WO2004079732A1 - Optical recording materials having high storage density - Google Patents

Optical recording materials having high storage density Download PDF

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Publication number
WO2004079732A1
WO2004079732A1 PCT/EP2004/050185 EP2004050185W WO2004079732A1 WO 2004079732 A1 WO2004079732 A1 WO 2004079732A1 EP 2004050185 W EP2004050185 W EP 2004050185W WO 2004079732 A1 WO2004079732 A1 WO 2004079732A1
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WO
WIPO (PCT)
Prior art keywords
substituted
unsubstituted
alkyl
radicals
different
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2004/050185
Other languages
English (en)
French (fr)
Inventor
Urs Lehmann
Peter Sutter
Beat Schmidhalter
Jean-Luc Budry
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Priority to HK06102760.8A priority Critical patent/HK1082980B/en
Priority to US10/546,077 priority patent/US20060159882A1/en
Priority to JP2006505428A priority patent/JP2006523553A/ja
Priority to DE602004001135T priority patent/DE602004001135T2/de
Priority to EP04713552A priority patent/EP1599878B1/en
Publication of WO2004079732A1 publication Critical patent/WO2004079732A1/en
Priority to JP2007500208A priority patent/JP2007535778A/ja
Priority to PCT/EP2005/050670 priority patent/WO2005081239A1/en
Priority to TW094105236A priority patent/TW200605063A/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D413/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D417/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07F1/00Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/08Copper compounds
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    • C07F15/04Nickel compounds
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Definitions

  • the invention relates to new optical recording materials that have excellent recording and playback quality especially at a wavelength of 350-500 nm. Recording and playback can be effected very advantageously with high sensitivity at the same wavelength, and the storage density that is achievable is significantly higher than in the case of known materials.
  • the materials according to the invention have very good storage properties before and after recording, even under especially harsh conditions, such as exposure to sunlight or fluorescent lighting, heat and/or high humidity.
  • their manufacture is simple and readily reproducible using customary coating processes, such as spin-coating.
  • WO 02/082438 discloses the use of ionic salts, including those with metal complex anions, for optical recording materials. Those colorants are always substituted by alkyl, alkenyl, aryl or heteroaryl at the nitrogen atom. Their optical properties do not, however, fully satisfy increased demands. In particular, the refractive index as well as the absorption and the steepness of the absorption band on its long wavelength flank in the solid still leave something to be desired.
  • JP-A-11/34500, JP-A-11/92479 and EP-A-0903733 disclose metal and boron
  • the optical properties, especially the spectral properties in or near the UV range that are necessary for the highest possible storage densities, and the information density per unit surface area are not able to satisfy the highest demands as desired.
  • the information density per unit surface area is far lower than is desirable.
  • J. Org. Chem. 67/16, 5753-5772 [2002] describes the synthesis of a number of bis(o-azaheteroaryl)methanes and their coordination properties with respect to divalent transition metals, heteroaryl being 1 ,3-azol-2 ⁇ yl, 1,3-benzazol-2-yl and azinyl and the transition metals being Zn, Cu, Co, Ni, Hg and Pd.
  • the aim of the invention is an optical recording medium having high information density, sensitivity and data reliability.
  • a recording medium should be robust, durable and easy to use. Furthermore, it should be inexpensive to manufacture as a mass-produced product and should require equipment that is as small and inexpensive as possible.
  • the invention therefore relates to an optical recording medium comprising a substrate, a recording layer and optionally one or more reflecting layers, wherein the
  • recording layer comprises a compound of formula (I) or a tautomer thereof, wherein G ⁇ and G 2 are each independently of the other
  • Mi is a transition metal of groups IX to XII, preferably Co, Cu, Ni, Pd or Zn, especially Co, Cu or Ni;
  • Q 1 and Q 2 are each independently of the other C(R ⁇ s) , N or P;
  • R1 , R 2 , R3 , R , R5 , Re , R7 , e and R M are each independently of the others hydrogen, Ri ⁇ , or Ce-C ⁇ 2 aryl, C -C ⁇ heteroaryl, C 7 -Ci 2 aralkyl or Cs-Ci ⁇ heteroaralkyI each unsubstituted or substituted by one or more, where applicable identical or different, radicals R ⁇ 8 ; or
  • R 1 and R 2 , R 3 and R 4 , R 5 and Re, R 5 and R 13 and/or R 5 and R ⁇ , together in pairs, are C 3 -C 6 alkylene or C 3 -C 6 alkenylene, each of which is unsubstituted or substituted by one or more, where applicable identical or different, radicals R 17 and may be uninterrupted or interrupted by O, S or N(R ⁇ 2 ), or 1 ,4-buta-1 ,3-dienylene, J ⁇
  • Rg , Ri 2 and R 13 are each independently of the others CrC 2 alkyl, C 3 -C 2 cycloalkyI, C 2 -C 24 alkenyl, C 3 -C 2 cycloalkenyl, CrC alkyl-[0-Ci-C alkylene] m or CrC 4 alkyl-[NH- C ⁇ -C 4 alkylene] m , each of which is unsubstituted or substituted by one or more, where applicable identical or different, radicals R 17 ; or C 6 -C ⁇ 2 aryl, C 4 -C 12 heteroaryl, C 7 -C ⁇ 2 aralkyl or C 5 -C ⁇ 2 heteroaralkyl, each of which is unsubstituted or substituted by one or more, where applicable identical or different, radicals R
  • R 16 is C 6 -C 12 aryl, C 4 -C ⁇ 2 heteroaryl, C 7 -C ⁇ 2 aralkyl or C ⁇ -C ⁇ 2 heteroaraIkyI, each of which is unsubstituted or substituted by one or more, where applicable identical or different, radicals R 28 ;
  • R17 is halogen, hydroxy, 0-R 25 , 0-CO-R 25 , S-R 25 , NH 2 , NH-R 25 , NR2SR26 , NH 3 + , NH 2 R 2 5 + , NHR 2 5R 2 6 + , NR 24 R2sR26 + , NR ⁇ -CO-R ⁇ , NR25COOR24, cyano, formyl, COO-R 25 , carboxy, carbamoyl, CONH-R 25 , CONR 2S R 26 , ureido, NH-CO-NHR 24 , NR 2 5-CO-NHR 24 , phosphato,
  • R.g , R20 and R23 are each independently of the others R 1 ⁇ , or C C 12 alkyl, C 3 -Ci 2 Cycloalkyl, C 2 -C ⁇ 2 alkenyl or C 3 -C 12 cycloalkenyl each unsubstituted or substituted by one or more, where applicable identical or different, halogen, hydroxy, C ⁇ -C 12 alkoxy or C 3 -Ci 2 Cycloalkoxy radicals; or
  • R14 and R- ⁇ 9 together, R 15 and Rig together and/or R 19 and R 23 together are C 2 -C 12 alkylene, G 3 -C ⁇ 2 cycloalkylene, C 2 -Ci 2 alkenylene or C 3 -G ⁇ 2 cycloalkenyle ⁇ e, each of which is unsubstituted or substituted by one or more, where applicable identical or different, halogen, hydroxy, C ⁇ -C ⁇ alkoxy or C 3 -C ⁇ 2 cycloalkoxy radicals; or
  • Ri 9 and R 2 o together with the common nitrogen are pyrrolidine, piperidine, piperazine or morpholine, each of which is unsubstituted or mono- to tetra-subslituled by CrC alkyl; or carbazole, phenoxazine or phenothiazine, each of which is unsub- stituted or substituted by one or more, where applicable identical or different, radicals R 28 ;
  • R 2 ⁇ and R ⁇ are each independently of the other NR 25 R 26 , CN, CONH 2 , CONHR-ig , CONR 19 R 20 or COOR 20 ;
  • R2 4 , R25 and R26 are each independently of the others C ⁇ -C ⁇ 2 alkyl, C3-C ⁇ 2 cycloalkyl, C 2 -Ci 2 alkenyl, C 3 -C ⁇ 2 cycIoalkenyl, C 4 -C 12 heteroaryl, C 7 -Ci 2 aralkyl or C 5 -C ⁇ 2 heteroaralkyl; or R 25 and R 2 ⁇ together with the common nitrogen are pyrrolidine, piperidine, piperazine or morpholine, each of which is unsubstituted or mono- to tetra-substituted by C C 4 alkyl;
  • R is C 6 -C ⁇ 2 aryl, C 4 -C 12 heteroaryl, C 7 -C ⁇ 2 aralkyl or C 5 -C ⁇ 2 heteroaralkyl, each of which is unsubstituted or substituted by one or more, where applicable identical or different, radicals R- ⁇ 8 ;
  • R 28 is nitro, S0 2 NHR 25 ⁇ S ⁇ 2NR 25 2 6 , or C ⁇ -C ⁇ 2 alkyl, C 3 -C. 2 cycloalkyl, CrC ⁇ 2 alkylthio, C 3 -C ⁇ 2 cycloalkylthio, d-C 12 alkoxy or C 3 -C ⁇ 2 cycloalkoxy each unsubstituted or substituted by one or more, where applicable identical or different, radicals R- ⁇ 7 ; and
  • n is a number from 1 to 10.
  • R 5 forms a bridge with R 6
  • Rs may not at the same time form a bridge with R 13 or R 14 .
  • acidic groups such as carboxy, sulfo, sulfato and phosphate
  • a salt for example an alkali metal, alkaline earth metal, ammonium or phosphonium salt, such as Li + , Na + , K + , Mg 2+ , Ca 21 , Cu 2+ , Ni 2+ , Fe 2+ , Co 2 , Zn 2H , Sn 21 , La 3 *, ammonium, methylammonium, ethylammonium, isopropylammonium, TMPrimene 81-R, TMRosin Amine D, penta- decylammonium, TMPrimene JM-T, dicyclohexylammonium, tetramethylammonium, tetraethyla mo ⁇ ium, tetrabutylammonium, benzyltrimethylammonium, benzyl- triethyl
  • Halogen is chlorine, bromine, fluorine or iodine, preferably fluorine or chlorine, especially fluorine on alkyl (for example trifluoromethyl, ⁇ ,oc, ⁇ -trifluoroethyl or perfluorinated alkyl groups, such as heptafluoropropyl) and chlorine on aryl, heteroaryl or on the aryl moiety of aralkyl or on the heteroaryl moiety of hetero- aralkyl.
  • alkyl for example trifluoromethyl, ⁇ ,oc, ⁇ -trifluoroethyl or perfluorinated alkyl groups, such as heptafluoropropyl
  • chlorine on aryl, heteroaryl or on the aryl moiety of aralkyl or on the heteroaryl moiety of hetero- aralkyl for example trifluoromethyl, ⁇ ,oc, ⁇ -trifluoroethyl or perfluorinated alkyl groups, such as
  • Alkyl, cycloalkyl, alkenyl or cycloalkenyl can be straight-chain or branched, or monocyclic or polycyclic.
  • Alkyl is, for example, methyl, straight-chain C -C 24 alkyl or preferably branched C 3 -C 24 alkyl.
  • Alkenyl is, for example, straight-chain C 2 -C 2 oalkenyl or preferably branched C 3 -C 24 alkenyl.
  • the invention therefore relates especially also to compounds of formula (I) containing branched C 3 -C 24 alkyl or branched C 3 -C 2 alkenyl, and also to optical recording materials comprising such compounds.
  • Ci-C 24 Alkyl is therefore, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-octyl, 1 ,1,3,3-tetramethylbutyl, 2-ethylhexyI, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, heneicosyl, docosyl or tetracosyl.
  • Cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, menthyl, thujyl, bornyl, 1 -adamantyl or 2-adamantyl.
  • C ⁇ -C ⁇ AIkenyl and C 3 -C 2 ocycloalkenyl are C 2 -C 2 oalkyI and C 3 -C 2 ocycloalkyl that is mono- or poly-unsaturated, wherein two or more double bonds may be isolated or conjugated, for example vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3- butadien-2-yl, 2-cyclobuten-1-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-yI, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10)-
  • C 7 -C ⁇ 2 Aralkyl is, for example, benzyl, 2-benzyl-2-propyl, ⁇ -phenyl-ethyl, 9-fluorenyI, ⁇ , ⁇ -dimethylbenzyl, co-phenyl-butyl or ophenyl-hexyl.
  • C -C ⁇ 2 aralkyl is substituted, both the alkyl moiety and the aryl moiety of the aralkyl group can be substituted, the latter alternative being preferred.
  • Aryl is, for example, phenyl, naphthyl, biphenylyl or 2-fluorenyl.
  • C 4 -C ⁇ 2 Heteroaryl is an unsaturated or aromatic radical having 4n+2 conjugated ⁇ -electrons, for example 2-thienyl, 2-furyI, 2-pyridyl, 2-thiazolyl, 2-oxazolyl, 2-imidazolyl, isothiazolyl, triazolyl or any other ring system consisting of thiophene, furan, pyridine, thiazole, oxazole, imidazole, isothiazole, triazole, pyridine and benzene rings and unsubstituted or substituted by from 1 to 6 ethyl, methyl, ethylene and/or methylene substituents, for example benzotriazolyl, and in the case of N- heterocycles where applicable also those in the form of their N-oxides.
  • 2-thienyl 2-furyI, 2-pyridyl, 2-thiazolyl, 2-oxazolyl, 2-imidazolyl, isothi
  • Cs-C 12 Heteroaralkyl is, for example, G ⁇ -G 8 alkyl substituted by C 4 -Cn heteroaryl.
  • aryl and aralkyl can also be aromatic groups bonded to a metal, for example in the form of metallocenes of transition metals known perse, more especially
  • the transition metal Mi is preferably in the form of a doubly positively charged cation, for example Co 2+ , Cu 2 ", Ni 2+ , Pd 2 * orZn 2+ , especially Co + , Cu 2+ or Ni 2+ .
  • the compound of formula (I) may also be a cation which has been neutralised with an inorganic, organic or organometallic anion, for example when one or more ammonium groups are present or when the transition metal has one or more excess positive charges, such as in Co 3+ .
  • the inorganic, organic or organometallic anion may be, for example, the anion of a mineral acid, of the conjugated base of an organic acid (for example an alcoholate, phenolate, carboxylate, sulfonate or phosphonate) or an organometallic complex anion, for example fluoride, chloride, bromide, iodide, perchlorate, periodate, nitrate, hydrogen carbonate, Vz carbonate, Vz sulfate, C ⁇ -C 4 alkyl sulfate, hydrogen sulfate, Vz phosphate, Vz hydrogen phos- phate, dihydrogen phosphate, Vz CrC 4 alkanephosphonate, CrC alkane-C ⁇ -C ⁇ 2 alkyl- phosphonate, di-C ⁇ -C 4 alkylphosphinate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, acetate, trifluor
  • Vz- S0 2 ⁇ 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, of formula
  • R 29 , R 3u and R 3 ⁇ are each independently of the others hydrogen, R 18 , or Ce-Ci 2 aryl, C 4 -G ⁇ 2 heteroaryl, or C 5 -C ⁇ 2 heteroaralkyl each unsubstituted or substituted by one or more, where applicable identical or different, radicals R ⁇ a, for example anions of C ⁇ -C ⁇ 2 alkylated, especially tert-C 4 -C 8 alkylated, phenols and benzoic acids, such as
  • Ai, A 2 and A 3 are each independently of the others O, S or N(R ⁇ 2 ) and/or Qi and Q 2 are C(R 15 ) or N;
  • i and G 2 are each independently of the other or
  • R-1, R2, R3, R 4 , R5, Re, R , Re and R14 are each independently of the others hydrogen, Ri ⁇ , or C ⁇ -C ⁇ 2 aryl or C 7 -C ⁇ 2 aralkyl each unsubstituted or substituted by one or more, where applicable identical or different, radicals R- ⁇ 8 ;
  • R 9 , R ⁇ 2 and R « are each independently of the others unsubstituted or R 17 -substituted C ⁇ -C 8 alkyl;
  • Ri ⁇ is unsubstituted or substituted C 6 -Ci 2 aryl or C 7 -C ⁇ 2 aralkyl, especially a metallocenyl radical;
  • R17 is halogen, hydroxy, O-R ⁇ s, amino, NH-R ⁇ s, NR 25 R 26 , NR 25 -CO-R 2 4,
  • R.g, R2 0 and R23 are each independently of the others CrC. 2 alkyl unsubstituted or substituted by one or more, where applicable identical or different, halogen, hydroxy or C ⁇ -C ⁇ 2 alkoxy radicals, or unsubstituted or C7-C ⁇ 2 aralkyl; or
  • R-ig and Raj together with the common nitrogen are morpholine, or piperidine N- substituted by C ⁇ -C 4 alkyl;
  • R 25 , R ⁇ and R 2 are each independently of the others CrC ⁇ 2 alkyl, C 2 -Ci 2 alkenyl, C 6 -C ⁇ 2 aryl or C 7 -C ⁇ 2 aralkyl; or
  • R 25 and R ⁇ together with the common nitrogen are morpholine, or piperidine N- substituted by G ⁇ -C 4 alkyl; and/or
  • n is a number from 1 to 4.
  • G and G 2 are ⁇ II J "R ⁇ 8 ; and Ai, A 2 and A 3 are O, S or N(R 12 ); ⁇ i ⁇
  • R 12 is C ⁇ -C 24 alkyl, Gi-G 4 alkyl-[0-CrC 4 alkylene] m or C ⁇ -C 4 alkyI-[NH-G ⁇ -C 4 alkylene] m , each of which is unsubstituted or substituted by one or more, where applicable identical or different, radicals R 17 , or C ⁇ -C ⁇ 2 aryl unsubstituted or substituted by one or more, where applicable identical or different, radicals R- ⁇ 8 ;
  • R15 is hydrogen, cyano, COO-R25 or C Ci 2 alkyl
  • R ⁇ 7 is halogen, hydroxy, 0-R 25 , cyano, COO-R ⁇ or carboxy;
  • the recording layer advantageously comprises a compound of formula (I) or a mixture of such compounds as main component, for example at least 30 % by weight, preferably at least 60 % by weight, especially at least 80 % by weight.
  • 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, 1 0 2 -, triplet- or luminescence-quenchers, melting-point reducers, decomposition accelerators or any other additives that have already been described in optical recording media.
  • stabilisers or fluoresence-quenchers are added if desired.
  • the amount of such chromophores should preferably be small, so that the absorption thereof at the wavelength of the inversion point of the longest-wavelength flank of the absorption of the entire solid layer is a fraction of the absorption of the pure compound of fo ⁇ nula (I) in the entire solid layer at the same wavelength, advantageously at most 1/3, preferably at most 1/5, especially at most 1/10.
  • the absorption maximum is preferably higher than 425 nm, especially higher than 500 nm.
  • Stabilisers, 1 0 2 -, 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-dimethylamino- dithiobenzil)nickel [CAS N° 38465-55-3], ® lrgalan 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, Para
  • optical recording media for example from US-5219 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, or metal complexes, illustrated, for example, by a compound of
  • 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).
  • the optical recording materials according to the invention exhibit excellent spectral properties of the solid amorphous recording layer.
  • the refractive index is extraordinarily high, in some cases even above 2.5.
  • the absorption band is narrow and intense, the absorption band being especially steep on the long- wavelength side.
  • Crystallites are unexpectedly and very advantageously not formed or are formed only to a negligible extent.
  • the reflectivity of the layers in the range of the writing and reading wavelength is very high in the unwritten state.
  • solutions can be used even in high concentrations without troublesome precipitation, for example during storage, so that problems during spin-coating are largely eliminated. This applies especially to compounds containing branched C 3 -C 8 alkyl.
  • Recording and playback can take place at the same wavelength, therefore advantageously requiring a simple optical system with a single laser source of advantageously from 350 to 500 nm, preferably from 370 to 450 nm.
  • the UV range from 370 to 390 nm, especially approximately 380 nm, or especially at the edge of the visible range of from 390 to 430 nm, more especially approximately 405 ⁇ 5 nm.
  • blue or violet laser diodes such as Nichia GaN 405 nm
  • the marks can be so small and the tracks so narrow that up to about 20 to 25 Gb per recording layer is achievable on a 120 mm disc.
  • UV-VCSELs Very-Cavity Surface-Emitting Laser
  • the invention therefore relates also to a method of recording or playing back data, wherein the data on an optical recording medium according to the invention are recorded or played back at a wavelength of from 350 to 500 nm.
  • the recording medium is based on the structure of known recording media and is, for example, analogous to those mentioned above. It may be composed, for example, of a transparent substrate, a recording layer comprising at least one of the compounds of formula (I), a reflector layer and a covering layer, the writing and readout being effected through the substrate.
  • Suitable substrates are, for example, glass, minerals, ceramics and thermosetting and 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.
  • Special preference is given to polycarbonate substrates which can be produced, for example, by injection-moulding.
  • the substrate can be in pure form or may comprise customary additives, for example UV absorbers or dyes, as proposed e.g. in JP-A-04/167239 as light stabilisation for the recording layer. In the latter case it may be that in the range of the writing wavelength (emission wavelength of the laser) the dye added to the support substrate has no or at most only very low absorption, preferably up to a maximum of about 20% of the laser light
  • the substrate is advantageously transparent over at least a portion of the range from 350 to 500 nm, so that it is permeable to, for example, at least 80 % of the incident light of the writing or readout wavelength.
  • the substrate is advantageously from 10 ⁇ m to 2 mm thick, preferably from 100 to 1200 ⁇ m thick, especially from 600 to 1100 ⁇ m thick, with a preferably spiral guide groove (track) on the coating side, a groove depth of from 10 to 200 nm, preferably from 80 to 150 nm, a groove width of from 100 to 400 nm, preferably from 150 to 250 nm, and a spacing between two turns of from 200 to 600 nm, preferably from 350 to 450 nm.
  • Grooves of different cross-sectional shape are known, for example rectangular, trapezoidal or V-shaped.
  • the guide groove may additionally undergo a small periodic or quasi-periodic lateral deflection (wobble), so that synchronisation of the speed of rotation and the absolute positioning of the reading head (pick-up) are made possible.
  • the same function can be performed by markings between adjacent grooves (pre-pits).
  • the recording medium is applied, for example, by application of a solution by spin- coating, the objective being to produce a layer that is as amorphous as possible, the thickness of which layer is advantageously from 0 to 40 nm, preferably from 1 to 20 nm, especially from 2 to 10 nm, on the surface ("land") and, depending upon the geometry of the groove, advantageously from 20 to 150 nm, preferably from 50 to 120 nm, especially from 60 to 100 nm, in the groove.
  • Reflecting materials suitable for the reflector 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.
  • the reflector layer is advantageously from 5 to 200 nm thick, preferably from 10 to 100 nm thick, especially from 40 to 60 nm thick, but reflector layers of greater thickness, for example 1 mm thick or even more, are also possible.
  • Materials suitable for the covering layer include chiefly plastics, which are applied in a thin layer to the reflector layer either directly or with the aid of adhesion promoters. It is advantageous to select mechanically and thermally stable plastics having good surface properties, which can be modified further, for example written on.
  • the plastics may be thermosetting plastics and thermoplastic plastics.
  • Directly applied covering layers are preferably radiation-cured (e.g. using UV radiation) coatings, which are particularly simple and economical to produce. A wide variety of radiation- curable materials are known.
  • radiation-curable monomers and oligomers are acrylates and methacrylates of diols, triols and tetrols, polyimides of aromatic tetracarboxylic acids and aromatic diamines having C ⁇ -C 4 alkyl groups in at least two ortho-positions of the amino groups, and oligomers with dialkylmaleinimidyl groups, e.g. dimethylmaleinimidyl groups.
  • adhesion promoters it is preferable to use the same materials as those used for the substrate layer, especially polycarbonates.
  • the adhesion promoters used are preferably likewise radiation-curable monomers and oligomers.
  • a second substrate comprising a recording and reflector layer, so that the recording medium is playable on both sides.
  • the optical properties of the covering layer, or the covering materials are essentially unimportant perse provided that, where applicable, curing thereof e.g. by UV radiation is achieved.
  • the function of the covering layer is to ensure the mechanical strength of the recording medium as a whole and, if necessary, the mechanical strength of thin reflector layers. If the recording medium is sufficiently robust, for example when a thick reflector layer is present, it is even possible to dispense with the covering layer altogether.
  • the thickness of the covering layer depends upon the thickness of the recording medium as a whole, which should preferably be a maximum of about 2 mm thick.
  • the covering layer is preferably from 10 ⁇ m to 1 mm thick.
  • the recording media according to the invention may also have additional layers, for example interference layers or barrier layers. It is also possible to construct recording media having a plurality of (for example from two to ten) recording layers. The structure and the use of such materials are known to the person skilled in the art. Where present, interference layers are preferably 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-A-0353 393 of Ti0 2 , Si 3 N 4 , ZnS or silicone resins.
  • the recording media according to the invention can be produced by processes known perse, it being possible for various methods of coating to be employed 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.
  • pouring methods solutions in organic solvents are generally employed.
  • solvents 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-0401 791.
  • the recording layer is applied preferably by the application of a dye solution by spin- coating, solvents that have proved satisfactory being especially alcohols, e.g. 2-methoxyethanol, isopropanol or n-butanol, hydroxyketones, for example diacetone alcohol or 3-hydroxy-3-methyl-2-butanone, hydroxy esters, for example lactic acid methyl ester or isobutyric acid methyl ester, or preferably fluorinated alcohols, for example 2,2,2-trifluoroethanol or2,2,3,3-tetrafluoro-1-prapanol, and mixtures thereof.
  • solvents that have proved satisfactory being especially alcohols, e.g. 2-methoxyethanol, isopropanol or n-butanol, hydroxyketones, for example diacetone alcohol or 3-hydroxy-3-methyl-2-butanone, hydroxy esters, for example lactic acid methyl ester or isobutyric acid methyl ester, or preferably fluorinated alcohols, for example 2,2,
  • the application of the metallic reflector layer is preferably effected by sputtering or by vapour-deposition in vacua. 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 operation can advantageously be carried out continuously and achieves good reflectivity and a high degree of adhesiveness of the metallic reflector layer.
  • Recording is carried out in accordance with known methods by writing pits (marks) of fixed or variable length by means of a modulated, focussed laser beam guided at a constant or variable speed over the surface of the recording layer.
  • Readout of information is carried out according to methods known perse by registering the change in reflection using laser radiation, for example as described in "CD-Player und R-DAT Recorder” (Claus Biaesch-Wiepke, Vogel Buchverlag, W ⁇ rzburg 1992). The person skilled in the art will be familiar with the requirements.
  • the information-containing medium according to the invention is especially an optical information material of the WORM type. It can be used, for example, analogously to CD-R (compact disc - recordable) or DVD-R (digital video disc - recordable) in computers, and also as storage material for identification and security cards or for the production of diffractive optical elements, for example holograms. Alternatively, however, there are also recording media which differ substantially from CD-R and DVD-R and in which recording and playback take place not through the substrate but through the covering layer ("in-groove recording"). Accordingly the respective roles of the covering layer and the substrate, especially the geometry and the optical properties, are reversed in comparison with the structure described above. Analogous concepts are described a number of times in Proceedings SPIE- Int. Soc.
  • the compounds of formula (I) according to the invention also meet the increased demands of an inverse layer structure surprisingly well. Preference is therefore given to an inverse layer structure having the layer sequence substrate, reflector layer, recording layer and covering layer.
  • the recording layer is therefore located between the reflector layer and the covering layer.
  • a thin covering layer approximately from 50 to 400 ⁇ m in thickness is especially advantageous (typically 100 ⁇ m at a numerical aperture of 0.85).
  • the recording and reflector layers in an inverse layer structure have in principle the same functions as indicated above. As with the groove geometry, they therefore usually have dimensions within the ranges indicated above.
  • the inverse layer structure requires particularly high standards, which the compounds used according to the invention fulfil astonishingly well, for example when the recording layer is applied to the metallic reflector layer and especially when a covering layer is applied to the recording layer, the covering layer being required to provide the recording layer with adequate protection against rubbing, photo- oxidation, fingerprints, moisture and other environmental effects and advantageously having a thickness in the range of from 0.01 to 0.5 mm, preferably in the range of from 0.05 to 0.2 mm, especially in the range of from 0.08 to 0.13 mm.
  • the covering layer preferably consists of a material that exhibits a transmission of 80% or above at the writing or readout wavelength of the laser.
  • Suitable materials for the covering layer include, for example, those materials mentioned above, but especially polycarbonate (such as Pure Ace ® or Panlite ® , Teijin Ltd), cellulose triacetate (such as Fujitac ® , Fuji Photo Film) or polyethylene terephthalate (such as Lumirror ® , Toray Industry), special preference being given to polycarbonate.
  • polycarbonate such as Pure Ace ® or Panlite ® , Teijin Ltd
  • cellulose triacetate such as Fujitac ® , Fuji Photo Film
  • polyethylene terephthalate such as Lumirror ® , Toray Industry
  • radiation-cured coatings such as those already described above, are advantageous, for example SD 347TM (Dainippon Ink).
  • the covering layer can be applied directly to the solid recording layer by means of a suitable adhesion promoter.
  • an additional, thin separating layer of a metallic, crosslinked organometallic or preferably dielectric inorganic material for example in a thickness of from 0.001 to 10 ⁇ m, preferably from 0.005 to 1 ⁇ m, especially from 0.01 to 0.1 ⁇ m, for example from 0.05 to 0.08 ⁇ m in the case of dielectric separating layers and from 0.01 to 0.03 ⁇ m in the case of metallic separating layers.
  • such coatings can be applied, for example, in the same thickness also between the support material and the metallic reflector layer or between the metallic reflector layer and the optical recording layer. This may be advantageous in certain cases, for example when a silver reflector is used in combination with sulfur-containing additives in the recording layer.
  • an additional, thin separating layer of a metallic, crosslinked organometallic or dielectric inorganic material for example in a thickness of from 0.001 to 10 ⁇ m, preferably from 0.005 to 1 ⁇ m, especially from 0.01 to 0.1 ⁇ m.
  • metallic separating layers should advantageously be a maximum of 0.03 ⁇ m thick.
  • the invention therefore relates also to compounds of formula (I), with the exception of the already known compounds of formula M 2 (Z ⁇ ) 2 , wherein:
  • M 2 is Co(II), Cu( ⁇ ), Hg( ⁇ ), Ni(JJ), Pd(H) or Zn( ⁇ ) and Z-, is
  • k is Co( ⁇ ), Cu(JJ), Ni( ⁇ ), Pd(JJ) or Zn( ⁇ ) and Z-i is ,[ N- ⁇
  • M 2 is Co( ⁇ ), Cu( ⁇ ), N IO or Znr ⁇ and Zi is • M 2 is Cu( ⁇ ), Pd(H) or Zn( ⁇ ) and Z-i is
  • M 2 is Co( ⁇ ), Cu( ⁇ ) or Zn(II) and Z-i is
  • M 2 is Co( ⁇ ) or Cu( ⁇ ) and Zi
  • hz is Pd(U) or Zn( ⁇ ) and Z-i is
  • Cu, Co, Ni or Pd and Z ⁇ is a radical of the following compounds:
  • a 3 in Gi and G 2 can be especially N(R- ⁇ ), O, S or, especially in formula (HI), C(CrCsalkyl) a .
  • a 3 dently of A 3 , has the same definition and the same preferred meanings as A 3 .
  • mixtures by mixed synthesis instead of preparing mixtures by mixing together the components, it is favourably possible to prepare mixtures by mixed synthesis, the metals being added in any desired order in succession or preferably simultaneously to a pre-prepared mixture of the ligands, or conversely the ligands being added in any desired order in succession or preferably all of them simultaneously to a pre-prepared mixture of the metals.
  • the mixtures prepared by mixed synthesis generally have somewhat better solubility than physical mixtures, possibly because of their asymmetric components.
  • the optical recording media according to the invention may also comprise other chromophores, preferably metal-free chromophores.
  • Other chromophores may, if desired, be added in an amount of from 1 to 200 % by weight, based on the total of the compounds of formula (I).
  • the amount of other chromophores is preferably from 5 to 100 % by weight, especially from 10 to 50 % by weight, based on the total of the compounds of formula (I).
  • Chromophores can be dyes or UV absorbers, preferably having an absorption maximum of from 350 to 400 nm or at from 600 to 700 nm, for example around 380 or 630 nm.
  • Especially preferred additional metal-free chromophores are cyanines, azacyanines, merocyanines and oxonols and also rhodamines, for example those disclosed in WO 04/006878, WO 02/082438 or EP-A-1 083555, and also
  • R ⁇ is CrC 24 alkyl or C 2 -C 24 alkenyl, each of which can be unsubstituted -or substituted, and R ⁇ is any substituent.
  • R 40 may be, for example, methyl, ethyl, vinyl, allyl, isopropyl, n-butyl, 2-isopropyloxy-ethyl, n-pentyl, 3-methyI-butyl, 3,3-dimethyl- butyl, 2-ethyl-hexyl, 2-cyano-ethyI, furan-2-yl-methyl or2-hydroxy-methyl;
  • f ⁇ i is, for example, C ⁇ -C-ioaryl, C ⁇ -C 2 alkyl or C 2 -C 2 alkenyl.
  • chromophores are:
  • Example 1 1.0 g of the compound of formula is applied in
  • Example 2 On the solid layer according to Example 1, marks are written into the ' recording layer using a pulsed dye laser (15 ns pulse length) at a wavelength of 405 nm at an energy density of 0.8 kJ/m 2 . The written sites exhibit a resulting change in reflectivity.
  • Example 3 0.5 g of the compound according to Example 1 is dissolved in 99.5 g of dioxane and applied by means of spin-coating to a silicon wafer. The colourless solid layer is measured using a spectral ellipsometer (Sopra). At a wavelength of 405 nm a refractive index of 2.52 is determined.
  • Example 4 1.0 g of the compound of formula is
  • the dye solution is then applied by rotation at 250 rev/min to a 1.2 mm thick, flat polycarbonate plate (diameter 120 mm). The rotational speed is then increased to 1200 rev/min, so that the excess solution is spun off, and a uniform solid layer is formed. After drying, the solid layer has an absorption of 0.61 at 382 nm.
  • an optical measuring system ETA-RT, STEAG ETA-Optik
  • the layer thickness and the complex refractive index are determined.
  • the dye layer has a layer thickness of 56 nm, a refractive index n of 1.95 and an extinction coefficient k of 0.090.
  • 0.5N aqueous copper(IT) acetate solution is added to a solution of 458 mg of the resulting ligand in 30 ml of ethanol until precipitation, which begins immediately, is complete. After filtration, the product is washed with ethanol and diethyl ether, and
  • Example 6 1.0 g of the complex according to Example 5 is dissolved in 99 g of 2,2,3,3-tetrafluoro-1-propanol and filtered through a 0.2 ⁇ m Teflon filter. The dye solution is then applied by rotation at 250 rev/min to a 1.2 mm thick, flat polycarbonate plate (diameter 120 mm); the rotational speed is then increased to 1500 rev/min, so that the excess solution is spun off and a uniform solid layer is formed. After drying, the solid layer has an absorption of 0.35 at 356 nm. Using an optical measuring system (ETA-RT, STEAG ETA-Optik), the layer thickness and the complex refractive index are determined. At 405 nm the dye layer has a layer thickness of 18 nm, a refractive index n of 2.25 and an extinction coefficient k of 0.031.
  • ETA-RT ETA-RT, STEAG ETA-Optik
  • Examples 7 - 38 The procedure is analogous to Example 6, but instead of the complex of Example 5 the following ligands and metal cations are used:
  • Examples 39 - 62 The procedure is analogous to Example 6, but instead of the complex of Example 5 the mixtures M1 to M24 are used.
  • Examples 63 - 86 The procedure is analogous to Example 6, but instead of the complex of Example 5 there are used mixtures having the same proportions of metal and ligand as mixtures M1 to M24 but the complexes are prepared by mixed synthesis (variant of the simultaneous addition of the metal mixture to the ligand mixture). The results are similar to those of Examples 39 - 62, but have surprisingly better solubility and solution stability.
  • Examples 87 - 94 The procedure is analogous to Example 6, but instead of the complex of Example 5 there are used the following mixtures of compounds of formula (I) with cyanines and merocyanines:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
PCT/EP2004/050185 2003-03-03 2004-02-23 Optical recording materials having high storage density Ceased WO2004079732A1 (en)

Priority Applications (8)

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HK06102760.8A HK1082980B (en) 2003-03-03 2004-02-23 Optical recording materials having high storage density
US10/546,077 US20060159882A1 (en) 2003-03-03 2004-02-23 Optical recording materials having high storage density
JP2006505428A JP2006523553A (ja) 2003-03-03 2004-02-23 高度の記録密度を有する光学記録材料類
DE602004001135T DE602004001135T2 (de) 2003-03-03 2004-02-23 Materialien für optische aufzeichnung mit hoher speicherdichte
EP04713552A EP1599878B1 (en) 2003-03-03 2004-02-23 Optical recording materials having high storage density
JP2007500208A JP2007535778A (ja) 2004-02-23 2005-02-16 高い記憶密度を有する光学的記録材料
PCT/EP2005/050670 WO2005081239A1 (en) 2004-02-23 2005-02-16 Optical recording materials having high storage density
TW094105236A TW200605063A (en) 2004-02-23 2005-02-22 Optical recording materials having high storage density

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Cited By (2)

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EP1710793A1 (de) * 2005-04-05 2006-10-11 Ciba SC Holding AG Metallchelate und ihre Verwendung in optischen Aufzeichnungsmedien mit hoher Speicherkapazität
EP2527404A4 (en) * 2010-01-19 2017-09-13 Sumitomo Seika Chemicals CO. LTD. Composition for ultraviolet ray-absorbable member, and ultraviolet ray-absorbable member comprising same

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WO2002082438A2 (en) * 2001-03-21 2002-10-17 Ciba Specialty Chemicals Holding Inc. Optical recording materials having high storage density
DE602004010451T2 (de) * 2003-04-15 2008-11-20 Ricoh Co., Ltd. Einmal beschreibbarer, mehrmals lesbarer optischer Datenträger und Verfahren zum Beschreiben und Lesen des Datenträgers
EP1719126A1 (en) * 2004-02-23 2006-11-08 CIBA SPECIALTY CHEMICALS HOLDING INC. Patent Departement Optical recording materials having high storage density
JP2008509029A (ja) * 2004-08-10 2008-03-27 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド 高い記憶密度を有する光記録材料
JP5400717B2 (ja) * 2010-06-30 2014-01-29 住友精化株式会社 合成樹脂用安定化剤、該安定化剤を含有する合成樹脂組成物および樹脂部材

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DE1932894A1 (de) * 1969-06-28 1971-01-28 Basf Ag Metallkomplexfarbstoffe
US5962657A (en) * 1996-12-20 1999-10-05 Ciba Specialty Chemicals Corporation Complex polymethine dyes and their use
EP1130584A2 (en) * 2000-02-28 2001-09-05 Mitsui Chemicals, Inc. Dipyrromethene-metal chelate compound and optical recording medium using thereof
US6376664B1 (en) * 1999-03-17 2002-04-23 The Ohio State University Cyclic bis-benzimidazole ligands and metal complexes thereof

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US6162520A (en) * 1997-09-17 2000-12-19 Mitsui Chemicals, Inc. Optical recording medium and dipyrromethene metal chelate compound for use therein
WO2002082438A2 (en) * 2001-03-21 2002-10-17 Ciba Specialty Chemicals Holding Inc. Optical recording materials having high storage density
EP1719126A1 (en) * 2004-02-23 2006-11-08 CIBA SPECIALTY CHEMICALS HOLDING INC. Patent Departement Optical recording materials having high storage density

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DE1932894A1 (de) * 1969-06-28 1971-01-28 Basf Ag Metallkomplexfarbstoffe
US5962657A (en) * 1996-12-20 1999-10-05 Ciba Specialty Chemicals Corporation Complex polymethine dyes and their use
US6376664B1 (en) * 1999-03-17 2002-04-23 The Ohio State University Cyclic bis-benzimidazole ligands and metal complexes thereof
EP1130584A2 (en) * 2000-02-28 2001-09-05 Mitsui Chemicals, Inc. Dipyrromethene-metal chelate compound and optical recording medium using thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1710793A1 (de) * 2005-04-05 2006-10-11 Ciba SC Holding AG Metallchelate und ihre Verwendung in optischen Aufzeichnungsmedien mit hoher Speicherkapazität
EP2527404A4 (en) * 2010-01-19 2017-09-13 Sumitomo Seika Chemicals CO. LTD. Composition for ultraviolet ray-absorbable member, and ultraviolet ray-absorbable member comprising same

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US20060159882A1 (en) 2006-07-20
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DE602004001135T2 (de) 2007-04-12
ATE329351T1 (de) 2006-06-15
KR20050115265A (ko) 2005-12-07
JP2006523553A (ja) 2006-10-19
EP1599878A1 (en) 2005-11-30
CN1757066A (zh) 2006-04-05
DE602004001135D1 (de) 2006-07-20
RU2005130516A (ru) 2006-06-27
TW200428381A (en) 2004-12-16

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