WO2007128691A1 - Support d'enregistrement optique a haute efficacite comprenant des paires d'ions organometalliques - Google Patents

Support d'enregistrement optique a haute efficacite comprenant des paires d'ions organometalliques Download PDF

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WO2007128691A1
WO2007128691A1 PCT/EP2007/054027 EP2007054027W WO2007128691A1 WO 2007128691 A1 WO2007128691 A1 WO 2007128691A1 EP 2007054027 W EP2007054027 W EP 2007054027W WO 2007128691 A1 WO2007128691 A1 WO 2007128691A1
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alkyl
halogen
independently
substituted
mono
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Jean-Pierre Bacher
Timothy Parks
Heinz Wolleb
Frédérique Wendeborn
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
Ciba Holding AG
Ciba SC Holding AG
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14—Monoazo compounds
    • C09B45/20—Monoazo compounds containing cobalt
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C09B69/04—Dyestuff salts, e.g. salts of acid dyes with basic dyes of anionic dyes with nitrogen containing compounds
    • C09B69/045—Dyestuff salts, e.g. salts of acid dyes with basic dyes of anionic dyes with nitrogen containing compounds of anionic azo dyes
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/249—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds

Definitions

  • the invention relates to new optical recording materials that have excellent recording and playback quality especially at a laser wavelength of 350-500 nm (for example HD DVDTM or Blu-ray DiscTM standards). Recording and playback can be effected very advantageously with high sensitivity, and the storage density that is achievable is significantly higher than in the case of materials recordable at a higher wavelength, such as around 658 ⁇ 5 nm (DVD-R or DVD+R standards).
  • 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.
  • EP 1 624029, EP 1 630205 and WO 2006/024642 disclose different salts of heterocyclic azo compounds.
  • WO-2006 / 106 1 10 is a patent application according to Art. 54(3) EPC and Rule 64.3 PCT.
  • the invention accordingly relates to an optical recording medium suitable for optical recording with a laser of wavelength below 600 nm, preferably from 350 to 500 nm, comprising a grooved substrate, a reflecting layer and a recording track of width from 100 to 400 nm, preferably from 150 to 250 nm, depth from 10 to 200 nm, preferably from 20 to 90 nm, and pitch from 250 to 430 nm, preferably from 310 to 400 nm, wherein the recording track comprises a compound of formula
  • M 1 is a metal cation in the oxidation state +3, a hydroxy or halogeno metal group wherein the metal is in the oxidation state +4, or an oxo metal group wherein the
  • 3+ 3+ metal is in the oxidation state +5, most preferred Cr or Co ;
  • Zi is a cation selected from the group consisting of cations of the formulae
  • Qi and Q 7 are each independently of the other O or S;
  • Q 2 is O, S, CR20R21 or NR 3 e;
  • Q 3 and Q 5 are each independently of the other O, S or NR51;
  • Q4 is N or CR52;
  • Qe is N, or is CR12 when Q 5 is O or S;
  • Q 8 , Q10 and Q12 are each independently of the other CR 53 R 54 , O, S or NR 5 i;
  • Q 9 and Qn are each independently of the other CR 55 or N ;
  • Ri, R 2 , R 3 and R 4 independently of one another are hydrogen, halogen, R 5 , NO 2 ,
  • R 5 and R 6 independently of one another are unsubstituted or hydroxyl-, halo- or Ci-C 6 alkoxy-substituted Ci-Ci 2 alkyl or C 6 -Cioaryl;
  • R 7 , R 8 , R9, R10, R12, Ri3, Ri4, Ri5, R16, R40, R41 , R42, R44, R45, R46, R47, R48, R49, R50, R 52 and R 55 are each independently of the other H, halogen, OR 56 , SR 56 , NR 5 iR 57 , NR 5 iCOR 58 , NR 5 iCOOR 59 , N R 5i CON R 59 R 60 , NR 5 iCN, OSiR 5 iR 58 R 6 i, COR51, CR 5 iOR 67 OR 68 , NO 2 , CN, COOR 56 , CONR 59 R 60 , SO2R51, SO 2 NR 59 R 60 , SO 3 R 59 ; Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3
  • Rn and R 36 are independently of each other Ci-C 20 alkyl, C 3 -Ci 2 cycloalkyl, Ci-Ci 2 heterocycloalkyl, C 2 -C 20 alkenyl, C 3 -Ci 2 cycloalkenyl, C 4 -Ci 2 heterocyclo- alkenyl, C 2 -C 20 alkynyl, C 7 -Ci 8 aralkyl, Ci-C 9 heteroaryl, C 2 -Ci 7 heteroaralkyl, C 6 -Ci 2 aryl or Ci-Ci 2 alkyl interrupted by from one to five non-successive oxygen and/or sulfur atoms and/or by from one to five identical or different groups NR 5 i , each unsubstituted or mono- or poly-substituted by halogen, OR 56 , SR 56 , NR 5 iR 57 , NR 5 iCOR 58 , NR 5 iCOOR 59
  • Ri 7 , Ris and Ri 9 are each independently of the other H, halogen, OR 56 , SR 56 , OSiR 5 I R 58 R 6 I, CR 5 I OR 67 OR 68 ; Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkenyl or C 2 -C 5 heterocycloalkyl each unsubstituted or mono- or poly-substituted by halogen, OR 56 , SR 56 , NR 5 iR 57 , NR 5 iCOR 58 , NR 5 iCOOR 56 , NR 5 I CON R 59 R 60 , NR 5 iCN, COR 5 I, CR 5 iOR 67 OR 68 , NO 2 , CN, COOR 56 , CONR 59 R 60 and/or SO 2 R 59 ; or C
  • R 20 and R 21 are each independently of the other Ci-Ci 2 alkyl, C 2 -Ci 2 alkenyl, C 2 -Ci 2 alkynyl, C 7 -Ci 2 aralkyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl or C 2 -Ci ihetero- cycloalkyl each unsubstituted or mono- or poly-substituted by halogen, OR 56 , SR 56 , NR 5 iR 57 , NR 5 iCOR 58 , NR 5 iCOOR 56 , N R 51 CON R 59 R 60 , NR 5 iCN, COR 51 , CR 5 IOR 67 OR 68 , NO 2 , CN, COOR 56 , CONR 59 R 60 and/or SO 2 R 59 ;
  • R 20 and R 21 are together C 2 -Ci 2 alkylen, C 2 -Ci 2 alkenylen, C 2 -Ci 2 cycloalkylen or C 2 -Ci 2 cycloalkenylen, one to five non-successive carbon atoms of which can be replaced by oxygen and/or sulfur atoms and/or by identical or different groups NR 5I , C 2 -Ci 2 alkylen, C 2 -Ci 2 alkenylen, C 2 -Ci 2 cycloalkylen or C 2 -Ci 2 cycloalkenylen being each unsubstituted or mono- or poly-substituted by halogen, OR 5 e, SR 5 6, NR51R57, NR51COR58, NR51COOR56, N R51 CON R 59 R 60 , NRsiCN, COR 5 i, CR 5 IOR 67 OR 68 , NO 2 ,
  • R22, R23, R25, R2 6 , R27, R28, R2 9 and Rso are each independently of the other H, halogen, C0R 5 i, NO 2 , CN, SO 3 R 59 ; or Ci-C 6 alkyl, C 6 -Ci 2 aryl, C 7 -Ci 2 aralkyl each unsubstituted or mono- or poly-substituted by halogen, Ci-C 8 alkyl and/or SO 3 R 59 ;
  • R 24 is halogen, COOR 56 , CONR 59 R 60 ; or Ci-C 20 alkyl, C 7 -d 8 aralkyl each unsubstituted or mono- or poly-substituted by halogen, Ci-C 8 alkyl, COR 5 i, COOR 56 , CONR 59 R 60 , OR 56 , CN and/or SO3R31;
  • R 3 i is Ci-Ci 2 alkyl, C 2 -Ci 2 alkenyl, C 2 -Ci 2 alkynyl, C 7 -Ci 2 aralkyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl or C 2 -Ci iheterocycloalkyl each unsubstituted or mono- or poly- substituted by halogen, OR 56 , SR 56 , NR 5 iR 57 , NR 5 iCOR 58 , NR 5 iCOOR 56 , NR 5 I CON R 59 R 60 , NR 5 iCN, COR51, CR 5 iOR 67 OR 68 , NO 2 , CN, COOR 56 , CONR 59 R 60 and/or SO 2 R 59 ;
  • Ri 6 and R 3 i are together with the nitrogen and the carbon atoms joining them together a 5- or a 6-membered ring;
  • R32, R33, R34 and R 35 are each independently of the other H, CH 3 or C 2 H 5 each unsubstituted or mono- or poly-substituted by halogen, OR 62 , SR 62 or NR 43 R 63 ;
  • R 37 and R 38 are each independently of the other H; Ci-Ci 2 alkyl, C 2 -Ci 2 alkenyl, C 2 -Ci 2 alkynyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl or C 2 -Ci iheterocycloalkyl each unsubstituted or mono- or poly-substituted by halogen, OR 62 , SR 62 or NR 43 R 63 ; or C 7 -Ci iaralkyl, C 6 -Ci 0 aryl or Ci-C 8 heteroaryl each unsubstituted or mono- or poly- substituted by Ci-C 4 alkyl, halogen, OR 62 , SR 62 , NR 43 R 63 , COR 63 , NO 2 , CN and/or COOCi-C 4 alkyl;
  • R 39 is COR 43 , COOR 43 , CONR 64 R 65 , CN, SO 2 NR 64 R 65 , SO 2 R 64 or SO3R31; or is Ci-C 4 alkyl mono- or poly-substituted by halogen; R 4 3, R57, R59, Reo, Re4 and R 6 5 are each independently of the others H; Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkenyl or C 2 -C 5 hetero- cycloalkyl each unsubstituted or mono- or poly-substituted by halogen, OR 6 e, SR 6 6, NR 6 iR 63 , CN and/or COOR 6 3; or C 6 -Ci 0 aryl, C 7 -Cnaralkyl or Ci-C 5 heteroaryl each unsubstituted
  • NR 64 R 65 and/or NR 59 R 60 is a five- or six-membered heterocycle which may contain a further N or O atom and which can be mono- or poly-substituted by methyl and/or ethyl;
  • R51, R 58 , R 6 i and R 63 are each independently of the others hydrogen, benzyl; or Ci-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, [C 2 -C 3 alkylen-O-] k -R 77 or [C 2 -C 3 alkylen- NR 78 -Jk-R 77 each unsubstituted or mono- or poly-substituted by halogen;
  • NR 43 R 63 , NR 5I R 57 , SiR 5 iR 58 and/or NR 6 iR 63 is a five- or six-membered heterocycle which may contain a further N or O atom and which can be mono- or poly-substituted by methyl and/or ethyl;
  • R 6 7 and R 68 are each independently of the others benzyl; or Ci-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, [C 2 -C 3 alkylen-O-] k -R77 or [C 2 -C 3 alkylen-NR 7 8-]k-R77 each unsubstituted or mono- or poly-substituted by halogen;
  • k is an integer 1 , 2, 3 or 4;
  • R53 and R 54 are each independently of the other Ci-Ci 2 alkyl, C 2 -Ci 2 alkenyl, C 2 -Ci 2 alkynyl, C 7 -Ci 2 aralkyl, C 3 -Ci 2 cycloalkyl, C 3 -Ci 2 cycloalkenyl or C 2 -Ci ihetero- cycloalkyl each unsubstituted or mono- or poly-substituted by halogen, OR 62 , SR 62 , NR 43 R 63 , NR 63 COR 6 I, NR 63 COOR 62 , NR 63 CONR 64 R 65 , NR 63 CN, COR 63 , CR 63 OR 68 OR 67 , NO 2 , CN, COOR 62 , CONR 64 R 65 and/or SO 2 R 64 ;
  • R 53 and R 54 are together as a pair C 2 -Ci 2 alkylen, C 2 -Ci 2 alkenylen, C 2 -Ci 2 cycloalkylen or C 2 -Ci 2 cycloalkenylen, one to five non-successive carbon atoms of which can be replaced by oxygen and/or sulfur atoms and/or by identical or different groups NR 63 , C 2 -Ci 2 alkylen, C 2 -Ci 2 alkenylen, C 2 -Ci 2 cycloalkylen or C 2 -Ci 2 cycloalkenylen being each unsubstituted or mono- or poly-substituted by halogen, OR 62 , SR 62 , NR 43 R 63 , NR 63 COR 6 I, NR 63 COOR 62 , NR 63 CONR 64 R 65 , NR 63 CN, COR 63 , CR
  • each R 56 or R 62 independently of any other R 56 or R 62 , is R 43 or R 79 ;
  • each R 66 is independently of the others Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkenyl or C 2 -C 5 hetero- cycloalkyl each unsubstituted or mono- or poly-substituted by halogen, NR 6 iR 63 , CN and/or COOR 63 ; or C 6 -Ci 0 aryl, C 7 -Ci iaralkyl or Ci-C 5 heteroaryl each unsubstituted or mono- or poly-substituted by Ci-C 4 alkyl, halogen, NR 6 iR 63 , COR 63 , CR 63 OR 67 OR 68 , NO 2 , CN and/or COOR 6 i;
  • R 69 , R 70 , R 7 i and R 72 are each independently of the other H, Ci-C 4 alkyl, halogen, OR 56 , SR 56 , NR 5 iR 57 , COR 5I , NO 2 , CN or COOCi-C 4 alkyl; or one or more pairs Reg and R 7 o, Rzo and R 7 i and/or R 7 i and R 72 are independently
  • R 73 , R74, R75 and R 76 are each independently of the other H, Ci-C 4 alkyl, halogen, OR 5 6 or SR 5 6, it being possible R 69 to form a 3-, A-, 5- or 6-membered ring with R 73 , R 70 to form a 3-, A-, 5- or 6-membered ring with R 74 , R 7 i to form a 3-, A-, 5- or 6-membered ring with R 76 or R 72 to form a 3-, A-, 5- or 6-membered ring with R 75 ; or R 69 and R 73 , R 70 and R 74 , R 7 i and R 75 or R 72 and R 76 are together NR 5 i, O or S;
  • R 77 and R 78 are each independently of the other methyl, ethyl, vinyl and/or allyl;
  • R 79 is COR 43 , COOR 43 , CONR 64 R 65 , CN, SO 2 NR 64 R 65 or SO 2 R 64 ;
  • Rso, Rsi, Rs2 and R 83 are each independently of the other H, Ci-C 4 alkyl, halogen, OR 56 , SR 56 , NR 5 iR 57 , COR 5I , NO 2 , CN or COOCi-C 4 alkyl; and
  • radicals of the same or different substituents each selected from the group consisting of Ri, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R10,
  • Ri 1 Ri2, Ri3, Ri4, Ri5, Ri6, Ri7, Ri8, Ri9, R20, R2I , R22, R23, R24, R25, R26, R27, R28,
  • R77, R79, Rso, Rsi, Rs2 and R 83 to be bonded to one another in pairs by way of a direct bond or an -O-, -S- or -N(R 78 )- bridge, optionally forming a compound comprising two or three identical or different moieties of formula (I).
  • Ri is more preferably an electron withdrawing substituent (such as NO 2 , CN, SO 2 NH 2 , SO 2 NHCH 3 , SO 2 CH 3 or SO 2 CF 3 ) in para position to the oxygen.
  • Preferred compounds of formula (I) are those of the formulae
  • the anions of the compounds of the formulae (I) are known as salts which can be found, for example, in Ullmanns Encyklopadie der ischen Chemie 23, 381 (4 th Edition 1983) or in the Colour Index 4, 4417 (3 rd Edition 1971 ). Some of them are still novel, but they can be prepared in analogy to the known compounds by methods known per se.
  • the recording laser has more preferably a wavelength of from 370 to 450 nm. Especially preferred is within the UV-A range a wavelength of 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 preferably approximately 405 ⁇ 5 nm.
  • the UV-A range is from 315 to 400 nm, the visible range from 400 to 700 nm.
  • the absorption maximum of the iodide salt of the cation Zi is preferably at a wavelength of up to 545 nm, more preferably from 350 to 520 nm, especially from 420 to 520 nm.
  • the 315 to 700 nm spectrum is most adequately measured at a concentration of 2 ⁇ 10 "4 mol/l in ethanol, or alternatively in dichloromethane if the solubility in ethanol is insufficient, or in N,N-dimethylformamide if the solubilities in both ethanol and dichloromethane are insufficient.
  • Substituents including a plurality of substituents having the same label, are generally independent from each other.
  • Preferred are compounds of formula (I), wherein n is 1 , as well as alternatively compounds of formula (I), wherein n is 2 and Zi ⁇ + consists of two identical or different cations Z/ linked together by way of a direct bond or an -O-, -S- or -N(R 78 )- bridge (further explanations given below).
  • Mi is a cation in the oxidation state +3, a hydroxy or halogen metal cation wherein the metal is in the oxidation state +4, or an oxo metal cation wherein the metal is in the oxidation state +5, of an at least trivalent metal of groups 3 to 15 (formerly groups IIIA to VB), preferably Al 3+ , As 3+ , Au 3+ , Bi 3+ , Ce 3+ , Co 3+ , Cr 3+ , Dy 3+ , Er 3+ , Eu 3+ , Fe 3+ , Gd 3+ , Ho 3+ , Ir 3+ , La 3+ , Lu 3+ , Mn 3+ , Mo 3+ , Nb 3+ , Nd 3+ , Pm 3+ , Pr 3+ , Rh 3+ , Ru 3+ , Sb 3+ , Sc 3+ , Sm 3+ , Ta 3+ , Tb 3+ , Ti 3+ , [TiCI] 3+ ,
  • Alkyl, alkenyl or alkynyl may be straight-chain or branched.
  • Alkenyl is alkyl that is mono- or poly-unsaturated, wherein two or more double bonds may be isolated or conjugated.
  • Alkynyl is alkyl or alkenyl that is doubly-unsaturated one or more times, wherein the triple bonds may be isolated or conjugated with one another or with double bonds.
  • Cycloalkyl or cycloalkenyl is monocyclic or polycyclic alkyl or alkenyl, respectively.
  • Ci-Ci 2 Alkyl can therefore be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methyl-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl.
  • Cycloalkyl can therefore be, for example, cyclopropyl, cyclopropyl-methyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexyl-methyl, trimethylcyclohexyl, thujyl, norbornyl, bornyl, norcaryl, caryl, menthyl, norpinyl, pinyl, 1 -adamantyl or 2-adamantyl.
  • C 2 -Ci 2 Alkenyl is, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1 -yl, 3-buten-1 -yl, 1 ,3-butadien-2-yl, 2-penten-1 -yl, 3-penten-2-yl, 2-methyl-1 -buten-3-yl, 2-methyl- 3-buten-2-yl, 3-methyl-2-buten-1 -yl, 1 ,4-pentadien-3-yl, or any isomer of hexenyl, octenyl, nonenyl, decenyl or dodecenyl.
  • Cycloalkenyl is, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclo- hexen-1 -yl, 3-cyclohexen-1 -yl, 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10)- thujen-10-yl, 2-norbornen-1-yl, 2,5-norbornadien-1-yl, 7,7-dimethyl-2,4-norcaradien- 3-yl or camphenyl.
  • C 2 -Ci 2 Alkynyl is, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1 -pentyn-5-yl, 2-methyl- 3-butyn-2-yl, 1 ,4-pentadiyn-3-yl, 1 ,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2- penten-4-yn-1 -yl, trans-3-methyl-2-penten-4-yn-1-yl, 1 ,3-hexadiyn-5-yl, 1-octyn-8- yl, 1-nonyn-9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.
  • C 7 -Ci 2 Aralkyl is, for example, benzyl, 2-benzyl-2-propyl, ⁇ -phenyl-ethyl, 9-fluorenyl, ⁇ , ⁇ -di methyl benzyl, co-phenyl-butyl, co-phenyl-octyl, ⁇ -phenyl-dodecyl or 3-methyl- ⁇ rj' ⁇ ' ⁇ '-tetramethyl-butyO-benzyl.
  • C 7 -Ci 2 aralkyl is substituted, both the alkyl moiety and the aryl moiety of the aralkyl group can be substituted, the latter alternative being preferred.
  • C 6 -Ci 2 Aryl is, for example, phenyl, naphthyl or biphenyl, always preferred phenyl.
  • Halogen is chlorine, bromine, fluorine or iodine, preferably chlorine or bromine on aryl or heteroaryl and fluorine on alkyl.
  • d-CgHeteroaryl is an unsaturated or aromatic radical having 4n+2 conjugated ⁇ -electrons, for example 2-thienyl, 2-furyl, 1-pyrazolyl, 2-pyridyl, 2-thiazolyl, 2-oxa- zolyl, 2-imidazolyl, isothiazolyl, triazolyl, tetrazolyl or any other ring system consis- ting of thiophene, furan, thiazole, oxazole, imidazole, isothiazole, thiadiazole, triazo- Ie, pyridine, pyrazine, pyrimidine, pyridazine and benzene rings and unsubstituted or substituted by from 1 to 6 substituents, for example methyl, ethyl, ethylene and/or methylene substituents.
  • substituents for example methyl, ethyl, ethylene and/or methylene substituents.
  • 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 wherein R 84 is CH 2 OH, CH 2 OR 43 or COOR 43 .
  • C 3 -Ci 2 Heterocycloalkyl is an unsaturated or partially unsaturated ring system radical, for example epoxy, oxetan, aziridine; tetrazolyl, pyrrolidyl, piperidyl, piperazinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, morpholinyl, quinuclidinyl; or some other C 4 -Ci 2 heteroaryl that is mono- or poly-hydrogenated.
  • ring system radical for example epoxy, oxetan, aziridine; tetrazolyl, pyrrolidyl, piperidyl, piperazinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, morpholinyl, quinuclidinyl; or some other C 4 -Ci 2 heteroaryl that is mono- or poly-hydrogenated.
  • 5- to 12-membered rings are, for example, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, preferably cyclopentyl and especially cyclohexyl.
  • R 54 is H, or together with R 44 is butadienylen either unsubstituted or substituted, preferably unsubstituted or substituted by one or more Ci-C 4 alkyl, halogen, OR 62 , SR 62 , NR 6 iR 63 , CF 3 , NO 2 , CN, COR 63 , COOR 62 , SO 2 R 63 and/or SO 3 R 62 .
  • each R 62 is independently of any other R 62 alkyl or H
  • each R 56 is independently of any other R 56 hydrogen or Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkenyl, C 2 -C 5 heterocycloalkyl or C 7 -Cnaralkyl each unsubstituted or mono- or poly-substituted by OR 66 , SR 66 , NR 6 iR 63 and/or COOR 63 .
  • n is preferably 1 or 2.
  • R 43 and/or R 63 are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, 3-pentyl, n-amyl, tert-amyl, neopentyl, 2,2-dimethyl-but-4-yl, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclobutylmethyl, cyclopentyl, cyclopentylmethyl or cyclohexyl, each unsubstituted or mono- or poly-substituted by fluorine.
  • R53 and R 54 are preferably both methyl, both ethyl or R 53 ethyl and R 54 methyl, or both together 1 ,5-pentylen.
  • Alkyl, alkenyl, alkynyl, cycloalkyl and heterocycloalkyl are generally preferably Ci-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl and epoxyalkyl, respectively. All these further preferences are fully applicable with particular benefits in the case of preferred R 56 and/or R 62 and/or n, too.
  • R 6 i, R 63 , R 67 and R 68 are bonded to one another in pairs by way of a direct bond or an -O-, -S- or -NR 78 - bridge, they are preferably so bonded that a five- or six-membered ring is formed.
  • Another aspect of the invention are compounds of formula (I) wherein two cations or two ligands of the anion are bridged, for example by way of direct bonds or -O-, -S- or -NR 78 - bridges between any substituents in formula (I), it being possible for the bridged ligands to be complexed either with the same metal cation or optionally with different metal cations, there being formed in the latter case oligomers which are, of course, also to be regarded as being subjects of the invention. Bridgings by way of O or N atoms of the cation or anion, either those in the chromophore or those on substituents, are especially advantageous.
  • X may be, for example, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, -(CH 2 ) 6 -, -(CH 2 ) 2 -O-(CH 2 ) 2 -, -(CH 2 ) 2 -NH-(CH 2 ) 2 -, -CH 2 -C(CHs) 2 -CH 2 - or -CH 2 -PC 6 H 4 -CH 2 - :
  • Particularly useful cations of formula (I) are those of the following formulae ( ⁇ ma ⁇ of iodide salts in ethanol):
  • anions and cations are known.
  • the anions and cations as well as the novel salts of formula (I) can be prepared according to or in close analogy to known methods, or according or in analogy to the examples given below. Less common ones of the preferred cations can for example be prepared according to Tetrahedron 42, 699 [1986] or J. Am. Chem. Soc. 63, 3192 [1941].
  • the anions are conveniently used as ammonium or alcali metal salts, and the cations as acetate, halogenide, perchlorate, hexafluorophosphate or tetrafluoroborate salts.
  • the compounds of formula (I) are new.
  • the invention also relates to a compound of formula (I), as well as to a process for the preparation of a thin layer on a substrate, wherein a solution of a compound of formula (I) in a volatile solvent is applied onto the rotating substrate and the solvent is then evaporated.
  • the solution comprises preferably from 0.1 to 20% of a compound of formula (I) in a solvent (preferably an organic solvent) having a boiling point of from 0 to 180°C, more preferably from 50 to 150°C, at 1 bar pressure.
  • the invention also pertains to the use of a compound of formula (I) for the preparation of a medium for optical recording with a laser of wavelength below 600 nm, preferably from 350 to 500 nm, especially from 350 to 450 nm, and to a process for the optical recording or playback of information, wherein a laser beam of wavelength below 600 nm, preferably from 350 to 500 nm, especially from 350 to 450 nm, is focussed onto the recording track of a recording medium comprising a compound of formula (I).
  • the recording layer advantageously comprises a compound of formula (I) or a mixture of such compounds as main component, for example at least 50% by weight, preferably at least 80% by weight, especially at least 90% 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 ⁇ 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 shortest-wavelength flank of the absorption of the entire solid layer is a fraction of the absorption of the pure compound of formula (I) in the entire solid layer at the same wavelength, advantageously at most 1 /3, preferably at most Vs, especially at most Vio.
  • the absorption maximum is preferably higher than 425 nm, especially higher than 460 nm.
  • Stabilisers, 1 O 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 0 38465-55-3], ® lrgalan Bordeaux EL, ® Cibafast N or similar compounds, hindered phenols and derivatives thereof, 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), and also diimmonium salts, ParaquatTM or OrthoquatTM salts, such as ® Kayasorb IRG 022,
  • optical recording media for example from US-5 219 707, JP-A-06/199045, JP-A-07/76169, JP-A-07/262604 or JP-A-2000/272241.
  • They may be, for example, salts of the metal complex anions disclosed above with any desired cations, for example the cations disclosed above, or metal complexes, illustrated, for example, by a
  • concentrations of additives are, for example, from 0.001 to 100% 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 aggregation tendency in the solid is surprisingly low for such compounds.
  • 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 suitable for both low to high and high to low systems.
  • 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-Bnitting 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 below 600 nm, preferably 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 20 to 90 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 300 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 position- ing of the reading head (pick-up) are made possible.
  • the same function can be performed by markings between adjacent grooves (pre-pits). With such geometry, it is advantageously possible to meet the HD DVDTM specifications.
  • 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 60 nm, preferably from 10 to 55 nm, especially from 20 to 50 nm, on the surface ("land") and, depending upon the geometry of the groove, advantageously from 20 to 150 nm, preferably from 30 to 100 nm, especially from 40 to 80 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 13- 15 and of the Sub-Groups 3 - 12 of the Periodic Table of the Elements.
  • the reflector layer is advantageously from 5 to 200 nm thick, preferably from 10 to 150 nm thick, especially from 50 to 120 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 Ci-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.
  • additional layers for example interference layers or barrier layers.
  • 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-O 353 393 of TiO2, SJsN 4 , ZnS or silicone resins.
  • recording media having a plurality of recording layers (for example 2, 3, 4, 5, 6, 7, 8, 9 or 10).
  • a dual layer disk where both recording layers can be recorded and read from the same side can be used: for example Dual Layer HD DVD-RTM featuring 30 GB/side.
  • the instant compounds can be in one or more of the layers, for example in layer (LO), in layer (L1 ) or in both layers (LO) and (L1 ) of a Dual Layer disk.
  • 2P Process uses the following embodiment: transparent substrate / recording material / semi-reflective layer / spacer layer applied by spin-coating and cured through a transparent stamper / second recording layer / reflective layer / adhesive layer / second half disk. Intermediate protective layers can be introduced when required.
  • inverted stack or "reversed stack”
  • transparent substrate / recording layer or “reversed stack”
  • another half-disk with an inverted layer sequence: substrate / reflective layer / recording layer.
  • the two half-disks are then bonded together with an adhesive layer so that the two substrates form the two sides of the final disk.
  • Intermediate protective layers can be introduced at various places when required, for example between the recording material and the adhesive layer. Such technique is described for example in WO 04/021 336 and in WO 04/042717.
  • the groove geometries and layer thicknesses are essentially in the same range as described above, with the difference for the inverted stack half disk that recording is made on-groove.
  • the thickness of the recording layer in the latter case is advantageously from 20 to 150 nm, preferably from 30 to 100 nm, especially from 40 to 80 nm on the groove, and, depending upon the geometry of the groove, advantageously from 30 to
  • 200 nm preferably from 40 to 150 nm, especially from 50 to 100 nm, in the groove.
  • the invention also pertains to an optical recording medium suitable for optical recording with a laser of wavelength below 600 nm, preferably from 350 to 500 nm, comprising a grooved substrate, a reflecting layer and at least two recor- ding tracks, wherein at least one recording track comprises a compound of formula [(Li)M i(L 2 )] m ⁇ Zi ⁇ + (I), or a mesomeric or tautomeric form thereof.
  • 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-O 401 791.
  • 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 or 2,2,3,3-tetrafluoro-1-propanol, 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,
  • the application of the metallic reflector layer is preferably effected by sputtering or by vapour-deposition in vacuo. 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, Wurzburg 1992).
  • CD-Player und R-DAT Recorder Claus Biaesch-Wiepke, Vogel Buchverlag, Wurzburg 1992.
  • the person skilled in the art will be familiar with the requirements.
  • the information-containing medium according to the invention may be 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 d_isc - recordable) in computers, and also as storage material for identification and security cards or for the production of diffractive optical elements, for example holograms.
  • CD-R compact disc - recordable
  • DVD-R digital video d_isc - recordable
  • 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 for recording and reading with 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.
  • 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 0.001 to 0.02 ⁇ 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 0.02 ⁇ m thick.
  • 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).
  • optical recording disks comprising the compounds of formula (I) lead to excellent results when recorded and played back at 405 nm, particularly with respect to the reflectivity, modulation, jitter, PRSNR and/or SbER. As disclosed above, it is possible to use them for high to low recording as well as for low to high recording.
  • the invention also pertains to an instant recording medium, wherein the maximum reflectivity of the recording track after recording is from 14 to 28%, on which track pits are writable with a 405 ⁇ 5 nm laser of power 7 ⁇ 5 mW, and the modulation of the pits measured with a 405 ⁇ 5 nm laser of power 0.4 ⁇ 0.2 mW is at least 30%, preferably from 38 to 60%.
  • the instant optical recording media are thus compatible with the HD DVD-RTM standard.
  • the invention further pertains to an instant recording medium, wherein the reflectivity of the recording track after recording is from 10 to 30%, preferably from 12 to 25%, on which track pits are writable with a 405 ⁇ 5 nm laser of power 5 ⁇ 4 mW, and the modulation of the pits measured with a 405 ⁇ 5 nm laser of power 0.35 ⁇ 0.15 mW is at least 30%, preferably from 38 to 60%.
  • the instant optical recording media are thus compatible with the Blu-ray DiskTM standard, too.
  • the optical properties of the instant compounds change in a fully unexpected way.
  • the imaginary part of the complex index of refraction (k) is readily lowered with high sensitivity, while the real part of the index of refraction (n) remains significant without changing much.
  • this unique combination leads to optical recording systems wherein the reflectivity decreases upon irradiation with a laser of power 5 ⁇ 4 mW having a wavelength of 350-500 nm.
  • Such high to low optical recording medium has preferably a reflectivity of from 10 to 30%, preferably from 12 to 25%, and a reflectivity of from 0 to 20%, preferably from 1 to 15% after irradiation with a laser of power 5 ⁇ 4 mW having a wavelength of 350-500 nm.
  • the compound of formula (I) used in such medium has an index of refraction (n) of 1.5 ⁇ 0.4, especially 1.5 ⁇ 0.25, most preferred 1.5 ⁇ 0.15, with an extinction coefficient (k) of more than 0.20, typically from 0.25 to 0.60, especially from 0.25 to 0.50, most preferred from 0.30 to 0.40 at the laser writing and/or reading wavelength.
  • n index of refraction
  • k extinction coefficient
  • the invention therefore provides an optical recording medium which is compatible with the Blu-ray DiscTM standard, enabling to use existing readers.
  • Example 1 48 g of ORASOL ® orange G (Ciba Specialty Chemicals Inc., humid, around 80% solid contents) are dissolved in 2 liters of methanol and filtered. To this solution is added a solution of 17.5 g MAXILON ® Goldyellow GL (Ciba Specialty Chemicals Inc.) in 500 ml of methanol. The mixture is stirred for 4 hours at 23°C. The dark brown solution is cooled to 10°C, then filtered with suction. The suction- filtered material is washed with ice cooled 500 ml of methanol and dried for 24 hours at 50°C / 10 3 Pa, yielding 33.5 g red product of formula:
  • Example 2 1.5 g of the compound according to example 1 are dissolved in 98.5 g of 2,2,3,3-tetrafluoropropanol and filtered through a 0.2 ⁇ m TeflonTM filter. The dye solution is then applied at 250 rev/min to a 1.2 mm thick, planar polycarbonate disc (diameter 120 mm) and the speed of rotation is increased to 1200 rev/min so that the excess of solution is spun off and a uniform solid layer is formed. After drying at 70°C for 20 minutes, the layer thickness and the complex refractive index of the solid layer are determined by means of spectral transmission and reflection measurements using an optical measuring system (ETA-RTTM, ETA-Optik GmbH, Germany).
  • ETA-RTTM ETA-Optik GmbH, Germany
  • the dye layer has a refractive index n of 1.52 and an extinction coefficient k of 0.37.
  • the photostability is determined with a calibrated xenon lamp (Hanau), the relative decrease in absorption -D 24 measured after 24 hours' irradiation is 4%.
  • Example 76 1.4 g of the compound according to example 1 is dissolved in 100 ml of 2,2,3,3-tetrafluoropropanol and filtered through a 0.2 ⁇ m TeflonTM filter.
  • the dye solution is applied by spin-coating to the surface of a 0.6 mm thick, grooved polycarbonate disc (groove depth 50 nm, groove width 230 nm, track pitch 400 nm) having a diameter of 120 mm.
  • the excess of solution is spun off by increasing the speed of rotation up to 4000 r.p.m.
  • the solvent is evaporated off, the dye remains behind in the form of a uniform, amorphous solid layer, characterized by an optical density of 0.46.
  • Drying is carried out in a circulating-air oven at 7 u0°C for 20 minutes.
  • a vacuum-coating apparatus (SwivelTM, Unaxis) a 120 nm thick silver layer is then applied to the recording layer by sputter coating.
  • An adhesive layer of a UV-curable photopolymer (XD 4760TM, Huntsman) is then applied thereto by spin-coating, and a second polycarbonate disc (0.6 mm thick, 120 mm diameter) is adhesively bonded thereto.
  • the recording characteristics are outstanding and overall meet the specifications of the HD DVD-RTM format.
  • the smallest marks (2T) can be precisely written and detected, leading to particularly good signal asymmetries.
  • Example 77 It is proceeded analogously to example 76, with the difference that the product according to example 1 is replaced by the product according to example 3 .
  • Example 78 It is proceeded analogously to example 76, with the difference that the product according to example 1 is replaced by the product according to example 5.
  • Example 79 It is proceeded analogously to example 76, with the difference that the product according to example 1 is replaced by the product according to example 36.
  • Example 80 It is proceeded analogously to example 79, with the difference that the recording speed is set to 13.22 m s -1 (2x).
  • Examples 81 - 143 It is proceeded analogously to example 76, with the difference that the product according to example 1 is replaced by the products according to examples 4, 7 -9, 12 - 14, 17-35 and 37 -73, respectively.
  • Example 144 5.00 g of 3-ethyl-2-methylbenzthiazolium iodide and 5.45 g of 3- anilinoacrylanilide hydrochloride are introduced into 40 ml of acetic anhydride in a 100 ml multi-necked flask equipped with a magnetic stirrer, thermometer and nitrogen transfer line. The mixture is heated to reflux for 15 minutes, then quickly cooled with an ice bath. 50 ml of tert.-butyl-methylether are added dropwise and the suspension is stirred for 1 hour, then filtered. The residue is washed three times with 20 ml of ice-cold tert.-butyl-methylether then dried at 50°C/2.5 ⁇ 10 3 Pa. Brown crystals of 2-[4-(acetyl-phenyl-amino)-buta-1 ,3-dienyl]-3-ethyl-benzthiazol-3-ium iodide are obtained in 70% yield.
  • Example 145 It is proceeded analogously to example 144, but replacing 3-ethyl-2- methylbenzthiazolium iodide by 3-ethyl-2-methylbenzoxazolium iodide.
  • the product of following formula is obtained:
  • Example 146 It is proceeded analogously to example 76, with the difference that Dual Layer HD DVD-RTM disks comprising two recording layers are made, wherein the outer recording layer (LO) has the same composition as in example 1 , and the inner recording layer (L1 ) consists essentially of the compound of the formula:
  • the disc is constructed following the "inverted stack" manufacturing procedure.
  • the LO half disc is made essentially as described in example 76, with the exception that a 10 nm thick silver layer is applied to the recording layer by sputtering forming a semi-transparent layer.
  • a 120 nm thick silver layer is applied onto a second grooved polycarbonate substrate (groove depth 20 nm, groove width 220 nm, track pitch 400 nm).
  • 2.8 g of the compound of above formula are dissolved in 100 ml of 2,2,3, 3-tetrafluoropropanol and filtered through a 0.2 ⁇ m TeflonTM filter.
  • the dye solution is applied by spin-coating onto the silver layer of the L1 half disc, forming a uniform, amorphous solid layer, with an optical density of 0.65. Drying is carried out in a circulating-air oven at 70°C for 20 minutes. In a vacuum-coating apparatus, a 10 nm thick SiN layer is then applied to the recording layer by DC sputtering. An adhesive layer of a UV-curable photopolymer (XD 4820TM, Huntsman) is then finally applied by spin-coating, and the first LO half-disc is adhesively bonded thereto with its semi-transparent layer in contact with the adhesive.
  • XD 4820TM UV-curable photopolymer
  • Example 147 It is proceeded analogously to example 146, with the difference that the inner recording layer (L1 ) consists of the compound according to example 36 and the outer recording layer (LO) consists of the compound of the formula:
  • the disc is prepared following the "2P" manufacturing method.
  • the LO half-disc is made essentially as described in example 146, with the exception that a 10 nm thick silver layer is applied to the recording layer by sputtering, thus forming a semi- transparent layer.
  • an adhesive layer of a UV-curable photopolymer (XD 4820TM, Huntsman) is applied by spin-coating, and before curing the adhesive a transparent stamper made of ZeonorTM (Zeon Corp., Japan) is stuck to the adhesive.
  • the transparent stamper is removed from the disc, leaving the adhesive layer with a grooved structure (groove depth 60 nm, groove width 220 nm, track pitch 400 nm).
  • 1.4 g of the compound according to example 36 is dissolved in 100 ml of 2,2,3, 3-tetrafluoropropanol and filtered through a 0.2 ⁇ m TeflonTM filter.
  • the dye solution is applied by spin-coating onto the silver layer, forming a uniform, amorphous solid layer having an optical density of 0.4. Drying is carried out in a circulating-air oven at 70°C for 20 minutes. In a vacuum-coating apparatus, a 120 nm thick silver layer is then applied to the second recording layer by sputtering.
  • Examples 148-213 It is proceeded analogously to example 146, with the difference that the product according to example 1 is replaced by the products according to examples 3 -5, 7 -9, 12 - 14 and 17 -73, respectively.
  • Examples 214 -279 It is proceeded analogously to example 147, with the difference that the product according to example 36 is replaced by the products according to examples 1 , 3 -5, 7 -9, 12 - 14, 17- 35 and 37 - 73, respectively.

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Abstract

La présente invention concerne un support d'enregistrement optique qui convient à un enregistrement optique avec un laser d'une longueur d'onde comprise entre 350 et 500nm, plus particulièrement environ 405nm, dans lequel la piste d'enregistrement comprend : des composés représentés par la formule [(L1)M1(L2)]m- Z1n+ (I), ou une forme mésomère ou tautomère de cette dernière, dans laquelle L1 et L2 sont divalents indépendamment l'un de l'autre, de préférence des ligands azo jaunes ou oranges, et au sein de laquelle M1 est un cation métallique à l'état d'oxydation +3 ; un groupe d'hydroxyde ou d'halogène métallique au sein duquel le métal est dans un état d'oxydation +4, ou un groupe oxométallique au sein duquel le métal est dans un état d'oxydation +5 ; m est 1 ; n est un nombre entier 1,2 ou 3 ; et Z1 est un cation choisi à partir d'un choix de chromophores organiques dont l'absorption maximale se trouve principalement dans la gamme jaune à orange.
PCT/EP2007/054027 2006-05-05 2007-04-25 Support d'enregistrement optique a haute efficacite comprenant des paires d'ions organometalliques Ceased WO2007128691A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP06113573 2006-05-05
EP06113573.7 2006-05-05
EP06113742 2006-05-10
EP06113742.8 2006-05-10

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WO2007128691A1 true WO2007128691A1 (fr) 2007-11-15

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TW (1) TW200746132A (fr)
WO (1) WO2007128691A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP6201377B2 (ja) * 2013-04-01 2017-09-27 ソニー株式会社 光記録媒体

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998032802A1 (fr) * 1997-01-27 1998-07-30 Ciba Specialty Chemicals Holding Inc. Chromophores solubles presentant des groupes de solubilisation
US5958650A (en) * 1996-12-20 1999-09-28 Ciba Specialty Chemicals Corporation Complex polymethine dyes and their use
EP1170339A2 (fr) * 2000-07-05 2002-01-09 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Colorants styryliques
JP2005305836A (ja) * 2004-04-21 2005-11-04 Tdk Corp 光記録材料及び光記録媒体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5958650A (en) * 1996-12-20 1999-09-28 Ciba Specialty Chemicals Corporation Complex polymethine dyes and their use
WO1998032802A1 (fr) * 1997-01-27 1998-07-30 Ciba Specialty Chemicals Holding Inc. Chromophores solubles presentant des groupes de solubilisation
EP1170339A2 (fr) * 2000-07-05 2002-01-09 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Colorants styryliques
JP2005305836A (ja) * 2004-04-21 2005-11-04 Tdk Corp 光記録材料及び光記録媒体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 2003, no. 12 5 December 2003 (2003-12-05) *

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TW200746132A (en) 2007-12-16

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