and Y ⁶ independently of one another represent O, S, NR ⁵⁷ or CR ⁵⁸ R ⁵⁹ ,

Z, Y ⁷ and Y ⁷ independently of one another represent N, CH or C-CN,

Y ⁸ and Y ⁸ independently of one another represent O or S,

R ⁵⁸ and R ⁵⁹ independently of one another represent hydrogen or C 1 -C ₄ -alkyl or

CR ₍ 5 ³ 8 ^δ Rτ 5'9 ^y for a ring of the formulas

^• o ^* or 0, wherein of the harvest d (*) atom multiple bonds emanating two inputs,

R ⁵⁰ for hydrogen, halogen, d- to C ₄ -alkyl, C to C ₄ -alkoxy, d- to C ₄ -

Alkylthio, cyano, nitro, Ci to C ₄ alkoxycarbonyl, mono- or dialkyl amino, pyrrolidino, piperidino or morpholino, or

R ⁵⁰ ; R ^{60 form} a -CH = CH-CH = CH bridge, R ⁶⁹ and R ⁷⁵ independently of one another for hydrogen, C ₁ -C ₄ -alkyl or for a radical of the formulas

stand,

R ⁷⁰ and R ⁷⁰ independently of one another represent hydrogen, halogen, Ci to C ₈ alkyl, Ci to C ₈ alkoxy or d to C alkylthio or together form a - CH = CH-CH = CH bridge or R ⁷⁰ with R ⁷⁷ a - (CH ₂ ) ₂ - or -

(CH ₂ ) ₃ bridge can form

R ⁷¹ for hydrogen, halogen, d- to C ₈ -alkyl, Ci- to C ₈ -alkoxy, C _t - to C ₄ -alkylthio, mono- or di-Cj- to C ₈ -alkylamino, anilino or N-Ci - to C ₈ - alkyl anilino,

A for a rest of the formulas

stands,

B ^{1 stands} for a direct bond, -CH = CH- or -C≡C-,

B ^{2 represents} a direct bond, -CH = CH-, -C≡C- or thien-2,5-diyl, Het represents a five- or six-membered aromatic or quasi-aromatic heterocyclic ring which contains 1 to 3 heteroatoms of the N, O or S series and which is benzannelated and / or substituted by up to three nonionic radicals,

m represents an integer from 1 to 3, where, if m> 1, the radicals indicated with m can have different meanings and

n represents an integer from 1 to 2.

Examples of heterocyclic rings Het are thiazolyl, benzthiazolyl, thienyl, benzothienyl, pyrazolyl, thiadiazolyl, pyridyl.

The radical-cationic oxidation state SEM of the formula corresponding to formula (XXV) is also suitable as M ^{1 "}

where R »61. and . r R> 62 have the meaning given above.

In a particularly preferred form, the xanthene dyes used are those of the formula (II)

embedded image in which

R ¹ to R ⁴ independently of one another are hydrogen, methyl, ethyl, propyl, butyl,

Cyanoethyl, hydroxyethyl, hydroxypropyl, cyclohexyl, benzyl or phenyl or

NR'R ² or NR ³ R ⁴ independently of one another represent pyrrolidino, piperidino or morpholino,

R 5, τ R, 6, _n R8 and R independently of one another represent hydrogen, methyl or methoxy or

R ^ R ⁵ , R ² ; R ⁶ , R ³ ; R ⁸ or R ⁴ ; R ⁹ independently of one another for a -CH ₂ CH ₂ CH ₂ -

Stand bridge,

M ⁺ for a cation or an equivalent of a polycation of one of the formulas (X) to (XII), (XV), (XVI), (XVIII) to (XX), (XXIV), (XXVI), (XXVII) or ( XXVIII)

wherein R ²¹ to R ²³ , R ³⁶ , R ³⁷ , R ³⁹ to R ⁴² , R ⁵⁷ , R ⁶¹ to R ⁶⁶ , R ⁷² , R ⁷³ , R ^{72 '} , R ^73' , R ⁷⁶ , R ⁷⁷ , R ⁸⁰ and R ⁸¹ independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, cyanoethyl, hydroxyethyl, hydroxypropyl, cyclohexyl, benzyl or phenyl or

NR ²¹ R ²² , NR ³⁶ R ³⁷ NR ³⁹ R ⁴⁰ , NR ⁴¹ R ⁴² , NR ⁶¹ R ⁶² and NR ⁸⁰ R ⁸¹ independently of one another represent pyrrolidino, piperidino or morpholino,

R ⁵ to R, R ³² , R ³ and R independently of one another represent methyl, ethyl, propyl, butyl, cyanoethyl, hydroxyethyl, hydroxypropyl, cyclohexyl or benzyl,

R ²⁴ , R ^{24 '} , R ³⁴ , R ³⁵ and R ⁷⁹ independently of one another represent hydrogen, chlorine, methyl, methoxy, cyano or nitro or

two adjacent radicals R ²⁴ , R ³⁴ or R ³⁵ stand for a -CH = CH-CH = CH bridge,

R ³⁰ and R ^{31 are the} same and represent methyl, ethyl, propyl, 2-propyl, butyl or tert-butyl,

R for hydrogen, chlorine, methyl, methoxy, cyano, nitro, methoxycarbonyl,

Acetylamino or methanesulfonylamino,

R ⁴³ to R ⁴⁸ , R ⁶⁷ , R ⁶⁸ and R ⁸² independently of one another represent hydrogen, chlorine, methyl or methoxy,

R ⁴⁹ , R ⁷⁴ and R ⁷⁴ independently of one another represent methyl, cyclohexyl or phenyl,

B ^{1 stands} for a direct bond, Y ² and Y ^{3 are the} same and stand for O, S, NR ⁵⁷ , CR ⁵⁸ R ⁵⁹ or -CH = CH-,

Y ° represents O, S or NR 5 ³ 7 ',

R ⁵⁸ and R ^{59 are the} same and represent methyl,

Z, Y ⁷ and Y ^{7 '} stand for CH,

Y ⁸ and Y ⁸ stand for O or S and are the same,

R ^{69 represents} hydrogen or a radical of the formula

stands,

R ⁷⁵ for hydrogen or for a radical of the formulas

stands,

R ⁷⁰ and R ⁷⁰ independently of one another represent hydrogen, chlorine, methyl or methoxy or together form a -CH = CH-CH = CH bridge, R 71 stands for hydrogen, chlorine, methyl, methoxy, ethoxy, dimethylamino, diethylamino, N-methyl-N-cyanoethylamino, N-methyl-N-hydroxyethylamino, anilino or N-methylanilino,

for a rest of the formulas

stands,

m represents an integer from 1 to 3, where, if m> 1, the radicals indicated with m can have different meanings.

In a very particularly preferred form, the xanthene dyes used are those of the formula (II-A)

embedded image in which R ¹ to R ⁴ and R ²¹ to R ²³ independently of one another represent hydrogen, methyl, ethyl, propyl or butyl or

NR R, NR R or NR R independently of one another represent pyrrolidino, piperidino or morpholino,

R, 5, R, R and R independently of one another represent hydrogen or methyl or

R '; R ⁵ , R ² ; R °, R ³ ; R ⁸ or R ⁴ ; R ⁹ independently of one another represent a -CH ₂ CH ₂ CH ₂ bridge,

R, 24 stands for hydrogen, methyl or methoxy or two adjacent radicals R 24 stand for a -CH = CH-CH = CH bridge and

m represents 1 to 2.

In a likewise very particularly preferred form, the xanthene dyes used are those of the formula (II-B)

embedded image in which

R ¹ to R ⁴ and R ²⁵ independently of one another represent hydrogen, methyl, ethyl, propyl or butyl or NR'R ² or NR ³ R ⁴ independently of one another represent pyrrolidino, piperidino or mo holino,

R, R, R and R independently of one another represent hydrogen or methyl or

R '; R ⁵ , R ² ; R ⁶ , R ³ ; R ⁸ or R ⁴ ; R ⁹ independently of one another represent a -CH ₂ CH ₂ CH ₂ bridge,

R »24 stands for hydrogen, methyl or methoxy or two adjacent radicals R 24 stand for a -CH = CH-CH = CH bridge and

m represents 1 to 2.

In a likewise very particularly preferred form, the xanthene dyes used are those of the formula (II-C)

embedded image in which

R ¹ to R ⁴ , R ²⁵ and R ²⁶ independently of one another represent hydrogen, methyl, ethyl, propyl or butyl or NR'R ² or NR ³ R ⁴ independently of one another represent pyrrolidino, piperidino or morpholino,

R, 5, R, R and R independently of one another represent hydrogen or methyl or

B ^{1 stands} for a direct bond,

R ^{24 stands} for hydrogen, methyl or methoxy or two adjacent radicals R ²⁴ stand for a -CH = CH-CH = CH bridge and

m represents 1 to 2.

In a likewise very particularly preferred form, the xanthene dyes used are those of the formula (II-D)

wherein

R ¹ to R ⁴ independently of one another represent hydrogen, methyl, ethyl, propyl or butyl or NR'R ² or NR ³ R ⁴ independently of one another represent pyrrolidino, piperidino or morpholino,

R 5, R r 6, R and R independently of one another represent hydrogen or methyl or

R '; R ⁵ , R ² ; R °, R ³ ; R ⁸ or R ⁴ ; R ⁹ independently of one another represent a -CH ₂ CH ₂ CH ₂ bridge and

R ^{24 represents} hydrogen, methoxy, ethoxy, butoxy or octoxy.

In a likewise very particularly preferred form, the xanthene dyes used are those of the formula (II-E)

wherein

R to R independently of one another represent hydrogen, methyl, ethyl, propyl or butyl or

NO ^! R ² or NR ³ R ⁴ independently of one another represent pyrrolidino, piperidino or morpholino,

R> 5, τ R> 6, τ R) 8 and, R r, 9 independently of one another represent hydrogen or methyl or R '; R ⁵ , R ² ; R ⁶ , R ³ ; R ⁸ or R ⁴ ; R ⁹ independently of one another represent a -CH ₂ CH ₂ CH ₂ bridge and

R and R are the same and represent hydrogen, methyl or tert-butyl.

In a likewise very particularly preferred form, the xanthene dyes used are those of the formula (II-F)

embedded image in which

R ¹ to R ⁴ , R ³² and R ³³ independently of one another represent hydrogen, methyl, ethyl, propyl or butyl or

R 5, R, R and R independently of one another represent hydrogen or methyl or

R ^ R ⁵ , R ² ; R ⁶ , R ³ ; R ⁸ or R »4 ⁴ ; .τR» 9 ^y independently of one another represent a -CH ₂ CH ₂ CH ₂ bridge and R ³⁴ and R ³⁵ independently of one another represent hydrogen, methyl, methoxy or methoxycarbonyl or two adjacent radicals represent a -CH = CH-CH = CH- bridge,

m represents 1 or 2,

Y ² and Y ^{3 are} independently O, S, C (CH ₃ ) or -CH = CH- and

stands for CH.

Preferably Y ^{2 is} S or C (CH ₃ ) ₂ and Y ^{3 is} -CH = CH-.

In a likewise very particularly preferred form, the xanthene dyes used are those of the formula (II-G)

embedded image in which

R ¹ to R ⁴ , R ³² , R ³⁶ and R ³⁷ independently of one another represent hydrogen, methyl, ethyl, propyl or butyl or

NR R, NR ³ R and NR R independently of one another represent pyrrolidino, piperidino or morpholino and R »36 additionally represents phenyl, methoxyphenyl or ethoxyphenyl,

R, 5, R, R and R independently of one another represent hydrogen or methyl or

R '; R ⁵ , R ² ; R ⁶ , R ³ ; R ⁸ or R ⁴ ; R ⁹ independently of one another represent a -CH ₂ CH ₂ CH ₂ bridge and

R, 34 represents hydrogen, methyl, methoxy or methoxycarbonyl,

R, 38 represents hydrogen, methyl, methoxy, cyano, acetylamino or methanesulfonylamino,

m stands for 1 and

Y ^{2 represents} O, S, C (CH ₃ ) ₂ or -CH = CH-.

In a likewise very particularly preferred form, the xanthene dyes used are those of the formula (II-H)

embedded image in which

R ¹ to R ⁴ and R ³⁹ to R ⁴² independently of one another represent hydrogen, methyl, ethyl, propyl or butyl or NR'R ² , NR ³ R ⁴ , NR ³⁹ R ⁴⁰ and NR ⁴¹ R ⁴² independently of one another represent pyrrolidino, piperidino or morpholino,

R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ⁴³ , R ⁴⁴ , R ⁴⁶ and R ^{47 are} independently hydrogen or

Stand methyl or

R '; R ⁵ , R ² ; R ⁶ , R ³ ; R ⁸ , R ⁴ ; R ⁹ , R ³⁹ ; R ⁴³ , R ⁴⁰ ; R ⁴⁴ , R ^4I ; R ⁴⁶ and R ⁴² ; R ⁴⁷ independently for a -CH ₂ CH ₂ CH ₂ bridge stand,

R ⁴⁵ and R ^{48 represent} hydrogen and

R, 49 represents hydrogen, methyl or phenyl.

In a likewise very particularly preferred form, the xanthene dyes used are those of the formula (II-J)

embedded image in which

R to R and R to R independently of one another represent hydrogen, methyl, ethyl, propyl or butyl or

NR ^J R ² , NR ³ R ⁴ , NR ⁶³ R ° ⁴ and NR ⁶⁵ R ⁶⁶ independently of one another represent pyrrolidino, piperidino or morpholino, R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ⁶⁷ and R ⁶⁸ independently of one another represent hydrogen or methyl or

R '; R ⁵ , R ² ; R ⁶ , R ³ ; R ⁸ , R ⁴ ; R ⁹ , R ⁶³ ; R ⁶⁷ and R ⁶⁵ ; R ⁶⁸ independently of one another represent a - CH ₂ CH ₂ CH ₂ bridge,

R ^{69 represents} hydrogen, phenyl, 2-chloro-phenyl, 4-dimethylaminophenyl, 4-diethylaminophenyl, 4-anilinophenyl, naphthyl, 4-dimethylaminonaphthyl or 4-anilinonaphthyl.

In a likewise very particularly preferred form, the xanthene dyes used are those of the formula (II-K)

wherein

R ¹ to R ⁴ , R ⁷² , R ⁷³ , R ^{72 '} and R ^73' independently of one another represent hydrogen, methyl, ethyl, propyl or butyl, where R ⁷² and R ⁷² or R ⁷³ and R ^{73 are the} same or

NO ^! R ² , NR ³ R ⁴ , NR ⁷² R ⁷³ and NR ⁷² R ^{73 '} independently of one another are pyπolidino, piperidino or Moφholino, where NR ⁷² R ⁷³ and NR ⁷² R ^{73 are the} same,

R ⁵ , R ⁶ , R ⁸ and R ⁹ independently of one another represent hydrogen or methyl or R ^ R ⁵ , R ² ; R ⁶ , R ³ ; R ⁸ and R ⁴ ; R ⁹ independently of one another represent a -CH ₂ CH ₂ CH ₂ bridge,

7 7 'Y and Y are the same and stand for N or CH,

Y ⁸ and Y ^{8 are the} same and stand for S,

R ⁷⁴ and R ^{74 'are} identical and represent hydrogen, methyl, ethyl, propyl, butyl or phenyl,

R ^{75 represents} hydrogen, phenyl, 4-dimethylaminophenyl or 4-diethylaminophenyl and

A for 4-dimethylaminophenyl, 4-diethylaminophenyl, 4-N-methyl-cyanoethyl aminophenyl, 4-N-methyl-hydroxyethylaminophenyl or a radical of the formula

stands.

In a likewise very particularly preferred form, the xanthene dyes used are those of the formula (II-L) embedded image in which

R ¹ to R ⁴ , R ⁸⁰ and R ⁸¹ independently of one another represent hydrogen, methyl, ethyl, propyl or butyl or

NR'R ² , NR ³ R ⁴ and NR ⁸⁰ R ⁸¹ independently of one another represent pyrrolidino, piperidino or Moφholino,

R 7'8 ^{8 represents} methyl, ethyl, benzyl, cyanoethyl or hydroxyethyl,

R »5, R, R, R and R» 82 independently of one another represent hydrogen or methyl or

R '; R ⁵ , R ² ; R ⁶ , R ³ ; R ⁸ , R ⁴ ; R ⁹ and R ⁸⁰ ; R ⁸² independently of one another represent a - CH ₂ CH ₂ CH ₂ bridge, the bridge R ⁸⁰ ; R ⁸² can be substituted by 1 to 3 methyl groups, and

70

R represents hydrogen or bromine.

For a write-once optical data carrier according to the invention, which is written and read with the light of a blue laser, those xanthene dyes are preferred whose absorption maximum λ _m j _{u is} in the range 420 to 550 nm, the wavelength λι / 2 at which the extinction in the short-wave flank of the absorption maximum of the wavelength λm _a ^ half of the absorbance value λ _max2 , and the wavelength λy _{\ 0} , at which the extinction in the short-wave flank of the absorption maximum of the wavelength λ _{max2 is} one tenth of the extinction _value at λ _maX2 , preferably not more than 50 nm apart. Such a xanthene dye preferably has no shorter-wave maximum λ _max ι up to a wavelength of 350 nm, particularly preferably up to 320 nm, very particularly preferably up to 290 nm.

Xanthene dyes with an absorption maximum λ _ma χ ₂ of 410 to 530 nm are preferred.

Xanthene dyes with an absorption maximum λ _maX2 of 420 to 510 nm are particularly preferred.

Xanthene dyes with an absorption maximum λ _maX 2 of 430 to 500 nm are very particularly preferred.

With these xanthene dyes, λ _\ a and λ no, as defined above, are preferably not more than 40 nm apart, particularly preferably not more than 30 nm apart, very particularly preferably not more than 20 nm apart.

For a write-once optical data carrier according to the invention which is written and read with the light of a red laser, preference is given to xanthene dyes whose absorption maximum λ _{maX2 is} in the range from 500 to 650 nm, the wavelength λι / ₂ at which the absorbance in the long-wave flank of the absorption maximum of the wavelength λ _ma χ ₂ is half the extinction _value at _max2 , and the wavelength λ] / ι ₀ , at which the extinction in the long-wave flank of the absorption maximum of the wavelength λ _{maX2 is} one tenth of the extinction _value at λ _max2 are preferably no more than 50 nm apart. Such a xanthene dye preferably has a wavelength of up to 750 nm, particularly preferably up to 800 nm, very particularly preferably up to 850 nm, no longer-wave maximum λ _max3 .

Xanthene dyes with an absorption maximum λ _max2 of 530 to 630 nm are preferred.

Xanthene dyes with an absorption maximum λ _max2 of 550 to 620 nm are particularly preferred.

Xanthene dyes with an absorption maximum λ _m ax2 of 580 to 610 nm are very particularly preferred.

With these xanthene dyes, λ ₂ and λ] _{/ 10} , as defined above, are preferably not more than 40 nm apart, more preferably not more than 30 nm apart, very particularly preferably not more than 20 nm apart.

At the absorption _maximum λ _{max, the} xanthene dyes have a molar extinction coefficient ε> 40,000 l / mol cm, preferably> 60,000 l / mol cm, particularly preferably> 80,000 l / mol cm, very particularly preferably> 100,000 l / mol cm.

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

Xanthene dyes of the formula (I) with cations other than the invention are known in some cases.

Another object of the invention are xanthene dyes of the formula (I), in which the substituents have the general, special and very special meanings given above and the provisions given above apply.

The xanthene dyes of the formula (I) are prepared, for example, by

Implementation of Xanthene dyes of the formula (I) in which M ^{+ represents} a cation M ⁺ not according to the invention, for example an alkali metal ion such as Li ⁺ , Na ⁺ , K ⁺ , a proton H * or an ammonium ion such as NH ₄ ⁺ , trimethylammonium or tetramethylammonium,

with salts M ⁺ Z ^" , in which M ^{+ has} the meaning according to the invention given above and Z ^{" stands} for an anion, for example for chloride, bromide, hydrogen sulfate, V% sulfate, methosulfate, acetate or tetrafluoroborate,

in a suitable solvent in which the starting materials of the formulas (I) with M ⁺ = M ⁺ and M ⁺ Z ^" preferably dissolve at least partially and the product of the formula (I) according to the invention has a lower solubility Suitable solvents are for example water, alcohols such as methanol, ethanol, propanol, methoxyethanol, methoxypropanol, nitriles such as acetonitrile, amides such as dimethylformamide, N-methylpyrrolidone and esters such as γ-butyrolactone or mixtures thereof.

Another process for the preparation of the xanthene dyes according to the invention

Formula (I) is that xanthene dyes of the formula (I), in which M ^{+ stands} for a cation M ⁺ not according to the invention, for example for an alkali metal ion such as Li ⁺ , Na ⁺ , K ⁺ , a proton H ⁺ or an ammonium ion such as NH ⁺ , Trimethylammonium or tetramethylammonium, can be reacted with cation exchangers which are loaded with the cations M ⁺ according to the invention. Suitable solvents are also those described above. This process is advantageous if the xanthene dyes of the formula (I) according to the invention are readily soluble in the solvent selected. They are then isolated, for example, by stripping off the solvent or by precipitation with a solvent in which they are sparingly soluble. Such solvents can e.g. B. aromatics such as toluene or

Be esters such as ethyl acetate. The light-absorbing substances described 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 illumination with focused light if the light wavelength is in the range from 360 to 460 nm and 600 to 680 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 xanthene dyes are preferably applied to the optical data carrier by spin coating. The xanthene dyes can be mixed with one another or with other dyes with similar spectral properties. In particular, dyes can also be mixed with different cations. The

In addition to the xanthene dyes, 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. Metals and dielectric layers serve u. a. to adjust the reflectivity and the heat balance. Depending on the laser wavelength, metals can be gold, silver, aluminum and the like. a. 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. 1): 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 preferably:

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.

Alternatively, the optical data carrier has, for example, the following layer structure

(cf. FIG. 2): a preferably transparent substrate (11), an information layer (12), optionally a reflection layer (13), optionally an adhesive layer (14), another preferably transparent substrate (15).

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

The following examples illustrate the subject matter of the invention.

Examples

example 1

6.3 g of the xanthene dye of the formula

(Rhodamine 660) were dissolved in 200 ml of water. 2.8 g of ferrocenyl tetrafluoroborate were slowly sprinkled in at room temperature with stirring. The mixture was allowed to stir at room temperature overnight and suction filtered through a G4 frit. 4.5 g (57% of theory) of a shiny golden powder of the formula were obtained

Mp> 300 ° C max (methanol) = 578 nm ε = 121217 1 / mol cm

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

Suitable xanthene dyes are listed in the table, which can be prepared analogously to Example 1:

^1} in methanol unless otherwise stated.

Example 40

A 4% by weight solution of the dye from Example 15 in 2,2,3,3-tetrafluoropropanol was prepared at room temperature. This solution was applied to a pregrooved polycarbonate substrate using spin coating. The pregrooved polycarbonate substrate was produced as a disk using injection molding. The dimensions of the disc and the groove structure corresponded to those which are usually used for DVD-R. The disk with the dye layer as the information carrier was sputtered with 100 nm silver. A UV-curable acrylic lacquer was then applied by spin coating and cured using a UV lamp. The disk was created with a dynamic writing test set up on an optical bench consisting of a diode laser (λ = 656 nm)

Generation of linear polarized light, a polarization-sensitive beam splitter, a λ / 4 plate and a movably suspended converging lens with a numerical aperture NA = 0.6 (actuator lens) were tested. The light reflected from the reflection layer of the disk was coupled out of the beam path with the aid of the polarization-sensitive beam splitter mentioned above and focused on a four-quadrant detector by an astigmatic lens. at a linear velocity V = 3.5 m / s and a write power P _w - 15 mW, a signal-to-noise ratio C / N = 52 dB was measured. The write power was applied as an oscillating pulse sequence, the disk being alternately irradiated for 1 μs with the above-mentioned write power P _w and for 4 μs with the read power P _r »0.6 mW. The disc was irradiated with this oscillating pulse sequence until it had turned around once. The marking generated in this way was then read out with the reading power P _r and the above-mentioned signal-to-noise ratio C / N was measured.

Claims

claims

Optical data carrier containing a preferably transparent substrate, possibly already coated with one or more reflection layers, on the surface of which an information layer which can be written on with light, optionally one or more reflection layers and optionally a protective layer or a further substrate or a covering layer are applied, which is coated with blue or red light , preferably laser light, can be written and read, the information layer being a light

10 absorbing compound and optionally a binder, characterized in that at least one xanthene dye, which contains at least two anionic groups and has at least one cation, which contains at least one conjugated π system with at least 6 π electrons, is used as the light-absorbing compound with the proviso that the cation is not benzyltrimethylammonium, benzyltriethylammonium, tetraphenylphosphonium, butyltriphenylphosphonium or ethyltriphenylphosphonium.

2. Optical data carrier according to claim 1, characterized in that the 0 xanthene dye of the formula (I)

corresponds,

»5 wonn R ¹ to R ⁴ independently of one another for hydrogen, Cj to Cι ₆ alkyl, C ₃ to C ₆ alkenyl, C ₅ to C ₇ cycloalkyl, C ₇ to C ₆ aralkyl, C ₆ to C ₁₀ - Aryl or a heterocyclic radical, which can be substituted by nonionic radicals or an anionic group X ^" or

R ⁵ to R ¹⁰ independently represent hydrogen, halogen, C _\ - to C ₁₆ - alkyl, d- to C ₁₆ alkoxy, d- to C ₁₆ - alkylthio, cyano or nitro or

R '; R ⁵ , R ² ; R ⁶ , R ³ ; R ⁸ or R ⁴ ; R ⁹ independently of one another represent a two- or three-membered bridge which may contain an N or O and / or may be substituted by nonionic radicals .

R ¹ 'represents hydrogen, C ₆ -C ₆ alkyl, C ₅ - to C ₇ cycloalkyl, C ₆ - to o-aryl or a heterocyclic radical which is nonionic

Radicals or an anionic group X ^" can be substituted,

X ^"represents an anionic group of the formulas -COO ^' , -SO ₃ ^" or -O-SO ^" or an equivalent of the di-anionic groups of the formulas - PO ₃ ^2" or -O-PO ₃ ^{2 "} ,

n represents an integer from 1 to 3, with the proviso that M ⁺ does not represent benzyltrimethylammonium, benzyltriethylammonium, tetraphenylphosphonium, butyltriphenylphosphonium or ethyltriphenylphosphomum.

Optical data carrier according to claim 1 or 2, characterized in that

M ⁺ for

a) an aromatic or heteroaromatic substituted ammonium, sulfonium or iodonium salt, b) a cyclic onium salt, c) a redox system in its oxidized cationic or radical-cationic form, d) a cationic dye system.

4. Optical data carrier according to one or more of claims 1 to 3, characterized in that in formula (I)

R ¹ to R ⁴ independently of one another are hydrogen, methyl, ethyl, propyl,

Butyl, chloroethyl, cyanoethyl, hydroxyethyl, hydroxypropyl,

-CH ₂ CH ₂ COO ^" , -CH ₂ CH ₂ CH ₂ COO ^" , -CH ₂ CH ₂ CH ₂ CH ₂ COO \

-CH ₂ CH ₂ SO ₃ ^" , -CH ₂ CH ₂ CH ₂ SO ₃ ^' , -CH ₂ CH ₂ CH ₂ CH ₂ SO ₃ ^" , -CH ₂ CH ₂ OSO ₃ ^" , allyl, cyclopentyl, cyclohexyl, benzyl, phenethyl,

Phenyl, tolyl, anisyl, -C ₆ H ₄ -SO ₃ ^" , pyridyl or furyl or

NR'R ² or N ³ R ⁴ independently of one another represent pyrrolidino, piperidino, Moφholino, piperazino or N-methylpiperazino, R ⁵ to R ¹⁰ independently of one another represent hydrogen, chlorine, methyl or methoxy or

R '; R ⁵ , R ² ; R ⁶ , R ³ ; R ⁸ or R ⁴ ; R ⁹ independently of one another for a -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH2- or -CH ₂ CH ₂ -O- Stand bridge,

R "for hydrogen, -CH ₂ CH ₂ COO ^" , -CH ₂ CH ₂ CH ₂ COO ^" ,

-CH ₂ CH ₂ CH ₂ CH ₂ COO-, -CH ₂ CH ₂ SO ₃ \ -CH ₂ CH ₂ CH ₂ SO ₃ \

-CH ₂ CH ₂ CH ₂ CH ₂ SO ₃ \ -CH ₂ CH ₂ OSO ₃ ^" , phenyl, naphthyl or pyridyl, which can be substituted by up to two residues -COO ^" , -SO ₃ ^" , CN, -COO-methyl to

-Butyl are substituted,

where the radicals R ¹ to R ⁴ and R ¹¹ contain a total of at least two -COO ^" or -SO ₃ ^" groups,

M ^{+ represents} a cation or an equivalent of a polycation of one of the following formulas,

Mn " ¹ (XVII), co ^ o ⁰⁰ (XVIII)

(XXIII)

(XXVII)

(XXVIII)

embedded image in which

R> 2 ^Δ 1 ^l to R »2" 3, R »3 ^J 6 ⁰ , R r» 3 ^J 7 ^/ , R> 3 ^j 9 ^y to R, 4 "2, τ R> ³ l ¹ to R ₅ ³ 4 ^* , R »5 ^J 7 ^/ , R, 6 ⁰ 1 ¹ to R, 6 ° 6 °, _D R7'3, _n R 2 '

R ^{73 '} , R ⁷⁶ , R ⁷⁷ , R ⁸⁰ and R ⁸¹ independently of one another are hydrogen, Ci to C ₁₆ alkyl, C ₃ to C ₆ alkenyl, C ₅ to C ₇ cycloalkyl, C ₇ to Ci ₆ aralkyl or C ₆ to Cio aryl, which can be substituted by nonionic radicals or

R ²⁵ to R ²⁷ , R ³² , R ³³ and R ⁷⁸ independently of one another for Cj to Cι ₆ alkyl, C ₃ to C ₆ alkenyl, C ₅ to C ₇ cycloalkyl, C to d _ö aralkyl or C ₆ to C ₁₀ aryl, which can be substituted by nonionic radicals, R ²⁸ for hydrogen, chlorine, amino, Ci- to Cι ₆ alkyl, C ₃ - to C ₆ alkenyl, C ₅ - to C cycloalkyl, C ₇ - to Cι ₆ - aralkyl or C ₆ - to Cio-aryl stands,

R ²⁴ , R ^{24 '} , R ²⁹ to R ³¹ , R ³⁴ , R ³⁵ and R ⁷⁹ independently of one another for hydrogen, halogen, d- to C ₈ -alkyl, d- to C ₈ -alkoxy, Ci bis

C ₄ - alkylthio, cyano or nitro or

two adjacent radicals R ²⁴ , R ²⁹ , R ³⁴ and R ³⁵ stand for a -CH = CH- CH = CH bridge,

R ³⁸ , R ⁵⁵ and R ⁵⁶ independently of one another for hydrogen, halogen, Ci bis

C - alkyl, Ci to C ₄ alkoxy, cyano, nitro, Cp to C ₄ alkoxycarbonyl, Ci to C alkanoylamino or Ci to C ₄ alkanesulfonylamino and R ³⁸ with R ^{36 is} a - (CH ₂ ) ₂ - or - <CH ₂ ) ₃ bridge can form,

R ⁴³ to R ⁴⁸ , R ⁶⁰ , R ⁶⁷ , R ⁶⁸ and R ⁸² independently of one another for hydrogen,

Halogen, Ci to C ₈ - alkyl, Ci to C ₈ - alkoxy or Ci- to C ₄ -

Alkylthio and R ⁴³ with R ³⁹ , R ⁴⁴ with R ⁴⁰ , R ⁴⁶ with R ⁴¹ , R ⁴⁷ with R ⁴¹ , R ⁶⁷ with R ⁶³ , R ⁶⁸ with R ⁶⁵ and R ⁸² with R ⁸⁰ a - (CH ₂ ) ₂ - or -

(CH ₂ ) ₃ bridge can form

R ⁴⁹ , R ⁷⁴ and R ⁷⁴ independently of one another represent hydrogen, Ci to C ₁₆ alkyl, C ₅ to C ₇ cycloalkyl or C ₆ to Cio aryl, which can be substituted by nonionic radicals,

Y ^{4 represents} CR ⁶⁰ or N,

Y ⁵ and Y ⁶ independently of one another represent O, S, NR ⁵⁷ or CR ⁵⁸ R ⁵⁹ , Z, Y ⁷ and Y ⁷ independently of one another represent N, CH or C-CN,

Y ⁸ and Y ⁸ independently of one another represent O or S,

R, 58 and R, 59 independently of one another represent hydrogen or Cj- to C - alkyl or

CR, 5 ^D 8 ^β Rr, 5 ³ 9 ^y for a ring of the formulas

or stands, whereby two single bonds originate from the yesterday (*) atom,

R ^{50 represents} hydrogen, halogen, d- to C ₄ -alkyl, d- to C ₄ -alkoxy, C to C ₄ -alkylthio, cyano, nitro, d- to C ₄ -alkoxycarbonyl, mono- or dialkylamino, pyrrolidino, piperidino or Moφholino stands or

R ⁵⁰ ; R ^{60 form} a -CH = CH-CH = CH bridge,

R, 69. and . τ R, 75 independently of one another for hydrogen, C to C ₄ alkyl or for a radical of the formulas

stand, R ⁷⁰ and R ⁷⁰ are independently hydrogen, halogen, Ci to C ₈ - alkylthio or are together a -CH = CH-CH = CH-bridge - alkyl, C _\ - to C ₈ -alkoxy or C ₄ to C form or R ^{70 can} form a - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ bridge with R ⁷⁷ ,

R ⁷¹ for hydrogen, halogen, Ci to C ₈ alkyl, d to C ₈ alkoxy, d to C alkyl thio, mono- or di-Ci to C ₈ alkylamino, anilino or N-Ci to C ₈ alkyl anilino,

A for a rest of the formulas

stands,

B 'represents a direct bond, -CH = CH- or -C≡C-,

B ^{2 represents} a direct bond, -CH = CH-, -C≡C- or thien-2,5-diyl,

Het represents a five- or six-membered aromatic or quasi-aromatic heterocyclic ring which contains 1 to 3 heteroatoms of the series N, O or S and which can be benzene-fused and / or substituted by up to three nonionic radicals,

m represents an integer from 1 to 3, where, if m> 1, the radicals indicated with m can have different meanings and n represents an integer from 1 to 2.

5. Optical data carrier according to one or more of claims 1 to 4, characterized in that the xanthene dye corresponds to the formula (II),

embedded image in which

R ¹ to R ⁴ independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, cyanoethyl, hydroxyethyl, hydroxypropyl, cyclohexyl, benzyl or phenyl or

NR R ² or NR ³ R ⁴ independently of one another are pyπolidino, piperidino or Moφholino,

R »5, τ R> 6, r R> 8 r R» 9 independently of one another represent hydrogen, methyl or methoxy or

to R, 6 ⁰ 6 ⁰ , τ R »7" 2, " R7'2 ^Δ ', τ R>^7/3', R r, 7'6 °, τ Rj7 "7, - Rr, 8 ⁸ 0 ^υ and R ⁸¹ R; R ^5, R ^2; R ^6, ^R! ³ ; R ⁸ or R ⁴ ; R ⁹ independently of one another represent a -CH ₂ CH ₂ CH ₂ bridge, M ⁺ for a cation or an equivalent of a polycation of one of the formulas (X) to (XII), (XV), (XVI), (XVIII) to (XX), (XXIV), (XXVI), (XXVII) or ( XXVIII)

embedded image in which

R ²¹ to R ²³ , R ³⁶ , R ³⁷ , R ³⁹ to R ⁴² , R ⁵⁷ , R ⁶¹ to R ⁶⁶ , R ⁷² , R ⁷³ , R ^{72 '} , R ^73' , R ⁷⁶ , τι RΠ RI

R, R and R independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, cyanoethyl, hydroxyethyl, hydroxypropyl, cyclohexyl, benzyl or phenyl or

NR ²¹ R ²² , NR ³⁶ R ³⁷ NR ³⁹ R ⁴⁰ , NR ⁴¹ R ⁴² , NR ^6, R ⁶² and NR ⁸⁰ R ⁸¹ independently of one another stand for Pyπolidino, Piperidino or Moφholino,

R ²⁵ to R ²⁷ , R ³² , R ³³ and R ⁷⁸ independently of one another are methyl, ethyl,

Propyl, butyl, cyanoethyl, hydroxyethyl, hydroxypropyl, cyclohexyl or benzyl,

two adjacent radicals R ²⁴ , R ³⁴ or R ³⁵ stand for a -CH = CH-CH = CH- bridge,

R represents hydrogen, chlorine, methyl, methoxy, cyano, nitro, methoxycarbonyl, acetylamino or methanesulfonylamino, R ⁴³ to R ⁴⁸ , R ⁶⁷ , R ⁶⁸ and R ⁸² independently of one another represent hydrogen, chlorine, methyl or methoxy,

B ^{1 stands} for a direct bond,

Y ² and Y ^{3 are the} same and stand for O, S, NR ⁵⁷ , CR ⁵⁸ R ⁵⁹ or -CH = CH-,

represents O, S or NR 5 ³ 7 ',

R and R ^{59 are} identical and represent methyl,

Z, Y ⁷ and Y ^{7 '} stand for CH,

Y and Y stand for O or S and are the same,

R, 69 for hydrogen or for a radical of the formula

stands,

R> 75 for hydrogen or for a rest of the formulas stands,

R ⁷⁰ and R ⁷⁰ independently of one another represent hydrogen, chlorine, methyl or methoxy or together form a -CH = CH-CH = CH bridge,

R ^{71 represents} hydrogen, chlorine, methyl, methoxy, ethoxy, dimethylamino, diethylamino, N-methyl-N-cyanoethylamino, N-methyl-N-hydroxyethylamino, anilino or N-methyl-anilino,

A for a rest of the formulas

stands,

Xanthene dyes of the formula (I) embedded image in which

R ¹ to R ⁴ independently of one another for hydrogen, Ci to -C ₆ alkyl, C ₃ to C ₆ alkenyl, C ₅ to C ₇ cycloalkyl, C ₇ to C ₁₆ aralkyl, C ₆ to Cio - Aryl or a heterocyclic radical, which can be substituted by nonionic radicals or an anionic group X ^" or

R ⁵ to R ¹⁰ independently of one another are hydrogen, halogen, d to C ₆ alkyl, Ci to C ₆ alkoxy, C to C ₆ alkylthio, cyano or nitro or

R ¹ ; R ⁵ , R ² ; R ⁶ , R ³ ; R ⁸ or R ⁴ ; R ⁹ independently of one another represent a two- or three-membered bridge which may contain an N or O and / or which may be substituted by nonionic radicals,

R 11 for hydrogen, to Ci6-alkyl, C ₅ - to d-cycloalkyl, C ₆ - to Cio-aryl or a heterocyclic radical which can be substituted by nonionic radicals or an anionic group X ^" , X ^"represents an anionic group of the formulas -COO ^" , -SO ₃ ^" or -O-SO ₃ ^" or an equivalent of the di-anionic groups of the formulas - PO ₃ ^{2 '} or -O-PO ₃ ^{2 "} ,

> M ^{+ stands} for a cation or an equivalent of a polycation which contains at least one conjugated π system with at least 6 π electrons, and

n represents an integer from 1 to 3,

with the proviso that M ⁺ does not represent benzyltrimethylammonium, benzyltriethylammonium, tetraphenylphosphonium, butyltriphenylphosphonium or ethyltriphenylphosphomum.

7. A process for the preparation of xanthene dyes according to claim 6, characterized in that xanthene dyes of the formula (I), in which M ^{+ has} a different meaning than in claim 6 with salts of the formula

_M Θ _Z Θ where

M® has the meaning according to claim 6 and

Z ^{θ stands} for an anion in a solvent,

be implemented.

8. Use of xanthene dyes that are at least two anionic

Contain groups and have as counterion at least one cation which contains at least one conjugated π system with at least 6 π electrons, with the proviso that the cation is not benzyltrimethylammomum, ben- zyltriethylammonium, Tetraphenylphosphonium, Butyltriphenylphosphonium or Ethyltriphenylphosphomum is in the information layer of write-once optical data carriers, wherein the xanthene dyes have an absorption maximum λ _maX2 in the range from 420 to 650 nm.

9. Use of xanthene dyes which contain at least two anionic groups and have as counterion at least one cation which contains at least one conjugated π system with at least 6 π electrons, with the proviso that the cation is not benzyltrimethylammonium, benzyltriethylammonium, tetraphenylphosphonium , Butyltriphenylphosphonium or Ethyltriphenylphosphomum, in the information layer of write-once optical data carriers, the data carriers are written and read with a blue or red, in particular red, laser light.

10. 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, is coated with the xanthene dyes, optionally in combination with suitable binders and additives and optionally suitable solvents, and optionally with a Reflective layer, other intermediate layers and optionally a protective layer or another substrate or a cover layer.

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