# Patent

## Title
Fast-writable and precision-writable high-capacity optical storage media

## Abstract

The invention relates to an optical recording medium, comprising a substrate and a recording layer, wherein the recording layer comprises a compound of formula (I), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and R13 are each independently of the others hydrogen, G1 or C1-C24alkyl, C2-C24alkenyl, C2-C24alkynyl, C3-C24cycloalkyl, C3-C24cycloalkenyl, C7-C24aralkyl, C6-C24aryl, C4-C12heteroaryl or C1-C12heterocycloalkyl, each unsubstituted or substituted by one or more identical or different substituents G1, wherein R1 and R2, R1 and R13, R2 and R3, R3 and R4, R4 and R5, R5 and R6, R6 and R7, R7 and R8, R8 and R9, R9 and R10, R10 and R11, R11 and R12 and/or R12 and R13 can independently of one another be bonded to one another in pairs separately or, when they contain substitutable sites, via a direct bond or via a —CH2—, —O—, —S—, —NH— or —NC1-C24alkyl-bridge in such a manner that, together with the atoms and bonds indicated in formula (I), five- or six-membered, saturated, unsaturated or aromatic, unsubstituted or G1-substituted rings are formed, G1 is any desired substituent,? xm- is an inorganic, organic organometallic anion, Yn+ is a proton or a metal, ammonium or phosphonium cation, and m and n are each independently of the other a number from 1 to 5, and p and q are each independently of the other O or a number from 0.2 to 6, the ratio of p and q to one another, depending upon m and n and, as applicable, the number of charged G1, being such that in formula (I) there is no excess positive or negative charge. Generally the optical recording medium according to the invention additionally comprises a reflecting layer. The recording media according to the invention exhibit high sensitivity and good playback characteristics, especially at high recording and playback speeds. The light stability is also excellent.

## Background
The field of the invention is the optical storage of information on write-once storage media, the information pits being differentiated by the different optical properties of a colorant at written and unwritten sites. This technology is usually termed “WORM” (for example “CD-R” or “DVD-R”); those terms have been retained herein.
Compact discs that are writable at a wavelength of from 770 to 830 nm are known from “Optical Data Storage 1989”, Technical Digest Series, Vol. 1, 45 (1989). They are read at a reduced readout power. According to the Orange Book Standard, at the recording wavelength the medium must have a base reflectivity of 65% or more. As recording media it is possible to use, for example, cyanine dyes (JP-58/125246), phthalocyanines (EP-A-676 751, EP-A-712 904), azo dyes (U.S. Pat. No. 5,441,844), double salts (U.S. Pat. No. 4,626,496), dithioethene metal complexes (JP-A-63/288785, JP-A-63/288786), azo metal complexes (U.S. Pat. No. 5,272,047, U.S. Pat. No. 5,294,471, EP-A-649 133, EP-A-649 880) or mixtures thereof (EP-A-649 884).
By using more recent compact high-performance red diode lasers that emit in the range of from 600 to 700 nm it is possible in principle to achieve a 6- to 8-fold improvement in data packing density, in that the track spacing (distance between two turns of the information track) and the size of the pits as well as the redundancy can each be reduced to approximately half the value in comparison with conventional CDs.
This imposes extraordinarily high demands on the recording layer to be used, however, such as high refractive index, high light stability in daylight and under laser radiation of low power density (readout) with, at the same time, high sensitivity under laser radiation of high power density (writing), uniformity of script width at different length pulse durations and also high contrast. The known recording layers still do not possess these properties to an entirely satisfactory extent.
EP-A-0 805 441 describes an optical recording medium comprising xanthene dyes, which can be both recorded and read at from 600 to 700 nm. In the Examples, good results are achieved with a 10 mW laser diode of wavelength 635 nm. It has been found, however, that under practical conditions the results for the dyes disclosed in EP-A-0 805 441 are not able fully to satisfy the demands (which have increased in the interim) in respect of sensitivity, recording speed and mark accuracy and reproducibility, especially in the range from 640 to 680 nm.
U.S. Pat. No. 3,781,711 discloses laser dye compositions comprising dyes having a rigid structure, including 9,9-dimethyl-2-dimethylamino-7H,9H-anthracene-7-dimethyliminium nitrate. Such compounds are used in high dilution.
WO-A-00/64986 describes carbopyronine fluorescent dyes and their use as marker groups in diagnostics. The absorption maxima and the fluorescent yield are not appreciably altered by coupling such compounds to carriers and biomolecules.
The aim of the invention is to provide an optical recording medium, the recording layer of which has high storage capacity combined with excellent other properties. The recording medium should be both writable and readable, with a minimum of errors, at the same wavelength in the range of from 600 to 700 nm (preferably from 630 to 690 nm) at high speed.
Very surprisingly, by the use of certain carbopyronine dyes as recording layer it has been possible to provide an optical recording medium having properties that are astonishingly better than those of recording media known hitherto.
The invention accordingly relates to an optical recording medium comprising a substrate and a recording layer, wherein the recording layer comprises a compound of formula (I) 




    
    
        wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and R13 are each independently of the others hydrogen, G1, or C1-C24alkyl, C2-C24alkenyl, C2-C24alkynyl, C3-C24cycloalkyl, C3-C24cycloalkenyl, C7-C24aralkyl, C6-C24aryl, C4-C12heteroaryl or C1-C12heterocycloalkyl, each unsubstituted or substituted by one or more identical or different substituents G1,
        wherein R1 and R2, R1 and R13, R2 and R3, R3 and R4, R4 and R5, R5 and R6, R6 and R7, R7 and R8, R8 and R9, R9 and R10, R10 and R11, R11 and R12 and/or R12 and R13 can independently of one another be bonded to one another in pairs separately or, when they contain substitutable sites, via a direct bond or via a —CH2—, —O—, —S—, —NH— or —NC1-C24alkyl-bridge in such a manner that, together with the atoms and bonds indicated in formula (I), five- or six-membered, saturated, unsaturated or aromatic, unsubstituted or G1-substituted rings are formed,
    
    


G1 is any desired substituent,
Xm− is an inorganic, organic or organometallic anion,
Yn+ is a proton or a metal, ammonium or phosphonium cation, and
m and n are each independently of the other a number from 1 to 5, and p and q are each independently of the other 0 or a number from 0.2 to 6, the ratio of p and q to one another, depending upon m and n and, as applicable, the number of charged G1 substituents, being such that in formula (I) there is no excess positive or negative charge.
Generally the optical recording medium according to the invention additionally comprises a reflecting layer, but this is not absolutely necessary per se and it can be omitted depending upon the type of detector.
Each G1 is, where applicable independently of any other G1, any desired substituent, for example halogen, —OH, —O−, —OA, ═O, —SH, —S−, —SA, ═S, —NO2, —CN, —NH2, —NHA, —N(A)2, —N+H3, —N+H2A, —N+H(A2), —N+(A)3, —NHCOA, —N(A)COA, —CHO, —C(A)═O, —CH(OA)2, —C(A)(OA)2, —C(OA)3, —CH═N—A, —C(A)═N—A, —N═CH—A, —N═C(A)2, —N═N—A, —COO−, —COOH, —COOA, —CONH2, —CONHA, —CON(A)2, —NHCONH2, —NHCONHA, —NHCON(A)2, —N(A)CONH2, —N(A)CONHA, —N(A)CON(A)2, —SO2A, —SO3−, —SO3H, —SO3A, —PO3−, —PO(OA)2, —Si(A)3, —OSi(A)3, —Si(OA)2(A) or —Si(OA)3, each A being independently of the others alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aralkyl, aryl or heteroaryl, each of which can be uninterrupted or interrupted by one or more hetero atoms, such as N, O, P and S, for example in the form of a polyalkylene glycol chain, pyrrolidinyl, piperidyl, piperazinyl, morpholinyl, oxybisphenylene or heteroaryl, such as pyridyl, furyl, thienyl or phenothiazinyl.
A is typically C1-C24alkyl, C2-C24alkenyl, C2-C24alkynyl, C3-C24cycloalkyl, C3-C24cycloalkenyl, C7-C24aralkyl, C6-C24aryl or C4-C12heteroaryl.
It will be understood that different As can also be combined, such as, for example, in chromanyl, phosphindolinyl or 1-phenyl-2-pyrazolinyl, that is to say, for example, in substituted form azo-3-methyl-5-oxo-1-phenyl-2-pyrazolin-(4)-yl. It is also possible for alkylene, arylene or aralkylene to be used in place of two As, for example morpholino in place of methyl-3-oxabutyl-amino or 4-methyl-piperidino in place of ethyl-3-azabutyl-amino.
When G1 contains a radical A, that radical can be unsubstituted or substituted by from 1 to 5 identical or different substituents G2, each G2 being as defined for G1, except that G2 can only be unsubstituted or mono-substituted by G3, where G3 likewise is as defined for G1, except that G3 is not further substituted.
Especially the following substituents may be mentioned as G1: —CH2—CH2—OH, —CH2—O—CH3, —CH2—O—(CH2)7—CH3, —CH2—CH2—O—CH2—CH3, —CH2—CH(OCH3)2, —CH2—CH2—CH(OCH3)2, —CH2—C(OCH3)2—CH3, —CH2—CH2—O—CH2—CH2—O—CH3, —(CH2)3—OH, —(CH2)6—OH, —(CH2)7—OH, —(CH2)8—OH, —(CH2)9—OH, —(CH2)10—OH, —(CH2)11—OH, —(CH2)12—OH, —CH2—Si(CH3)3, —CH2—CH2—O—Si(CH3)2—C(CH3)3, —(CH2)3—O—Si(CH3)2—C(CH3)3, —(CH2)4—O—Si(C6H5)2—C(CH3)3, —(CH2)5—O—Si(CH(CH3)2)3, —CH2—CH2—CH(CH3)—CH2—CH2—CH(OH)—C(CH3)2—OH, —CH2—CH(CH3)—CH2—OH, —CH2—C(CH3)2—CH2—OH, —CH2—C(CH2—OH)3, —CH2—CH(OH)—CH3, —CH2—CH(OH)—CH2—OH, 




and —(CH2)2CH═N—R14, wherein R14 is C1-C24alkyl, C2-C24alkenyl, C2-C24alkynyl, C3-C24cycloalkyl, C3-C24cycloalkenyl, C7-C24aralkyl, C6-C24aryl, C4-C12heteroaryl or C1-C12heterocycloalkyl, each unsubstituted or substituted by one or more identical or different substituents G2, or is a metal complex. When R14 is C1-C24alkyl, it may be uninterrupted or interrupted by from 1 to 3 oxygen and/or silicon atoms. G2 or G3 may especially advantageously be alkyl unsubstituted or substituted by one or two hydroxy substituents or by a metallocenyl or azo metal complex radical. Such radicals G1 are of very special importance as R6.

The compound of formula (I) may optionally also be a dimer of formula 




wherein R1′ to R13′ have the same meanings as R1 to R13 and an R substituent selected from R1 to R13 is bonded to an R′ substituent selected from R1′ to R13′, for example via a direct bond, an alkylene group or a hetero atom, or an R′ substituent selected from R1′ to R13′ is a direct bond to an R substituent selected from R1 to R13.

Great importance is attached especially to compounds of formula (II) wherein R6 is bonded to R6′, or R6′ is a direct bond to R6.
When the numbers p and q are not whole numbers, it is to be understood by formulae (I) and (II) that there is a mixture of a certain molar composition, the individual components of which may also have different stoichiometry.
Alkyl, alkenyl or alkynyl may be straight-chain or branched. Alkenyl is alkyl that is mono- or poly-unsaturated, wherein two or more double bonds may be isolated or conjugated. Alkynyl is alkyl or alkenyl that is double-unsaturated one or more times, wherein the triple bonds may be isolated or conjugated with one another or with double bonds. Cycloalkyl or cycloalkenyl is monocyclic or polycyclic alkyl or alkenyl, respectively.
C1-C24Alkyl can therefore be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methyl-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl or tetracosyl.
C3-C24Cycloalkyl can therefore be, for example, cyclopropyl, cyclopropyl-methyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexyl-methyl, trimethyl-cyclohexyl, thujyl, norbornyl, bornyl, norcaryl, caryl, menthyl, norpinyl, pinyl, 1-adamantyl, 2-adamantyl, 5α-gonyl or 5ξ-pregnyl.
C2-C24Alkenyl is, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, or any desired isomer of hexenyl, octenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, eicosenyl, heneicosenyl, docosenyl, tetracosenyl, hexadienyl, octadienyl, nonadienyl, decadienyl, dodecadienyl, tetradecadienyl, hexadecadienyl, octadecadienyl or eicosadienyl.
C3-C24Cycloalkenyl is, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10)-thujen-10-yl, 2-norbornen-1-yl, 2,5-norbornadien-1-yl, 7,7-dimethyl-2,4-norcaradien-3-yl or camphenyl.
C1-C24Alkoxy is O—C1-C24alkyl, and C1-C24alkylthio is S—C1-C24alkyl.
C2-C24Alkynyl is, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl or 1-tetracosyn-24-yl.
C7-C24Aralkyl is, for example, benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, 9-fluorenyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω-phenyl-octyl, ω-phenyl-dodecyl or 3-methyl-5-(1′,1′,3′,3′-tetramethyl-butyl)-benzyl. C7-C24Aralkyl can also be, for example, 2,4,6-tri-tert-butyl-benzyl or 1-(3,5-dibenzyl-phenyl)-3-methyl-2-propyl. When C7-C24aralkyl is substituted, either the alkyl moiety or the aryl moiety of the aralkyl group can be substituted, the latter alternative being preferred.
C6-C24Aryl is, for example, phenyl, naphthyl, biphenylyl, 2-fluorenyl, phenanthryl, anthracenyl or terphenylyl.
Halogen is chlorine, bromine, fluorine or iodine, preferably chlorine or bromine.
C4-C12Heteroaryl is an unsaturated or aromatic radical having 4n+2 conjugated π-electrons, for example 2-thienyl, 2-furyl, 1-pyrazolyl, 2-pyridyl, 2-thiazolyl, 2-oxazolyl, 2-imidazolyl, isothiazolyl, triazolyl or any other ring system consisting of thiophene, furan, pyridine, thiazole, oxazole, imidazole, isothiazole, thiadiazole, triazole, pyridine and benzene rings and unsubstituted or substituted by from 1 to 6 ethyl, methyl, ethylene and/or methylene substituents.
Furthermore, aryl and aralkyl can also be aromatic groups bonded to a metal, for example in the form of metallocenes of transition metals known per se, more especially 




wherein R15 is CH2OH, CH2OA, COOH, COOA and COO−.

C1-C12Heterocycloalkyl is an unsaturated or partially unsaturated ring system radical, for example tetrazolyl; pyrrolidyl, piperidyl, piperazinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, morpholinyl, quinuclidinyl or another C4-C12heteroaryl that is mono- or poly-hydrogenated.
Yn+ as a metal, ammonium or phosphonium cation is, for example, Li+, Na+, K+, Mg2+, Ca2+, Cu2+, Ni2+, Fe2+, Co2+, Zn2+, Sn2+, Cr3+, La3+, methylammonium, ethylammonium, pentadecylammonium, isopropylammonium, dicyclohexylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltrimethylammonium, benzyltriethylammonium, methyltrioctylammonium, tridodecylmethylammonium, tetrabutylphosphonium, tetraphenylphosphonium, butyltriphenylphosphonium or ethyltriphenylphosphonium, or protonated Primen 81RTM or Rosin Amin DTM.
Xm− as an inorganic, organic or organometallic anion is, for example, the anion of a mineral acid, the conjugate base of an organic acid or an organometal complex anion, for example fluoride, chloride, bromide, iodide, perchlorate, periodate, nitrate, 1⁄2 carbonate, hydrogen carbonate, C1-C4alkyl sulfate, 1⁄2 sulfate, hydrogen sulfate, 1⁄3 phosphate, 1⁄2 hydrogen phosphate, dihydrogen phosphate, 1⁄2 C1-C4alkanephosphonate, C1-C4alkane-C1-C12alkyl-phosphonate, di-C1-C4alkylphosphinate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, acetate, trifluoroacetate, heptafluorobutyrate, 1⁄2 oxalate, methanesulfonate, trifluoromethanesulfonate, tosylate, benzenesulfonate, p-chlorobenzenesulfonate, p-nitrobenzenesulfonate, an alcoholate, phenolate (e.g. phenolate itself), carboxylate (also e.g. benzoate), sulfonate or phosphonate) or a negatively charged metal complex.
The person skilled in the art will readily recognise that it is also possible to use other anions with which he is familiar. It will be self-evident to him that 



  1
  x




of an inorganic, organic or organometallic anion having x negative charges, for example 1⁄2.SO42−, is a multiply charged anion which neutralises several singly charged cations or a cation having x charges, as the case may be.

Phenolates or carboxylates are, for example, anions of C1-C12alkylated, especially tert-C4-C8alkylated, phenols or benzoic acids, such as 




When Xm− is an organometallic anion, it is preferably a metal complex of formula [(L1)M1(L2)]m− (III) or [(L3)M2(L4)]− (IV), wherein M1 and M2 are a transition metal, preferably M1 being Cr3+ or Co3+ and M2 being Ni2+, Co2+ or Cu2+, m is a number from 1 to 6, L1 and L2 are each independently of the other a ligand of formula 







and L3 and L4 are each independently of the other a ligand of formula 




wherein R16, R17, R18, R19, R20 and R21 are each independently of the others hydrogen, halogen, cyano, R24, NO2, NR24R25, NHCO—R24, NHCOOR24, SO2—R24, SO2NH2, SO2NHR24, SO2NR24R25, SO3− or SO3H, preferably hydrogen, chlorine, SO2NH2 or SO2NHR24, and R22 and R23 are each independently of the other CN, CONH2, CONHR24, CONR24R25, COOR24 or COR24, wherein R24 and R25 are each independently of the other C1-C12alkyl, C1-C12alkoxy-C2-C12alkyl, C7-C12aralkyl or C6-C12aryl, preferably C1-C4alkyl, each unsubstituted or substituted by hydroxy, halogen, sulfato, C1-C6alkoxy, C1-C6alkylthio, C1-C6alkylamino or by di-C1-C6alkylamino, or R24 and R25 together are C4-C10heterocycloalkyl; it also being possible for R16 and R17, R18 and R19, and/or R20 and R21 to be bonded together in pairs in such a manner that a 5- or 6-membered ring is formed.

Reference is made by way of illustration, but on no account as a limitation, to the individual compounds disclosed in U.S. Pat. No. 5,219,707, U.S. Pat. No. 6,168,843, U.S. Pat. No. 6,242,067, WO-01/19923, WO-01/62853, EP-A-1 125 987, EP-A-1 132 902, JP-A-06/199045, JP-A-07/262604, JP-A-2000/190642 and JP-A-2000/198273.
It is also possible, however, to use any other known transition metal complex anion that contains, for example, a phenolic or phenylcarboxylic azo compound as ligand L1 or L2.
Preference is given to compounds of formula (I) wherein R1, R4, R5, R7, R8 and R11 are hydrogen; R2, R3, R9, R10, R12 and R13 are each independently of the others methyl, ethyl or R14, it being possible for R2 and R3, R9 and R10, R12 and R13 and/or R9 and R10 also to be bonded together in pairs via a direct bond, methylene, —O— or —N(C1-C4alkyl); and R6 is hydrogen or C1-C12alkyl, C6-C12aryl or C7-C13aralkyl, each unsubstituted or mono- to tetra-substituted by halogen, —O−, —OR26, —CN, —NR26R27, —N+R26R27R28, —N(R26)COR27, —COO−, —COOR26, —CONR26R27, R14 or by —N(R26)COR27R28, wherein R26, R27 and R28 are each independently of the others C1-C12alkyl, C6-C12aryl or C7-C13aralkyl;
all the bridging possibilities, limitations and definitions indicated above otherwise remaining unchanged.
When R6 is unsubstituted or substituted C6-C12aryl, it is preferably 




wherein R29, R30 and R31 are each independently of the others hydrogen, halogen, COOR32, OR32 or NR32R33, wherein R32 and R33 are each independently of the other hydrogen or C1-C12alkyl, C2-C12alkenyl, C1-C12cycloalkyl, C2-C12cycloalkenyl, C6-C12aryl or C7-C13aralkyl, each unsubstituted or substituted by one or two hydroxy substituents or by a metallocenyl or azo metal complex radical and uninterrupted or interrupted by 1, 2, 3, 4 or 5 oxygen and/or silicon atoms. R29 is preferably hydrogen, carboxy or COO—C1-C8alkyl, R30 is hydrogen or halogen, and R31 is hydrogen, C1-C8alkoxy or di-C1-C8alkyl-amino.

Special preference is given to compounds of formula (I) wherein R6 is 




or R37, and R34, R35 and R36 are each independently of the others hydrogen or R37.

When R6 is substituted by R37, then it is preferably substituted by a single R37. The total number of radicals R37 in formula (I) is preferably 0, 1 or 2, especially 0 or 1. The total number of radicals R37 in formula (II) is preferably 0, 1, 2, 3 or 4, especially 0 or 2.
R37 is preferably alkyl uninterrupted or interrupted by from 1 to 3 oxygen and/or silicon atoms and unsubstituted or substituted by one or two hydroxy substituents or by a metallocenyl or azo metal complex radical, especially C1-C8alkyl, CH2—CH2—OH, —CH2—O—CH3, —CH2—O—(CH2)7—CH3, —CH2—CH2—O—CH2—CH3, —CH2—CH(OCH3)2, —CH2—CH2—CH(OCH3)2, —CH2—C(OCH3)2—CH3, —CH2—CH2—O—CH2—CH2—O—CH3, —(CH2)3—OH, —(CH2)6—OH, —(CH2)7—OH, —(CH2)8—OH, —(CH2)9—OH, —(CH2)10—OH, —(CH2)11—OH, —(CH2)12—OH, —CH2—Si(CH3)3, —CH2—CH2—O—Si(CH3)2—C(CH3)3, —(CH2)3—O—Si(CH3)2—C(CH3)3, —(CH2)4—O—Si(C6H5)2—C(CH3)3, —(CH2)5—O—Si(CH(CH3)2)3, —CH2—CH2—CH(CH3)—CH2—CH2—CH(OH)—C(CH3)2—OH, —CH2—CH(CH3)—CH2—OH, —CH2—C(CH3)2—CH2—OH, —CH2—C(CH2—OH)3, —CH2—CH(OH)—CH3, —CH2—CH(OH)—CH2—OH, 




C2-C8alkylene-O—CO-, C2-C8alkylene-COO- or C2-C8alkylene-N═CH-, wherein  is 




Azo metal complex radicals have, for example, the formula —[(L1)M1(L2)]m−.
Metallocenyl radicals preferably contain as metal Ni, Co, Cu, Ti or especially Fe. For example, R37 in formula (I) or (II) as a metallocenyl radical may be 




[—C2-C8alkylene-SO2]2-Ø-{hacek over (S)}, [—C2-C8alkylene-O—C2-C8alkylene-NHSO2]2-Ø-{hacek over (S)}, [—C2-C8alkylene-NHSO2]2-Ø-{hacek over (S)}, [—C2-C8alkylene-NH—C2-C8alkylene-SO2]2-Ø-{hacek over (S)} or [—C2-C8alkylene-N(C1-C8alkyl)-C2-C8alkylene-SO2]2-Ø-{hacek over (S)}; or in formula (II) as an azo metal complex radical may be [—C2-C8alkylene-SO2]2-Ø-, [—C2-C8alkylene-NHSO2]2-Ø-, [—C2-C8alkylene-O—C2-C8alkylene-NHSO2]2-Ø-, [—C2-C8alkylene-NH—C2-C8alkylene-SO2]2-Ø- or [—C2-C8alkylene-N(C1-C8alkyl)-C2-C8alkylene-SO2]2-Ø-, wherein {hacek over (S)} is SO3-, SO2-C1-C8alkyl, SO2NR39R40, R39 and R40 are each independently of the other hydrogen or C1-C12alkyl, C2-C12alkenyl, C1-C12cycloalkyl, C2-C12cycloalkenyl, C6-C12aryl or C7-C13aralkyl, each uninterrupted or interrupted by from 1 to 5 oxygen and/or silicon atoms and unsubstituted or substituted by one or two hydroxy substituents, and Ø is the bivalent radical of an organometallic anion selected from the group consisting of 










and those of the formulae Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, Q10, Q11, Q12, Q13, Q14, Q15, Q16, Q17, Q18, Q19, Q20, Q21, Q22, Q23, Q24 and Q25 given hereinbelow.

-Alkylene-SO2-Ø, -alkylene-NHSO2-Ø, -alkylene-O-alkylene-NHSO2-Ø, -alkylene-NH-alkylene-SO2-Ø or -alkylene-N(alkyl)-alkylene-SO2-Ø are preferably —(CH2)2—SO2-Ø, —(CH2)2—NHSO2-Ø, —(CH2)2—O—(CH2)2—NHSO2-Ø, —(CH2)2—NH—(CH2)2—SO2-Ø, —(CH2)6—NHSO2-Ø or —(CH2)2—N(C4H9)—(CH2)2—SO2-Ø.

Of special interest are compounds of formula (I) substituted by azo metal complex radicals such as, for example, 




and also compounds of formula (II) wherein two radicals of formula (I) are linked via a bridge of formula 







Those preferences apply to each of the sub-structures contained in formula (I) or (II), in each case independently of any other sub-structures which may be present, provided that the condition inherent in formula (I) or (II) is fulfilled, i.e. that the resulting compound does not have an excess positive or negative charge. Sub-structures of formula (I) or (II) are to be understood as including their three components carbopyronine, (Xm−)p and (Yn+)q that are not bonded to one another.
Special preference is given also to compounds of formula (I) or (II) wherein Yn+ is [NH2R38R39]+, R38 being hydrogen or C1-C12alkyl and R39 being C1-C24alkyl or C7-C24aralkyl, and R38 and R39 together having from 8 to 25 carbon atoms.
Special preference is given also to compounds of formula (I) or (II) wherein m and n are each the number 1, p is a number from 1 to 21⁄2, and q is a number from 0 to 11⁄2, the sum of positive charges in formula (I) or (II) being equal to the sum of negative charges.
Very special preference is given to the compounds of formula [G+]1-[Q−]1 (V) or [G+]1(F)r(Cl)s-[Q−]1 (VI), wherein G+ is a cation selected from the group consisting of 

























and tautomers thereof, r is a number from 1 to 6, s is a number from 1 to 4, and Q− is an organometallic anion selected from the group consisting of 






















In formula (VI), preferably r is 0 and s is 1 or 2, or especially r is 1 and s is 0, for example compounds wherein G+ is 




The compounds of formulae (I) and (II) are in some cases known compounds which can be found, for example, in the prior art mentioned above. Some of them are new, but they can be prepared analogously to the known compounds by methods known per se, for example by methods disclosed in J. Chem. Soc. III 1963/2655-2662, J. Chem. Soc. (B) 1967/91-92, J. Chem. Soc. (B) 1969/1068-1071, J. Chem. Soc. (B) 1971/319-324, J. Chem. Soc. (B) 1971/1468-1471 or Heterocycles 21/1, 167-190 [1984]. The compounds used according to the invention can also be prepared from their leuco forms, some of which are known for photographic and electrophotographic applications, according to methods known to the person skilled in the art. Metal complexes, preferably those of formula (III), are well known from the specialist literature. In particular, they may be those metal complexes described in GB 1 599 812 or EP 450 421, and reference is made expressly to the teaching contained therein.
Compounds of formula (I) or their precursors are preferably prepared by oxidation of a compound of formula 




it having been found, most surprisingly, that liquid acids, for example acetic acid, are especially advantageous solvents and (meta)periodate is an especially advantageous oxidising agent, especially in combination. The reaction proceeds more selectively and the compounds in question are obtained in better yield and better purity, which results in better application-related properties in optical storage media. Ammonium (meta)periodates, especially tetrabutylammonium (meta)periodate, and acetic acid, especially glacial acetic acid, are particularly advantageous.

The invention accordingly relates also to a process for the preparation of a compound of formula (I), wherein a compound of structure 




is oxidised in the presence of a C1-C18carboxylic acid. The amount of C1-C18carboxylic acid is advantageously from 0.1 to 10 000 parts by weight, based on (X).

The carbopyronine dyes used according to the invention have in ethanolic solution a narrow absorption band having its maximum at from 540 to 640 nm. Very surprisingly, they also have a comparatively weak tendency towards agglomeration in the solid state, so that the absorption curve remains advantageously narrow also in the solid state. This is true especially in the presence of metal-containing anions (Xm−)p, for example the metal complex anions indicated above.
The carbopyronine dyes used according to the invention also have, in the form of a solid film, as used in optical storage media, at the longer wavelength flank of the absorption band a high refractive index which preferably achieves a peak value of from 2.0 to 3.0 in the range of from 600 to 700 nm, so that a medium having high reflectivity as well as high sensitivity and good playback characteristics in the desired spectral range is achieved.
The substrate, which functions as support for the layers applied thereto, is advantageously semi-transparent (T≧10%) or preferably transparent (T≧90%). The support can have a thickness of from 0.01 to 10 mm, preferably from 0.1 to 5 mm.
The recording layer is preferably arranged between the transparent substrate and the reflecting layer. The thickness of the recording layer is from 10 to 1000 nm, preferably from 30 to 300 nm, especially about 80 nm, for example from 60 to 120 nm. The absorption of the recording layer is typically from 0.1 to 1.0 at the absorption maximum. The layer thickness is very especially chosen in known manner depending upon the respective refractive indices in the non-written state and in the written state at the reading wavelength, so that in the non-written state constructive interference is obtained, but in the written state destructive interference is obtained, or vice versa.
The reflecting layer, the thickness of which can be from 10 to 150 nm, preferably has high reflectivity (R≧45%, especially R≧60%), coupled with low transparency (T≦10%). In further embodiments, for example in the case of media having a plurality of recording layers, the reflector layer may likewise be semi-transparent, that is to say may have comparatively high transparency (for example T≧50%) and low reflectivity (for example R≦30%).
The uppermost layer, for example the reflective layer or the recording layer, depending upon the layer structure, is advantageously additionally provided with a protective layer having a thickness of from 0.1 to 1000 μm, preferably from 0.1 to 50 μm, especially from 0.5 to 15 μm. Such a protective layer can, if desired, serve also as adhesion promoter for a second substrate layer applied thereto, which is preferably from 0.1 to 5 mm thick and consists of the same material as the support substrate.
The reflectivity of the entire recording medium is preferably at least 15%, especially at least 40%.
The main features of the recording layer according to the invention are the very high initial reflectivity in the said wavelength range of the laser diodes, which can be modified with especially high sensitivity; the high refractive index; the narrow absorption band in the solid state; the good uniformity of the script width at different pulse durations; the good light stability; and the good solubility in polar solvents.
The recording medium according to the invention is neither writable nor readable using the infra-red laser diodes of customary CD apparatus in accordance with the requirements of the Orange Book Standard, because at 780 nm the refractive indices (n) characteristically lie between 1.4 and 1.9 and their imaginary components (k) between 0 and a maximum of 0.04. As a result, the risk of damage in the event of an erroneous attempt at writing using an apparatus not capable of high resolution is largely averted, which is of advantage. The use of dyes of formula (I) results in advantageously homogeneous, amorphous and low-scatter recording layers having a high refractive index, and the absorption edge is surprisingly especially steep even in the solid phase. Further advantages are high light stability in daylight and under laser radiation of low power density with, at the same time, high sensitivity under laser radiation of high power density, uniform script width, high contrast, and also good thermal stability and storage stability.
At a relatively high recording speed, the results obtained are surprisingly better than with previously known recording media. The marks are more precisely defined relative to the surrounding medium, and thermally induced deformations do not occur. The error rate (BLER) and the statistical variations in mark length (jitter) are also low both at normal recording speed and at relatively high recording speed, so that an error-free recording and playback can be achieved over a large speed range. There are virtually no rejects even at high recording speed, and the reading of written media is not slowed down by the correction of errors. The advantages are obtained in the entire range of from 600 to 700 nm (preferably from 630 to 690 nm), but are especially marked at from 640 to 680 nm, more especially from 650 to 670 nm, particularly at 658±5 nm.
Suitable substrates are, for example, glass, minerals, ceramics and thermosetting or thermoplastic plastics. Preferred supports are glass and homo- or co-polymeric plastics. Suitable plastics are, for example, thermoplastic polycarbonates, polyamides, polyesters, polyacrylates and polymethacrylates, polyurethanes, polyolefins, polyvinyl chloride, polyvinylidene fluoride, polyimides, thermosetting polyesters and epoxy resins. The substrate can be in pure form or may also comprise customary additives, for example UV absorbers or dyes, as proposed e.g. in JP 04/167 239 as light-stabilisers for the recording layer. In the latter case it may be advantageous for the dye added to the support substrate to have an absorption maximum hypsochromically shifted relative to the dye of the recording layer by at least 10 nm, preferably by at least 20 nm.
The substrate is advantageously transparent over at least a portion of the range from 600 to 700 nm (preferably as indicated above), so that it is permeable to at least 90% of the incident light of the writing or readout wavelength. The substrate has preferably on the coating side a spiral guide groove having a groove depth of from 50 to 500 nm, a groove width of from 0.2 to 0.8 μm and a track spacing between two turns of from 0.4 to 1.6 μm, especially having a groove depth of from 100 to 200 nm, a groove width of 0.3 μm and a spacing between two turns of from 0.6 to 0.8 μm. The storage media according to the invention are therefore suitable especially advantageously for the optical recording of DVD media having the currently customary pit width of 0.4 μm and track spacing of 0.74 μm. The increased recording speed relative to known media allows synchronous recording or, for special effects, even accelerated recording of video sequences with excellent image quality.
The recording layer, instead of comprising a single compound of formula (I) or (II), may also comprise a mixture of such compounds having, for example, 2, 3, 4 or 5 carbopyronine dyes according to the invention. By the use of mixtures, for example mixtures of isomers or homologues as well as mixtures of different structures, the solubility can often be increased and/or the amorphous content improved. If desired, mixtures of ion pair compounds may have different anions, different cations or both different anions and different cations.
For a further increase in stability it is also possible, if desired, to add known stabilisers in customary amounts, for example a nickel dithiolate described in JP 04/025 493 as light stabiliser.
The recording layer comprises a compound of formula (I) or (II) or a mixture of such compounds advantageously in an amount sufficient to have a substantial influence on the refractive index, for example at least 30% by weight, preferably at least 60% by weight, especially at least 80% by weight. The recording layer can especially valuably comprise a compound of formula (I) or a mixture of a plurality of such compounds as main component, or may consist exclusively or substantially of one or more compounds of formula (I).
Further customary constituents are possible, for example other chromophores (for example those disclosed in WO-01/75873, or others having an absorption maximum at from 300 to 1000 nm), stabilisers, 1O2—, triplet- or luminescence-quenchers, melting-point reducers, decomposition accelerators or any other additives that have already been described in optical recording media. Preferably, stabilisers or fluoresence-quenchers are added if desired.
When the recording layer comprises further chromophores, they may in principle be any dye that can be decomposed or modified by the laser radiation during the recording, or they may be inert towards the laser radiation. When the further chromophores are decomposed or modified by the laser radiation, this can take place directly by absorption of the laser radiation or can be induced indirectly by the decomposition of the compounds of formula (I) or (II) according to the invention, for example thermally.
Naturally, further chromophores or coloured stabilisers may influence the optical properties of the recording layer. It is therefore preferable to use further chromophores or coloured stabilisers, the optical properties of which conform as far as possible to those of the compounds formula (I) or (II) or are as different as possible, or the amount of further chromophores is kept small.
When further chromophores having optical properties that conform as far as possible to those of compounds formula (I) or (II) are used, preferably this should be the case in the range of the longest-wavelength absorption flank. Preferably the wavelengths of the inversion points of the further chromophores and of the compounds of formula (I) or (II) are a maximum of 20 nm, especially a maximum of 10 nm, apart. In that case the further chromophores and the compounds of formula (I) or (II) should exhibit similar behaviour in respect of the laser radiation, so that it is possible to use as further chromophores known recording agents the action of which is synergistically enhanced or heightened by the compounds of formula (I) or (II).
When further chromophores or coloured stabilisers having optical properties that are as different as possible from those of compounds of formula (I) or (II) are used, they advantageously have an absorption maximum that is hypsochromically or bathochromically shifted relative to the dye of formula (I) or (II). In that case the absorption maxima are preferably at least 50 nm, especially at least 100 nm, apart. Examples thereof are UV absorbers that are hypsochromic to the dye of formula (I) or (II), or coloured stabilisers that are bathochromic to the dye of formula (I) or (II) and have absorption maxima lying, for example, in the NIR or IR range. Other dyes can also be added for the purpose of colour-coded identification, colour-masking (“diamond dyes”) or enhancing the aesthetic appearance of the recording layer. In all those cases, the further chromophores or coloured stabilisers should preferably exhibit behaviour towards light and laser radiation that is as inert as possible.
When another dye is added in order to modify the optical properties of the compounds of formula (I) or (II), the amount thereof is dependent upon the optical properties to be achieved. The person skilled in the art will find little difficulty in varying the ratio of additional dye to compound of formula (I) or (II) until he obtains his desired result.
When chromophores or coloured stabilisers are used for other purposes, the amount thereof should preferably be small so that their contribution to the total absorption of the recording layer in the range of from 600 to 700 nm is a a maximum of 20%, preferably a maximum of 10%. In such a case, the amount of additional dye or stabiliser is advantageously a maximum of 50% by weight, preferably a maximum of 10% by weight, based on the recording layer.
Most preferably, however, no additional chromophore is added, unless it is a coloured stabiliser.
Further chromophores that can be used in the recording layer in addition to the compounds of formula (I) or (II) are, for example, cyanines and cyanine metal complexes (U.S. Pat. No. 5,958,650), styryl compounds (U.S. Pat. No. 6,103,331), oxonol dyes (EP-A-833 314), azo dyes and azo metal complexes (JP-A-11/028865), phthalocyanines (EP-A-232 427, EP-A-337 209, EP-A-373 643, EP-A-463 550, EP-A-492 508, EP-A-509 423, EP-A-511 590, EP-A-513 370, EP-A-514 799, EP-A-518 213, EP-A-519 419, EP-A-519 423, EP-A-575 816, EP-A-600 427, EP-A-676 751, EP-A-712 904, WO-98/14520, WO-00/09522, PCT/EP-02/03945), porphyrins and azaporphyrins (EP-A-822 546, U.S. Pat. No. 5,998,093), dipyrromethene dyes and metal chelate compounds thereof (EP-A-822 544, EP-A-903 733), xanthene dyes and metal complex salts thereof (U.S. Pat. No. 5,851,621) or quadratic acid compounds (EP-A-568 877), or oxazines, dioxazines, diazastyryls, formazans, anthraquinones or phenothiazines; this list is on no account exhaustive and the person skilled in the art will interpret the list as including further known dyes.
Stabilisers, 1O2—, triplet- or luminescence-quenchers are, for example, metal complexes of N- or S-containing enolates, phenolates, bisphenolates, thiolates or bisthiolates or of azo, azomethine or formazan dyes, such as bis(4-dimethyl-aminodithiobenzil)nickel [CAS No 38465-55-3], ®Irgalan Bordeaux EL, ®Cibafast N or similar compounds, hindered phenols and derivatives thereof (optionally also as counter-ions X), such as ®Cibafast AO, o-hydroxyphenyl-triazoles or -triazines or other UV absorbers, such as ®Cibafast W or ®Cibafast P or hindered amines (TEMPO or HALS, also as nitroxides or NOR-HALS, optionally also as counter-ions X), and also as cations diimmonium, ParaquatTM or OrthoquatTM salts, such as ®Kayasorb IRG 022, ®Kayasorb IRG 040, optionally also as radical ions, such as N,N,N′,N′-tetrakis(4-dibutylaminophenyl)-p-phenylene-amine-ammonium hexafluorophosphate, hexafluoroantimonate or perchlorate. The latter are available from Organica (Wolfen/DE); ®Kayasorb brands are available from Nippon Kayaku Co. Ltd., and ®Irgalan and ®Cibafast brands are available from Ciba Spezialitätenchemie AG.
Many such structures are known, some of them also in connection with optical recording media, for example from U.S. Pat. No. 5,219,707, JP-A-06/199045, JP-A-07/76169, JP-A-07/262604 or JP-A-2000/272241. They may be, for example, salts of the metal complex anions disclosed above with any desired cations, for example the cations disclosed above.
Also suitable are neutral metal complexes, for example those metal complexes disclosed in EP 0 822 544, EP 0 844 243, EP 0 903 733, EP 0 996 123, EP 1 056 078, EP 1 130 584 or U.S. Pat. No. 6,162,520, for example 







and also those of the formula (L3)M2(L5) (VII), (L6)M2(L7) (VIII) or M2(L8) (IX), wherein L5 is C1-C12alkyl-OH, C6-C12aryl-OH, C7-C12aralkyl-OH, C1-C12alkyl-SH, C6-C12aryl-SH, C7-C12aralkyl-SH, C1-C12alkyl-NH2, C6-C12aryl-NH2, C7-C12aralkyl-NH2, di-C1-C12alkyl-NH, di-C6-C12aryl-NH, di-C7-C12aralkyl-NH, tri-C1-C12alkyl-N, tri-C6-C12aryl-N or tri-C7-C12aralkyl-N, 




M2 and R16 to R21 being as defined above.
A particular example of an additive of formula (IX) that may be mentioned is a copper complex, illustrated e.g. by a compound of formula 




A particular example of an additive of formula (VII) that may be mentioned is a nickel bisphenolate, illustrated e.g. by the compound of formula 




The person skilled in the art will know from other optical information media, or will easily identify, which additives in which concentration are best suited to which purpose. Suitable concentrations of additives are, for example, from 0.001 to 1000% by weight, preferably from 1 to 50% by weight, based on the recording medium of formula (I) or (II).
The recording medium according to the invention, in addition to comprising compounds of formula (I) or (II), may additionally comprise salts, for example ammonium chloride, pentadecylammonium chloride, sodium chloride, sodium sulfate, sodium methyl sulfonate or sodium methyl sulfate, the ions of which may originate e.g. from the components used. The additional salts, if present, may be present preferably in amounts of up to 20% by weight, based on the total weight of the recording layer.
Reflecting materials suitable for the reflective layer include especially metals, which provide good reflection of the laser radiation used for recording and playback, for example the metals of Main Groups III, IV and V and of the Sub-Groups of the Periodic Table of the Elements. Al, In, Sn, Pb, Sb, Bi, Cu, Ag, Au, Zn, Cd, Hg, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu and alloys thereof are especially suitable. Special preference is given to a reflective layer of aluminium, silver, copper, gold or an alloy thereof, on account of their high reflectivity and ease of production.
Materials suitable for the protective layer include chiefly plastics, which are applied in a thin layer to the support or the uppermost layer either directly or with the aid of adhesive layers. It is advantageous to select mechanically and thermally stable plastics having good surface properties, which may be modified further, for example written. The plastics may be thermosetting plastics and thermoplastic plastics. Preference is given to radiation-cured (e.g using UV radiation) protective layers, which are particularly simple and economical to produce. A wide variety of radiation-curable materials are known. Examples of radiation-curable monomers and oligomers are acrylates and methacrylates of diols, triols and tetrols, polyimides of aromatic tetracarboxylic acids and aromatic diamines having C1-C4alkyl groups in at least two ortho-positions of the amino groups, and oligomers with dialkylmaleinimidyl groups, e.g. dimethylmaleinimidyl groups.
The recording media according to the invention may also have additional layers, for example interference layers. It is also possible to construct recording media having a plurality of (for example two) recording layers. The structure and the use of such materials are known to the person skilled in the art. Preferred, if present, are interference layers that are arranged between the recording layer and the reflecting layer and/or between the recording layer and the substrate and consist of a dielectric material, for example as described in EP 353 393 of TiO2, Si3N4, ZnS or silicone resins.
The recording media according to the invention can be produced by processes known per se, various methods of coating being employable depending upon the materials used and their function.
Suitable coating methods are, for example, immersion, pouring, brush-coating, blade-application and spin-coating, as well as vapour-deposition methods carried out under a high vacuum. When pouring methods are used, for example, solutions in organic solvents are generally used. When solvents are employed, care should be taken that the supports used are insensitive to those solvents. Suitable coating methods and solvents are described, for example, in EP-A-401 791.
The recording layer is preferably applied by spin-coating with a dye solution, solvents that have proved satisfactory being especially alcohols, e.g. 2-methoxyethanol, n-propanol, isopropanol, isobutanol, n-butanol, amyl alcohol or 3-methyl-1-butanol or preferably fluorinated alcohols, e.g. 2,2,2-trifluoro-ethanol or 2,2,3,3-tetrafluoro-1-propanol, and mixtures thereof. It will be understood that other solvents or solvent mixtures can also be used, for example those solvent mixtures described in EP-A-511 598 and EP-A-833 316. Ethers (dibutyl ether), ketones (2,6-dimethyl-4-heptanone, 5-methyl-2-hexanone) or saturated or unsaturated hydrocarbons (toluene, xylene) can also be used, for example in the form of mixtures (e.g. dibutyl ether/2,6-dimethyl-4-heptanone) or mixed components.
The person skilled in the art of spin-coating will in general routinely try out all the solvents with which is he is familiar, as well as binary and ternary mixtures thereof, in order to discover the solvents or solvent mixtures which result in a high-quality and, at the same time, cost-effective recording layer containing the solid components of his choice. Known methods of process engineering can also be employed in such optimisation procedures, so that the number of experiments to be carried out can be kept to a minimum.
The invention therefore relates also to a method of producing an optical recording medium, wherein a solution of a compound of formula (I) in an organic solvent is applied to a substrate having pits. The application is preferably carried out by spin-coating.
The application of the metallic reflective layer is preferably effected by sputtering, vapour-deposition in vacuo or by chemical vapour deposition (CVD). The sputtering technique is especially preferred for the application of the metallic reflective layer on account of the high degree of adhesion to the support. Such techniques are known and are described in specialist literature (e.g. J. L. Vossen and W. Kern, “Thin Film Processes”, Academic Press, 1978).
The structure of the recording medium according to the invention is governed primarily by the readout method; known function principles include the measurement of the change in the transmission or, preferably, in the reflection, but it is also known to measure, for example, the fluorescence instead of the transmission or reflection.
When the recording material is structured for a change in reflection, the following structures, for example, can be used: transparent support/recording layer (optionally multilayered)/reflective layer and, if expedient, protective layer (not necessarily transparent); or support (not necessarily transparent)/reflective layer/recording layer and, if expedient, transparent protective layer. In the first case, the light is incident from the support side, whereas in the latter case the radiation is incident from the recording layer side or, where applicable, from the protective layer side. In both cases the light detector is located on the same side as the light source. The first-mentioned structure of the recording material to be used according to the invention is generally preferred.
When the recording material is structured for a change in light transmission, the following different structure, for example, comes into consideration: transparent support/recording layer (optionally multilayered) and, if expedient, transparent protective layer. The light for recording and for readout can be incident either from the support side or from the recording layer side or, where applicable, from the protective layer side, the light detector in this case always being located on the opposite side.
Suitable lasers are those having a wavelength of 600-700 nm, for example commercially available lasers having a wavelength of 602, 612, 633, 635, 647, 650, 670 or 680 nm, especially semi-conductor lasers, such as GaAsAl, InGaAlP or GaAs laser diodes having a wavelength especially of about 635, 650 or 658 nm. The recording is effected, for example, point for point in a manner known per se, by modulating the laser in accordance with the mark lengths and focussing its radiation onto the recording layer. It is known from the specialist literature that other methods are currently being developed which may also be suitable for use.
The process according to the invention allows the storage of information with great reliability and stability, distinguished by very good mechanical and thermal stability and by high light stability and by sharp boundary zones of the pits. Special advantages include the high contrast, the low jitter and the surprisingly high signal/noise ratio, so that excellent readout is achieved. The high storage capacity is especially valuable in the field of video.
The readout of information is carried out according to methods known per se by registering the change in absorption or reflection using laser radiation, for example as described in “CD-Player und R-DAT Recorder” (Claus Biaesch-Wiepke, Vogel Buchverlag, Würzburg 1992).
The information-containing medium according to the invention is especially an optical information material of the WORM type. It may be used, for example, as a playable DVD (digital versatile disk), as storage material for a computer or as an identification and security card or for the production of diffractive optical elements, for example holograms.
The invention accordingly relates also to a method for the optical recording, storage and playback of information; wherein a recording medium according to the invention is used. The recording and the playback advantageously take place in a wavelength range of from 600 to 700 nm.


The following Examples illustrate the invention in greater detail:
EXAMPLE 1
98.22 g of N-[7-(dimethylamino)-9,9-dimethyl-2(9H)-anthracenyl-idene]-N-methyl-perchlorate are dissolved in 25 liters of ethanol. Separately, 256.25 g of the sodium salt of the metal complex of formula Q20 (in each case based on dry weight) are then dissolved in 40 liters of ethanol, with heating to 65° C. After cooling to 23° C., the two solutions are combined (for example by pumping the second solution into the first), stirred for 30 minutes to complete the reaction and clarified by filtration. The solution is concentrated by evaporation under a low vacuum using a rotary evaporator with a water bath at a temperature of about 65° C., yielding 353.63 g of crude product. 15 liters of water are added to the crude product and the mixture is treated mechanically and/or by ultrasound for 30 minutes at 10-20° C. in order to dissolve the inorganic salts. After filtration and washing with 10 liters of water, the filtration residue is dried at 80° C./1.6·103 Pa, yielding 322.30 g of the product of formula 




EXAMPLE 2
The procedure is as in Example 1, but instead of N-[7-(dimethylamino)-9,9-dimethyl-2(9H)-anthracenylidene]-N-methyl-perchlorate there is used an equimolar amount of the product of formula 




EXAMPLE 3
The procedure is as in Example 1, but instead of N-[7-(dimethylamino)-9,9-dimethyl-2(9H)-anthracenylidene]-N-methyl-perchlorate there is used an equimolar amount of the product of formula 




EXAMPLE 4
The procedure is as in Example 1, but instead of N-[7-(dimethylamino)-9,9-dimethyl-2(9H)-anthracenylidene]-N-methyl-perchlorate there is used an equimolar amount of the product of formula 




EXAMPLE 5
The procedure is as in Example 1, but instead of N-[7-(dimethylamino)-9,9-dimethyl-2(9H)-anthracenylidene]-N-methyl-perchlorate there is used an equimolar amount of the product of formula 




EXAMPLE 6
The procedure is as in Example 1, but instead of the metal complex of formula Q20 there is used an equimolar amount of the metal complex of formula Q3.
EXAMPLE 7
2% by weight of the product according to Example 1 are dissolved in 2,2,3,3-tetrafluoro-1-propanol and the solution is filtered through a Teflon filter of pore size 0.2 μm and applied by spin-coating at 1000 rev/min to the surface of a 0.6 mm thick, grooved polycarbonate disc (groove depth: 170 nm, groove width: 350 nm, track spacing: 0.74 μm) of 120 mm diameter. The excess solution is spun off by increasing the rotational speed. On evaporation of the solvent, the dye remains behind in the form of a uniform, amorphous solid layer. After drying in a circulating-air oven at 70° C. (10 min), the solid layer exhibits an absorption of 0.45 at 625 nm. In a vacuum coating apparatus (TwisterTM, Balzers Unaxis), a 60 nm thick silver layer is then applied to the recording layer by atomisation. Then a 6 μm thick protective layer of a UV-curable photopolymer (650-020, DSM) is applied thereto by means of spin-coating. The recording support exhibits a reflectivity of 47% at 658 nm. The optical constants (absorption maximum λmax, refractive index at 658 nm n658, absorption coefficient at 658 nm k658) are determined reflectometrically (ETA-RTTM, ETA-Optik Steag-Hamatech):

λmax=624 nm; n658=2.29; k658=0.21.

Using a commercial test apparatus (DVDT-R 650TM, Expert Magnetics), marks are written into the active layer at a speed of 3.5 m/sec using a laser diode of wavelength 658 nm and laser power of 9.2 mW. Then, using the same test apparatus, the dynamic parameters are determined, there being obtained good measured values:

    
    
        DTC Jitter=8.8%; R14H=47%; |14/|14H=0.72.
    
    


EXAMPLE 8
The procedure is as in Example 7, but the product according to Example 6 is used instead of the product according to Example 1. The optical constants are determined reflectometrically as in Example 7:

    
    
        λmax=626 nm; n658=2.55; k658=0.33.
    
    


COMPARISON EXAMPLE 9
The procedure is as in Examples 7 and 8, but the product according to Example A8 of EP-A-0 805 441 is used instead of the products according to Examples 1 and 6. The optical constants are determined reflectometrically in the same way:

    
    
        λmax=581 nm; n658=1.94; k658=0.016.
    
    


This disc cannot be written using commercial recording apparatus (Pioneer A03 DVD-R(G)) on account of insufficient sensitivity.
EXAMPLES 10-2094
The procedure is as in Examples 7-9, but the following compounds of formula [G+].[X−], which can be prepared analogously to Examples 1-6, are used:












Ex.
[G+]
[X−]

















10
G1
Q2


11
G2
Q2


12
G3
Q2


13
G4
Q2


14
G5
Q2


15
G6
Q2


16
G7
Q2


17
G8
Q2


18
G9
Q2


19
G10
Q2


20
G11
Q2


21
G12
Q2


22
G13
Q2


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780
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781
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782
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790
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870
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912
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927
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928
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930
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956
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960
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961
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963
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969
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978
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979
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980
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981
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987
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G23
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989
G24
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990
G25
Q13


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1000
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1001
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1003
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1004
G39
Q13


1005
G40
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1006
G41
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1007
G42
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1008
G43
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1009
G44
Q13


1010
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1011
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1012
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1016
G51
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G54
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G55
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1021
G56
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1022
G57
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1023
G58
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1024
G59
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1025
G60
Q13


1026
G61
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1070
G18
Q14


1071
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1073
G21
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1074
G22
Q14


1075
G23
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G24
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Q14


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1080
G28
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1081
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1084
G32
Q14


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G33
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G34
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G35
Q14


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1089
G37
Q14


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G38
Q14


1091
G39
Q14


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G40
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G41
Q14


1094
G42
Q14


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G43
Q14


1096
G44
Q14


1097
G45
Q14


1098
G46
Q14


1099
G47
Q14


1100
G48
Q14


1101
G49
Q14


1102
G50
Q14


1103
G51
Q14


1104
G52
Q14


1105
G53
Q14


1106
G54
Q14


1107
G55
Q14


1108
G56
Q14


1109
G57
Q14


1110
G58
Q14


1111
G59
Q14


1112
G60
Q14


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G61
Q14


1114
G62
Q14


1115
G63
Q14


1116
G64
Q14


1117
G65
Q14


1118
G66
Q14


1119
G67
Q14


1120
G68
Q14


1121
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Q14


1122
G70
Q14


1123
G71
Q14


1124
G72
Q14


1125
G73
Q14


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Q14


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Q14


1128
G76
Q14


1129
G77
Q14


1130
G78
Q14


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G79
Q14


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G80
Q14


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G81
Q14


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G82
Q14


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Q14


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Q14


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Q14


1138
G86
Q14


1139
G87
Q14


1140
G1
Q15


1141
G2
Q15


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Q15


1143
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Q15


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G5
Q15


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Q15


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Q15


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Q15


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Q15


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Q15


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Q15


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Q15


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G20
Q15


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G21
Q15


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G23
Q15


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Q15


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Q15


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Q15


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Q15


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Q15


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Q15


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G54
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G55
Q15


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G56
Q15


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G57
Q15


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G58
Q15


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G59
Q15


1199
G60
Q15


1200
G61
Q15


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G62
Q15


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G63
Q15


1203
G64
Q15


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G65
Q15


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G66
Q15


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G67
Q15


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G68
Q15


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Q15


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G70
Q15


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Q15


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Q15


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G73
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Q15


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G75
Q15


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Q15


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Q15


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Q15


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Q15


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Q15


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Q15


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Q15


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G84
Q15


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Q15


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Q15


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Q15


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Q16


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Q16


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Q16


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G6
Q16


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Q16


1234
G8
Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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G75
Q16


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Q16


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G77
Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


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Q16


1314
G1
Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


1371
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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


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Q17


1397
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Q17


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Q17


1399
G86
Q17


1400
G87
Q17


1401
G1
Q18


1402
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Q18


1403
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Q18


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1406
G6
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Q18


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Q18


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Q18


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Q18


1413
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Q18


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Q18


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Q18


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1422
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Q18


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1455
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1457
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Q18


1458
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Q18


1459
G59
Q18


1460
G60
Q18


1461
G61
Q18


1462
G62
Q18


1463
G63
Q18


1464
G64
Q18


1465
G65
Q18


1466
G66
Q18


1467
G67
Q18


1468
G68
Q18


1469
G69
Q18


1470
G70
Q18


1471
G71
Q18


1472
G72
Q18


1473
G73
Q18


1474
G74
Q18


1475
G75
Q18


1476
G76
Q18


1477
G77
Q18


1478
G78
Q18


1479
G79
Q18


1480
G80
Q18


1481
G81
Q18


1482
G82
Q18


1483
G83
Q18


1484
G84
Q18


1485
G85
Q18


1486
G86
Q18


1487
G87
Q18


1488
G1
Q19


1489
G2
Q19


1490
G3
Q19


1491
G4
Q19


1492
G5
Q19


1493
G6
Q19


1494
G7
Q19


1495
G8
Q19


1496
G9
Q19


1497
G10
Q19


1498
G11
Q19


1499
G12
Q19


1500
G13
Q19


1501
G14
Q19


1502
G15
Q19


1503
G16
Q19


1504
G17
Q19


1505
G18
Q19


1506
G19
Q19


1507
G20
Q19


1508
G21
Q19


1509
G22
Q19


1510
G23
Q19


1511
G24
Q19


1512
G25
Q19


1513
G26
Q19


1514
G27
Q19


1515
G28
Q19


1516
G29
Q19


1517
G30
Q19


1518
G31
Q19


1519
G32
Q19


1520
G33
Q19


1521
G34
Q19


1522
G35
Q19


1523
G36
Q19


1524
G37
Q19


1525
G38
Q19


1526
G39
Q19


1527
G40
Q19


1528
G41
Q19


1529
G42
Q19


1530
G43
Q19


1531
G44
Q19


1532
G45
Q19


1533
G46
Q19


1534
G47
Q19


1535
G48
Q19


1536
G49
Q19


1537
G50
Q19


1538
G51
Q19


1539
G52
Q19


1540
G53
Q19


1541
G54
Q19


1542
G55
Q19


1543
G56
Q19


1544
G57
Q19


1545
G58
Q19


1546
G59
Q19


1547
G60
Q19


1548
G61
Q19


1549
G62
Q19


1550
G63
Q19


1551
G64
Q19


1552
G65
Q19


1553
G66
Q19


1554
G67
Q19


1555
G68
Q19


1556
G69
Q19


1557
G70
Q19


1558
G71
Q19


1559
G72
Q19


1560
G73
Q19


1561
G74
Q19


1562
G75
Q19


1563
G76
Q19


1564
G77
Q19


1565
G78
Q19


1566
G79
Q19


1567
G80
Q19


1568
G81
Q19


1569
G82
Q19


1570
G83
Q19


1571
G84
Q19


1572
G85
Q19


1573
G86
Q19


1574
G87
Q19


1575
G2
Q20


1576
G3
Q20


1577
G4
Q20


1578
G5
Q20


1579
G6
Q20


1580
G7
Q20


1581
G8
Q20


1582
G9
Q20


1583
G10
Q20


1584
G12
Q20


1585
G13
Q20


1586
G14
Q20


1587
G15
Q20


1588
G16
Q20


1589
G17
Q20


1590
G18
Q20


1591
G19
Q20


1592
G20
Q20


1593
G21
Q20


1594
G22
Q20


1595
G23
Q20


1596
G24
Q20


1597
G25
Q20


1598
G26
Q20


1599
G27
Q20


1600
G28
Q20


1601
G29
Q20


1602
G30
Q20


1603
G31
Q20


1604
G32
Q20


1605
G33
Q20


1606
G34
Q20


1607
G35
Q20


1608
G36
Q20


1609
G37
Q20


1610
G38
Q20


1611
G39
Q20


1612
G40
Q20


1613
G41
Q20


1614
G42
Q20


1615
G43
Q20


1616
G44
Q20


1617
G45
Q20


1618
G46
Q20


1619
G47
Q20


1620
G48
Q20


1621
G49
Q20


1622
G50
Q20


1623
G51
Q20


1624
G52
Q20


1625
G53
Q20


1626
G54
Q20


1627
G55
Q20


1628
G56
Q20


1629
G57
Q20


1630
G58
Q20


1631
G59
Q20


1632
G60
Q20


1633
G61
Q20


1634
G62
Q20


1635
G63
Q20


1636
G64
Q20


1637
G65
Q20


1638
G66
Q20


1639
G67
Q20


1640
G68
Q20


1641
G69
Q20


1642
G70
Q20


1643
G71
Q20


1644
G72
Q20


1645
G73
Q20


1646
G74
Q20


1647
G75
Q20


1648
G76
Q20


1649
G77
Q20


1650
G78
Q20


1651
G79
Q20


1652
G80
Q20


1653
G81
Q20


1654
G82
Q20


1655
G83
Q20


1656
G84
Q20


1657
G85
Q20


1658
G86
Q20


1659
G87
Q20


1660
G1
Q21


1661
G2
Q21


1662
G3
Q21


1663
G4
Q21


1664
G5
Q21


1665
G6
Q21


1666
G7
Q21


1667
G8
Q21


1668
G9
Q21


1669
G10
Q21


1670
G11
Q21


1671
G12
Q21


1672
G13
Q21


1673
G14
Q21


1674
G15
Q21


1675
G16
Q21


1676
G17
Q21


1677
G18
Q21


1678
G19
Q21


1679
G20
Q21


1680
G21
Q21


1681
G22
Q21


1682
G23
Q21


1683
G24
Q21


1684
G25
Q21


1685
G26
Q21


1686
G27
Q21


1687
G28
Q21


1688
G29
Q21


1689
G30
Q21


1690
G31
Q21


1691
G32
Q21


1692
G33
Q21


1693
G34
Q21


1694
G35
Q21


1695
G36
Q21


1696
G37
Q21


1697
G38
Q21


1698
G39
Q21


1699
G40
Q21


1700
G41
Q21


1701
G42
Q21


1702
G43
Q21


1703
G44
Q21


1704
G45
Q21


1705
G46
Q21


1706
G47
Q21


1707
G48
Q21


1708
G49
Q21


1709
G50
Q21


1710
G51
Q21


1711
G52
Q21


1712
G53
Q21


1713
G54
Q21


1714
G55
Q21


1715
G56
Q21


1716
G57
Q21


1717
G58
Q21


1718
G59
Q21


1719
G60
Q21


1720
G61
Q21


1721
G62
Q21


1722
G63
Q21


1723
G64
Q21


1724
G65
Q21


1725
G66
Q21


1726
G67
Q21


1727
G68
Q21


1728
G69
Q21


1729
G70
Q21


1730
G71
Q21


1731
G72
Q21


1732
G73
Q21


1733
G74
Q21


1734
G75
Q21


1735
G76
Q21


1736
G77
Q21


1737
G78
Q21


1738
G79
Q21


1739
G80
Q21


1740
G81
Q21


1741
G82
Q21


1742
G83
Q21


1743
G84
Q21


1744
G85
Q21


1745
G86
Q21


1746
G87
Q21


1747
G1
Q22


1748
G2
Q22


1749
G3
Q22


1750
G4
Q22


1751
G5
Q22


1752
G6
Q22


1753
G7
Q22


1754
G8
Q22


1755
G9
Q22


1756
G10
Q22


1757
G11
Q22


1758
G12
Q22


1759
G13
Q22


1760
G14
Q22


1761
G15
Q22


1762
G16
Q22


1763
G17
Q22


1764
G18
Q22


1765
G19
Q22


1766
G20
Q22


1767
G21
Q22


1768
G22
Q22


1769
G23
Q22


1770
G24
Q22


1771
G25
Q22


1772
G26
Q22


1773
G27
Q22


1774
G28
Q22


1775
G29
Q22


1776
G30
Q22


1777
G31
Q22


1778
G32
Q22


1779
G33
Q22


1780
G34
Q22


1781
G35
Q22


1782
G36
Q22


1783
G37
Q22


1784
G38
Q22


1785
G39
Q22


1786
G40
Q22


1787
G41
Q22


1788
G42
Q22


1789
G43
Q22


1790
G44
Q22


1791
G45
Q22


1792
G46
Q22


1793
G47
Q22


1794
G48
Q22


1795
G49
Q22


1796
G50
Q22


1797
G51
Q22


1798
G52
Q22


1799
G53
Q22


1800
G54
Q22


1801
G55
Q22


1802
G56
Q22


1803
G57
Q22


1804
G58
Q22


1805
G59
Q22


1806
G60
Q22


1807
G61
Q22


1808
G62
Q22


1809
G63
Q22


1810
G64
Q22


1811
G65
Q22


1812
G66
Q22


1813
G67
Q22


1814
G68
Q22


1815
G69
Q22


1816
G70
Q22


1817
G71
Q22


1818
G72
Q22


1819
G73
Q22


1820
G74
Q22


1821
G75
Q22


1822
G76
Q22


1823
G77
Q22


1824
G78
Q22


1825
G79
Q22


1826
G80
Q22


1827
G81
Q22


1828
G82
Q22


1829
G83
Q22


1830
G84
Q22


1831
G85
Q22


1832
G86
Q22


1833
G87
Q22


1834
G1
Q23


1835
G2
Q23


1836
G3
Q23


1837
G4
Q23


1838
G5
Q23


1839
G6
Q23


1840
G7
Q23


1841
G8
Q23


1842
G9
Q23


1843
G10
Q23


1844
G11
Q23


1845
G12
Q23


1846
G13
Q23


1847
G14
Q23


1848
G15
Q23


1849
G16
Q23


1850
G17
Q23


1851
G18
Q23


1852
G19
Q23


1853
G20
Q23


1854
G21
Q23


1855
G22
Q23


1856
G23
Q23


1857
G24
Q23


1858
G25
Q23


1859
G26
Q23


1860
G27
Q23


1861
G28
Q23


1862
G29
Q23


1863
G30
Q23


1864
G31
Q23


1865
G32
Q23


1866
G33
Q23


1867
G34
Q23


1868
G35
Q23


1869
G36
Q23


1870
G37
Q23


1871
G38
Q23


1872
G39
Q23


1873
G40
Q23


1874
G41
Q23


1875
G42
Q23


1876
G43
Q23


1877
G44
Q23


1878
G45
Q23


1879
G46
Q23


1880
G47
Q23


1881
G48
Q23


1882
G49
Q23


1883
G50
Q23


1884
G51
Q23


1885
G52
Q23


1886
G53
Q23


1887
G54
Q23


1888
G55
Q23


1889
G56
Q23


1890
G57
Q23


1891
G58
Q23


1892
G59
Q23


1893
G60
Q23


1894
G61
Q23


1895
G62
Q23


1896
G63
Q23


1897
G64
Q23


1898
G65
Q23


1899
G66
Q23


1900
G67
Q23


1901
G68
Q23


1902
G69
Q23


1903
G70
Q23


1904
G71
Q23


1905
G72
Q23


1906
G73
Q23


1907
G74
Q23


1908
G75
Q23


1909
G76
Q23


1910
G77
Q23


1911
G78
Q23


1912
G79
Q23


1913
G80
Q23


1914
G81
Q23


1915
G82
Q23


1916
G83
Q23


1917
G84
Q23


1918
G85
Q23


1919
G86
Q23


1920
G87
Q23


1921
G1
Q24


1922
G2
Q24


1923
G3
Q24


1924
G4
Q24


1925
G5
Q24


1926
G6
Q24


1927
G7
Q24


1928
G8
Q24


1929
G9
Q24


1930
G10
Q24


1931
G11
Q24


1932
G12
Q24


1933
G13
Q24


1934
G14
Q24


1935
G15
Q24


1936
G16
Q24


1937
G17
Q24


1938
G18
Q24


1939
G19
Q24


1940
G20
Q24


1941
G21
Q24


1942
G22
Q24


1943
G23
Q24


1944
G24
Q24


1945
G25
Q24


1946
G26
Q24


1947
G27
Q24


1948
G28
Q24


1949
G29
Q24


1950
G30
Q24


1951
G31
Q24


1952
G32
Q24


1953
G33
Q24


1954
G34
Q24


1955
G35
Q24


1956
G36
Q24


1957
G37
Q24


1958
G38
Q24


1959
G39
Q24


1960
G40
Q24


1961
G41
Q24


1962
G42
Q24


1963
G43
Q24


1964
G44
Q24


1965
G45
Q24


1966
G46
Q24


1967
G47
Q24


1968
G48
Q24


1969
G49
Q24


1970
G50
Q24


1971
G51
Q24


1972
G52
Q24


1973
G53
Q24


1974
G54
Q24


1975
G55
Q24


1976
G56
Q24


1977
G57
Q24


1978
G58
Q24


1979
G59
Q24


1980
G60
Q24


1981
G61
Q24


1982
G62
Q24


1983
G63
Q24


1984
G64
Q24


1985
G65
Q24


1986
G66
Q24


1987
G67
Q24


1988
G68
Q24


1989
G69
Q24


1990
G70
Q24


1991
G71
Q24


1992
G72
Q24


1993
G73
Q24


1994
G74
Q24


1995
G75
Q24


1996
G76
Q24


1997
G77
Q24


1998
G78
Q24


1999
G79
Q24


2000
G80
Q24


2001
G81
Q24


2002
G82
Q24


2003
G83
Q24


2004
G84
Q24


2005
G85
Q24


2006
G86
Q24


2007
G87
Q24


2008
G1
Q25


2009
G2
Q25


2010
G3
Q25


2011
G4
Q25


2012
G5
Q25


2013
G6
Q25


2014
G7
Q25


2015
G8
Q25


2016
G9
Q25


2017
G10
Q25


2018
G11
Q25


2019
G12
Q25


2020
G13
Q25


2021
G14
Q25


2022
G15
Q25


2023
G16
Q25


2024
G17
Q25


2025
G18
Q25


2026
G19
Q25


2027
G20
Q25


2028
G21
Q25


2029
G22
Q25


2030
G23
Q25


2031
G24
Q25


2032
G25
Q25


2033
G26
Q25


2034
G27
Q25


2035
G28
Q25


2036
G29
Q25


2037
G30
Q25


2038
G31
Q25


2039
G32
Q25


2040
G33
Q25


2041
G34
Q25


2042
G35
Q25


2043
G36
Q25


2044
G37
Q25


2045
G38
Q25


2046
G39
Q25


2047
G40
Q25


2048
G41
Q25


2049
G42
Q25


2050
G43
Q25


2051
G44
Q25


2052
G45
Q25


2053
G46
Q25


2054
G47
Q25


2055
G48
Q25


2056
G49
Q25


2057
G50
Q25


2058
G51
Q25


2059
G52
Q25


2060
G53
Q25


2061
G54
Q25


2062
G55
Q25


2063
G56
Q25


2064
G57
Q25


2065
G58
Q25


2066
G59
Q25


2067
G60
Q25


2068
G61
Q25


2069
G62
Q25


2070
G63
Q25


2071
G64
Q25


2072
G65
Q25


2073
G66
Q25


2074
G67
Q25


2075
G68
Q25


2076
G69
Q25


2077
G70
Q25


2078
G71
Q25


2079
G72
Q25


2080
G73
Q25


2081
G74
Q25


2082
G75
Q25


2083
G76
Q25


2084
G77
Q25


2085
G78
Q25


2086
G79
Q25


2087
G80
Q25


2088
G81
Q25


2089
G82
Q25


2090
G83
Q25


2091
G84
Q25


2092
G85
Q25


2093
G86
Q25


2094
G87
Q25









EXAMPLES 2095-2442
The procedure is as in Examples 7-9, but the following compounds of formula [G+].[Xm−]p.[Yn+]q (XI), which can be prepared analogously to Examples 1-6, are used:















Ex.
G+
Xm−
p
Yn+
q







2095
G1
Q1
1⁄2

0


2096
G2
Q1
1⁄2

0


2097
G3
Q1
1⁄2

0


2098
G4
Q1
1⁄2

0


2099
G5
Q1
1⁄2

0


2100
G6
Q1
1⁄2

0


2101
G7
Q1
1⁄2

0


2102
G8
Q1
1⁄2

0


2103
G9
Q1
1⁄2

0


2104
G10
Q1
1⁄2

0


2105
G11
Q1
1⁄2

0


2106
G12
Q1
1⁄2

0


2107
G13
Q1
1⁄2

0


2108
G14
Q1
1⁄2

0


2109
G15
Q1
1⁄2

0


2110
G16
Q1
1⁄2

0


2111
G17
Q1
1⁄2

0


2112
G18
Q1
1⁄2

0


2113
G19
Q1
1⁄2

0


2114
G20
Q1
1⁄2

0


2115
G21
Q1
1⁄2

0


2116
G22
Q1
1⁄2

0


2117
G23
Q1
1⁄2

0


2118
G24
Q1
1⁄2

0


2119
G25
Q1
1⁄2

0


2120
G26
Q1
1⁄2

0


2121
G27
Q1
1⁄2

0


2122
G28
Q1
1⁄2

0


2123
G29
Q1
1⁄2

0


2124
G30
Q1
1⁄2

0


2125
G31
Q1
1⁄2

0


2126
G32
Q1
1⁄2

0


2127
G33
Q1
1⁄2

0


2128
G34
Q1
1⁄2

0


2129
G35
Q1
1⁄2

0


2130
G36
Q1
1⁄2

0


2131
G37
Q1
1⁄2

0


2132
G38
Q1
1⁄2

0


2133
G39
Q1
1⁄2

0


2134
G40
Q1
1⁄2

0


2135
G41
Q1
1⁄2

0


2136
G42
Q1
1⁄2

0


2137
G43
Q1
1⁄2

0


2138
G44
Q1
1⁄2

0


2139
G45
Q1
1⁄2

0


2140
G46
Q1
1⁄2

0


2141
G47
Q1
1⁄2

0


2142
G48
Q1
1⁄2

0


2143
G49
Q1
1⁄2

0


2144
G50
Q1
1⁄2

0


2145
G51
Q1
1⁄2

0


2146
G52
Q1
1⁄2

0


2147
G53
Q1
1⁄2

0


2148
G54
Q1
1⁄2

0


2149
G55
Q1
1⁄2

0


2150
G56
Q1
1⁄2

0


2151
G57
Q1
1⁄2

0


2152
G58
Q1
1⁄2

0


2153
G59
Q1
1⁄2

0


2154
G60
Q1
1⁄2

0


2155
G61
Q1
1⁄2

0


2156
G62
Q1
1⁄2

0


2157
G63
Q1
1⁄2

0


2158
G64
Q1
1⁄2

0


2159
G65
Q1
1⁄2

0


2160
G66
Q1
1⁄2

0


2161
G67
Q1
1⁄2

0


2162
G68
Q1
1⁄2

0


2163
G69
Q1
1⁄2

0


2164
G70
Q1
1⁄2

0


2165
G71
Q1
1⁄2

0


2166
G72
Q1
1⁄2

0


2167
G73
Q1
1⁄2

0


2168
G74
Q1
1⁄2

0


2169
G75
Q1
1⁄2

0


2170
G76
Q1
1⁄2

0


2171
G77
Q1
1⁄2

0


2172
G78
Q1
1⁄2

0


2173
G79
Q1
1⁄2

0


2174
G80
Q1
1⁄2

0


2175
G81
Q1
1⁄2

0


2176
G82
Q1
1⁄2

0


2177
G83
Q1
1⁄2

0


2178
G84
Q1
1⁄2

0


2179
G85
Q1
1⁄2

0


2180
G86
Q1
1⁄2

0


2181
G87
Q1
1⁄2

0


2182
G1
Q26
1⁄2

0


2183
G2
Q26
1⁄2

0


2184
G3
Q26
1⁄2

0


2185
G4
Q26
1⁄2

0


2186
G5
Q26
1⁄2

0


2187
G6
Q26
1⁄2

0


2188
G7
Q26
1⁄2

0


2189
G8
Q26
1⁄2

0


2190
G9
Q26
1⁄2

0


2191
G10
Q26
1⁄2

0


2192
G11
Q26
1⁄2

0


2193
G12
Q26
1⁄2

0


2194
G13
Q26
1⁄2

0


2195
G14
Q26
1⁄2

0


2196
G15
Q26
1⁄2

0


2197
G16
Q26
1⁄2

0


2198
G17
Q26
1⁄2

0


2199
G18
Q26
1⁄2

0


2200
G19
Q26
1⁄2

0


2201
G20
Q26
1⁄2

0


2202
G21
Q26
1⁄2

0


2203
G22
Q26
1⁄2

0


2204
G23
Q26
1⁄2

0


2205
G24
Q26
1⁄2

0


2206
G25
Q26
1⁄2

0


2207
G26
Q26
1⁄2

0


2208
G27
Q26
1⁄2

0


2209
G28
Q26
1⁄2

0


2210
G29
Q26
1⁄2

0


2211
G30
Q26
1⁄2

0


2212
G31
Q26
1⁄2

0


2213
G32
Q26
1⁄2

0


2214
G33
Q26
1⁄2

0


2215
G34
Q26
1⁄2

0


2216
G35
Q26
1⁄2

0


2217
G36
Q26
1⁄2

0


2218
G37
Q26
1⁄2

0


2219
G38
Q26
1⁄2

0


2220
G39
Q26
1⁄2

0


2221
G40
Q26
1⁄2

0


2222
G41
Q26
1⁄2

0


2223
G42
Q26
1⁄2

0


2224
G43
Q26
1⁄2

0


2225
G44
Q26
1⁄2

0


2226
G45
Q26
1⁄2

0


2227
G46
Q26
1⁄2

0


2228
G47
Q26
1⁄2

0


2229
G48
Q26
1⁄2

0


2230
G49
Q26
1⁄2

0


2231
G50
Q26
1⁄2

0


2232
G51
Q26
1⁄2

0


2233
G52
Q26
1⁄2

0


2234
G53
Q26
1⁄2

0


2235
G54
Q26
1⁄2

0


2236
G55
Q26
1⁄2

0


2237
G56
Q26
1⁄2

0


2238
G57
Q26
1⁄2

0


2239
G58
Q26
1⁄2

0


2240
G59
Q26
1⁄2

0


2241
G60
Q26
1⁄2

0


2242
G61
Q26
1⁄2

0


2243
G62
Q26
1⁄2

0


2244
G63
Q26
1⁄2

0


2245
G64
Q26
1⁄2

0


2246
G65
Q26
1⁄2

0


2247
G66
Q26
1⁄2

0


2248
G67
Q26
1⁄2

0


2249
G68
Q26
1⁄2

0


2250
G69
Q26
1⁄2

0


2251
G70
Q26
1⁄2

0


2252
G71
Q26
1⁄2

0


2253
G72
Q26
1⁄2

0


2254
G73
Q26
1⁄2

0


2255
G74
Q26
1⁄2

0


2256
G75
Q26
1⁄2

0


2257
G76
Q26
1⁄2

0


2258
G77
Q26
1⁄2

0


2259
G78
Q26
1⁄2

0


2260
G79
Q26
1⁄2

0


2261
G80
Q26
1⁄2

0


2262
G81
Q26
1⁄2

0


2263
G82
Q26
1⁄2

0


2264
G83
Q26
1⁄2

0


2265
G84
Q26
1⁄2

0


2266
G85
Q26
1⁄2

0


2267
G86
Q26
1⁄2

0


2268
G87
Q26
1⁄2

0


2269
G1
Q1
1
NH4+
1


2270
G2
Q1
1
NH4+
1


2271
G3
Q1
1
NH4+
1


2272
G4
Q1
1
NH4+
1


2273
G5
Q1
1
NH4+
1


2274
G6
Q1
1
NH4+
1


2275
G7
Q1
1
NH4+
1


2276
G8
Q1
1
NH4+
1


2277
G9
Q1
1
NH4+
1


2278
G10
Q1
1
NH4+
1


2279
G11
Q1
1
NH4+
1


2280
G12
Q1
1
NH4+
1


2281
G13
Q1
1
NH4+
1


2282
G14
Q1
1
NH4+
1


2283
G15
Q1
1
NH4+
1


2284
G16
Q1
1
NH4+
1


2285
G17
Q1
1
NH4+
1


2286
G18
Q1
1
NH4+
1


2287
G19
Q1
1
NH4+
1


2288
G20
Q1
1
NH4+
1


2289
G21
Q1
1
NH4+
1


2290
G22
Q1
1
NH4+
1


2291
G23
Q1
1
NH4+
1


2292
G24
Q1
1
NH4+
1


2293
G25
Q1
1
NH4+
1


2294
G26
Q1
1
NH4+
1


2295
G27
Q1
1
NH4+
1


2296
G28
Q1
1
NH4+
1


2297
G29
Q1
1
NH4+
1


2298
G30
Q1
1
NH4+
1


2299
G31
Q1
1
NH4+
1


2300
G32
Q1
1
NH4+
1


2301
G33
Q1
1
NH4+
1


2302
G34
Q1
1
NH4+
1


2303
G35
Q1
1
NH4+
1


2304
G36
Q1
1
NH4+
1


2305
G37
Q1
1
NH4+
1


2306
G38
Q1
1
NH4+
1


2307
G39
Q1
1
NH4+
1


2308
G40
Q1
1
NH4+
1


2309
G41
Q1
1
NH4+
1


2310
G42
Q1
1
NH4+
1


2311
G43
Q1
1
NH4+
1


2312
G44
Q1
1
NH4+
1


2313
G45
Q1
1
NH4+
1


2314
G46
Q1
1
NH4+
1


2315
G47
Q1
1
NH4+
1


2316
G48
Q1
1
NH4+
1


2317
G49
Q1
1
NH4+
1


2318
G50
Q1
1
NH4+
1


2319
G51
Q1
1
NH4+
1


2320
G52
Q1
1
NH4+
1


2321
G53
Q1
1
NH4+
1


2322
G54
Q1
1
NH4+
1


2323
G55
Q1
1
NH4+
1


2324
G56
Q1
1
NH4+
1


2325
G57
Q1
1
NH4+
1


2326
G58
Q1
1
NH4+
1


2327
G59
Q1
1
NH4+
1


2328
G60
Q1
1
NH4+
1


2329
G61
Q1
1
NH4+
1


2330
G62
Q1
1
NH4+
1


2331
G63
Q1
1
NH4+
1


2332
G64
Q1
1
NH4+
1


2333
G65
Q1
1
NH4+
1


2334
G66
Q1
1
NH4+
1


2335
G67
Q1
1
NH4+
1


2336
G68
Q1
1
NH4+
1


2337
G69
Q1
1
NH4+
1


2338
G70
Q1
1
NH4+
1


2339
G71
Q1
1
NH4+
1


2340
G72
Q1
1
NH4+
1


2341
G73
Q1
1
NH4+
1


2342
G74
Q1
1
NH4+
1


2343
G75
Q1
1
NH4+
1


2344
G76
Q1
1
NH4+
1


2345
G77
Q1
1
NH4+
1


2346
G78
Q1
1
NH4+
1


2347
G79
Q1
1
NH4+
1


2348
G80
Q1
1
NH4+
1


2349
G81
Q1
1
NH4+
1


2350
G82
Q1
1
NH4+
1


2351
G83
Q1
1
NH4+
1


2352
G84
Q1
1
NH4+
1


2353
G85
Q1
1
NH4+
1


2354
G86
Q1
1
NH4+
1


2355
G87
Q1
1
NH4+
1


2356
G1
Q26
1
NH4+
1


2357
G2
Q26
1
NH4+
1


2358
G3
Q26
1
NH4+
1


2359
G4
Q26
1
NH4+
1


2360
G5
Q26
1
NH4+
1


2361
G6
Q26
1
NH4+
1


2362
G7
Q26
1
NH4+
1


2363
G8
Q26
1
NH4+
1


2364
G9
Q26
1
NH4+
1


2365
G10
Q26
1
NH4+
1


2366
G11
Q26
1
NH4+
1


2367
G12
Q26
1
NH4+
1


2368
G13
Q26
1
NH4+
1


2369
G14
Q26
1
NH4+
1


2370
G15
Q26
1
NH4+
1


2371
G16
Q26
1
NH4+
1


2372
G17
Q26
1
NH4+
1


2373
G18
Q26
1
NH4+
1


2374
G19
Q26
1
NH4+
1


2375
G20
Q26
1
NH4+
1


2376
G21
Q26
1
NH4+
1


2377
G22
Q26
1
NH4+
1


2378
G23
Q26
1
NH4+
1


2379
G24
Q26
1
NH4+
1


2380
G25
Q26
1
NH4+
1


2381
G26
Q26
1
NH4+
1


2382
G27
Q26
1
NH4+
1


2383
G28
Q26
1
NH4+
1


2384
G29
Q26
1
NH4+
1


2385
G30
Q26
1
NH4+
1


2386
G31
Q26
1
NH4+
1


2387
G32
Q26
1
NH4+
1


2388
G33
Q26
1
NH4+
1


2389
G34
Q26
1
NH4+
1


2390
G35
Q26
1
NH4+
1


2391
G36
Q26
1
NH4+
1


2392
G37
Q26
1
NH4+
1


2393
G38
Q26
1
NH4+
1


2394
G39
Q26
1
NH4+
1


2395
G40
Q26
1
NH4+
1


2396
G41
Q26
1
NH4+
1


2397
G42
Q26
1
NH4+
1


2398
G43
Q26
1
NH4+
1


2399
G44
Q26
1
NH4+
1


2400
G45
Q26
1
NH4+
1


2401
G46
Q26
1
NH4+
1


2402
G47
Q26
1
NH4+
1


2403
G48
Q26
1
NH4+
1


2404
G49
Q26
1
NH4+
1


2405
G50
Q26
1
NH4+
1


2406
G51
Q26
1
NH4+
1


2407
G52
Q26
1
NH4+
1


2408
G53
Q26
1
NH4+
1


2409
G54
Q26
1
NH4+
1


2410
G55
Q26
1
NH4+
1


2411
G56
Q26
1
NH4+
1


2412
G57
Q26
1
NH4+
1


2413
G58
Q26
1
NH4+
1


2414
G59
Q26
1
NH4+
1


2415
G60
Q26
1
NH4+
1


2416
G61
Q26
1
NH4+
1


2417
G62
Q26
1
NH4+
1


2418
G63
Q26
1
NH4+
1


2419
G64
Q26
1
NH4+
1


2420
G65
Q26
1
NH4+
1


2421
G66
Q26
1
NH4+
1


2422
G67
Q26
1
NH4+
1


2423
G68
Q26
1
NH4+
1


2424
G69
Q26
1
NH4+
1


2425
G70
Q26
1
NH4+
1


2426
G71
Q26
1
NH4+
1


2427
G72
Q26
1
NH4+
1


2428
G73
Q26
1
NH4+
1


2429
G74
Q26
1
NH4+
1


2430
G75
Q26
1
NH4+
1


2431
G76
Q26
1
NH4+
1


2432
G77
Q26
1
NH4+
1


2433
G78
Q26
1
NH4+
1


2434
G79
Q26
1
NH4+
1


2435
G80
Q26
1
NH4+
1


2436
G81
Q26
1
NH4+
1


2437
G82
Q26
1
NH4+
1


2438
G83
Q26
1
NH4+
1


2439
G84
Q26
1
NH4+
1


2440
G85
Q26
1
NH4+
1


2441
G86
Q26
1
NH4+
1


2442
G87
Q26
1
NH4+
1









EXAMPLE 2443
The procedure is as in Examples 7-9, but the product of formula G89 according to Example 4 is used together with 20% by weight (based on the product according to Example G89) of the product of formula 




EXAMPLE 2444
The procedure is as in Example 2443, but the product of formula G89 according to Example 4 is used together with 20% by weight (based on the product according to Example G89) of the product of formula 




EXAMPLE 2445
The procedure is as in Example 2443, but the product of formula G89 according to Example 4 is used together with 20% by weight (based on the product according to Example G89) of the product of formula 




EXAMPLE 2446
The procedure is as in Example 2443, but the product of formula G89 according to Example 4 is used together with 20% by weight (based on the product according to Example G89) of the product of formula 




EXAMPLE 2447
The procedure is as in Example 2443, but the product of formula G89 according to Example 4 is used together with 20% by weight (based on the product according to Example G89) of the product of formula 




EXAMPLES 2448-2452
The procedure is as in Examples 2443-2447, but the product of formula G90 according to Example 5 is used instead of the product of formula G89 according to Example 4.
EXAMPLE 2453
12.1 g of N-ethylaniline are stirred in 22 ml of 2-chloropropionic acid ethyl ester in the presence of 10.6 ml of sodium carbonate and 0.2 g of potassium iodide until the N-ethylaniline can no longer be detected in thin-layer chromatography. The chloropropionic acid ester is distilled off, and the oil that remains is taken up in ethyl acetate and extracted with water until salt-free. The dried organic phase is concentrated, yielding 20 g of an oily mass of formula: 




EXAMPLE 2454
7.1 g of the compound according to Example 2453 are introduced into 20 ml of N,N-dimethylformamide and cooled in an ice bath. 3.2 ml of phosphorus oxytrichloride are then slowly added dropwise and the mixture is stirred first at 20° C., and then for a further 4 hours at 60° C. The cooled reaction mass is discharged into a small amount of ice-water and neutralised with dilute sodium hydroxide solution. The resulting oil is taken up in ethyl acetate and washed with sodium chloride solution. The organic phase is dried and concentrated, yielding 6.7 g of the product of formula: 




EXAMPLE 2455
6.7 g of the compound according to Example 2454 are dissolved in 50 ml of methanol, and 0.43 g of sodium borohydride is added. After 30 minutes at 20° C., the starting material can no longer be detected. The reaction solution is freed of methanol by distillation and the residue is taken up in ethyl acetate and washed with concentrated sodium chloride solution. The dried ethyl acetate phase is concentrated by evaporation; yielding 4.6 g of an oil of formula 




EXAMPLE 2456
4.25 g of the compound according to Example 2455 are dissolved in 25 ml of dichloromethane, and 2.6 ml of 3-isopropenyl-N,N-dimethylaniline are added. While cooling with an ice bath, 16 ml of a 1M boron trichloride solution in dichloromethane are added and the mixture is left to react overnight in the initial ice-bath to complete the reaction. Then, while cooling in an ice bath, 16 ml of concentrated sulfuric acid are added dropwise. The resulting reaction mixture is discharged onto ice, neutralised with sodium hydroxide solution and taken up in dichloromethane. After being washed, the organic phase is dried and the dichloromethane is distilled off, leaving behind 5.8 g of a blue-green, very oxygen-senstive oil of formula 




EXAMPLE 2457
5.8 g of the compound according to Example 2456 are dissolved in 40 ml of 100% acetic acid, and 150 drops of 60% perchloric acid are added. 1.65 g of tetrabutylammonium (meta)periodate are added to the resulting mixture. Stirring is carried out for 3 hours at 40° C., and the reaction mass is discharged into 250 ml of water and 25 g of sodium perchlorate monohydrate and the oily mass obtained is treated with a potassium perchlorate solution. After working up, 3.4 g of crude product are obtained. Repeated chromatographic purification of the crude product yields the analytically pure compound of the following formula: 




EXAMPLE 2458
1.33 g of analytically pure product according to Example 2457 are dissolved in acetone with 2.78 g of the cobalt complex of structure Q20 and the solution is concentrated by evaporation. The residue is taken up in methylene chloride, extracted by shaking repeatedly with deionised water and, without drying of the organic phase, concentrated to dryness without residue, yielding 3.13 g of compound of formula: 




EXAMPLE 2459
The procedure is as in Example 7, but instead of the product according to Example 1 there is used an equal amount of the product according to Example 2458. The absorption maximum of a recording support produced analogously to Example 7 is at 623 nm.
EXAMPLE 2460
2.7 g of 4-fluorobenzaldehyde are stirred at 110° C. in 20 ml of dimethyl sulfoxide with 3.74 g of morpholine and 3 g of potassium carbonate for 6 hours. Customary working-up yields 0.95 g of crystalline product of formula 




That product is processed further analogously to Examples 2455 to 2458; yielding the compound of formula: 




EXAMPLE 2461
The procedure is as in Example 7, but instead of the product according to Example 1 there is used an equal amount of the product according to Example 2460. The absorption maximum of a recording support produced analogously to Example 7 is at 626 nm.
EXAMPLE 2462
The procedure is as in Example 7, but instead of the product according to Example 1 there is used an equal amount of the product according to Example 3. The absorption maximum of the recording support is at 625 nm.
EXAMPLE 2463
The procedure is as in Example 3, but instead of the metal complex of formula Q20 there is used an equimolar amount of the metal complex of formula Q16. The absorption maximum of a recording support produced analogously to Example 7 is at 631 nm.
EXAMPLE 2464
The procedure is as in Example 1, but instead of the sodium salt of the metal complex of formula Q20 there is used the same amount of the product of formula 




The absorption maximum of a recording support analogous to Example 7 is at about 630 nm.

EXAMPLES 2465-2470
Analogously to Example 7, recording supports are produced using the products of other Examples. The following absorption maxima are obtained:













Recording




support comprising



product according to


Example
Example:
Absorption maximum







2465
 98
623 nm


2466
 183
636 nm


2467
1227
632 nm


2468
1576
621 nm


2469
1583
625 nm


2470
1921
633 nm

## Claims

1. An optical recording medium, comprising a substrate and a recording layer, wherein the recording layer comprises a compound of formula (I) 



wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and R13 are each independently of the others hydrogen, G1, or C1-C24alkyl, C2-C24alkenyl, C2-C24alkynyl, C3-C24cycloalkyl, C3-C24cycloalkenyl, C7-C24aralkyl, C6-C24aryl, C4-C12heteroaryl or C1-C12heterocycloalkyl, each unsubstituted or substituted by one or more identical or different substituents G1, 
wherein R1 and R2, R1 and R13, R2 and R3, R3 and R4, R4 and R5, R5 and R6, R6 and R7, R7 and R8, R8 and R9, R9 and R10, R10 and R11, R11 and R12 and/or R12 and R13 can independently of one another be bonded to one another in pairs separately or, when they contain substitutable sites, via a direct bond or via a —CH2—, —O—, —S—, —NH— or —NC1-C24alkyl-bridge in such a manner that, together with the atoms and bonds indicated in formula (I), five- or six-membered, saturated, unsaturated or aromatic, unsubstituted or G1-substituted rings are formed, 
G1 is any desired substituent, 
Xm− is an inorganic, organic or organometallic anion, 
Yn+ is a proton or a metal, ammonium or phosphonium cation, and 
m and n are each independently of the other a number from 1 to 5, and p and q are each independently of the other 0 or a number from 0.2 to 6, 
the ratio of p and q to one another, depending upon m and n and, as applicable, the number of charged G1, being such that in formula (I) there is no excess positive or negative charge.

2. A recording medium according to claim 1, which additionally comprises a reflecting layer.

3. A recording medium according to claim 1, wherein R6 is 




and R29, R30 and R31 are each independently of the others hydrogen, halogen, COOR32, OR32 or NR32R33, wherein R32 and R33 are each independently of the other hydrogen or C1-C12alkyl, C2-C12alkenyl, C1-C12cycloalkyl, C2-C12cycloalkenyl, C6-C12aryl or C7-C13aralkyl, each unsubstituted or substituted by one or two hydroxy substituents or by a metallocenyl or azo metal complex radical and uninterrupted or interrupted by 1, 2, 3, 4 or 5 oxygen and/or silicon atoms.

4. A recording medium according to claim 1, wherein R1, R4, R5, R7, R8 and R11 are hydrogen; R2, R3, R9, R10, R12 and R13 are each independently of the others methyl, ethyl or R14, it being possible for R2 and R3, R9 and R10, R12 and R13 and/or R9 and R10 also to be bonded together in pairs via a direct bond, methylene, —O— or —N(C1-C4alkyl); and R6 is hydrogen or C1-C12alkyl, C6-C12aryl or C7-C13aralkyl, each unsubstituted or mono- to tetra-substituted by halogen, —O−, —OR26, —CN, —NR26R27, —N+R26R27R28, —N(R26)COR27, —COO−, —COOR26, —CONR26R27, R14 or by —N(R26)COR27R28, wherein R26, R27 and R28 are each independently of the others C1-C12alkyl, C6-C12aryl or C7-C13aralkyl.

5. A recording medium according to claim 3, wherein R6 is 




or R37, and R34, R35 and R36 are each independently of the others hydrogen or R37, R37 being alkyl uninterrupted or interrupted by from 1 to 3 oxygen and/or silicon atoms and unsubstituted or substituted by one or two hydroxy substituents or by a metallocenyl or azo metal complex radical.

6. A recording medium according to claim 1, wherein Xm− is a metal complex of formula [(L1)M1(L2)]m− (III) or [(L3)M2(L4)]− (IV), wherein M1 and M2 are a transition metal, m is a number from 1 to 6, L1 and L2 are each independently of the other a ligand of the formula 







and L3 and L4 are each independently of the other a ligand of formula 




wherein R16, R17, R18, R19, R20 and R21 are each independently of the others hydrogen, halogen, cyano, R24, NO2, NR24R25, NHCO—R24, NHCOOR24, SO2—R24, SO2NH2, SO2NHR24, SO2NR24R25, SO3− or SO3H, and R22 and R23 are each independently of the others CN, CONH2, CONHR24, CONR24R25, COOR24 or COR24, wherein R24 and R25 are each independently of the other C1-C12alkyl, C1-C12alkoxy-C2-C12alkyl, C7-C12aralkyl or C6-C12aryl, each unsubstituted or substituted by hydroxy, halogen, sulfato, C1-C6alkoxy, C1-C6alkylthio, C1-C6alkylamino or by di-C1-C6alkylamino, or R24 and R25 together are C4-C10heterocycloalkyl; it also being possible for R16 and R17, R18 and R19, and/or R20 and R21 to be bonded together in pairs in such a manner that a 5- or 6-membered ring is formed.

7. A recording medium according to claim 1, wherein Yn+ is [NH2R38R39]+, R38 being hydrogen or C1-C12alkyl and R39 being C1-C24alkyl or C7-C24aralkyl, and R38 and R39 together having from 8 to 25 carbon atoms.

8. A recording medium according to claim 1, wherein m and n are each the number 1, p is a number from 1 to 21⁄2, and q is a number from 0 to 11⁄2, the sum of positive charges in formula (I) or (II) being equal to the sum of negative charges.

9. A recording medium according to claim 1, wherein the dye of formula (I) has an absorption maximum at from 540 to 640 nm in ethanolic solution and a refractive index of from 2.0 to 3.0 in the range of from 600 to 700 nm in the solid.

10. A recording medium according to claim 1, wherein the substrate has a transparency of at least 90% and a thickness of from 0.01 to 10 mm, preferably from 0.1 to 5 mm.

11. A recording medium according to claim 2, wherein the reflecting layer consists of aluminium, silver, copper, gold or an alloy thereof and has a reflectivity of at least 45% and thickness of from 10 to 150 nm.

12. A recording medium according to claim 2, wherein the recording layer is located between the transparent substrate and the reflecting layer and has a thickness of from 10 to 1000 nm.

13. A recording medium according to claim 2, the uppermost layer of which is provided with an additional protective layer having a thickness of from 0.1 to 1000 μm to which there may be applied a second substrate layer that is from 0.1 to 5 mm thick and consists of the same material as the support substrate.

14. A recording medium according to claim 1, which has a reflectivity of at least 15%.

15. A recording medium according to claim 2, wherein between the recording layer and the reflecting layer and/or between the recording layer and the substrate there is additionally arranged at least one interference layer consisting of a dielectric material.

16. A method for optical recording, storage and playback of information, which comprises the optical recording, storage and playback of the information from a recording medium according to claim 1.

17. A method according to claim 16, wherein the recording and the playback take place in a wavelength range of from 600 to 700 nm.

18. A process for the production of an optical recording medium, wherein a solution of a compound of formula (I) according claim 1 in an organic solvent is applied to a substrate having pits.

19. A process according to claim 18, wherein the application is carried out by means of spin-coating.

20. A compound of formula (I) according to claim 1.

21. A process for the preparation of a compound of formula (I) according to claim 1, wherein a compound of structure 




is oxidised in the presence of a C1-C18carboxylic acid.

22. A process according to claim 21, wherein (meta)periodate is used as oxidising agent.