Optical data medium containing, in the information layer, a dye as a light-absorbing compound

Information

  • Patent Application
  • 20030113665
  • Publication Number
    20030113665
  • Date Filed
    March 20, 2002
    22 years ago
  • Date Published
    June 19, 2003
    20 years ago
Abstract
Optical data medium containing a preferably transparent substrate which is optionally already coated with one or more barrier layers and on the surface of which an information layer which can be recorded on using light, optionally one or more barrier layers, and a cover layer, have been applied, which data medium can be recorded on and read using focused blue light through the cover layer on the information layer, preferably laser light with the wavelength between 360 nm and 460 nm, the information layer containing a light-absorbing compound and optionally a binder, characterized in that at least one dye is used as the light-absorbing compound wherein the cover layer on the top of the information layer including the adhesive layer do have a total thickness of 10 μm to 177 μm and the numerical aperture NA of the focusing objective lens setup is greater or equal 0.8.
Description


PRIOR ART

[0001] The invention relates to a, preferably singly recordable, optical data medium which contains, in the information layer, at least one dye as a light-absorbing compound, and has a defined thickness of all the cover layers and can be recorded and readout with a focusing optical setup with a defined numerical aperture and a process for its production.


[0002] “The term” singly recordable” has the same meaning as the term “once recordable”.


[0003] The singly recordable optical data media using special light-absorbing substances or mixtures thereof are suitable in particular for use in the case of high-density recordable optical data media which operate with blue laser diodes, in particular GaN or SHG laser diodes (360-460 nm) and/or for use in the case of DVD-R or CD-R discs which operate with red (635-660 nm) or infrared (760-830 nm) laser diodes, and the application of the abovementioned dyes to a polymer substrate, made from for example polycarbonates, copolycarbonates, polycycloolefines, polyolefines, by spin-coating, vapour deposition or sputtering.


[0004] The singly recordable compact disc (CD-R, 780 nm) has recently been experiencing enormous growth in quantity and is a technically established system.


[0005] Recently, the next generation of optical data stores—the DVD—was launched on the market. By using shorter-wave laser radiation (635 to 660 nm) and a higher numerical aperture NA, the storage density can be increased. In this case, the singly recordable format is the DVD-R.


[0006] Optical data storage formats which use blue laser diodes (based on GaN, JP-A-08 191 171 or Second Harmonic Generation SHG JP-A-09 050 629) (360 nm to 460 nm) having a high laser power are now being developed. Recordable optical data stores are therefore also used in this generation. The recordable storage density depends on the focusing of the laser spot in the information plane. The spot size is scaled with the laser wavelength λ/NA. NA is the numerical aperture of the lens used. In order to obtain as high a storage density as possible, the use of as short a wavelength λ as possible is desirable. At present, 390 nm are possible on the basis of semiconductor laser diodes.


[0007] The patent literature describes recordable optical data stores which are based on dyes and are just as suitable for CD-R and DVD-R systems (JP-A 11 043 481 and JP-A 10 181 206). Here, for high reflectivity and a high modulation amplitude of the read-out signal, and for sufficient sensitivity during recording, use is made of the fact that the IR wavelength 780 nm of the CD-R lies at the foot of the long-wave flank of the absorption peak of the dye, and the red wavelength 635 nm or 650 nm of the DVD-R also lies at the foot of the long-wave flank of the absorption peak of the. This concept is extended to include the region of 450 nm operating wavelength on the long-wave flank of the absorption peak.


[0008] In addition to the abovementioned optical properties, the recordable information layer comprising light-absorbing organic substances must have a morphology which is as amorphous as possible, in order to minimize the noise signal during recording and read-out. For this purpose, it is particularly preferred if, during application of the substances by spin-coating from a solution, by sputtering or by vapour deposition and/or sublimation, crystallization of the light-absorbing substances is prevented during the subsequent overcoating with metallic or dielectric layers in vacuo.


[0009] The amorphous layer of light-absorbing substances should preferably have a high heat distortion resistance, since otherwise further layers of organic or inorganic material which are applied by sputtering or vapour deposition to the light-absorbing information layer will form ill-defined interfaces through diffusion and thus adversely affect the reflectivity. In addition, light-absorbing substances having too low a heat distortion resistance at the interface with a polymeric substrate can diffuse into the latter and once again adversely affect the reflectivity.


[0010] If a light-absorbing substance has too high a vapour pressure, said substance can sublime during the abovementioned sputtering or vapour deposition of further layers in a high vacuum and hence reduce the desired layer thickness. This in turn leads to an adverse effect on the reflectivity.


[0011] Upon comprising a high NA lens as an objective lens in purpose to achieve as high areal density as possible, the thickness of transparent layer, which a readout beam transmit through when focusing on the information layer, namely the substrate or cover layer, will restrict its skew margin. Since the NA of CD and DVD objective lens are 0.45 and 0.60 respectively, their substrate thickness were chosen as 1.2 mm and 0.6 mm respectively to assure its sufficient skew margin for mass productive optical drives. The thickness of the cover layer is of significant importance for mass production since the production process will be totally different from the conventional medium, and accordingly the recording/readout performance of the medium should also be optimised for such newly designed medium. Since such thin cover layer will be easily bent and thus it is not appropriate to coat the information layer directly on the cover, the information layer and protective layer will be formed on a thick substrate before the cover layer is fixed on the substrate. CD-R and DVD-R utilize a UV resin hard cover both on purpose for the protective layer and also to cover the information layer with sufficient hardness to improve its recording properties(JP-A 2834420).


[0012] It is accordingly an object of the invention to provide suitable compounds which meet the high requirements (such as light stability, advantageous signal/noise ratio, damage-free application to the substrate material, etc.) for use in the information layer in a singly recordable optical data medium, in particular for high-density recordable optical data storage formats in a laser wavelength range of from 360 to 460 nm.


[0013] Surprisingly, it was found that light-absorbing compounds from the group consisting of dyes in combination with special parameters of the cover layer thickness accompanied with the NA, preferably phthalocyanine dyes and merocyanine dyes can fulfil the abovementioned requirement profile particularly well. Especially Phthalocyanines have an intense absorption in the wavelength range of 360-460 nm important for the laser, i.e. the B or Soret band. Merocyanines have an intense absorption in the wavelength range of 420-550 nm making them suited for the laser.


[0014] The present invention therefore relates to an optical data medium, containing a preferably transparent substrate which is optionally already coated with one or more barrier layers and on the surface of which an information layer which can be recorded on using light, optionally one or more barrier layers and a cover layer, applied by an adhesive layer, have been applied, which can be recorded on and read using focused blue light through the cover layer on the information layer, preferably laser light, particularly preferably light at 360-460 nm, in particular 380-440 nm, very particularly preferably at 395-415 nm, the information layer containing a light-absorbing compound and optionally a binder, characterized in that at least one dye is used as the light-absorbing compound wherein the cover layer on the top of the information layer including the adhesive layer do have a total thickness of 10 μm to 177 μm and the numerical aperture NA of the focusing objective lens setup is greater or equal 0.8 preferable 0.80 to 0.95.


[0015] Preferred are merocyanines as light-absorbing compound, most preferably compounds of the formula
1


[0016] are preferred, wherein


[0017] A represents a radical of the formula
2


[0018] X1 represents CN, CO—R1, COO—R2, CONHR3 or CONR3R4,


[0019] X2 represents hydrogen, C1- to C6-alkyl, C6- to C10-aryl, a five- or six-membered heterocyclic radical, CN, CO—R1, COO—R2, CONHR3 or CONR3R4 or


[0020] CX1X2 represents a ring of the formulae
3


[0021]  which can be benzo- or naphtha-fused and/or substituted by non-ionic or ionic radicals and wherein the asterisk (*) indicates the ring atom from which the double bond emanates,


[0022] X3 represents N or CH,


[0023] X4 represents O, S, N, N—R6 or CH, wherein X3 and X4 do not simultaneously represent CH,


[0024] X5 represents O, S or N—R6,


[0025] X6 represents O, S, N, N—R6, CH or CH2,


[0026] the ring B of the formula (II)
4


[0027]  together with X4, X3 and the C atom bound there-between


[0028] and the ring C of the formula (V)
5


[0029]  together with X5, X6 and the C atom bound there-between independently of one another represent a five- or six-membered aromatic or quasi-aromatic heterocyclic ring which can contain 1 to 4 hetero atoms and/or can be benzo- or naphtha-fused and/or substituted by non-ionic or ionic radicals,


[0030] Y1 represents N or C—R7,


[0031] Y2 represents N or C—R8,


[0032] R1 to R6 independently of one another represent hydrogen, C1 to C6-alkyl, C3 to C6-alkenyl, C5 to C7-cycloalkyl, C6- to C10-aryl or C7 to C15-aralkyl,


[0033] R7 and R8 independently of one another represent hydrogen, cyano or C1 to C6-alkyl,


[0034] R9 and R10 independently of one another represent C1 to C6-alkyl, C6 to C10-aryl or C7 to C15-aralkyl or


[0035] NR9R10 represents a 5- or 6-membered saturated heterocyclic ring.


[0036] Oligomeric and polymeric merocyanine dyes of the formula (I) are also preferred in which at least one of the radicals R1 to R10 or at least one of the non-ionic radicals represent a bridge. This bridge can link two or more merocyanine dyes to form oligomers or polymers. It can however also represent a bridge to a polymeric chain. In this case the merocyanine dyes are bonded in a comb-like fashion to such a chain.


[0037] Suitable bridges are for example those of the formulae —(CH2)n— or —(CH2)m—Z—(CH2)p—,


[0038] wherein


[0039] n and m independently of each other represent an integer from 1 to 20 and


[0040] Z represents —O— or —C6H4—.


[0041] Polymeric chains are for example polyacrylates, polymethacrylates, polyacrylamides, polymethacrylamides, polysiloxanes, poly-α-oxiranes, polyethers, polyamides, polyurethanes, polyureas, polyesters, polycarbonates, polystyrene or polymaleic acid.


[0042] Suitable non-ionic radicals are for example C1 to C4-alkyl, C1 to C4-alkoxy, halogen, cyano, nitro, C1 to C4-alkoxycarbonyl, C1 to C4-alkylthio, C1- to C4-alkanoylamino, benzoylamino, mono- or di-C1 to C4-alkylamino, pyrrolidino, piperidino, piperazino or morpholino.


[0043] Suitable ionic radicals are for example ammonium radicals or COO— or SO3—radicals which can be bonded via a direct bond or via —(CH2)n—, wherein n represents an integer from 1 to 6.


[0044] Alkyl, alkoxy, aryl and heterocyclic radicals can optionally contain other radicals such as alkyl, halogen, nitro, cyano, CO—NH2, alkoxy, trialkylsilyl, trialkylsiloxy or phenyl, the alkyl and alkoxy radicals can be straight-chained or branched, the alkyl radicals can be partially halogenated or perhalogenated, the alkyl and alkoxy radicals can be ethoxylated or propoxylated or silylated, adjacent alkyl and/or alkoxy radicals on aryl or heterocyclic radicals can together form a three- or four-membered bridge and the heterocyclic radicals can be benzo-fused and/or quaternized.


[0045] Particularly Preferably


[0046] the ring B of the formula (II) represents furan-2-yl, thiophen-2-yl, pyrrol-2-yl, benzofuran-2-yl, benzothiophen-2-yl, thiazol-5-yl, imidazol-5-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl, 2- or 4-pyridyl, 2- or 4-quinolyl, wherein the individual rings can be substituted by C1 to C6-alkyl, C1 to C6-alkoxy, fluorine, chlorine, bromine, iodine, cyano, nitro, C1 to C6-alkoxycarbonyl, C1- to C6-alkylthio, C1 to C6-acylamino, C6 to C10-aryl, C6 to C10-aryloxy, C6 to C10-arylcarbonylamino, mono- or di-Ci to C6-alkylamino, N—C1 to C6-alkyl-N—C6 to C10-arylamino, pyrrolidino, morpholino or piperidino and


[0047] the ring C of the formula (V) represents benzothiazol-2-ylidene, benzoxazol-2-ylidene, benzimidazol-2-ylidene, thiazol-2-ylidene, isothiazol-3-ylidene, isoxazol-3-ylidene, imidazol-2-ylidene, pyrazol-5-ylidene, 1,3,4-thiadiazol-2-ylidene, 1,3,4-oxadiazol-2-ylidene, 1,2,4-thiadiazol-5-ylidene, 1,3,4-triazol-2-ylidene, 3H-indol-2-ylidene, dihydropyridin-2- or -4-ylidene, or dihydroquinolin-2- or -4-ylidene, wherein the individual rings can be substituted by C1 to C6-alkyl, C1 to C6-alkoxy, fluorine, chlorine, bromine, iodine, cyano, nitro, C1 to C6-alkoxycarbonyl, C1 to C6-alkylthio, C1 to C6-acylamino, C6 to C10-aryl, C6- to C10-aryloxy, C6 to C10-arylcarbonylamino, mono- or di-C1 to C6-alkylamino, N—C1 to C6-alkyl-N—C6 to C10-arylamino, pyrrolidino, morpholino or piperidino.


[0048] In a particularly preferred form the merocyanines used are those of the formula (VI)
6


[0049] wherein


[0050] X1 represents CN, CO—R1 or COO—R2,


[0051] X2 represents hydrogen, methyl, ethyl, phenyl, 2- or 4-pyridyl, thiazol-2yl, benzothiazol-2-yl, benzoxazol-2-yl, CN, CO—R1 or COO—R2, or


[0052] CX1X2 represents a ring of the formulae
7


[0053]  which can be substituted by up to 3 radicals from the group comprising methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, cyano, nitro, methoxycarbonyl, ethoxycarbonyl, phenyl,
8


[0054] SO3M+ and —CH2—SO3M+,


[0055] and wherein the asterisk (*) indicates the ring atom from which the double bond emanates,


[0056] An represents an anion,


[0057] M+ represents a cation,


[0058] X3 represents CH,


[0059] X4 represents O, S or N—R6,


[0060] the ring B of the formula (II) represents furan-2-yl, thiophen-2-yl, pyrrol-2-yl or thiazol-5-yl, wherein the above-mentioned rings can each be substituted by methyl, ethyl, propyl, butyl, methoxy, ethoxy, fluorine, chlorine, bromine, cyano, nitro, methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, dimethylamino, diethylamino, dipropylamino, dibutylamino, N-methyl-N-phenylamino, pyrrolidino or morpholino,


[0061] Y1 represents N or C—R7,


[0062] R1, R2, R5 and R6 independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl or benzyl and


[0063] R 5 additionally represents —(CH2)3—N(CH3)2 or —(CH2)3—N+(CH3)3 An and


[0064] R7 represents hydrogen or cyano.


[0065] In a form also particularly preferred the merocyanines used are those of the formula (VII)
9


[0066] in which


[0067] X1 represents CN, CO—R1 or COO—R2,


[0068] X2 represents hydrogen, methyl, ethyl, phenyl, 2- or 4-pyridyl, thiazol-2yl, benzothiazol-2-yl, benzoxazol-2-yl, CN, CO—R1 or COO—R2 or


[0069] CX1X2 represents a ring of the formulae
10


[0070]  which can be substituted by up to 3 radicals from the group comprising methyl, ethyl, methoxy, ethoxy, fluorine, chlor, bromine, cyano, nitro, methoxycarbonyl, ethoxycarbonyl, phenyl,
11


[0071] SO3M+ and —CH2—SO3M+,


[0072] and wherein the asterisk (*) indicates the ring atom from which the double bond emanates,


[0073] An represents an anion,


[0074] M+ represents a cation,


[0075] X5 represents N—R6,


[0076] X6 represents S, N—R6 or CH2,


[0077] the ring C of the formula (IV) represents benzothiazol-2-ylidene, benzimidazol-2-ylidene, thiazol-2-ylidene, 1,3,4-thiadiazol-2-ylidene, 1,3,4-triazol-2-ylidene, dihydropyridin-4-ylidene, dihydroquinolin-4-ylidene or 3H-indol-2-ylidene, wherein the above-mentioned rings can each be substituted by methyl, ethyl, propyl, butyl, methoxy, ethoxy, fluorine, chlorine, bromine, cyano, nitro, methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, dimethylamino, diethylamino, dipropylamino, dibutylamino, N-methyl-N-phenylamino, pyrrolidino or morpholino,


[0078] Y2—Y1 represents N—N or (C—R8)—(C—R7),


[0079] R1, R2, R5 and R6 independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl or benzyl and


[0080] R5 additionally represents —(CH2)3—N(CH3)2 or —(CH2)3—N+(CH3)3 An and


[0081] R7 and R8 represent hydrogen.


[0082] In a form also particularly preferred the merocyanines used are those of the formula (VIII)
12


[0083] wherein


[0084] X1 represents CN, CO—R1 or COO—R2,


[0085] X2 represents hydrogen, methyl, ethyl, phenyl, 2- or 4-pyridyl, thiazol-2yl, benzo-thiazol-2-yl, benzoxazol-2-yl, CN, CO—R1 or COO—R2, or


[0086] CX1X2 represents a ring of the formulae
13


[0087]  which can be substituted by up to 3 radicals from the group comprising methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, bromine, cyano, nitro, methoxycarbonyl, ethoxycarbonyl, phenyl,
14


[0088] SO3M+ and —CH2—SO3M+,


[0089] and wherein the asterisk (*) indicates the ring atom from which the double bond emanates,


[0090] An represents an anion,


[0091] M+ represents a cation,


[0092] NR9R10 represents dimethylamino, diethylamino, dipropylamino, dibutylamino, N-methyl-N-phenylamino, pyrrolidino or morpholino,


[0093] Y1 represents N or C—R7,


[0094] R1, R2 and R5 independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl or benzyl and


[0095] R5 additionally represents —(CH2)3—N(CH3)2 or —(CH2)3—N+(CH3)3 An.


[0096] Suitable anions An are all monovalent anions or one equivalent of a polyvalent anion. Preferably the anions are colourless. Suitable anions are for example chloride, bromide, iodide, tetrafluoroborate, perchlorate, hexafluorosilicate, hexafluoro-phosphate, methosulphate, ethosulphate, C1 to C10-alkanesulphonate, C1 to C10-perfluoroalkanesulphonate, C1 to C10-alkanoate optionally substituted by chlorine, hydroxyl or C1 to C4-alkoxy, benzene sulphonate, naphthalene sulphonate or biphenyl sulphonate, which are optionally substituted by nitro, cyano, hydroxyl, C1 to C25-alkyl, perfluoro-C1 to C4-alkyl, C1 to C4-alkoxycarbonyl or chlorine, benzene disulphonate, naphthalene disulphonate or biphenyl disulphonate, which are optionally substituted by nitro, cyano, hydroxyl, C1 to C4-alkyl, C1 to C4-alkoxy, C1- to C4-alkoxycarbonyl or chlorine, benzoate which is optionally substituted by nitro, cyano, C1 to C4-alkyl, C1 to C4-alkoxy, C1 to C4-alkoxycarbonyl, benzoyl, chloro-benzoyl or toluoyl, the anion of naphthalenedicarboxylic acid, diphenyl ether disulphonate, tetraphenyl borate, cyanotriphenyl borate, tetra-Ci to C20-alkoxyborate, tetraphenoxyborate, 7,8- or 7,9-dicarba-nido-undecaborate(1) or (2), which are optionally substituted on the B and/or C atoms by one or two C1 to C12-alkyl or phenyl groups, dodecahydro-dicarbadodecaborate(2) or B—C1 to C12-alkyl-C-phenyl-dodecahydro-dicarbadodeca-borate(1).


[0097] Bromide, iodide, tetrafluoroborate, perchlorate, methane sulphonate, benzene sulphonate, toluene sulphonate, dodecylbenzene sulphonate and tetradecane sulphonate are preferred.


[0098] Suitable M+ cations are all monovalent cations or one equivalent of a polyvalent cation. The cations are preferably colourless. Suitable cations are for example lithium, sodium, potassium, tetramethyl ammonium, tetraethyl ammonium, tetrabutyl ammonium, trimethylbenzyl ammonium, trimethylcapryl ammonium or Fe(C5H5)2+(in which C5H5=cyclopentadienyl).


[0099] Tetramethyl ammonium, tetraethyl ammonium and tetrabutyl ammonium are preferred.


[0100] For a, preferably singly recordable, optical data carrier according to the invention which is written and read by light from a blue laser such merocyanine dyes are preferred whose absorption maximum λmax2 is in the range from 420 bis 550 nm, wherein the wavelength λ½ at which the extinction on the shortwave slope of the absorption maximum of the wavelength λmax2 is half the extinction value at λmax2 and the wavelength λ{fraction (1/10)} at which the extinction on the shortwave slope of the absorption maximum of the wavelength λmax2 is a tenth of the extinction value at λmax2, are preferably in each case no further than 50 nm away from each other. Preferably such a merocyanine dye does not display a shorter-wave maximum λmax1 at a wavelength below 350 nm, particularly preferably below 320 nm, and very particularly preferably below 290 nm.


[0101] Preferred merocyanine dyes are those with an absorption maximum λmax2 of 410 to 530 nm.


[0102] Particularly preferred merocyanine dyes are those with an absorption maximum λmax2 of 420 to 510 nm.


[0103] Very particularly preferred merocyanine dyes are those with an absorption maximum λmax2 of 430 to 500 nm.


[0104] Preferably λ½ and λ{fraction (1/10)}, as defined above, are no further than 40 nm, particularly preferably no further than 30 nm, and very particularly preferably no further than 20 nm away from each other in the merocyanine dyes.


[0105] The merocyanine dyes have a molar extinction coefficient ε of >40000 l/mol cm, preferably >60000 l/mol cm, particularly preferably >80000 l/mol cm, and very particularly preferably >100000 l/mol cm at the absorption maximum λmax2.


[0106] The absorption spectra are measured for example in solution.


[0107] Suitable merocyanines having the required spectral properties are in particular those in which the change in dipole moment Δμ=|μgag|, i.e. the positive difference between the dipole moments in the ground state and in the first excited state, is as small as possible, preferably <5 D, and particularly preferably <2 D. One method of determining such a change in dipole moment Δμ is described for example in F. Würthner et al., Angew. Chem. 1997, 109, 2933 and in the literature cited therein. Low solvatochromism (dioxane/DMF) is also a suitable criterion for selection. Merocyanines are preferred whose solvatochromism Δλ=|λDMFdioxane|, i.e. the positive difference between the absorption wavelengths in the solvents dimethylformamide and dioxane is <20 nm, particularly preferably <10 nm and very particularly preferably <5 nm.


[0108] Merocyanines which are very particularly preferred according to the invention are those of the formula
15


[0109] in which


[0110] X101 represents O or S,


[0111] X102 represents N or CR104,


[0112] R101 and R102 independently of one another represent methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, benzyl or phenyl and R101 additionally represents hydrogen or


[0113] NR101R102 represents pyrrolidino, piperidino or morpholino,


[0114] R103 represents hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, phenyl, tolyl, methoxyphenyl, thienyl, chlorine or NR101R102 and


[0115] R104 represents hydrogen, methyl, ethyl, phenyl, chlorine, cyano, formyl or a radical of the formula
16


[0116]  wherein the alkyl radicals such as propyl, butyl, etc. can be branched.


[0117] The attachment of a bridge for oligomeric or polymeric structures takes place via R101.


[0118] Merocyanines which are also very particularly preferred according to the invention are those of the formula
17


[0119] in which


[0120] X101 represents O or S,


[0121] X102 represents N or CR104,


[0122] R101 and R102 independently of one another represent methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, benzyl or phenyl and R101 additionally represents hydrogen or


[0123] NR101R102 represents pyrrolidino, piperidino or morpholino,


[0124] R103 represents hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, phenyl, tolyl, methoxyphenyl, thienyl, chlorine or NR101R102,


[0125] R104 represents hydrogen, methyl, ethyl, phenyl, chlorine, cyano, formyl or a radical of the formula
18


[0126] Y101 represents N or CH,


[0127] CX103X104 represents a ring of the formulae
19


[0128]  wherein the asterisk (*) indicates the ring atom from which the double bond emanates,


[0129] R105 represents hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxyethyl, methoxypropyl, cyanoethyl, hydroxyethyl, acetoxyethyl, chloroethyl, cyclohexyl, phenyl, tolyl, methoxyphenyl or


[0130] a radical of the formula
20


[0131]  wherein in the case of the formula (CX) the two radicals R105 can be different,


[0132] R106 represents hydrogen, methyl, ethyl, propyl, butyl or trifluoromethyl,


[0133] R107 represents cyano, methoxycarbonyl, ethoxycarbonyl, —CH2SO331 M+ or a radical of the formulae
21


[0134] M+ represents a cation and


[0135] An represents an anion,


[0136] wherein the alkyl radicals such as propyl, butyl, etc. can be branched.


[0137] The attachment of a bridge for oligomeric or polymeric structures takes place via R101 or R105.


[0138] Merocyanines which are also very particularly preferred according to the invention are those of the formula
22


[0139] in which


[0140] X101 represents O or S,


[0141] X102 represents N or CR104,


[0142] R101 and R102 independently of one another represent methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, benzyl or phenyl and R101 additionally represents hydrogen or


[0143] NR101R102 represents pyrrolidino, piperidino or morpholino,


[0144] R103 represents hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, phenyl, tolyl, methoxyphenyl, thienyl, chlorine or NR101R102,


[0145] R104 represents hydrogen, methyl, ethyl, phenyl, chlorine, cyano, formyl or a radical of the formula
23


[0146] Y101 represents N or CH,


[0147] X103 represents cyano, acetyl, methoxycarbonyl or ethoxycarbonyl and


[0148] X104 represents 2-, 3- or 4-pyridyl, thiazol-2-yl, benzothiazol-2-yl, oxazol-2-yl, benzoxazol-2-yl, benzimidazol-2-yl, N-methyl- or N-ethyl-benzimidazol-2-yl,


[0149] wherein the alkyl radicals such as propyl, butyl, etc. can be branched.


[0150] The attachment of a bridge for oligomeric or polymeric structures takes place via R101 or X103, if the latter represents an ester grouping.


[0151] Preferably, in the merocyanines of the formulae (CI) and (CIII)


[0152] R103 represents hydrogen, methyl, i-propyl, tert.-butyl or phenyl and


[0153] R104 represents hydrogen or cyano.


[0154] Merocyanines which are also very particularly preferred according to the invention are those of the formula
24


[0155] in which


[0156] X105 represents S or CR110R111,


[0157] R108 represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy-ethyl, methoxypropyl, cyanoethyl, hydroxyethyl, acetoxyethyl, chloroethyl, cyclohexyl, benzyl or phenethyl,


[0158] R109 represents hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, chlorine, tri-fluoromethyl, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl,


[0159] R110 and R111 independently of one another represent methyl or ethyl or CR110R111 represents a bivalent radical of the formula
25


[0160]  wherein two bonds emanate from the atom with an asterisk (*),


[0161] wherein the alkyl radicals such as propyl, butyl, etc. can be branched.


[0162] The attachment of a bridge for oligomeric or polymeric structures takes place via R108.


[0163] Merocyanines which are also very particularly preferred according to the invention are those of the formula
26


[0164] in which


[0165] X105 represents S or CR110R111,


[0166] R108 represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy-ethyl, methoxypropyl, cyanoethyl, hydroxyethyl, acetoxyethyl, chloroethyl, cyclohexyl, benzyl or phenethyl,


[0167] R109 represents hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, chlorine, tri-fluoromethyl, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl,


[0168] R110 and R111 independently of one another represent methyl or ethyl or


[0169] CR110R111 represents a bivalent radical of the formula
27


[0170]  wherein two bonds emanate from the atom with an asterisk (*),


[0171] Y101 represents N or CH,


[0172] CX103X104 represents a ring of the formulae
28


[0173]  wherein the asterisk (*) indicates the ring atom from which the double bond emanates,


[0174] R105 represents hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxyethyl, methoxypropyl, cyanoethyl, hydroxyethyl, acetoxyethyl, chloroethyl, cyclohexyl, phenyl, tolyl, methoxyphenyl or


[0175] a radical of the formula
29


[0176] R106 represents hydrogen, methyl, ethyl, propyl, butyl or trifluoromethyl,


[0177] R107 represents cyano, methoxycarbonyl, ethoxycarbonyl, —CH2SO3 M+ or a radical of the formulae
30


[0178] M+ represents a cation and


[0179] An represents an anion,


[0180] wherein the alkyl radicals such as propyl, butyl, etc. can be branched.


[0181] The attachment of a bridge for oligomeric or polymeric structures takes place via R108 or R105.


[0182] Merocyanines which are also very particularly preferred according to the invention are those of the formula
31


[0183] in which


[0184] X105 represents S or CR110R111,


[0185] R108 represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy-ethyl, methoxypropyl, cyanoethyl, hydroxyethyl, acetoxyethyl, chloroethyl, cyclohexyl, benzyl or phenethyl,


[0186] R109 represents hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, chlorine, tri-fluoromethyl, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl,


[0187] R110 and R111 independently of one another represent methyl or ethyl or


[0188] CR110R111 represents a bivalent radical of the formula
32


[0189]  wherein two bonds emanate from the atom with an asterisk (*),


[0190] Y101 represents N or CH,


[0191] X103 represents cyano, acetyl, methoxycarbonyl or ethoxycarbonyl,


[0192] X104 represents 2-, 3- or 4-pyridyl, thiazol-2-yl, benzothiazol-2-yl, oxazol-2-yl, benzoxazol-2-yl, benzimidazol-2-yl, N-methyl- or N-ethyl-benzimidazol-2-yl, preferably 2-pyridyl,


[0193] wherein the alkyl radicals such as propyl, butyl, etc. can be branched.


[0194] The attachment of a bridge for oligomeric or polymeric structures takes place via R108 or X103, if the latter represents an ester grouping.


[0195] Merocyanines which are also very particularly preferred according to the invention are those of the formula
33


[0196] wherein


[0197] R112 represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy-ethyl, methoxypropyl, cyanoethyl, hydroxyethyl, acetoxyethyl, chloroethyl, cyclohexyl, benzyl or phenethyl,


[0198] R113 and R114 represent hydrogen or together represent a —CH═CH—CH═CH— bridge,


[0199] wherein the alkyl radicals such as propyl, butyl etc. can be branched.


[0200] The attachment of a bridge for oligomeric or polymeric structures takes place via R112.


[0201] Merocyanines which are also very particularly preferred according to the invention are those of the formula
34


[0202] in which


[0203] R112 represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy-ethyl, methoxypropyl, cyanoethyl, hydroxyethyl, acetoxyethyl, chloroethyl, cyclohexyl, benzyl or phenethyl,


[0204] R113 and R114 represent hydrogen or together represent a —CH═CH—CH═CH— bridge,


[0205] Y101 represents N or CH,


[0206] CX103X104 represents a ring of the formulae
35


[0207]  wherein the asterisk (*) indicates the ring atom from which the double bond emanates,


[0208] R105 represents hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxyethyl, methoxypropyl, cyanoethyl, hydroxyethyl, acetoxyethyl, chloroethyl, cyclohexyl, phenyl, tolyl, methoxyphenyl or


[0209] a radical of the formula
36


[0210] R106 represents hydrogen, methyl, ethyl, propyl, butyl or trifluoromethyl,


[0211] R107 represents cyano, methoxycarbonyl, ethoxycarbonyl, —CH2SO3 M+ or a radical of the formulae
37


[0212] M+ represents a cation and


[0213] An represents an anion,


[0214] wherein the alkyl radicals such as propyl, butyl, etc. can be branched.


[0215] The attachment of a bridge for oligomeric or polymeric structures takes place via R112 or R105.


[0216] Merocyanines which are also very particularly preferred according to the invention are those of the formula
38


[0217] in which


[0218] R112 represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy-ethyl, methoxypropyl, cyanoethyl, hydroxyethyl, acetoxyethyl, chloroethyl, cyclohexyl, benzyl or phenethyl,


[0219] R113 and R114 represent hydrogen or jointly represent a —CH═CH—CH═CH— bridge,


[0220] Y101 represents N or CH,


[0221] X103 represents cyano, acetyl, methoxycarbonyl or ethoxycarbonyl,


[0222] X104 represents 2-, 3- or 4-pyridyl, thiazol-2-yl, benzothiazol-2-yl, oxazol-2-yl, benzoxazol-2-yl, benzimidazol-2-yl, N-methyl- or N-ethyl-benzimidazol-2-yl,


[0223] wherein the alkyl radicals such as propyl, butyl, etc. can be branched.


[0224] The attachment of a bridge for oligomeric or polymeric structures takes place via R112 or X103, if the latter represents an ester grouping.


[0225] Merocyanines which are also very particularly preferred according to the invention are those of the formula
39


[0226] in which


[0227] R115 and R116 independently of one another represent methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, benzyl or phenethyl or


[0228] NR115R116 represents pyrrolidino, piperidino or morpholino,


[0229] CX103X104 represent a ring of the formulae
40


[0230]  wherein the asterisk (*) indicates the ring atom from which the double bond emanates,


[0231] R105 represents hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxyethyl, methoxypropyl, cyanoethyl, hydroxyethyl, acetoxyethyl, chloroethyl, cyclohexyl, phenyl, tolyl, methoxyphenyl or a radical of the formula
41


[0232] R106 represents hydrogen, methyl, ethyl, propyl, butyl or trifluoromethyl,


[0233] R107 represents cyano, methoxycarbonyl, ethoxycarbonyl, —CH2SO3 M+ or a radical of the formulae
42


[0234] M+ represents a cation and


[0235] An represents an anion,


[0236] wherein the alkyl radicals such as propyl, butyl, etc. can be branched.


[0237] The attachment of a bridge for oligomeric or polymeric structures takes place via R115 or R105.


[0238] Merocyanines which are also very particularly preferred according to the invention are those of the formula
43


[0239] in which


[0240] R115 and R116 independently of one another represent methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, benzyl or phenethyl or


[0241] NR115R116 represents pyrrolidino, piperidino or morpholino,


[0242] X103 represents cyano, acetyl, methoxycarbonyl or ethoxycarbonyl,


[0243] X104 represents 2-, 3- or 4-pyridyl, thiazol-2-yl, benzothiazol-2-yl, oxazol-2-yl, benzoxazol-2-yl, benzimidazol-2-yl, N-methyl- or N-ethyl-benzimidazol-2-yl, preferably 2-pyridyl,


[0244] wherein the alkyl radicals such as propyl, butyl etc. can be branched.


[0245] The attachment of a bridge for oligomeric or polymeric structures takes place via R115 or X103, if the latter represents an ester grouping.


[0246] In the formulae (CIII), (CXVI) and (CXVIII)


[0247] Y101 preferably represents CH and


[0248] in the formulae (CIII), (CXVI), (CXVIII) and (CXIX)


[0249] CX103X104 preferably represents a ring of the formulae (CV), (CVII) and (CIX) or a radical of the formulae
44


[0250]  wherein the double bond emanates from the C atom with an asterisk (*).


[0251] —(CH2)2—, —(CH2)3—, —(CH2)4—, —(CH2)2—O—(CH2) 2— and —CH2—C6H4—CH2— are preferred bridges.


[0252] Polyacrylate and polymethacrylate and copolymers thereof with acrylamides are preferred polymer chains. The abovementioned radicals R101, R105, R108, R112 and R115 then for example represent a monomer unit of the formula
45


[0253] in which


[0254] R represents hydrogen or methyl and a single bond to the N atom of the merocyanine dye emanates from the atom marked with a tilde (˜) and the atoms with an asterisk (*) represent the continuation of the chain.


[0255] Some of the merocyanines of the formula (I) are known, for example from F. Wüirthner, Synthesis 1999, 2103; F. Wüirthner, R. Sens, K.-H. Etzbach, G. Seybold, Angew. Chem. 1999, 111, 1753; DE-OS 43 44 116; DE-OS 44 40 066; WO 98/23688: JP 52 99 379; JP 53 14 734.


[0256] Also preferred are phthalocyanines as light-absorbing compounds.


[0257] In a preferred embodiment, the phthalocyanine used is a compound of the formula (1)


MPc[R3]w[R4]x[R5]y[R6]z  (1),


[0258] in which


[0259] Pc represents a phthalocyanine or a naphthocyanine, where in both cases the aromatic rings also may be heterocycles, for example tetrapyridinopor-phyrazines,


[0260] M represents two independent H atoms, represent a divalent metal atom or represents a trivalent axially monosubstituted metal atom of the formula (1a)
46


[0261]  or represents a tetravalent axially disubstituted metal atom of the formula (1b)
47


[0262]  or represents a trivalent axially monosubstituted and axially monocoordinated metal atom of the formula (1c)
48


[0263]  where, in the case of a charged ligand X2 or X1, the charge being compensated by an opposite ion, for example an anion An⊖ or cation Kat⊕,


[0264] the radicals R3 to R6 corresponding to substituents of the phthalocyanine ring, in which


[0265] X1 and X2, independently of one another, represent halogen as F, Cl, Br, I, hydroxyl, oxygen, cyano, thiocyanato, cyanato, alkenyl, alkinyl, arylthio, dialkylamino, alkyl, alkoxy, acyloxy, alkylthio, aryl, aryloxy, —O—SO2R8, —O—PR10R11, —O—P(O)R12R13, —O—SiR14R15R16, NH2, alkylamino and the radical of a hetero-cyclic amine,


[0266] R3, R4, R5 and R6, independently of one another, represent halogen as F, Cl, Br, I, cyano, nitro, alkyl, aryl, alkylamino, dialkylamino, alkoxy, alkylthio, aryloxy, arylthio, SO3H, SO2NR1R2, CO2R9, CONR1R2, NH—COR7 or a radical of the formula —(B)m—D, in which


[0267] B denotes a bridge member from the group consisting of a direct bond, CH2, CO, CH(alkyl), C(alkyl)2, NH, S, O or —CH═CH—, (B)m denoting a chemically reasonable sequence of bridge members B where m is from 1 to 10, preferably m is 1, 2, 3 or 4,


[0268] D represents the monovalent radical of a redox system of the formula
49


[0269]  or represents a metallocenyl radical or metallocenylcarbonyl radical, titanium, manganese, iron, ruthenium or osmium being suitable as the metal centre,


[0270] Z1 and Z2, independently of one another, represent NR′R″, OR″ or SR″,


[0271] Y1 represents NR′, O or S, Y2 represents NR′,


[0272] n represents 1 to 10 and


[0273] R′ and R″, independently of one another, represent hydrogen, alkyl, cycloalkyl, aryl or hetaryl, or form. a direct bond or bridge to one of the C atoms of the
50


[0274] w, x, y and z, independently of one another, represent 0 to 4 and w+x+y+z≦16,


[0275] R1and R2, independently of one another, represent hydrogen, alkyl, hydroxyalkyl, or aryl, or R1 and R2, together with the N atom to which they are bonded, form a heterocyclic 5-, 6- or 7-membered ring, optionally with participation of further hetero atoms, in particular from the group consisting of O, N and S, NR1R2 representing in particular pyrrolidino, piperidino or morpholino,


[0276] R7 to R16, independently of one another, represent alkyl, aryl, hetaryl or hydrogen, in particular represent alkyl, aryl or hetaryl,


[0277] An represents an anion, in particular represents halide, C1- to C20-alkylCOO, formate, oxalate, lactate, glycolate, citrate, CH3OSO3, NH2SO3, CH3SO3, ½ SO42− or ⅓ PO43−.


[0278] Where M represents a radical of the formula (1c), in particular with Co(III) as the metal atom, preferred heterocyclic amine ligands or substituents in the meaning of X1 and X2 are morpholine, piperidine, piperazine, pyridine, 2,2-bipyridine, 4,4-bipyridine, pyridazine, pyrimidine, pyrazine, imidazole, benzimidazole, isoxazole, benzisoxazole, oxazole, benzoxazole, thiazole, benzothiazole, quinoline, pyrrole, indole and 3,3-dimethylindole, each of which is coordinated with or substituted by the metal atom at the nitrogen atom.


[0279] The alkyl, alkoxy, aryl and heterocyclic radicals can optionally carry further radicals, such as alkyl, halogen, hydroxyl, hydroxyalkyl, amino, alkylamino, dialkylamino, nitro, cyano, CO—NH2, alkoxy, alkoxycarbonyl, morpholino, piperidino, pyrrolidino, pyrrolidono, trialkylsilyl, trialkylsiloxy or phenyl. The alkyl and alkoxy radicals may be saturated, unsaturated, straight-chain or branched, the alkyl radical may be partly halogenated or perhalogenated and the alkyl and alkoxy radical may be ethoxylated, propoxylated or silylated. Neighbouring alkyl and/or alkoxy radicals on aryl or heterocyclic radicals may together form a three- or four-membered bridge.


[0280] Preferred compounds of the formula (1) are those in which the following applies for the radical R1to R16, R′ and R″ and for the ligands or substituents X1 and X2:


[0281] substituents with the designation “alkyl” preferably denote C1-C16-alkyl, in particular C1-C6-alkyl, which are optionally substituted by halogen, such as chlorine, bromine or fluorine, hydroxyl, cyano and/or C1-C6-alkoxy;


[0282] substituents with the designation “alkoxy” preferably denote C1-C16-alkoxy, in particular C1-C6-alkoxy which are optionally substituted by halogen, such as chlorine, bromine or fluorine, hydroxyl, cyano and/or C1-C6-alkyl;


[0283] substituents with the designation “cycloalkyl” preferably denote C4-C8-cycloalkyl, in particular C5- to C6-cycloalkyl, which are optionally substituted by halogen, such as chlorine, bromine or fluorine, hydroxyl, cyano and/or C1-C6-alkyl.


[0284] substituents with the designation “alkenyl” preferably denote C6-C8-alkenyl which are optionally substituted by halogen, such as chlorine, bromine or fluorine, hydroxyl, cyano and/or C1-C6-alkyl, alkenyl denoting in particular allyl,


[0285] substituents with the meaning “hetaryl” preferably represent heterocyclic radicals having 5- to 7-membered rings which preferably contain hetero atoms from the group consisting of N, S and/or O and are optionally fused with aromatic rings or optionally carry further substituents, for example halogen, hydroxyl, cyano and/or alkyl, the following being particularly preferred: pyridyl, furyl, thienyl, oxazolyl, thiazolyl, imidazolyl, quinolyl, benzoxazolyl, benzothiazolyl and benzimidazolyl, the substituents with the designation “aryl” are preferably C6-C10-aryl, in particular phenyl or naphthyl, which are optionally substituted by halogen, such as F or Cl, hydroxyl, C1-C6-alkyl, C1-C6-alkoxy, NO2 and/or CN.


[0286] R3, R4, R5 and R6, independently of one another preferably represent chlorine, fluorine, bromine, iodine, cyano, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, tert-amyl, hydroxyethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, phenyl, p-tert-butylphenyl, p-methoxyphenyl, iso-propylphenyl, trifluoromethylphenyl, naphthyl, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, tert-butylamino, pentylamino, tert-amylamino, benzylamino, methylphenylhexylamino, hydroxyethylamino, aminopropylamino, aminoethylamino, 3-dimethylamino-propylamino, 3-diethylaminopropylamino, diethylaminoethylamino, dibutyl-aminopropylamino, morpholinopropylamino, piperidinopropylamino, pyrrolidinopropylamino, pyrrolidonopropylamino, 3-(methylhydroxyethyl-amino)propylamino, methoxyethylamino, ethoxyethylamino, methoxypropyl-amino, ethoxypropylamino, methoxyethoxypropylamino, 3-(2-ethylhexyl-oxy)propylamino, isopropyloxypropylamino, dimethylamino, diethylamino, diethanolamino, dipropylamino, diisopropylamino, dibutylamino, diiso-butylamino, di-tert-butylamino, dipentylamino, di-tert-amylamino, bis(2-ethylhexyl)amino, bis(aminopropyl)amino, bis(aminoethyl)amino, bis(3-dimethylaminopropyl)amino, bis(3-diethylaminopropyl)amino, bis(diethyl-aminoethyl)amino, bis(dibutylaminopropyl)amino, di(morpholinopropyl)-amino, di(piperidinopropyl)amino, di(pyrrolidinopropyl)amino, di(pyrroli-donopropyl)amino, bis(3-(methyl-hydroxyethylamino)propyl)amino, dimethoxyethylamino, diethoxyethylamino, dimethoxypropylamino, diethoxypropyl-amino, di(methoxyethoxyethyl)amino, di(methoxyethoxypropyl)amino, bis(3-(2-ethylhexyloxy)propyl)amino, di(isopropyloxyisopropyl)amino, methoxy,ethoxy, propyloxy, isopropyloxy, butyloxy, isobutyloxy, tert-butyloxy, pentyloxy, tert-amyloxy, methoxyethoxy, ethoxyethoxy, methoxypropyloxy, ethoxypropyloxy, methoxyethoxypropyloxy, 3-(2-ethylhexyloxy)propyloxy, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, tert-butylthio, pentylthio, tert-amylthio, phenyl, methoxyphenyl, trifluoro-methylphenyl, naphthyl, CO2R7, CONR1R2, NH—COR7, SO3H, SO2NR1R2 or preferably represent a radical of the formula
51


[0287]  where the asterisk (*) indicates the link with the 5-membered ring,


[0288] M1 represents an Mn or Fe cation,


[0289] w, x, y and z, independently of one another, represent 0 to 4 and w+x+y+z≦12,


[0290] NR1R2 preferably represent amino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, tert. butylamino, pentylamino, tert. amylamino, benzylamino, methylphenylhexylamino, 2-ethyl-1-hexyl-amino, hydroxyethylamino, aminopropylamino, aminoethylamino, 3-di-methylaminopropylamino, 3-diethylaminopropylamino, morpholinopropyl-amino, piperidinopropylamino, pyrrolidinopropylamino, pyrrolidono-propylamino, 3-(methyl-hydroxyethylamino)propylamino, methoxyethyl-amino, ethoxyethylamino, methoxypropylamino, ethoxypropylamino, methoxyethoxypropylamino, 3-(2-ethylhexyloxy)propylamino, isopropyloxy-isopropylamino, dimethylamino, diethylamino, dipropylamino, diisopropyl-amino, dibutylamino, diisobutylamino, di-tert-butylamino, dipentylamino, di-tert-amylamino, bis(2-ethylhexyl)amino, dihydroxyethylamino, bis(amino-propyl)amino, bis(aminoethyl)amino, bis(3-dimethylaminopropyl)amino, bis-(3-diethylaminopropyl)amino, di(morpholinopropyl)amino, di(piperidinopropyl)amino, di(pyrrolidinopropyl)amino, di(pyrrolidonopropyl)amino, bis(3-(methyl-hydroxyethylamino)propyl)amino, dimethoxyethylamino, diethoxy-ethylamino, dimethoxypropylamino, diethoxypropylamino, di(methoxy-ethoxypropyl)amino, bis(3-(2-ethylhexyloxy)propyl)amino, di(isopropyloxy-isopropyl)amino, anilino, p-toluidino, p-tert-butylanilino, p-anisidino, isopropylanilino or naphtylamino or NR1R2 preferably represent pyrrolidino, piperidino, piperazino or morpholino,


[0291] R7 and R16, independently of one another preferably represent hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, tert-amyl, phenyl, p-tert-butylphenyl, p-methoxyphenyl, isopropylphenyl, p-trifluoromethyl-phenyl, cyanophenyl, naphthyl, 4-pyridyl, 2-pyridyl, 2-quinolinyl, 2-pyrrolyl or 2-indolyl,


[0292] it being possible for the alkyl, alkoxy, aryl and heterocyclic radicals optionally to carry further radicals, such as alkyl, halogen, hydroxyl, hydroxyalkyl, amino, alkyl-amino, dialkylamino, nitro, cyano, CO—NH2, alkoxy, alkoxycarbonyl, morpholino, piperidino, pyrrolidino, pyrrolidono, trialkylsilyl, trialkylsilyloxy or phenyl, for the alkyl and/or alkoxy radicals to be saturated, unsaturated, straight-chain or branched, for the alkyl radicals to be partly halogenated or perhalogenated, for the alkyl and/or alkoxy radicals to be ethoxylated, propoxylated or silylated, and for neighbouring alkyl and/or alkoxy radicals on aryl or heterocyclic radicals together to form a three- or four-membered bridge.


[0293] In the context of this application, redox systems are understood as meaning in particular the redox systems described in Angew. Chem. 1978, page 927, and in Topics of Current Chemistry, Vol. 92, page 1 (1980).


[0294] p-Phenylenediamines, phenothiazines, dihydrophenazines, bipyridinium salts (viologens) and quinodimethanes are preferred.


[0295] In a preferred embodiment, phthalocyanines of the formula (1),


[0296] in which


[0297] M represents two independent H atoms or represents a divalent metal atom Me from the group consisting of Cu, Ni, Zn, Pd, Pt, Fe, Mn, Mg, Co, Ru, Ti, Be, Ca, Ba, Cd, Hg, Pb and Sn


[0298] or


[0299] M represents a trivalent axially monosubstituted metal atom of the formula (1a), in which the metal Me is selected from the group consisting of Al, Ga, Ti, In, Fe and Mn, or


[0300] M denotes a tetravalent axially disubstituted metal atom of the formula (1b), in which the metal Me is selected from the group consisting of Si, Ge, Sn, Zr, Cr, Ti, Co and V, are used.


[0301] X1 and X2 are particularly preferably halogen, in particular chlorine, aryloxy, in particular phenoxy, or alkoxy, in particular methoxy.


[0302] R3-R6 represent in particular halogen, C1-C6-alkyl or C1-C8-alkoxy.


[0303] Phthalocyanines of the formula I in which M represents a radical of the formula (1a) or (1b) are very particular preferred. Very particular preferred w, x, y and z each represent 0. X1 and/or X2 in formula (1a) or (1b) each denote halogen in a very particularly preferred way.


[0304] The phthalocyanines used according to the invention can be prepared by known methods, for example:


[0305] by synthesis of the nucleus from correspondingly substituted phthalodinitriles in the presence of the corresponding metals, metal halides or metal oxides,


[0306] by chemical modification of a phthalocyanine, for example by sulpho-chlorination or chlorination of phthalocyanines and further reactions, for example condensations or substitutions of the products resulting therefrom,


[0307] the axial substituents X1 and X2 are usually prepared from the corresponding halides by exchange.


[0308] The light-absorbing compound should preferably be thermally modifiable. Thermal modification is preferably effected at a temperature of <700° C. Such a modification may be, for example, decomposition, morphology change or chemical modification of the chromophoric centre of the light-absorbing compound.


[0309] The light-absorbing substances described guarantee a sufficiently high reflectivity of the optical data medium in the unrecorded state and sufficiently high absorption for the thermal degradation of the information layer during illumination at a point with focused blue light, in particular laser light, preferably having a light wavelength in the range from 360 to 460 nm. The contrast between recorded and unrecorded parts on the data medium is realized through the change in reflectivity in terms of the amplitude as well as the phase of the incident light as a result of the changed optical properties of the information layer after the recording. In particular the light absorbing substances guarantees a well defined shape of the readout signal with a drop of the reflectivity in the recorded mark.


[0310] In other words, the optical data medium can preferably be recorded on and read using laser light having a wavelength of 360-460 nm.


[0311] The coating with the phthalocyanines is preferably effected by spin-coating, sputtering or vacuum vapour deposition. By vacuum vapour deposition or sputtering, it is possible to apply in particular the phthalocyanines which are insoluble in organic or aqueous media, preferably those of the formula (1) in which w, x, y and z each denote 0 and M represents
52


[0312] in which X1 and X2 have the abovementioned meaning.


[0313] In particular, the phthalocyanines which are soluble in organic or aqueous media are suitable for application also by spin-coating. The phthalocyanines can be mixed with one another or with other dyes having similar spectral properties. The information layer may contain additives, such as binders, wetting agents, stabilizers, diluents and sensitizers, and further components in addition to the phthalocyanines.


[0314] The merocyanine dyes are applied to the optical data carrier preferably by spin-coating or vacuum evaporation. The merocyanines can be mixed with each other or with other dyes having similar spectral properties. In addition to the merocyanine dyes the information layer can contain additives such as binders, wetting agents, stabilizers, diluents and sensitizers as well as other components.


[0315] The optical data store may carry further layers, such as metal layers, dielectric layers, barrier layers, and protective layers, in addition to the information layer. Metal and dielectric and/or barrier layers serve, inter alia, for adjusting the reflectivity and the heat balance. Metals may be gold, silver, aluminium, alloys, etc., depending on the laser wavelength. Dielectric layers are, for example, silica and silicon nitride. Barrier layers can be comprised of dielectric layers or metal layers. Protective layers are, for example, photocurable coats, melt adhesive layers, pressure sensitive adhesive layers and protective films.


[0316] Pressure sensitive adhesive layers in preferably composed of acrylic adhesives, for example, Nitto Denko DA-8320 or DA-83 10 fits for this usage as disclosed in JP-A 11-273147.


[0317] As shown in FIG. 1 the optical data store preferably contains a substrate (1), optionally a barrier layer (2), an information layer (3), optionally a further barrier layer (4), optionally an adhesive layer (5), and a cover layer (6).


[0318] Preferably, the structure of the optical data medium can:


[0319] contain a preferably transparent substrate (1) on the surface of which at least one information layer (3) which can be recorded on using light, optionally a barrier layer (4) and optionally an adhesive layer (5) and a covering layer (6) have been applied.


[0320] contain a preferably transparent substrate (1) on the surface of which optionally a barrier layer (2), at least one information layer (3) which can be recorded on using light, optionally an adhesive layer (5) and a transparent covering layer (6) have been applied.


[0321] contain a preferably transparent substrate (1) on the surface of which optionally a barrier layer (2), at least one information layer (3) which can be recorded on using light, optionally a barrier layer (4), optionally an adhesive layer (5) and a transparent covering layer (6) have been applied.


[0322] contain a preferably transparent substrate (1) on the surface of at least one information layer (3) which can be recorded on using light, optionally an adhesive layer (5) and a transparent covering layer (6) have been applied


[0323] The invention furthermore relates to optical data media according to the invention which can be recorded on using blue light, in particular laser light, particularly preferably laser light having a wavelength of 360-460 nm.


[0324] The following Examples illustrate the subject of the invention.


[0325] The invention furthermore relates to optical data media according to the invention which can be recorded on using blue light, in particular laser light, particularly preferably laser light having a wavelength of 360-460 nm.


[0326] The following Examples illustrate the subject of the invention.







EXAMPLES


Example 1

[0327]

53






[0328] The dye monochloro-aluminium-phthalocyanine (AlClPc) was applied for the information layer. The disc structure employed was as shown in FIG. 2a.


[0329] The polycarbonate substrate was molded by injection method to form a groove structure of 0.64 μm picth and the depth of 40 nm. Directly on top of the grooved surface the information layer of 40 nm was coated by vacuum vapor deposition method. To prevent the information layer to diffuse into the adhesive layer, the information layer was covered with a SiO2 buffer layer of 25 nm thickness by RF reactive sputtering method. A pressure sensitive adhesive (PSA; Nitto Denko DA/8320) was then applied as an adhesive layer and an additional cover layer (polycarbonate) on the incident beam side of the medium. Total thickness of the adhesive layer and the cover layer was set as 100 μm.


[0330] The parameters of readout/recording setup was as follows.


[0331] Wavelength of the laser=405 nm


[0332] Numerical aperture of the objective lens=0.85, two element lens


[0333] Readout laser power=0.30 mW


[0334] Writing laser power=6.0 mW


[0335] Line velocity of the disc rotation=5.72 m/s


[0336] Writing mark and space length=0.69 μm, periodic


[0337] Pulse strategy=7 pulses with 50% duty inside one mark


[0338] As a result, after recording on a groove track, a rectangular waveform was obtained as shown in the FIG. 2. Here R represents the reflectivity from the media, and RInit represents the initial reflectivity. It is clearly seen in this figure that the recorded area showed uniformly lower reflectivity as it is desired. The carrier-to-noise ratio (C/N) was 48.4 dB at 30 kHz resolution band width (RBW). Although the information layer was covered only with thin SiO2 buffer layer and soft PSA layer, its readout stability was surprisingly good, almost the same level as the CD-R or DVD-R media which comprises a UV resin hard cover. Similar result was also obtained when recording was performed on the land surface of the grooved structure.



Example 2

[0339]

54






[0340] The dye dichloro-silicon-phthalocyanine (SiCl2Pc) was applied for the information layer. The disc structure employed was identical to example 1, except the SiO2 thickness, which was set as 40 nm. Recording condition was also identical to the example 1.


[0341] The result shows that the rectangular waveform was clearly recorded in this media with very low noise and high modulation ratio (FIG. 3). The carrier-to-noise ratio was 55 dB at 30 kHz RBW. Distortion of the readout marks was very small that it is clear that the combination of this dye and the layer structure matched to such media format and the optical pick-up parameters. Also, it showed a very high readout stability. Up to 0.7 mW of readout power, the C/N level remained at this high level.


[0342] According to its high performance of the recording and readout stability, this media showed excessively high potential for the high density recording. A random pattern recording with (1,7) RLL modulation was performed with the smallest mark length of 0.173 μm. The data capacity on a single side 12 cm diameter disc will correlate to 21 GB, when it is recorded both on land and in groove. A clear eye pattern on land recording was obtained as shown in the FIG. 4, with its jitter level of 10%. Similar result was obtained in groove, thus it showed its potential for over 21 GB capacity on a single-sided disc.



Example 3

[0343]

55






[0344] The above dye was applied for the information layer. The disc structure and the recording parameters are identical to example 2. Similar to example 1 and example 2, it showed a rectangular waveform with high readout stability (FIG. 5). The C/N level was 45 dB with 30 kHz resolution band width.


[0345] In a similar way the dyes of example 3-23 can be used.



Examples 3-23

[0346]

1











(MeX1X2)PcR3R4R5R6














Nr.
Me
X1
X2
R3
R4
R5
R6





 4
Al
O—C6H5







 5
Zn








 6
V
═O







 7
Ga
Cl







 8
In
Cl







 9
Ge
Cl
Cl






10
Si
OCH2CH3
OCH2CH3






11
Si
CH3
Cl






12
Si
Phenyl
Cl






13
Si
CH3
OCH2CH3






14
Si
OSi(CH3)3
OSi(CH3)3






15
Si
Cl
Cl
C(CH3)3
C(CH3)3




16
Si
Cl
Cl
C(CH3)3
C(CH3)3
C(CH3)3
C(CH3)3


17
Al
Cl

C(CH3)3
C(CH3)3
C(CH3)3
C(CH3)3


18
Al
OH







19
Al
Cl

Si(CH3)3
Si(CH3)3
Si(CH3)3
Si(CH3)3


20
Ti
OSi(CH3)3
OSi(CH3)3






21
Sn
OSi(CH3)3
OSi(CH3)3






22
Zr
OSi(CH3)3
OSi(CH3)3






23
Ru
OCH2CH3
OCH2CH3















Example 24

[0347] 2.1 g of 1-butyl-3-cyano-4-methyl-6-hydroxy-2-pyridone and 2.0 g of 1,3,3-trime-thylindole-2-methylene-ω-aldehyde were stirred into 5 ml of acetic anhydride for 2 hours at 90° C. After cooling, the mixture was discharged onto 100 ml of iced water, filtered off with suction and the residue washed with water. It was then stirred into 20 ml of water/methanol 3:1, filtered off with suction and dried. 3.3 g (85% of theory) of a red powder of the formula
56


[0348] were obtained.


[0349] M.p.=249-251° C.


[0350] UV (dioxane): λmax=520 nm


[0351] UV (DMF): λmax=522 nm


[0352] ε=113100 l/mol cm


[0353] Δλ=2 nm


[0354] λ½{fraction (1/10)} (longwave slope)=12 nm


[0355] Solubility: >2% in TFP (2,2,3,3-tetrafluoropropanol).



Example 25

[0356] Following the same procedure 2.6 g (79% of theory) of a red powder of the formula
57


[0357] were obtained using 1.7 g of 1-propyl-3-cyano-4-methyl-6-hydroxy-2-pyridone and 1.7 g of N-methyl-N-(4-methoxyphenyl)-acrolein.


[0358] M.p. =206-216° C.


[0359] UV (dioxane): λmax=482 nm


[0360] UV (DMF): λmax=477 nm


[0361] ε=73013 l/mol cm


[0362] Δλ=5 nm


[0363] λ½{fraction (1/10)} (shortwave slope)=33 nm


[0364] Solubility: >2% in TFP.



Example 26

[0365]

2
,03 g of 3-pyridinio-4-methyl-6-hydroxy-pyridone chloride and 2,0 g of 1,3,3-trime-thylindole-2-methylene-ω-aldehyde were stirred into 10 ml of acetic anhydride for 2 hours at 90° C. After cooling, the mixture was discharged onto 200 ml of water. 2.8 g of sodium tetrafluoroborate were added to the orange solution. After stirring the mixture overnight it was filtered off with suction and the residue was washed with 20 ml of water and dried. 3.3 g (74% of theory) of a reddish orange powder of the formula
58


[0366] were obtained.


[0367] M.p. >300° C.


[0368] UV (methanol): λmax=513 nm


[0369] ε=86510l/mol cm


[0370] λ½{fraction (1/10)} (shortwave slope)=38 nm


[0371] Solubility: >2% in TFP.



Example 27

[0372] 0,7 g of 5-dimethylaminofuran-2-carbaldehyde and 1.5 g of N-methyl-N′-dodecyl-barbituric acid were stirred into 15 ml of acetic anhydride for 30 mins. at 90° C. After cooling, the mixture was discharged onto 100 ml of iced water, filtered off with suction and the residue washed with water. 1.7 g (79% of theory) of an orange powder of the formula
59


[0373] was obtained.


[0374] M.p. 118-120° C.


[0375] UV (dioxane): λmax=483 nm


[0376] ε=53360 l/mol cm


[0377] λ½{fraction (1/10)} (shortwave slope)=32 nm


[0378] Solubility: >1% in benzyl alcohol.


[0379] Other examples according to the invention are summarized in the following tables:
2TABLE 1(Formula (VI)Ex.60Y1═CX1X2λmax1)/ nmε/l/ mol cmλ1/21/10/ nmΔλ2)/nm2861C—CN═C(CN2)47040990323)162962CH6350262860333)3064CH65539146480184)1.53166CH6747270880323)53268CH69490 (DMF)3370CH715391066403472CH733574CH75508784003676CH775361122603778CH79483533603880CH815351289601.33982CH83536 (DMF)11560324084CH85535112260134)4186CH874288CH894390N914492C—CN═C(CN)24593CH944695CH964797CH984899CH10049101CH10245550103CH10453851105CH10653713286052107CH10849035000403)2353109CH110431 (DMF)54111CH112536 (DMF)55113CH114536 (DMF)1)in dioxane, unless indicated otherwise 2)= |λDMF − λdioxane|3)on the shortwave slope 4)on the longwave slope


[0380]

3





TABLE 2










(Formula (VII)
























Ex.


115





Y2—Y1
═CX1X2
λmax1)/ nm
ε/l/ mol cm
λ1/21/10/ nm
Δλ2)/nm



























56


116





CH—C(CN)
═C(CN)2
499
46470
363)
5





57


117





CH—CH


118





429
60390
303)
7





58


119





CH—CH


120





487
102220
353)
6





59


121





CH—CH


122





448
76260
273)
2





60


123





CH—CH


124





469
76130
283)
3





61


125





CH—CH


126





520
113100
124)
2





62


127





CH—C(CN)
═C(CN)2
511
31345
363)
6





63


128





CH—C(CN)
═C(CN)2
503
41530
363)
6





64


129





CH—CH


130





519
55910
114)





65


131





CH—CH


132










66


133





CH—CH


134





486
115091





67


135





CH—CH


136










68


137





CH—CH


138










69


139





CH—CH


140





473
47640





70


141





CH—CH


142










71


143





CH—CH


144





496
62720





72


145





CH—CH


146





500
110332





73


147





CH—CH


148










74


149





CH—CH


150





490 (DMF)
109380

5





75


151





CH—CH


152





450





76


153





CH—CH


154





462
57230
343)





77


155





CH—C(CN)
═C(CH)2
500





78


156





CH—CH


157





521 (DMF)








1)
in dioxane, unless indicated otherwise







2)
= |λDMF − λdioxane|







3)
on the shortwave slope







4)
on the longwave slope









[0381]

4





TABLE 3










(Formula (VIII)


















λmax1)/
ε/l/
λ1/21/10/



Ex.
NR9R10
Y1
═CX1X2
nm
mol cm
nm
Δλ2)/nm



























79


158





CH


159





462
77180
283)
8





80


160





CH


161










81


162





CH


163










82


164





CH


165





918 (DMF)
89100





83


166





CH


167





458
89800
283)





84


168





CH


169





447
84070





85


170





CH


171





480
79685

1.3





86


172





CH


173





453 (DMF)








1)
in dioxane, unless indicated otherwise







2)
= |λDMF − λdioxane|







3)
on the shortwave slope







4)
on the longwave slope










Example 87

[0382] The dye shown above in example 76, which has the formula
174


[0383] was applied for the information layer. The disc structure employed was as shown in FIG. 2a.


[0384] The polycarbonate substrate was molded by injection method to form a groove structure of 0.64 m pitch and the depth of 40 nm. Directly on top of the grooved surface the information layer was coated by spin-coating method. The parameters for spin-coating were as follows.
5Solvent:Tetrafluoropropanol (TFP)Solution:1.0 wt.%Disc rotation speed for coating the solvent: 220 rpm, 12 secondsDisc rotation speed for spin off and drying:1200 rpm, 30 seconds


[0385] Thickness of the dye layer in groove and on land was 80 nm and 60 nm respectively. To prevent the information layer to diffuse into the adhesive layer, the information layer was covered with a SiN buffer layer of 40 nm thickness by RF reactive sputtering method. A pressure sensitive adhesive (PSA; Nitto Denko DA/8320) was then applied as an adhesive layer and an additional cover layer (polycarbonate) on the incident beam side of the medium. Total thickness of the adhesive layer and cover layer was set as 100 μm.


[0386] The parameters of readout/recording set-up were as follows.


[0387] Wavelength of the laser=404 nm


[0388] Numerical aperture of the objective lens=0.85, two element lens


[0389] Readout laser power=0.30 mW


[0390] Writing laser power=6.0 mW


[0391] Line velocity of the disc rotation=5.72 m/s


[0392] Writing mark and space length=0.69 μm, periodic


[0393] Pulse strategy=7 pulses with 50% duty inside one mark


[0394] As a result, after recording on a groove track, a clear rectangular waveform was obtained as shown in the FIG. 6a and 6b for groove and land area respectively. Here R represents the reflectivity from the media, and RInit represents the initial reflectivity. It is clearly seen in this figure that the recorded area showed uniformly lower reflectivity as it is desired. The carrier-to-noise ratio (C/N) measurement was performed using Takeda Riken TR4171, resulting in 57.4 dB and 53.0 dB for groove and land respectively at 30 kHz resolution band width (RBW). These high C/N prove its high performance for high density recording, since this media was recordable on both land/groove, which lead to practically a doubled track pitch, namely 0.32 μm. Also, point to be noted is that the modulation ratio (reflectivity from the marks/RInit) was reaching almost 80%. With such huge modulation ratio, this media presents an ideal signal quality and ultimate carrier level.


[0395] Additionally, a small mark recording was performed with the parameters as follows.


[0396] Writing mark and space length=0.17 m, periodic


[0397] Pulse strategy=1 pulse inside one mark


[0398] Other conditions are identical to 0.69 μm mark recording.


[0399] As a result, a clear waveform was observed as shown in FIG. 7. The modulation amplitude is smaller than FIG. 6a or 6b, however, it is close to a theoretical value for such a small mark near the cut-off frequency of the readout optics. The C/N value for this readout signal was 40.0 dB. Using the mark length of 0.17 μm as a smallest mark of (1,7) RLL modulation, the capacity for a 12 cm diameter single-sided disc reaches 21 GB. This dye showed its possibility for such a high density recording.


Claims
  • 1. Optical data medium containing a preferably transparent substrate which is optionally already coated with one or more barrier layers and on the surface of which an information layer which can be recorded on using light, optionally one or more barrier layers, and a cover layer, have been applied, which data medium can be recorded on and read using focused blue light through the cover layer on the information layer, preferably laser light with the wavelength between 360 nm and 460 nm, the information layer containing a light-absorbing compound and optionally a binder, characterized in that at least one dye is used as the light-absorbing compound wherein the cover layer on the top of the information layer including the adhesive layer do have a total thickness of 10 μm to 177 μm and the numerical aperture NA of the focusing objective lens setup is greater or equal 0.8.
  • 2. Optical data medium according to claim 1, wherein the dye used as the light absorbing compound is a phthalocyanine or a napthalocyanine, where in both cases the aromatic rings also may be heterocycles.
  • 3. Optical data medium according to claim 1, wherein the dye used as the light absorbing compound is a merocyanine dye.
  • 4. Optical data medium according to claim 1, wherein the barrier layers on top of the information layer at least contain one dielectric layer.
  • 5. Optical data medium according to claim 1, wherein the barrier layers contain a dielectric layer directly on top of the information layer and a pressure sensitive adhesive layer on the dielectric layer and a top cover layer thereover.
  • 6. Optical data medium according to claim 1 wherein the top cover layer is a polycarbonate, a copolycarbonate, a polycycloolefine or polyolefine.
  • 7. Optical data medium according to claim 1, characterized in that the dye corresponds to the formula (I)
  • 8. Optical data media according to claim 7, characterized in that M represents two independent H atoms or represents a divalent metal atom from the group consisting of Cu, Ni, Zn, Pd, Pt, Fe, Mn, Mg, Co, Ru, Ti, Be, Ca, Ba, Cd, Hg, Pb and Sn or represents a trivalent axially monosubstituted metal atom of the formula (Ia) in which Me represents Al, Ga, Ti, In, Fe or Mn or represents a tetravalent metal atom of the formula (Ib) in which Me represents Si, Ge, Sn, Zn, Cr, Ti, Co or V.
  • 9. Optical data media according to claim 2, characterized in that M represents a radical of the Formula (Ia) or (Ib), in which Me represents Al or Si, X1 and X2 represent halogen, in particular chlorine, aryloxy, in particular phenoxy, or alkoxy, in particular methoxy, and w, x, y and z each represent 0.
  • 10. Optical data medium according to claim 1, wherein the light absorbing compound is a merocyanine.
  • 11. Optical data medium according to claim 1, wherein the light absorbing compound corresponds to formula (1)
  • 12. Process for the production of the optical data media according to claim 1, which is characterized in that a preferably transparent substrate optionally already coated with a barrier layer is coated with the dye, optionally in combination with suitable binders and additives and optionally suitable solvents, and is optionally provided with a barrier layer, further intermediate layers and a cover layer applied by an adhesive layer.
  • 13. Process for the production of the optical data media according to claim 1, characterized in that the coating with the dye is effected by means of spin-coating, sputtering or vapour deposition.
  • 14. Optical data media having a recordable information layer, obtainable by recording on optical data media according to claim 1 using blue light, preferably laser light, in particular laser light having a wavelength of 360-460 nm.
Priority Claims (14)
Number Date Country Kind
10115227.2 Mar 2001 DE
10117461.6 Apr 2001 DE
10117462.4 Apr 2001 DE
10117463.2 Apr 2001 DE
10117464.0 Apr 2001 DE
10124585.8 May 2001 DE
10136064.9 Jul 2001 DE
10136063.0 Jul 2001 DE
10140165.5 Aug 2001 DE
01123810.2 Oct 2001 EP
01130527.3 Dec 2001 DE
10200484.6 Jan 2002 DE
1020257.1 Jan 2002 DE
02005505.9 Mar 2002 EP