TW200805362A - High capacity optical storage media comprising organometallic ion pairs - Google Patents

Abstract

The invention, wherein the recording track comprises a compound of formula or a mesomeric or tautomeric form thereof and are each independently of the other or; is or C2-C8heteroaryl unsubstituted or mono-or poly-substituted by R47, R48, R49, and/or R50; Q1 and Q6 are each independently of the other O or S; Q2 and Q4 are each independently of the other O, S or NR51; Q3 is N or CR52; Q5 is N, or is CR14 when Q4 is O or S; Q7 is O, S, CR22R23 or NR35; Q8 and Q10 are each independently of the other CR53R54, O, S or NR55; Q9 is CR43 or N; Q11 is CR56 or N; Q12, Q14 and Q16 are each independently of the other CR57R58, O, S or NR51; Q13 and Q15 are each independently of the other CR59 or N. The structures of the cations and the substituents are defined in the description. The invention also pertains to the use of compounds of the formula (I) in optical recording with a blue laser as well as to optical recording processes wherein pits of either lower or higher reflecticity are written on a track comprising compounds of the formula (I). Hence, the invention finally also relates to an optical recording medium comprising a recording dye which is bathochromic as compared with the laser wavelength, on which medium pits of lower reflectivity are written on a higher reflectivity track.

Description

200805362 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a novel optical recording material having good recording and playback quality, especially at a laser wavelength of 350_50() 11111 (eg, 5 HD DVD) -RTM or Bhi-rayDiscTM standard). Recording and playback can be dominated by high sensitivity, and the achievable storage density is significantly higher than that of higher wavelength recordable materials, such as about 658 um 5 nm (DVD-R or DVD+R standard). In addition, the materials of the present invention have very good storage characteristics, both before and after record 10, even under very severe conditions, such as exposure to sunlight or fluorescent, heat and/or south humidity. It is relatively simple to manufacture and can be replicated immediately, using a general coating method such as spin coating. WO 04/088 649 discloses an optical recording medium comprising a wide range of selected metal complex dyes and recorded at a laser scale of about 658 ± 5 nm. However, the exemplary dyes are not suitable for use with short-wavelength laser beams, such as 405 ± 5 nm.

WO 06/018 352 is a patent application filed in accordance with the PCT Application No. 54(3) EPC and Rule 64.3 PCT, which is related to an optical recording medium and can be read by a laser having a wavelength of about 658 m 5 nm (DVD-R or DVD). +R). 20 It has now been found that certain selected dyes are widely included in % 〇 04/088 649 or WO 06/018 352, and are particularly suitable for use in short wavelengths when the disc is constructed differently. EP-1 265 233 discloses an optical information medium suitable for use in the 4〇5 nm record, which uses a mixture of two dyes, one of which absorbs 0.007 at 200805362 at the recorded wavelength. Example 1 uses a mixture of cyanogen and anthraquinone dyes. US-2002/0 034 605 discloses an optical recording medium in which the dye is absorbed at a higher wavelength than the written light. The cyanide dye was recorded at 390-450 nm. US-2004/0 058 274 and WO 02/102 598 follow the same general idea as having a trimethinecyanine dye. EP-1 587 092 and EP-1 587 093 disclose low to high recording media for 405 nm, using color component C (see Figure 1, Figure 1), with the following formula

Its maximum absorption wavelength is 542 nm in sterols. 10 WO 2005/123 842 discloses the use of specific hemicynin dyes having inorganic anions in optical recording media, which are suitable for use in the blue laser range. However, there are still no prior art techniques that can be completely satisfactory. In addition, 'the same recording dye does not meet all the blue laser standards, which is highly desirable for 15 people. Because of the conversion from one recording dye to another, it represents a considerable amount of development work, and the time to clean the production line, and A parent dye must be registered and meet each standard. It is also not desirable to produce two dyes simultaneously in parallel in the same machine. A surprisingly significant improvement has been found, using the anionic and heterocyclic cations disclosed in WO 04/088 649 7 200805362, which is lighter than previously assumed.

Hs9 .CH (hypsochromical) (eg

Its UV/VIS maximum I CH absorption is at 555 nm in ethanol). Due to the unique optical properties of the sample compounds, high to low, and low to high recording modes, it is surprising that the same recording dye can be used, thus meeting the two criteria. SUMMARY OF THE INVENTION Accordingly, the present invention is directed to an optical recording medium suitable for optical recording with a laser having a wavelength of less than 600 nm, preferably 350 to 500 nm, comprising a grooved substrate and a reflective layer. And a recording pass, width 10 from 100 to 400 nm, preferably from 150 to 250 nm, depth from 10 to 200 nm, preferably from 20 to 90 nm, distance from 250 to 430 nm, preferably from 310 to 399.9 nm, where the record contains a compound of the formula

3 RZ; (I), or its meso or tautomeric form, wherein 15 Mi is a metal cation, hydroxyl or halogen metal group in the oxidation state of +3, wherein the metal has an oxidation state of +4, Or an oxygenated metal group, wherein the metal has an oxidation state of +5; Z! is a cation having n positive charges, and the iodide salt has an absorption band of UV-A or visible light 8 200805362, and the absorption maximum is located at At a wavelength of 350 to 550 nm, wherein the cation is selected from the group consisting of cations of the formula:

9 200805362

N^N-

I /C_- G3u| d 43

3, the heart is R

Q R 45

R 46

Q

In: 13 ^46N^i: or, 〇Γ4ν_ <丨

R C 14 G4

R

R 16 is R18 ~ or c2-ca substituted, or R47, R48, R49 and na- or polysubstituted heteroaryl;

Each of Ql and Q6 is independently 〇 or s; (^ and 仏 are each unique, the ground is Ο S or NR51, Q4N or Cr52; q^n, or CR14, 'Q4 is 0 or 3 ; Q7 is 0, S, CR22R23 or nr35, · Q^Q10 each; are independently CR53R54, Ο, S or nr55; q9 is Cr4^n; qih CR5dN 'Ql2, Qi4 and Q16 are each independently Is CR57R58, 〇, 10 10 200805362 or NR51; each of Ql3 and Ql5 is independently CR59 or N; R!, R3, R4, R5, 117 and 118 are each independently Η, halogen, OR6〇 , SR60, NR41R55, NR55COR61, 〇SiR55R61R62, c〇R55, CR55OR6i〇R62, N〇2, CN, COOR60, CONR63R64, so2r55, 5 S02NR63R64, S03R63; CrQ base, c2_c6 base, c2_c6 alkynyl, C3-C6 a ring-based group, a succinyl group or a C2-C5 heterocyclic group, each unsubstituted or mono- or polysubstituted by halogen; or a C7_Cn aralkyl group, a c6_c10 aryl group, or a CrC8 heteroaryl group, each They are unsubstituted or mono- or poly-substituted by alkyl, halogen, OR60, SR60, NR41R55, COR55, N02, CN and/or COOCi-C^10 alkyl; R2 and/or 1 are 〇, S Or NR65; R9, Rio, Rll, R12, Rl4, Rl 5. Rl6, Rl7, Rl8, R38, R39, R40, R44, R45, R46, R47, R48, R49, R50, R52 and R59, each of which is independently Η, i, OR66, SR66, NR51R67, 15 NR51COR68 ^ NR5iCOOR69 ^ NR5iCONR69R7〇' NR51CN ^ OSiR51R68R71, C0R51, CR51OR68OR71, N02, CN, COOR66, CONR69R70, SO2R51, SO2NR69R70, SO3R69, Ci_C6 alkyl, c2-c6 alkenyl, c2-c6 alkynyl, 〇: 3 6 cycloalkyl, 〇3 <6 cycloalkenyl or c2_c5 heterocycloalkyl, each unsubstituted, or via i, OR66, SR66, 20 NR5iR67 ' NR5iCOR68 ' NR51COOR66 ' NR51CONR69R70 ^ NR51CN, C0R51, CR51OR68OR71 , N02, CN, coor66, CONR69R7 and/or S02R69 mono- or poly-substituted; or, CVCu aralkyl, c6-c1G aryl or crc8 heteroaryl, each unsubstituted or crc4 alkyl , halogen, OR66, SR66, NR51R67, C0R51, N02, 11 200805362 CN and/or COOCrC4 alkyl mono- or poly-substituted;

Rl3 and ruler 35 are each independently CrC2 alkyl, C3-C12 cycloalkyl, CrC12 heterocycloalkyl, C2-C2G alkenyl, (: 3-(:12cycloalkenyl, c4_c12 heterocycloalkenyl) a C2-C20 alkynyl group, a C7_Ci8 aryl group, a Q-C9 heteroaryl group, a C2-C17 5 heteroaryl group, a C6-Cn aryl group or a CrC12 alkyl group, and one to five discontinuous oxygen and/or Or a sulfur atom, and/or one to five groups identical or different from nr51, each unsubstituted or via halogen, OR66, SR66, NR5iR67^NR51COR68^NR5iCOOR69 > NR51CONR69R70^NR51CN, OSiR51R68R71, COR51, CR51OR68OR71, N02, CN, 10 coor66, conr69r7〇, so2r51, so2nr69r7〇, S03R69 mono- or poly-substituted; R19, R2〇 and R21 are each independently Η, halogen, OR66, SR66, OSiR51R68R71, CR51OR68OR71; CrQ alkyl, C2-C6 alkenyl, CVC6 alkynyl, (: 3 < 6 cycloalkyl, 〇 3 < 6 cycloalkenyl or c2-c5 heterocycloalkyl, each of which is unsubstituted, or Halogen, OR66, SR66, NR51R67, NR51COR68 λ NR5iCOOR66 ' NR5iCONR69R7〇^ NR51CN - COR51, CH51〇R68〇R71, n〇2, CN, COOR66, conr69r7 0 and / or s 〇 2R6 single or more _ substitution; or c7_Cll aralkyl, c6_Cl0 aryl or Q-C8 heteroaryl, each unsubstituted, or by Cl-c4 alkyl, halogen, 20 OR66, SR66, NR51R67, (:01151 and / or COOCrQ alkyl single- or poly-substituted; R22 and R23 are each independently CrCl2 alkyl, c2-c12 alkenyl, c2-c12 fast radical, c7_Ci2 aromatic Alkyl, c3_Ci2 cycloalkyl, c3-Cl2 cycloalkenyl, or C^Cu heterocycloalkyl, each unsubstituted, or via halogen, 〇r66, 12 200805362 SR66 ^ NR5iR67 > NR5iCOR68 ^ NR5iCOOR66 ^ NR5iCONR69R7〇^nr51cn, COR51, CR51OR68OR71, N02, CN, COOR66, CONR69R70 and/or s〇2R69 mono- or poly-substituted; or R22 and R23 together are C2_C12 alkylene, (: 2-(:12-eneene) a 5 C 2 —cn cycloalkylene group or a c 2−12 12 cycloalkenylene group in which one to five discontinuous carbon atoms may be bonded to oxygen and/or sulfur atoms, and/or to NR 51 , c 2 -c 12 alkylene groups, CVC n ia Alkenyl, c2-C12 cycloalkylene, or c2-c12 cycloalkenylene substituted with the same or different groups, each unsubstituted, or via halogen, hydrazine R66, SR66> NR51R67-NR5iCOR68^ NR5iCOOR66> NR5iCONR69R7〇^ 10 NR51CN, COR51, CR51OR68OR71, N02, CN, COOR66, CONR69R70 and/or S02R69 single- or multi-substituted; R24, R25, R27, ruler 28, ruler 29, R30, R31 and R32, each All independently are 11, halogen, (: 01151, :^02, 0^, 3031169; or (: 1-(:6 alkyl, C6_C12 aryl, C7-C12 arylalkyl) each without Substituted, or mono- or poly-substituted by halogen, 15 crc8 alkyl, and/or so3r69; rule 26 is halogen, 0: 〇〇1166, (: €^11691170; or (: 1-(:20 alkyl, (37-0:18 aralkyl, each unsubstituted or mono- or poly-substituted by halogen, CrC8 alkyl, COR51, COOR66, CONR69R7, OR66, CN, and/or s〇3R69; 20 is known as a ^2, C2-C12 alkenyl, (: 2-(: 12 alkynyl, C7-C12# alkyl, CrCi2 cycloalkyl, Cs-Cn cycloalkenyl, or C2-Cn heterocycloalkane) Base, each unsubstituted, or via halogen, hydrazine, R66, sr66, nr51r67, NR5iCOR68 - NR51COOR66 - NR51CONR69R70 > NR51CN -COR51, CRmORmOR^, N02, CN, COOR66, CONR69R70, 13 200805362 and / or S02R69 - or more · replaced; or Ri4 and R33 together with nitrogen and carbon atoms form a 5- or 6-membered ring; R34 is Η, CH3 or C2H5, each unsubstituted, or halogen, 5 〇R60, SR60 or NR41R55 Mono- or poly-substituted; each of R6 and R37 is independently Η; CrC12 alkyl, 〇2 <12 alkenyl, yl, CrCi2 cycloalkyl, C3_C12 cycloaliphatic, or C2-Cu heterocyclic Bases, each unsubstituted, or mono- or polysubstituted by halogen, 〇r6〇, §6〇 or nr41r55, or c7-cu aralkyl, c6_Cl0 aryl or Cl_C8 10 heteroaryl, each Neither unsubstituted or mono- or poly-substituted by CrC4 alkyl, halogen, hydrazine R60, SR6, NR41R55, COR55, N02, CN, and/or C00CrC4; R4I, 63, R64, R67 Each of R69 and R70 is independently Η; C-C6, C2_C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 15 cycloalkenyl, or C2-C5 heterocycle Alkyl groups, each unsubstituted, or mono- or poly-substituted with halogen, OR72, SR72, NR55R62, CN and/or COOR55; or C6-CiQ aryl, C7-C11 aryl or C1-C5 Heteroaryl, each unsubstituted, or via CrC4 alkyl, halogen, OR72, sr72, nr55r61, COR55, CR55OR61OR62, N02, CN and/or COORd- or poly-substituted; 20 or NR63R64 and/or NR69R7G are five- or six-membered heterocyclic rings, which may further comprise an N or a ruthenium atom, And it may be mono- or poly-substituted via methyl and/or ethyl; each of R42, R43 and R56 is independently hydrazine, halogen, OR60, SR60, NR41R55, NR55COR61, NR55COOR63, NR55CONR63R64, NR55CN, OSiR55R61R62, COR55, CR55OR61OR62, N02, CN, 14 200805362 COOR6. , C〇NR63R64, SO2R55, s〇2NR63R64, so3r63, PO(OR55)(OR61); CrC6 radical, CVc6 dilute, C2-C6 alkynyl, Crc6 cycloalkyl, CVC6 cyclodecyl, or CrC5 heterocyclic Base, each unsubstituted, or via halogen, 〇r60, sr60, NR41R55, NR55COR61, 5 NR55COOR60, NR55CONR63R64, NR55CN > COR55, CR55OR61OR62, n〇2, CN, coor60, conr63r64, and/or so2r63 - or poly-substituted; or C7-Cn aralkyl, CVCh) aryl or (^-(:8 heteroaryl, each unsubstituted, or via CrC4 alkyl, halogen, OR60, SR6() , nr41r55, con55, N02, CN and/or COOCrC4 alkyl mono- or poly-10 substituted; or one or more pairs R9 and R10, R10 and Ru, Rn and R12, ruler 14 and R15, Rh and R2G, R14 And R21, R15 and R16, 1115 and 1119, Rl^R2〇, 1116 and 1117, R16 and r52, r17 and ri8, Rl7 and r2〇, r17 and r8 and R33, R18 and R52, R2 and R52. , R2^Rs2, R2々r25, Han" and heart, 15 R29 and R3〇, R30 and R31, R3^r32, "and", R42 and ', heart and R56, R44 and R59, and / or ruler 47 R48, these pairs are independent of each other and are bivalent with the following formula Group combination R74 x77/' x73

R 75 ^80^76 '74

R. or

77/^73 74

78

R79R75, thus bonding with it - adjacent carbon atoms form benzene, cyclohexene, cyclohexadiene, cyclopentadiene, or cyclopentene, R51, R55, R6i, R62, R68 and R71 are each independently知15 20 200805362 benzyl; or CrC4 alkyl, c2-C4 alkenyl, c2-c4 alkynyl, [c2-c3 alkylene CHk-Rw, or [c2-c3 alkylene-NR82-]k-R81 , each unsubstituted, or mono- or poly-substituted by halogen; or NR51R67, 51r68, NR41R55, and/or NR55R61 is a five or six 5-membered heterocyclic ring, which further comprises an N or a ruthenium atom, It may be mono- or poly-substituted by methyl and/or ethyl; each of R53, R54, R57 and r58 is independently CrC12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, c7-C12# Alkyl, c3_c12 cycloalkyl, c3-c12 cycloalkenyl or c2-cn heterocycloalkyl, each unsubstituted, or halogen, 10 OR60, sr60, nr41r55, NR55COR61, NR55COOR60, NR55CONR63R64, NR55CN, COR55, CR55OR61OR62, N02, CN, COOR60, CONR63R64 and/or S02R63 mono- or poly-substituted; or R53 and R54, and/or R57 and R58 together (: 2-(:12 alkylene, 〇2-(: 12 alkenylene, c2_c12 cycloalkylene Or a c2-c12 cycloalkenylene pair, one to five non-contiguous carbon atoms may be substituted by an oxygen and/or sulfur atom, and/or with NR55, (:2-(:12 alkylene, (:2- (: 12 alkenylene, (: 2-(: 12-cycloalkylene, or c2-c12 cycloalkenylene substituted with the same or different groups, each unsubstituted) or halogen, OR60, SR60 , NR41R55, NR55COR6I, NR55COOR6〇, NR55CONR63R64, NR55CN, COR55, 20 CR55OR61OR62, N02, CN, COOR60, CONR63R64&/ or so2r63 single- or multi-substituted; each R60 or R*66, independent of any other ruler 60 or 66' is R41 or 65; r65 is cor41, coor41, CONR63H64, CN, so2nr63r64 or S02R63; 16 200805362 R72 'is independent of any other r72, each independently Ci-C6 alkyl, C2-C6 Alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, or C2_C5 heterocycloalkyl, each unsubstituted, or halogen, NR55R62, CN and/or CO〇 R55 mono- or poly-substituted; or C6-C10 aryl, C7-Cu aralkyl 5- or CrC5 heteroaryl, each unsubstituted, or via CrC4 alkyl, halogen, NR55R61, COR55, CR55OR61OR62, N〇2, CN and/or COOR62 mono- or poly-substituted; R73, R74, R75 and R76 are each independently Η, CrC4 alkyl, halogen, 〇R66, SR66, NR51R67, COR51, N02 , CN, or COOCrC^ 10 alkyl; or R73 and R74, R74 and R75, and/or one or more of R75 and R76 are ^83 R84〆, independently

86 or, bonded, thus forming a benzene or a partially or fully saturated Bu ring with two adjacent carbon atoms bonded thereto; R77, R78, R79 and R8 are each independently I·!, CVC4 alkyl, halogen, 0R66 or SR66, R73 can form a 3-4, 5 or 6-membered ring with R77, R74 can form a 3-, 4-, 5- or 6-membered ring with R%, and R?5 can form 3_ with R8G. , heart, 5_ or 6-membered ring, or r76 can be combined with 'form 3_, 4_, 5 Cheng & element ring; or ^ and ~, R74 and r78, r75 and r79, or r76 and R8〇 together for 胤51 , 〇 or § ; each of the two is independently methyl 'ethyl, vinyl, and / or allyl; each of the feet 83, R84, R85 and R86 is independently Η, Ci_C4 Institute, 17 200805362 Halogen, OR66, SR66, 5 paws 7, c〇R5, N〇2, CN, or C〇〇Ci-C4 alkyl; may be the same or different substituents - or multiple free Bases, each selected from *Ri, R3, r4, R5, R7, R8, r9, Ri. ,

Rll, R12 5 R13 R24 Ruler 38 R49 ^63 10 Rsi , Rl4 , Rl5 '16, R17, Rl8, R19, R20, r21, R22, R23, R25, R26 ' R27, R28, R29, R30, R31, R32 , R34, R35, R39, R40 ' R41, R42, R43, R44, R45, R46, R47, R48, R5O, Ruler 51 ' R53, R55, Ruler 56, R57, R59, Ruler 60, R61, Ruler 62 , R65, Ruler 66 ^ 67 Λ 68, Rule 69, R72, R73, R74, R75, R76, R83, Ruler 84, and R86, can be paired with the other by direct key A compound is selectively formed via a _〇_, -S- or -N(R82) bridge, which comprises two or three identical or different fragments of formula (1); k is 1, 2, 3 Or an integer of 4; n is an integer 丨, 2 or 3. The recorded laser preferably has a wavelength of 370 to 450 nm. It is particularly preferred to be in the UV-A range with a wavelength of 37 Å to nm, especially about 38 angstroms, or 390 to 43 〇 nm at the edge of the visible range, more preferably about 405 Å to 5 nm. The UV-A range is 315 to 4 〇〇 nm and the visible range is 4 〇〇 to 7 〇〇 nm. The maximum absorption wavelength of the cationic Zl iodide salt is at most 545 rnn, more preferably 350 to 520 nm, especially 42 to 520 nm. The spectrum of 315 to 700 nm is 20 optimal 'measured at a concentration of 2.10_4 mol/l, in ethanol, or in di-methane, if the solubility in ethanol is insufficient, or N,N-dimethylformamide In the case, if the solubility in ethanol and dichloromethane is insufficient. Substituents, including a plurality of substituents having the same label, are generally independent of one another. Preferred is a compound of the formula (1), wherein η is 1, or the compound of the formula (1) is 18 200805362, wherein η is 2, and z, is composed of two identical or different cations Z/, which are directly bonded or 〇 _, -S- or 氺 (r82)_ bridge mode combination. Μι is a cation, the oxidation state is +3, a radical or a halogen metal cation, wherein the metal oxidation state is +4, or an oxygenated metal cation, wherein the gold 5 is in an oxidation state of +5, and is at least a 3rd to 15th a trivalent metal of the family (IIIA to VB), preferably Al3+, As3+, Au3+, Bi3+, Ce3+, Co3+, Cr3+,

Dy3+, Er3+, Eu3+, Fe3+, Gd3+, Ho3+, Ir3+, La3+, Lu3+, Mn3+, Mo3+, Nb3+, Nd3+, Pm3+, Pr3+, Rh3+, RU3+, Sb3+, Sc3+, Sm3+, Ta3+, Tb3+, Ti3+, [TiCl]3 +,[Ti〇H]3+, Tm3+, V3+, 10 [V〇]3+, W3+, Y3' Yb, [ZrC1]3+ or [Zr0H strict, best in ten or

Cr3+. The alkyl, alkenyl or alkynyl group can be straight or branched. The alkenyl group is a mono- or poly-unsaturated alkyl group containing two or more double bonds separated or in common. An alkynyl group is an alkyl or a dilute group having one or more diunsaturated groups wherein the triple bond can be separated or shared with another triple bond or double bond. The cycloalkyl or cyclodecyl group is a monocyclic or polycyclic pendant or alkenyl group, respectively. C--Ci2 alkyl may be, for example, anthracenyl, ethyl, n-propyl, isopropyl, η-butyl, second-butyl, isobutyl, tert-butyl, 2-fluorenyl -butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, hexyl, heptyl, 2〇n-octyl, 1,1,3,3-tetra Butyl, 2-ethylhexyl, anthracenyl, fluorenyl, undecyl or dodecyl. Thus, the 'C^-C^2 ring-based group can be, for example, 'cyclopropyl, cyclopropyl-methyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexyl-fluorenyl, trimethylcyclohexyl, side Thujyl, borneol, borneol, orthoquinone | n〇rcaryl, 19 200805362 cararyl, menthyl, n〇rpinyl, pine oil riding — ^, 1-adamantyl or 2-adamantyl. The C2-CW group is 'for example' vinyl, allyl, 2-propenyl, 2-butan-1-yl' 3-butene small group, u-butadiene_2-yl, 2-pentyl , 3-penten-2-yl, 2-indenyl-butenyl, 2-hydrazino-3-butenyl-methyl-2-butene, ls4•pentane, or Any of the isomers of hexyl, octyl, sulfhydryl, decenyl or dodecenyl. 10 15 20 C3_Cl2 cycloalkenyl is, for example, cyclobuten-1-yl, 2-cyclopentene small group, 2-cyclohexene] group, 3·cyclohexylene] group, 2,4 ring Two private base, ¥ mint " · base, 4 called cedarene _1G_ base, 2 _ original borneol 丄 · base, 2, 5 _ original borneol dilute + base, mouth · dimethyl from the original 楷Burn the second thin (deep let dien) · 3- base or! ^Base (camphenyi). The c2-c12 alkynyl group is, for example, a c-block _3_ group, an i-butynyl group, a b-butyl group, a :=, a 1-hexyl-6-yl group, a cis_3_methyl·2 dice... ^ ^ , 丞I3·hexyne alkyl group, b octyne _8_ group, azuldinyl winter group, 1_癸 block-10-yl group, or 1-tine block _12_ group. C7-c-octyl dimethylation group, phenyl-butyl group, phenyl group _ twelve group, or methyltetramethyl _ butyl bismuth =1 咖 基 代 代 代 代 代 代The square group m may be substituted, and the latter is preferably substituted. The base is 'for example, 'phenyl, zeoliyl or bisphenyl, preferably benzene 20 200805362 halogen is chlorine, desert, fluorine or angstrom, preferably Chlorine or on an aryl or heteroaryl group, fluorine on a burnt group. CVC9 heteroaryl is an unsaturated or aryl radical having, for example, +2 co-rotating π-electrons, such as 2-mercapto, 2 - mercapto, 丨-pyrazolyl, 2^ butyl, 5.2-thiazolyl, 2-oxazolyl, 2-imidazolyl, isothiazolyl, triazolyl, tetrazolyl' or any other Cyclosporin ' consists of η 塞 phen, ϋ 喃 嗟, 嗟 坐 sit, chew saliva, imidazole, isothiazole, thiadiazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine and benzene ring, and Substituted, or substituted with 1 to 6 substituents, for example, methyl, ethyl, vinyl, and/or nonenyl substituents. 10 In addition, aryl and aralkyl groups may also be bonded to the aroma of the metal. Group,

Fe2+ is, for example, a metallocene form of a transition metal, more preferably <>

Fe2+ pe2+ Fe + wherein R87 is CH2〇H, CH2OR41 or COOR41. ^/^ Heterocycloalkyl is an unsaturated or partially unsaturated ring system free of 15 groups such as epoxy, oxetan, aziridine; tetrazolyl, pyrrolidine Base, benzylidene, piperazinyl, imidazolinyl, ° ratio of 0, oxazolidinyl, morphinyl, quinolidine; or some other mono- or poly-hydrogenated (^-0 : 12heteroaryl. The t to 12-membered ring is, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclo 20 octyl group, preferably a cyclopentyl group, and more preferably a cyclohexyl group. 21 200805362

/C:: .0-- 0 <ι N... and/or N-better is independently

. G! is best equal to G2. More

G3^?+ R4T<\ X VN R4T<f^f preferably, I represents Ql3, b or <, wherein CR^R54 is preferably CrC6 alkylene, or CrC6 cycloalkylene, more preferably Cyclohexylene, especially 2-butylene, wherein R53 and R54 are together = 1,5-pentylene, or R53 = methyl / R54 = ethyl). Q8 is preferably S. The quinoid structure having a double bond on R2 and R6 is, of course, the only racemic form of the compound of formula (1), which is the most similar structure shown on the spectral data. Further, 112 or 116 may also attract a phenyl azo group having a single bond, 10 and a negative charge on R2 or R6, which may be further protonated by mutual change. However, the non-regionalization of electrons via meso-isolation is an essential feature of the invention, with the advantage that the anions can be stabilized via additional bonding to the metal. Therefore, R2 and/or R6 are preferably 0, S, N-CN, or N-S02CF3, and particularly preferably Ο. 15 Whether combined with the preferred R2 and/or 116, or independent, R3 and/or R7 are preferably H, self, N〇2, CN, cor55, coor6〇, so3r60, NCO or SCN 'better η. Independent of the structure of the opposite ion (c〇unter丨(10)), these preferred substituents, surprisingly, produce enhanced light and multiple read stability' when used in optical recording media, whether 22 200805362 Mainly recorded dyes, or other additives for recording dyes. More preferably, when combined with preferred R2, R3, R6, and/or trans7, or independently, it is preferred to include at least one of 〇1 or 〇2' R42 and R56 in the heterocycle, especially R42, For CF3, N02, CN, COR55, COOR6〇, CR55〇R61〇R62, 5 CONR63R64, S02R55, SO3R6G, S02NR63R64, preferably cf3, N〇2, CN, cor55, coor6〇, so2r55 and/or s〇3r60 . Although both r4 and R56 are such preferred groups, preferably only one is such a preferred group, and the other is hydrogen or Ci-C: 4 alkyl, or 1^2 and ruler. 56 is a butadienylen, whether unsubstituted or substituted, preferably 10 unsubstituted, or substituted with CF3, N02, CN, COR55, C00R6G, and/or S03R6G. Preferably, whether in combination with the preferred R2, Rs, R6, R7, R42, and/or R56, or independently, especially in the heterocycle containing ^, the core 8 is 11 or F, or is bonded to R44. It is a butadienyl group, whether unsubstituted or taken for 15 generations, preferably unsubstituted, or one or more. _〇4 alkyl, cyclin, OR60, SR6G, NR55R61, CF3, n〇2, CN, c〇R55, C〇〇R60, S02R55, and/or s〇3R6G are substituted. Preferably, each r6 oxime is independently R6 decyl or H, and each ' _ is hydrogen, or CrC6 alkyl, c2_c6 alkenyl, c2_c6, c3_c6 20% alkyl c3-c6% Alkenyl, c2-c5 heterocycloalkyl, or c7-Cii aryl, each unsubstituted or mono- or poly-substituted by ORdR72, nr55r62, and/or COOR55. The number η is preferably 1 or 2. The cationic and anionic secondary structures contained in formula (1) are independent of each other. However, it is preferred to combine a preferred cation with a preferred anion. More preferably, a compound of formula (I) wherein R4 is hydrogen, hydroxy, CrC4 alkoxy, or Q-C4 alkyl; R42 is nitro or cyanide may be combined with any or all of the above preferences. a group, preferably a nitro group; and/or R55 or R41 is a methyl group, an ethyl group, an η-propyl group, an isopropyl group, an η-butyl group, a 2-butyl group, an isobutyl group, a third-butyl group. , 3-pentyl, η-pentyl, tri-pentyl, neopentyl, 2,2-dimethyl-butan-4-yl, cyclopropyl, cyclopropylindenyl, cyclobutyl, ring Butylmethyl, cyclopentyl, cyclopentylmethyl, or cyclohexyl, each unsubstituted or mono- or poly-substituted by fluorine. Preferably, both R53 and Rm are methyl, both of which are 10 ethyl, or R53 is ethyl and R54 is a fluorenyl group, or a combination of the two is a 1,5-pentenyl group. The alkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group and the heterocycloalkyl group are generally preferably a crc4 alkyl group, a c2-c4 alkenyl group, a c2-c4 alkynyl group and an epoxyalkyl group. All of these preferred applications are applicable and have particular advantages, preferably R2, r3, c:: R6, R7, R42, R43, R56, R60' and / or R66' and N and / or c:: 15 N—, Q8 and n are also. When R55, R61 and R62 are paired with the other, the bonding is preferably a direct bond or a -0-, -S- or -NR82-bridged mode to form a five or six-member defect. Another aspect of the invention is a compound of formula (I), wherein the dication of the dication or anion is bridged, for example, by a direct bond 20 or a _0-, -S- substituent between the substituents of formula (I) Or -NR82-bridged mode, the bridged ligand may be mismatched with the same metal cation, or selectively with a different metal cation, the latter forming a composition, of course, may also be considered as an object of the present invention. It is a special advantage whether it is a luminescent group or a substituent on the bridge of 200805362 or anion on the 0 or N atom. The compound of formula (I) comprising 2 or 3 different fragments, which may be symmetrical, preferably asymmetric, by bonding and/or bridging, may be prepared by a similar method of the known method. In the following examples (which are not intended to be limiting), X may be, for example, -CH2-, -CH2-CH2-, -CH2-0-CH2, or -CH2-NH-CH2-:

The recording medium of the present invention may contain, in addition to the compound of the formula (I), an additional salt such as ammonium chloride, sodium decyl carbonate, sodium iodide, sodium sulphate, sodium decyl sulfate or methyl sulfonate. Sodium, sodium toluene sulfonate, sodium acetate, sodium hexafluorophosphate, cobalt (II) acetate, or cobalt (II) chloride, the ions of which are derived, for example, from the ingredients used. The anion of formula (I) is of the following formula (all have six bond junctions 15 on the metal, with similar length, according to X-ray data): 25 200805362

26 200805362

27 200805362

5

• Interestingly, a compound of formula (I), one or more of its center to the ruler 4, different from the corresponding ruler 5 to 8 and/or wherein G1 is different from 仏, can be easily synthesized by mixing In the preparation of the steps, two different ligands can be simultaneously separated by a metal/a compound having the asymmetric formula (1), and can be isolated by a general method, such as chromatography, preferably using a formula having two identical ligands ( I) In a premix of the compound. 0 (1) interested in the _ sub is the following (U: 28 200805362

H3c-n

N-N (366 nm), CH,

(418 nm),

H5c2 (438 nm),

H

(440 nm),

〇^: OH N-N CHQ

HqC H5C2 CHq 〇-CH0 (449 nm) 5 (462 nm), =\ CH,

HX-N

◦九(492nm), O-CH (466 nm),

(506 nm),

(499 nm)9 9h3 -N \>-N. 'N N CH. NH0 (507 nm), 9h3 -N \>-N. 'N N CH0

HX-N (516 nm), \V^n-C4H9 c2h5 (548 nm), 29 200805362 and

Η3ς +

H3c (542 nm) o Both anions and cations can be prepared analogously to generally known methods, as disclosed in CH-390250, CH-560270, CH-577998, CH-608027, CH-1098125, DE-1083000, DE- 2262780, EP-0029003, GB-1111014, US-3,014,041, 5 US-2004/018723, WO95/01772 and WO04/088649, or similar to the following examples. Also applicable to the salts of formula (1), some examples are not intended to limit the invention,

30 200805362

c 3 F

s

〇 -C4H

〇

〇

〇 cl

F 〇

〇

c 3 H

CH

〇 31 200805362

32 200805362

33 200805362

H

5 H2 f-C-N H 2 c hqc-n

H3ct

FXO.S.

QH3 -N 'N NbhL

F

F H,

S

N N=<>-〇

X%N 〇=(^{

Br

S0oCFo

Br

S

-N and 34 200805362

Certain compounds of formula (i) are novel. Accordingly, the invention is also related to a compound of formula (I) wherein the cation is redundant and comprises a group of the formula:

35 200805362

The invention is also related to the use of a compound of formula (I) for light recording at a wavelength of less than 6 〇〇 nm ', preferably 350 to 500 nm, especially 350 to 450 nm, and related A method of optical recording or information playback wherein laser light having a wavelength of less than 600 nm, preferably 350 to 500 nm, especially 35 to 450 nm, is focused on the recording medium of a recording medium containing the compound of the formula (1). The recording layer preferably comprises a compound of the formula (I), or a mixture of the compounds, as a main component, for example at least 30% by weight, preferably at least 60% by weight, especially at least 80% by weight. Other general compositions can also be included, such as other chromophores (as described in WO 01/75873, or others having a maximum absorption wavelength of 300 to 1000 nm), stabilizers, triple or cold light quenchers ( Luminescence-quenchers), melting point depressants, decomposition accelerators, 15 or any other additive already described for optical recording media. Preferably, a stabilizer or a cold light quencher is added, if desired. When the recording layer contains more chromophores, the amount of the chromophore should preferably be a small amount such that its absorption at the transition point of the shortest wavelength side of the entire solid layer is at the same wavelength. The portion of the solid (1) compound 36 200805362 absorbed in the entire solid layer preferably has a maximum of 1/3, more preferably a maximum of i/5, and particularly preferably a maximum of 1/10. The absorption maximum is preferably above 425 nm, and more preferably above 500 nm. The stabilizer, Or, triple- or cold-light quencher is, for example, an enolate, a phenate, a bisphenolate, a thiolate or a dithiolate containing or 5 S_, or

A metal complex of a nitrogen sub-imine, or a formazan dye, such as bis(4-dimethylaminodithiobenzyl)nickel [CAS N. 38465-55-3], 8Irgalan Bordeaux EL·,® Cibafast N or similar compounds, hindered phenols and their derivatives, such as ® Cibafast AO, 〇-hydroxybenzene 10 yl triazole, or -triazine , or other UV absorbers such as ® Cibafast W, or 8 Cibafast P, or hindered amines (TEMPO or HALS, also known as nitrogen oxides or NOR-HALS), and diimine salts, ParaquatTM or OrthoquatTM salts Classes such as 8Kayasorb IRG 022, ® Kayasorb IRG 040, alternatively, may also be free radical ionic salts such as N, N, N, Nt_tetradecyldibutylaminophenyl)-p-phenylene Amine-ammonium hexafluorophosphate, hexafluoroantimonate or perchlorate. The latter is available from Organica (Wolfen/DE); the 8Kayasorb brand is available from Nippon Kayaku Co. Ltd., and the positive Irgalan and ^Cibafast brands are available from Ciba Specialty Chemicals Inc. Many such structures are known and some are associated with optical recording media, such as US-5 219 707, JP-A-06/199045, JP-A-07/76169, JP-A-07/262604 or JP- Rev. A-2000/272241. They may, for example, be a salt of a metal complex anion formed as described above and a desired cation, such as the cation disclosed above, or a metal complex as shown, 37 200805362, a compound having the formula

ΝΪ---ΝΗ c4h9

Ο This area of technology should be understood by other optical information media or easily identified as additive concentrations that are particularly suitable for a purpose. The additive is used at a concentration of 5 degrees, for example, 0.001 to 1000% by weight, preferably 1 to 50% by weight, based on the weight of the recording medium of the formula (I). The optical recording material of the present invention has an excellent solid amorphous recording layer spectral characteristic. The solids accumulation tendency of such compounds is surprisingly low. It is not desirable to have crystals, and fortunately, no crystals are formed or only negligible amounts are formed. The reflectance of each layer in the write and read wavelength ranges is suitable for low to high, and high to low systems. Due to the good properties of the layers, a fast optical record with high sensitivity, high repeatability and spatially accurate mark boundaries - and very short (2T) marks - can be obtained, and the refractive index and reflectivity of the complex will vary greatly, providing 15 height contrast. The difference between the mark length and the separation distance ("jitter") is quite small, which allows for a high storage density, using a relatively thin recording path with a narrow track space ("distance"). The dye layer is quite good in quality, producing high signal-to-noise ratio (CNR, PRSNR) and surprisingly low error rate (bER or SbER) during playback. 38 200805362 Due to good solubility, including in protic solvents, the solution can be used at high concentrations without problems with the stagnation, such as when storage, the problems encountered in spin coating are greatly reduced. This applies in particular to compounds containing a branch of €3-08. 5 Recording and playback can be performed at the same wavelength, so a simple optical system is preferred, with a single laser source, preferably from 350 to 500 nm, more preferably from 370 to 450 nm. It is especially preferred for the UV range, from 370 to 390 nm, especially about 380 nm, or at the edge of the visible range, from 390 to 430 nm, more preferably about 405 ± 5 nm. In the compression zone, a 10 gauge or violet laser diode with a high aperture optical system (such as Nichia GaN 405 nm) can be found on a 120 mm disc with a fairly small mark and a narrow track of about 2 〇 to 25 Gb per record layer. At 380 nm, indium-filled UV-VCSELs (Yertical-£_avity Surface-making partner) can be used, where the laser source has been prototyped [jung Han with α/·, see MRS Internet J. 15 Nitride Semicond· Res· 5S1, W6.2 (2000)]. Accordingly, the present invention is also related to a method of recording or playing back data in which the data on the optical recording medium of the present invention is recorded or played at a wavelength of less than 6 〇〇 nm', preferably from 350 to 5 feet. The recording medium is based on known recording media and is, for example, 20 similar to the above. It may be composed of, for example, a transparent substrate, a recording layer containing at least one compound of the formula (I), a reflective layer, and a cover layer, which may be affected by the substrate. Suitable substrates are, for example, glass, minerals, ceramics, and thermosets and thermoplastics. Preferred supports are glass, and homo- or copolymerized plastic 39 200805362. Suitable plastics are ', for example, thermoplastic polycarbonate, polyamide, polyester, polypropylene ester, and polymethyl (tetra) ester, polycarbazide, polyolefin, polyglycolated ethylene, polyfluorinated Ethylene, polyamidamine, thermoset polymer, and (iv) resin. Particularly preferred is a polycarbonate substrate, which may be, for example, an injection molding type 5 substrate. The substrate may be in a pure form, or may comprise a general additive such as a pre-6 UV absorber or dye such as Jp_A_〇. As described in 4/167239, it acts as a light stabilizer for the recording layer. In the latter case, in the wavelength range of the writing (laser emission wavelength), the dye added to the support substrate does not have or has only very low absorption, preferably up to about 2 G% of the laser light is focused on the recording layer. . 10 The substrate is preferably transparent, at least in the range of 350 to 500 nm, thus allowing at least 80% of the incident light to be at the write or read wavelength. The substrate is preferably 10 μηι to 2 mm, more preferably 1〇0 to 12〇〇μιιυ^, especially 600 to 1100 μηι thick, preferably having a spiral guiding groove (obedient) in the coating layer, the groove The groove depth is 10 to 20 〇 nm, preferably 2 〇 to 9 〇 11111, the groove width is 15 100 to 400 nm 'preferably 150 to 250 nm, and the space between the two turns is 2 〇〇 to 600 nm, preferably 300 to 450 nm. Grooves of different cross sections are known, for example, hexagonal, ladder or V-shaped. Similar to the known CD-R and dvd_r media, the guiding groove can additionally perform small-cycle or cycle-like side skewing (shake-free) to synchronize the speed of the transfer with the absolute positioning of the read head (Pidup). 20 is possible. In addition, or in addition to skewing, the same function can be performed by marking adjacent to the pre-pits. With this spatial distribution, it is more likely to comply with the HDDVD-RTM specification. The recording medium can be applied by, for example, spin-coating a solution for the purpose of producing a layer which is as amorphous as possible. The thickness of the layer is preferably 〇 to 4 〇 nm, and more preferably 40 200805362 is preferably 1 to 20 nm. 2 to 10 nm on the substrate ("land", depending on the geometry of the trench, preferably 20 to 150 nm, more preferably 30 to 100 nm, especially 40 to 80 nm, in the trench Reflective materials suitable for the reflective layer include, in particular, metals which provide good reflection of the laser light used for recording and playback, such as metals of the 13-15 family of major groups on the periodic table, and groups 3-12 of the minor groups. Metal. A1

In, Sn, Pb, Sb, Bi, Cu, Ag, Au, Zn, Cd, Hg, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni,

Ru, Rh, Pd, Os, Ir, Pt, and · metals Ce, Pr, Nd, Pm, 10 Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and alloys thereof, especially Be applicable. Reflective layers of aluminum, silver, gold or alloys thereof (e.g., platinum alloys), especially aluminum, are based on economic and ecological considerations due to their high reflectivity and ease of fabrication. The reflective layer is preferably 5 to 200 nm thick, more preferably 10 to 150 nm thick, and particularly preferably 50 to 120 nm thick, but a thicker reflective layer such as 1 15 or more may be used. Suitable materials for the cover layer, mainly including plastic, which can be applied to the reflective layer in a thin layer, either directly or with an adhesion promoter. The choice of mechanically and thermally stable plastics has good surface properties and can be further modified, such as writing. The plastic can be thermosetting plastic and hot 20 plastic. The cover layer is applied directly, preferably by radiation curing (e.g., using UV irradiation), which is particularly simple and economical to manufacture. A wide range of radiation curable materials are known. Examples of radiation curable monomers and oligomers are acrylates and methacrylates of diols, triols and tetraols, aromatic tetracarboxylic acids and aryl fluorene without amines, which have at least two of Ci_C4 based on amine groups. Adjacent to, 41 200805362 poly-liminamide, and a composition having a dicalcium-maleimine group, such as a dimercapto-maleimine group. For the use of the cover layer applied by the adhesion promoter, it is preferred to use the same material as the substrate layer, especially polycarbonate. The adhesion promoter used is preferably similar to the radiation curable monomer and the chelating agent. In addition to the use of an overlay applied by an adhesion promoter, a first substrate can be used, which includes a record and reflection | so that the recording medium can be played on both sides. Preferably, the symmetrical structure is bonded to the reflective side of the two portions by direct use of an adhesion promoter or via an intermediate layer. In this configuration, the optical properties of the cover layer, or cover material, are practically unimportant as long as they can be applied, such as by UV radiation. The function of the cover layer is to ensure the overall mechanical strength of the recording medium, if necessary, and the mechanical strength of the thin reflective layer. If the recording medium is strong enough, for example, when the thick reflective layer is present, the cover layer may be omitted. The thickness of the cover layer is about 2 mm thick depending on the recording medium. The cover layer is preferably from 1 〇 15 μηι to 1 mm thick. The recording medium of the present invention also has an additional layer. For example, the interference layer or the barrier layer can construct a recording medium having a plurality of recording layers (e.g., two to ten layers). The use of this material is known to those skilled in the art. Preferably, the interference layer is disposed between the recording layer and the reflective layer, and/or between the recording layer and the substrate, and is composed of 20 丨 electrically materials, for example, Ti02, Si3N4 described in ΕΡ-Α-0 353 393. , ZnS or silicone resin. It is also possible to construct a recording medium with multiple recording layers (for example, 2, 3, 4, 5, 6, 7, 8, 9, or (9). In particular, a double-layer disc can be used, of which two recording layers can be recorded from the same side. Read: for example, double-layer HDDVD-Rtm, feature 42 200805362 is 30GB/side. One method of lining layer media is called "2p method,", using the following examples: transparent substrate / recording material / semi-reflective layer / separator layer, applied by spin coating, and cured via a transparent stamper / second recording layer / reflective layer / sticky layer / second half of the disc. Can also introduce an intermediate protective layer, if necessary Another method of making double-layer media is called "reverse stacking", or ''reverse stack $' is made up of one side of the following non-panel: transparent substrate / recording layer / semi-reflective layer, and another Half-disc, with the opposite layer sequence: substrate / reflective layer / recording layer. The two halves are bonded together with an adhesive layer, so that the two substrates form the two sides of the final optical disc. Everywhere, when needed, such as between the recording layer and the adhesive layer. , as described in WO 04/021 336 and wo 04/042 717. The geometrical distribution of the groove and the layer thickness must be within the same range as described above, with the difference that the recording is performed on the groove by retro-disposing the semi-disc. The latter recording layer thickness of 15 degrees is preferably 20 to 150 nm, more preferably 30 to 1 〇〇 nm, and particularly preferably 40 to 80 nm 'on the groove' depending on the geometric distribution of the groove, preferably % To the nm, more preferably 4 〇 to 15 〇 nm, especially 5 〇 to 1 〇〇 nm, in the trench. Therefore, the present invention is also related to an optical recording medium suitable for use below 600 nm, preferably An optical record of 35 to 5 〇〇 laser, comprising 20 a grooved substrate, a reflective layer, and at least two record obstructions, wherein the record contains a compound of the formula 43

p G

R〇 ' —〇 The recording medium of this Ming, (1), cloth method, depending on the method of manufacture, can be used to support materials and materials. ^ Scraper-applied, as well as rotating, coating, re-entry, pouring, brush-coating, and lowering. f, for example, by =, and by vapor deposition, a solution under high vacuum. When using the "dissolving":: when the method is reversed, the solvents used in the organic solvent are not sensitive. Second,: Note that the support used should be in this eP-A-_791. The H cloth method and the solvent system are disclosed in For example, n spin coating is applied by dyeing, and it is known that: the agent is particularly an alcohol such as "oxyethanol, TM: alcohol, &butanol", such as diacetone alcohol or 3 - 3-methyl-2-butyl-, base-based, for example, lactic acid, or methyl butyrate, or preferably fluorinated alcohol, such as 2,2,3,3_tetrafluoro] Propanol, or like trifluoroethanol' and mixtures thereof. More suitable solvents are known in the art and are disclosed, for example, in ΕΡ-Α·0 483 387. The application of the metallic reflective layer is preferably affected by sputtering or vacuum vapor deposition. This technique is known and described in the specialist literature (e.g., J. V〇ssen and 20 W. Kern, "Thin Film Processes", Academic Press, 1978). The 44 200805362 operation is preferably continuous and achieves good reflectivity and high adhesion of the metal reflective layer. The recording is performed according to known methods by writing fixed or variable length holes (markers) to the surface of the recording layer with fixed or variable speed laser light at a fixed or variable speed of 5 degrees. The reading of the information is carried out according to known methods, using laser illumination by indicating a change in reflectance, as described in "CD-Player und R-DAT Recorder" (Claus Biaesch-Wiepke,

Vogel Buchverlag, Wtirzburg 1992). Those skilled in the art should be familiar with these devices. 10 The information medium of the present invention is specifically an optical information material in the form of WORM. Can be used, for example, in a computer-like CD-R (compressed disc - readable, compact st-lecordable) or DVD-R (digital video disc - readable, red igi yideo sc - recordable), Used as a storage material for identification and cryptographic cards, or for generating diffractive optical elements such as holograms. 15 In addition, however, there are also recording media that are substantially different from CD-R and DVD-R. Where recording and playback do not occur on the substrate, but in the overlay (recorded in the trench or on the trench). Therefore, the individual roles of the cover layer and the substrate, especially the geometric distribution and optical properties, are reversible compared to the above structure. A similar concept is described in Proceedings SHE-Int. Soc Opt Eng 2〇 i^3864, which describes the combination of digital image recording with a Rayleigh GaN laser diode. For this type of recording medium, it is particularly suitable for high storage density and has a relatively small mark ("hole"), and precise focus is so important that the manufacturing process, when substantially similar, is quite difficult to operate. However, the compound of the formula (I) of the present invention is also surprisingly consistent with the requirement of an increase in the reverse layering. Therefore, it is preferable to have a reverse layer structure in which the layer order is a substrate, a reflective layer, a recording layer, and a cover layer. Therefore, the recording layer is located between the reflective layer and the cover layer. The thickness of the thin cover layer is particularly preferably about 50 to 400 μm (typically recorded and read as 100 μm, having an aperture value of 0.85). 5 In the reverse layer structure, the recording and reflection layers have in principle the same structure, as described above. Due to the geometrical distribution of the grooves, they typically have the dimensions of the above range. The reverse layer structure requires a particularly high standard, and the compound of the invention used satisfies this criterion well, for example, when a recording layer is applied to the metal 10 reflective layer, particularly when a cover layer is required, to provide adequate protection against Wear, photo-oxidation, fingerprints, moisture and other environmental influences preferably have a thickness in the range of 0.01 to 0.5 mm, more preferably in the range of 0.05 to 0.2 mm, and particularly preferably in the range of 0.08 to 0.13 mm. The cover layer is preferably composed of a material having a transmittance of 80% or higher, 15 at a wavelength at which the laser is written or read. Suitable materials for the cover layer include, for example, the above materials, especially carbonates (such as Pure Ace® or Panlite®, Teijin Ltd), cellulose tristearate (such as Fujitac®, Fuji Photo Film), or polyethylene. Terephthalate (such as Lumirror®, Toray Industry), especially polycarbonate. Especially in the case of direct application to the cover layer, radiation curing 20 covers, as described above, preferably, such as SD347TM (Dainippon Ink). The cover layer can be applied directly to the solid record layer by means of a suitable adhesion promoter. In another embodiment, the solid recording layer is applied to an additional layer of a metal, a crosslinked organometallic, or preferably a dielectric inorganic material, such as a thickness of 0.001 to 10 μm, preferably 0.005 to 1 μm. More preferably 0.01 to 0.1 46 200805362 ' _, such as 〇.05 to 〇·08 _, in the dielectric separation layer, and 0.001 to 0 02 μπ^, in the metal separation material. The separation layer and the method of the method are disclosed in Fig. 2 438, which is specifically attached hereto. If desired, the cover can be applied at the same thickness between the support material and the metallic reflective layer or between the metallic reflective layer and the optical recording layer. This is quite advantageous in some cases, such as the use of a combination of a silver reflector and a sulfur-containing additive in the recording layer. In a particular variation, an additional layer of metal, crosslinked organometallic, or preferably a dielectric inorganic material is applied, such as a thickness of 0.001 to 10 (four), preferably 5 to 1 ceramic, and 1 to 1 0.1 (four), to the 10th layer of the solid record. Due to its high reflectivity, the metal separation layer preferably has a maximum thickness of 〇 2 μηι thick. The separation layer and the corresponding method are disclosed in the 〇 〇 fiber 2 pole, which is specifically attached hereto. In addition to containing - or a plurality of compounds of formula (1) and optionally general additives, the optical recording medium of the present invention may comprise other chromophores, preferably 15 being a metal-free chromophore. Other chromophores, if desired, may be added to a weight of 200% based on the total weight of the compound of formula (I), especially (7) to weight, based on the total weight of the compound of formula (I). An optical recording disc containing a compound of formula (I) will produce excellent results when recorded and played at 405 nm, especially for reflectivity, modulation, jitter, PRSNR, and/or bER or SbER aspect. As mentioned above, it can be used in the south to record low and low to high. Therefore, the present invention also includes an exemplary recording medium in which the maximum reflectance of the recorded light is 14 to 28%, and the upper orbital tunnel can be written with a power of 7±5 mW of 405 soil 5 nm laser light, and the hole is written. The modulation is measured at a power of 47 200805362 0.4 soil 0.2 mW 405 soil 5 nm laser, at least 〇·30, preferably 0.38 to 0.60. The modulation is as defined by the general art 'reflection ratio (R) before and after the cell tag information change: modulation KRmax - Rmin) / Rmax. 5 The present invention also includes an exemplary recording medium in which the pre-illumination reflectance of the recording is 10 to 30%, preferably 12 to 25%, and the upper orbital tunnel can have a power of 5 soils, 4 mW, 405 soils, 5 nm mines. For the ray writing, the hole modulation is measured by a 405-earth 5 nm laser with a power of 0.35 ft. 0.15 mW, which is at least 〇·3 〇, preferably 0.38 to 0.60. 10 After exposure to a laser with a wavelength of 350-500 nm, the optical properties of the exemplary compound will change in a completely unexpected manner. The imaginary part (k) of the complex index of refraction quickly decreases with high sensitivity, while the real part (η) of the complex index of the refractive index is maintained without significant change. Surprisingly, this unique combination produces an optical recording medium in which the reflectance is reduced when illuminated at a power of 15 ± 4 mW and a wavelength of 350-500 nm. An excellent case is that a standard groove geometry can be used, preferably in accordance with the Blu-ray DiscTM standard, as described above. Due to light interference, the disc can be prepared for high to low recording polarity, or for improved performance, when using low to record polarity. 20 Therefore, the present invention is ultimately also related to an optical recording medium comprising a recording dye which is a long wavelength, and the medium reflection channel having a low reflectance is written with a higher reflectance when compared with the laser wavelength. On the road. Preferably, the high-to-low optical recording medium has a pre-illumination reflectance of 1〇 to 30%, preferably 12 to 25%, and a post-illumination reflectance of 〇 to 20%, preferably 1 to 48 200805362 15%, on which The tunnel can be illuminated by 350-500 nm laser light with a power of 5 ± 4 mW. Preferably, the compound of formula (I) used in such a medium has a refractive index (η) of 1·5±〇·4, especially 1·5±0·25, and most preferably 1. 5±〇·15. , having an extinction coefficient (k) greater than 〇·2〇, generally 〇·25 to 5 〇·60, especially 0.25 to 0·50, optimally 0.30 to 0.40, written in laser and/or Or read at the wavelength. Surprisingly, the present invention provides an optical recording medium that is compatible with the Bhi-ray DiscTM standard and that can be used with existing readers. This goal has never been achieved in prior art. 1 〇 [Embodiment] The following examples are intended to illustrate the invention, but not to limit ("%, as a percentage by weight unless otherwise indicated": ΙΑ!: 60.0g of 97% 2-amino-5-nitro The thiazole is stirred and dissolved in 880 ml of 50% by volume sulfuric acid at 23t. The light brown solution is cooled to _ι〇15 0. Within 40 minutes, 1 〇〇ml of 4N sodium nitrite is added. Dark blue green The solution was stirred at -10 to continue stirring for 15 minutes. The 48 sec was dissolved in 4 ml of ethanol and cooled to _10 to -15 t: The resulting solution was slowly added to the diazonium ion solution. A thick, dark red precipitate formed and the temperature was raised to about 〇t. The reaction mixture was then stirred for 2 hours at 〇 to 5t: diluted with 20 500 ml of water and filtered by suction. The material filtered by suction was 4 liters of water is washed and dried at 60 ° C / 103 Pa for 24 hours, producing a red/brown product of 玍 / 8 g, with the following formula: 49 200805362 Η

OH 10 h-NMR [ppm]: 8·87 (s, Ha); 6.46 (s, Hb); 6·49/6 52 (d, Hc); 7.71/7.74 (d, Hd). Turtle 1:25 g of the compound of Example 1 was added to 1 ml of dimethylacetamide and stirred at 23 °C. Thereafter, l2jg of cobalt (π) acetate tetrahydrate was added. The starting material slowly dissolves and forms a nearly black solution. The rest is stirred at room temperature. After 3 smashes, the ice red sag forms, and the filter is also filtered by suction, and 2Gml dimethyl b _ is washed. _ Gas transition material The broth is in 1.2 liters of methanol. After addition of sodium hydride (anhydrous), the reaction mixture was heated to 6 Torr and clarified at this temperature. Reduce the liquid Concentrate to · ml using a cyclotron concentrator and cool to 5 (four). C, the opening is sweet. The sediments were filtered by suction and washed with methanol. (4) Drying according to Pa, obtaining a nearly black product of l5g, with the following formula: ' 〇 2Vs

X=N

Hd hi Ha \ ;N Hb 〇 ~C〇:

〇 〇

Hc H

Hr NO

Hb Na4 ]H-NMR [ppm]: 7.99 (s? H )· 5 / THW85 (d, Hd). 3), 5.32 (S, HW.25 (d, interesting (the synthesis of sputum ion): 4g of 2,5 • dimethyl and 3.48g of methyl iodide, stirred soil & 15ml of acetone. At 62 50 15 200805362. The mixture was heated and stirred for 5 hours, cooled to room temperature, and volatilized at i〇3Pa and 6 °C to obtain a large amount of 1,2,5-trimercaptobenzothiazole iodine. It is an off-white powder with the following formula:

CH, I

UlMI (synthesis of stupid vinyl thiazole ion): Example 3 of lg, with 0.58 g of 4-diethylaminobenzofural, dissolved in 15 ml of chloroform. The solution was heated at 62 ° C for 5 hours, cooled to 10 ° C and filtered. Each time it was washed twice with 10 ml of ice-cold methanol, the product was obtained as a dark purple solid with the following formula:

10 H (synthesis of salts): 0.66 g of the product of Example 2 was added to 10 ml of decyloxypropanol at 23 °C. 50 g of the product of Example 4 was added to 1 ml of methanol, and the resulting solution was stirred at 23 ° C for 15 h, thus obtaining a purple suspension. The product was suction filtered through a Biichner filter and washed with methanol, then washed with a mixture of methanol and water, and finally washed with methanol. Dry at 40 ° C / 103 Pa 15 dry, get 0. 67 § near black product, with the following formula:

51 200805362 'H-NMR [ppm]: 8.77 (m? 1 H); 8.33.7.80 (m? 7 H); 7.64-7.48 (m, 4 H); 7.32 (m, 1 H); 6.81 (m, 1 H); 6.22 (d, 2 H); 5.30 (s? 2 H); 4.15 (s? 3 H); 3.37 (m? 4 H); 3.13 (s, 3 H); 1.15 (t, 6 H ). 5 person max (B Sf*> valley solution): 523 nrn (£=: 113900). Fan Kui 6: The compound of Example 5 was dissolved in 98.5 g of 2,2,3,3-tetrafluoropropanol and filtered through a 0. 2 μιη TeflonTM filter. The dye solution is then applied to a flat polycarbonate plate (120 mm diameter) at a speed of 250 rpm. The rotation rate is increased to ^(9)^(5) so that the excess solution can be rotated 10 and a uniform solid is formed. Floor. After drying at 70 ° C for 20 minutes, the measured layer thickness and the composite refractive index of the solid layer were measured using spectral transmission and reflection measurements using an optical measurement system (ETA-RTTM, Steag ETA-Optik).

GmbH, Germany). At 405 nm, the dye layer has a refractive index n of 1.52 and an extinction coefficient k of 0.24. 15 Fan U 〇 6·: The following compounds were prepared and measured in a manner similar to the example 丨 -6: 52 200805362 Compound n k 7 °2 Ν γ8^Ν 〇-〇^, 〇 ": Ν = Ρ ^ 0 ό. A few s^no2 1.46 0.415 8 H3CN^0 〇2\nS>=N r-Y^N 0^=0=° 2 s^no2 1.40 0.39 9 J. H5C2, nXJ〇I〇0H3 乂0 ' 〇ΗΓβ\〇2 1.41 0.37 10 〇2NyS °^:;〇Χΐρ° h3c CH3 sn〇2 1.47 0.37 11 O3^: ch3 och3 sAno2 1.28 0.35 53 200805362 Compound nk 12 H3C〇 ^H〇h3c h5c2 ch3 0=〇=^n=<n. S n〇2 1.26 0.33 13 H3,HACH3 〇九' 1.33 0.30 14 nPH3 〇2\SM 〇^w=\nch3 〇Λ〇Ν=&lt ;^0 s^no2 1.29 0.33 15 OCH3 °2HyS HsC H5C2CH3 〇=ONn=<NS n〇2 1.24 0.33 16 ,Λ 〇2V HX-N+ y^x /=\ C2H5 L^N /=x V° n , \o2 1.34 0.25 17 s^no2 1.27 0.24 54 200805362 Compound η k 18 〇2n ss^no2 19 Qh3 〇2n C^N min NH2 IV=P=0 CH3.趟; s from n〇2 1.30 0.38 20 / 〇2N W, [n: Nn general. :\:heart. 3 Order '巧Μ n=< 1 ch3 S人〇2 1.25 0.29 21 ςΗ3 〇2Νγδ [Η 八(4) Ν 1 1 1 3 3 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.乂ν〇2 1.36 0.25 55 200805362 Compound nk 23 9h3 rN ί >-N, N ch3 -〇-n-(ch2)3-n^Q- "〇2nys-Im>=N /= Nx N=( ) =〇0=C^N \ N=U — ^ N〇2 — h3c + ,Ν-^ 1 - N h3c 2 1.25 0.30 24 一〇2NtVn H3C_N^M>nC2H5 〇:2N=0〇s8n〇2 1.53 0.20 25 〇2\ns>=n ηα A=CM^O oV^0 h3c h5c2CH3 s^no2 1.28 0.20 26 i>V^, —>H>.] 〇=CW \0 —” o: ch3 2 1.50 0.46 56 200805362 Compound nk 27 ,CHs ιίΝ^Ν^ _/=\ 〇^>Nn.\ sAcf3 1.30 0.38 28 Q^^nPHs VNn5>〇ch3 ^ ch3 〇Λ. - V CH3 S N〇2 1.42 0.32 29 02NyS H3C 0^CH3 I. H3c CHs ch3 s νο2 1.51 0.34 30 QH3 [\>-N ch3 points K 卜 —. 2\% _ Α〇ΐί>° — s^no2 _ h3c + , N^ 1 JN; h3c 2 1.22 0.33 31 H5C2/CH3 2 Y^N 〇V^° _s no2 1.24 0.34 57 200805362 Compound nk 32 Η°^ α Ί. —ν, \〇2 33 n H3C °2NvS H0^>° 52CH3 〇^H;N s 乂 n〇2 34 H3c °2NvS 52Ch3 0=C^ s^no2 1.24 0.36 35 >H>. n, \o2 1.46 0.44 36 N=< sn〇2 1.35 0.32 58 200805362 Compound nk 37 N, \〇2 1.35 0.43 38 -43⁄43⁄4 %=(>〇ohh2v 〇<^7\°~ 1.25 0.38 39 H3C0 ^N s 乂n〇2 1.35 0.32 40. You.CH;% servant c^5f a sn〇2 1.36 0.32 41 H r CH3 02NVS /h55^〇CH3 —,NV wc(,〇0=0^ s^ No2 1.21 0.31 59 200805362 Compound η k 42 °2Νγ8 h5〇, /^°crCH3 〇V^° s^no2 1.32 0.28 43 Η5〇2\ H5C2, + 〇2NVS η5〇/ν-^» 0 s s ν〇 2 1.33 0.29 44 ^0CH3h5c2 〇2n s Vnn=〇〇n, \o2 1.32 0.59 45 八v^NvS c. 〇vO TV^<>0 H5C2\ /=( /T^ JX /°^C〇' ^n^"^ H5C2 H3C, N=< s 乂n〇2 46 och3 Door J^N Only ¥ 5 0 Ganzi, 3 1.36 0.28 60 200805362 Compound nk 47 0Ά'0 ν, \〇2 1.61 0.33 48 CP^^nC2Hs 〇2N^Nn^>〇C2H5 C domain fsn〇2 1.41 0.19 49. 'Plus. 0 Na; sn〇2 1.48 0.18 50 €^^η5 2S"H>〇c2h5 c2h5 /°-Co ^〇>^ s^ho2 1.45 0.21 51 ^νν=〇,0 a sn〇2 1.42 0.38 61 200805362 Compound nk 52 〇2n s H3C_N:Kb--3 〇Λ〇^ί≫° s~〇2 1.50 0.46 53 HsC'Na^VC 〇2Ν?5=ς>〇C2H5 W〇, C〇_, nH n, \o2 1.38 0.28 54 ch3 w c2h5 w〇, \〇〇, corpse n, \02 1.37 0.31 55 0CH3 〇K>Nn=<' s^no2 1.60 0.35 56 3 ^5f s^no2 1.41 0.26 62 200805362 Compound nk 57 +-\ h3co ch 〇2nvs sn〇2 1.40 0.25 58 °&gt ;H>. d - 0=o=-sn\02 1.60 0.32 59 ::>^^2%>. 〇=<>nn>1 s 乂n〇2 1.49 0.24 60 |_J Q 〇2^N^-3 HsCS^^〇hAch3 sn〇2 1.51 0.29 61 H5C2n /T-^v H3C\ + 〇2NYSV_ 〇 ;; sn〇2 63 200805362 Compound nk 62 HX? ^ H3C 〇K^NV° n, \o2 1.50 0.19 63 h3c ch3 02n s °K=A^ N. N, \o2 1.25 0.37 64 0 \ \ sn〇2 1.52 0.24 65 c4~ch3 rH=〇. N:N ί^Ί) Ρ-ο〇^ί}=Λ / CH, S” h3c 3 1.47 0.33 66 〇CH3 s 00ΗαΛΤ 〇<^/v° -N%J 1.27 0.32 64 200805362 Compound nk 67 ch3 y rcN^ h3c〇^r〇^0_q 一〇2nys — Vnn=q,0 〇^0>=^ 〇〇N,\〇N%1 bn〇2 ,Hs9 + 〇ch3 2 68 Η5〇2ΪΗ3 〇CH3 〇Λο ^ 0=〇^.\ sn〇2 1.43 0.19 69 H5C2k Η3^ + 02N. 〇ha/N^K^ X,N 〇h5c2^h3 °^3〇-〇〇.〇>^ 0=〇νν> χ sn〇2 1.40 0.21 70 och3 ~cc2H5 n=/=^M'c", 〇0甘nn", f3 1.36 0.28 71 〇CHa °2NyS 〇V^° 0=〇Λ)Wei s^no2 1.39 0.22 65 200805362 Compound nk 72 h3cs s h3c + °2n¥s HACH3 〇οΝΐί SAN〇2 1.43 0.23 73 h3c CH3 〇2N^S sJsno2 1.44 0.31 74 rs OCH, L^N . Called 1.27 0.32 75 P. Xi Xi. W5x) 〇^° ^ -s\〇2 1.39 0.23 76 02N s OCH3 T >N /= h39+ N\ ν=^Λ=〇0=〇nn;n h3c c2h5 3 1.34 0.30 66 200805362 Compound nk 77 och3 〇 2Ν^ν γ=ν 0〇νν.\ s ν〇2 1.33 0.28 78 Gas 1.40 0.22 79 〇2N^q OCH X^N /=\ h3co<K;nV, 〇=CH^ H3CCH3L^J SAN〇2 1.39 0.27 80 OCH. 〇n 〇h3c chX) 0=0=^^ SAN〇2 1.40 0.28 81 H3Cp2H5 pj η3〇〇4^γ η d °2NSh> 〇r ◦ reading; Η3°°·^^ΛΝγ^ LN〇 2 0CV^CI 1.37 0.28 67 200805362 Compound nk

〇 1.41 0.28 83

H,C C2H5 OCH0 HoC0 HXO

〇CH ^cc2h5

0oN

N0o 1.41 0.30

0oN 84 〇CH HoC0

〇 7 'Π h5〇2ch, Cl °<>=v>x SAN〇. 〇 1.43 0.26 OCH, h3c〇 h3c〇

〇2\nS>=n \ \ H CH H3CCH3 S-

NO 2 1.37 0.28 68 200805362 Compound nk 86 h5c2^Pci 0=Onn=<n SAN〇2 87 〇2NTSvn °k>nnv SAN〇2 1.32 0.24 88 :5>^r) 5〇- 〇^nn>! SAN 〇2 1.32 0.21 89 〇ch3 〇2Nys>_N -43⁄4 A〇n^0 Cl h2^ci sn〇2 1.37 0.37 90 o2n s ^i0CV idO0 hAch3 N"s^n〇2 1.40 0.36 91 h3c h3c + °2nts / n'nM/N^ n"/Nv=^〇0=〇N)lsn〇2 1.44 0.41 69 200805362 Compound nk 92 H3c, h3c+ °2nysv 0~t〇” Wonderful. H3C〇0=ONn gas, SAN〇2 1.43 0.35 93 €rx^^: 3〇· h3〇nJ sn〇2 1.53 0.20 94 0^CH3 [S>-.N η3γ:〇η3 0=c=nn=&lt ;snj 1.47 0.33 95 〇^CH3 H3C CH3 tH3N=<S^ 1.46 0.33 96 〕 remaining. CH3 S^N〇2 1.40 0.32 97 HsCr^vV h3^ + 〇2N々nn=〇0 hAch3 n\>no2 1.46 0.19 70 200805362 Compound η k 98 PH3 rN+ Π VN^N ch3 N- 02ν〇=ν 〇 Ν\ ,Ν=〇"0 _ O^N〇l , ^\ h3c + νη(^ν 3ν+ Η W ΝΚ,1 h3c 2 1.39 0.30 99 F3C-N^>NH3CN; ,] 〇:\coNi&gt ;0 h3c ~O^N02 1.36 0.31 100 h2n general n,, h3Cn+ 〇心ΝΛ^ ρΛ〇-ΐ>° h3c 〇Κ>ν^Χν^ Ν"Ο~Ν02 1.33 0.34 101 Η 0^ch3 02ν-〇^ ν Ν\ J〇〇Λ〇Ν^° 〇 κ h3c ch3 νΧ>νο2 1.46 0.33 102 H3C, H3P+ 02Ν Μ'ΝΗΧί 〇\〇Ν^>° W H3C^^ ,\心. — ^ ΝΧ>Ν 〇2 1.39 0.34 71 200805362 Compound nk 103 fV\\ ch3 〇2N〇=n CnC^-Nch3 1.36 0.33 104 〇2Nib^>〇"Ο^Ν〇2 1.37 0.25 105 ^-νΛνη3Ρ+ nc^\n ηΛ =Λ 匕.'❸0 h3c 0=<^νΡ^ nO^cn 1.41 0.29 106 H3Vd Ν0^ν (i MX) oV^0 M H3CCH3 XN° 1.46 0.32 Figure 1 shows the composite refractive index of the solid layer of the compound of Example 10. Real part (η). Figure 2 shows the imaginary part of the composite refractive index of the solid layer of the compound of Example 10 (k) Figure 3 shows the absorption spectrum of the solid layer of the compound of Example 10. The light stability is determined by a calibrated xenon lamp (Hanau). The relative decrease in lmax absorption of all compounds of Examples 7 to 106 - D24, after 24 hours of UV illumination It is quite low. Qijiao: 0.95g of the compound of Example 41 is dissolved in 99g of 2,2,3,3-tetradungol and filtered through a 0.22 pm TeflonTM filter. The dye solution is 72 200805362 400 rpm • Velocity applied to a 〇.6mm thick, grooved polycarbonate disc surface (groove depth 49 nm, groove width 215 nm, distance 4 〇〇 nm) 'has a diameter of 120 mm. The excess solution is rotated by increasing the rate of rotation to 4 () () 〇Γ · ρ · ηι·. When the solvent evaporates, the dye maintains a uniform, amorphous 5 i solid layer form characterized by an optical density of 0.60. Drying is at 7 〇. The air circulation oven was operated for 20 minutes. In the vacuum coating apparatus, a 12 Å thick silver layer was applied to the recording layer by sputtering coating. The adhesive layer of the UV-curable photopolymer (XD4760TM, Huntsman) is applied to it by spin coating, and the second polycarbonate disc (0.6 mm thick, 120 mm in diameter) is adhered to the 10 bond. . On a commercially available test apparatus (ODU-100〇tm, puistec Japan), a laser diode was used, the wavelength was 405 nm, the aperture value was 0.65, and the mark was written into the active layer at a speed of 6.61 m.s-1. Then read on the same device, by applying a reading power of 0.4 mW, and then determine the kinetic parameters: optimal recording power, reflectivity, I11/I11H modulation, 2T-11T signal not 15 symmetry, CNR signal pairing Multi-channel PRSNR (Partial Response Signal to Noise Ratio). Examples 108-115: The same procedure as in Example 107 is used, with the exceptions of Examples 10, 12, 13, 15, 37, 38, and 63 (simultaneously preferred Examples 65, 66, 73, 74, 76, 83, 89) Compounds of 90, 91, 92, 94, 95, 96, 98, 20 99, 1 〇〇, 1 〇 1, 1 〇 2, 103 and 106) are used to replace the compound of Example 41. All test results of Examples 1〇7 to 115 are extracted from the following table: 73 200805362 Domain 荽Φ ί Soil Carving ♦ Weng Duan ffl SZ u -——^ § 00 107 41 0.60 9.0 17.4 27.5 0.37 0.02 45.6 12.89 108 10 0.53 7.0 11.6 21.6 0.47 0.09 37.4 109 12 0.53 8.0 13.1 24.0 0.45 -0.11 45.4 16.51 110 13 0.53 9.0 16.3 26.3 0.38 -0.01 49.1 17.24 111 15 0.59 8.0 15.1 27.8 0.46 0.02 46.2 18.14 112 35 0.52 8.0 9.7 21.3 0.54 -0.01 49.4 — , 31.60 113 37 0.49 8.0 13.1 24.4 0.46 0.02 48.3 ----- 28.35 114 38 0.58 9.0 15.5 26.4 0.41 0.03 47.1 15.30 115 63 0.54 8.0 14.4 24.0 0.40 0.02 46.7 15.08 The recording characteristics are very good and fully comply with the specifications of the HD DVD_RTM format. The minimum mark (2T) is accurately written and detected, resulting in a very good (nearly zero) asymmetry. 5 Thin 116: In a vacuum coating unit (CDFTM, Balzers), a 5 〇 thick silver reflective layer is applied to a 1.1 mm thick grooved polycarbonate disc (120 mm diameter, grooved distance 320 nm) , groove depth 21 rnn, groove width 150 nm). 2 g of the Example 10 compound was dissolved in 100 g of 2, 2, 3, 3, air-propanol and filtered through a 0.2 μm Teflon filter. The dye solution was applied to the reflective layer by a spin coating method to form a uniform solid film at 7 Torr. After drying in an oven for 15 minutes, it has an effective enthalpy and hydration at 560 nm, minus the absorption of the silver layer itself. A 40 nm thick dielectric layer (Si〇N) was applied in a vacuum coating unit (SDS131TM, Balzers) with continuous application of RF-sputtering 74 200805362. Finally, a polycarbonate film covering one side with a pressure-sensitive adhesive (Lintec, 100 μχη total thickness) was attached to the dielectric layer. Using a commercially available optical disc tester (ODU_1〇〇〇tm plus Blu-ray® Disc, Pulstec, Japan) with a 407 nm laser diode and an objective lens aperture value of 8585, the standard is fully recorded on the disc. The upper 'has a linear speed of 5.28 m/s and a laser power of 7_1 mW. After reading and unrecorded area, read 雷.35 mW laser power and measure signal parameters: pre-reading reflectance = 14%; reflectance measured on record mark (8T length) = 2.9%, display High to low signal polarity; modulation I8pp/I8H = 0.78; CNR = 52.8 dB; crosstalk = 28·3 10 dB. Example 117: A procedure similar to that of Example 107 was carried out, except that the compound of Example 15 (n4 〇 5 nm = 1.24 / k4 〇 5 nm = 0.33) was used to replace the compound of Example 41 and the groove depth was 6 〇 nm. , not 49 nm. The compound of Example 15 was dissolved in 99.2 g of 2,2,3,3-15 tetrafluoropropanol and filtered through a 〇·2 μηι TeflonTM filter. The dye solution was then applied at a rate of 400 r.p.m. to a polycarbonate disc with a groove of 58 mm thick (groove depth 75 nm, groove width i87mn, distance 400 nm) on a 120 mm diameter surface. The excess solution was spun out by increasing the rate of rotation to 4000 r.p.m. After evaporation of the solvent, the dye was maintained in a first uniform, 20 amorphous solid layer characterized by an optical density of 0.58 at 518 nm. Drying was carried out in a 70 ° C air circulating oven for 20 minutes. In a vacuum-coated apparatus (TwisterTM, Balzers Unaxis), a 7 nm thick translucent silver layer was applied to the recording layer in a sputter coating manner. Transparent UV-curable photopolymer (573TM, Eques) is applied to it by spin coating, second groove 75 200805362 grooved disc (from ZeonorTM (Nippon Zeon), thickness 0.6 mm, diameter 120 mm A 'trench depth of 81 nm, a groove width of 233 nm, a pitch of 400 nm) is bonded thereto, with a grooved surface facing the photopolymer. The photopolymer is cured under light to form a solid transparent layer of 25 μm thick. The ZeonorTM substrate 5 is then mechanically separated from the original disc and discarded. The second dye solution was prepared using the compound of Example 37, and the compound of lg was dissolved in 99 g of 2,2,3,3-tetrafluoropropanol. On the newly formed polymer grooved surface, the second dye solution was applied by spin coating, thereby obtaining a second uniform, amorphous solid layer having an optical density of 0.45 at 551 nm in an air 10 cycle oven. After drying, it is like the first layer. A 120 nm thick layer of silver is then applied to the second recording layer by smear coating in the same vacuum coating apparatus used for the translucent layer. The UV-curable photopolymer adhesive layer (XD482〇tm, Huntsman) is applied to it by spin coating, and the second imitation polycarbonate is adhered to 15 from the optical disc (thickness 0.6 mm, diameter 120 mm). . On a commercially available optical disc tester (ODU-1000TM, puistec Japan), a laser diode having a wavelength of 405 nm and a pore diameter of 0.65 was used, and the marks were written into the first and second active layers at a speed of 6.61 mi1. Then read on the same device, by applying a reading power of 0.6 mW, and then determining the dynamics 2〇 parameter··the best recording power, the post-reading reflectance, the II1/111H modulation, and the 2T-11T signal asymmetry. , CNR signal to noise ratio, multi-track PRSNR. The test results are summarized in the following table: 76 200805362 普νέιΙΙΓ ϋ rH HH rH ST HSl RK- 1 ug 00 PM Broken N 1 15 0.58 8.0 2.4 4.5 0.47 0.01 44.8 5.3 2 37 0.45 12.0 3.4 5.2 0.35 0.10 44.0 3.0 Second floor record The features are quite good. In this two dye set, the reflectivity and sensitivity of the two-layer disc can be adjusted to the specifications of the dual-layer HDDVD-RTM format. Example 119 (Comparative Example): As in Example 117, a compound of Example 15 is substituted with a compound of the formula (EP-1587092 and EP-1587093, compound 1; n4〇5nm = 1.48 / k4) 〇5nm= 0.29):

The test results of Examples 117 and 119 are summarized in the following table: 1 铷S 翁Κ HH w Hid Λ ^ SK- 1 u 00 Ph from N Pi w 117 15 0.60 8.0 14.5 26.6 0.45 0.03 48.7 19.84 6·10-6 119 (Π ) 0.59 9.0 11.9 17.5 0.32 -0.04 43.4 8.74 5.1〇-3 77 200805362 The recording medium containing the comparative compound of formula (II) has too low modulation, PRSNR and SbER, which are not in compliance with the HD DVD-Rtm specification, even if it is grooved. After the geometry is optimized. IL Example 120 (Comparative Example): A procedure similar to that of Example 117 was carried out, except that the compound of the formula (11) was substituted with a compound of the formula (11405^ = 1·30/^405ηηι ^ 0.25).

(III) 〇

10 The recording medium has very low modulation and very strong signal asymmetry, resulting in unmeasurable CNR, PRSN_SbE]m. Comparative Examples 119 and 120 clearly show that the choice of cations is as important as the yin =. A good result is obtained only from the combination of exemplary cations and anions of the compound of formula (1). [Simple description] 15 Figure 1 shows the real part (8) of the composite refractive index of the solid layer of the compound of Example 10. The ^2 plot shows the imaginary part of the composite refractive index of the solid layer of the compound of Example 10 (8). Figure 3 shows the absorption spectra of the solid layer of the compound of Example 10. [Main component symbol description] (none) 78

Claims (1)

200805362 X. Patent application scope · 1· An optical recording medium 'for optical recording with lasers below 600 nm, preferably from 350 to 500 nm, including a grooved substrate, a reflective layer' and a纟 recorded track, width 1 (8) to 400 nm, better than 5 from 150 to 250 nm, depth 10 to 200 nm, preferably from 20 to 90 nm, pitch is 250 to 430 nm, preferably from 310 to 399.9 nm, wherein the record contains a compound of the formula Or a meso or tautomer thereof, wherein 10 Mi is a metal cation, hydroxyl or halogen metal group having an oxidation state of +3, wherein the metal has an oxidation state of +4, or an oxygenated metal group, Wherein the oxidation state of the metal is +5; Zi is a cation having n positive charges, and the iodide salt has an absorption band in the range of UV-Α or visible light, and the absorption maximum is at a wavelength of 350 to 550 15 nm, wherein The cation is selected from the group consisting of cations of the formula: R1. R〇 Λ R17 Rl0rf Λ ^22 Latch 21 % R11 ^12 Ruler 13 H Rl4 ^R16 Rl5 -r R12 R*I3 Rl9 ^~R2〇 Rl5 79 200805362 13 R 4 and R 14 ; 80 200805362 N NyN-- Q R R 46 R 46 R, 14 45 , R45 Q N . , or b "4N: ·-<^Ί C G. R14 R15 17 or C2-C8 unsubstituted, or heteroaryl which is mono- or polysubstituted by R47, r48, r49 and palpitations; Ql and Q6 are each independently 〇 or S; q^q4 per- g is independently 〇, S_R51; Q3 is N or CR52; Q^N, or CRi4 when Q4 is 0 or S; Q7 is 〇, s, (3) such as or dish 35; each is independently CR* , 0, S or withdraw 55; q9 is CRJ 10 N, Qu is CR56 or N, and Qi2, q14 and Q16 are each independently CR57R58, 〇, s or nrs1; (^^ and 仏5 each Independently CR5 4N; Ri ' R3, R4, R5, 117 and 乂8 are each independently H, dentate, OR6〇, SR6〇, NR41R55, NR55COR61, 〇SiR55R61R62, COR55, CR55〇R61〇R62 , n〇2, CN, COOR60, CONR63R64, so2r55, so2nr63r64, so3R63; CrC6 alkyl, C2-C6 alkenyl, C2-C6 block, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, or C2- C5 heterocyclic ring 81 15 200805362 alkyl, each unsubstituted or mono- or polysubstituted by alizarin; or C7_Cn aralkyl, C6-C1G aryl, or Cl_c8 heteroaryl, each unsubstituted 'or by (^-(:4 alkyl, halogen, 〇R6〇, SR6〇, NR4iR55, c〇R55, N〇2, C N and / or COOCVC4 alkyl group or more _ substitution; R2 and / or R6 is 〇, S or NR65; K9' n1 () ' Hu ' n12' R14, Ri5, Ri6, Ri7, Ri8, R38, R39, R4〇, R44, R45, R46, r47, r48, r49, R5〇, r52 and r59, each independently H, halogen, 〇R66, Sr66, NR5iR67, NR51COR68, NR51COOR69, NR5lCONR69R7G, Nr5iCN, 〇SiR51R68R71 , COR51, CR51〇R68〇R71, N02, CN, coor66, CONR69R70, S02R51, s〇2NR69R70, S03R69; CrC6 alkyl, C2-C6 alkenyl, CVC6 alkynyl, c3-c6 cycloalkyl, c3-c6 ring Alkenyl or C2_C5 heterocycloalkyl, each unsubstituted, or halogen, OR66, SR66, nr51r67, nr51cor68, NR51CO〇R66, nr51conr69r70, NR51CN, COR51, CR51OR68OR71, no2, CN, COOR66, CONR69R70 and / Or SO2R69 mono- or poly-substituted; or 'C7-C11 aryl, C6_Ci aryl or Ci_Cs heteroaryl, each unsubstituted' or via C1-C4 alkyl, halogen, hydrazine R66, sr66 , nr51r67, cor51, N〇2, CN and/or COOCVC4 alkyl single or multiple-substituted; R13 and R35 are each independently Ci_C2 fluorenyl, C3- C12 cycloalkyl, CVC12 heterocycloalkyl, c2-c20 alkenyl, 〇3-0:12 cycloalkenyl, C4-CI2 heterocycloalkenyl, CVCm alkynyl, CVC]8 aralkyl, crc9 heteroaryl , c2-c17 heteroarylalkyl, c6-c12 aryl, or crc12 alkyl, inserted one to 82 200805362 five discontinuous oxygen and/or sulfur atoms, and/or one to five inserted or equal to nr51 Groups, each unsubstituted or halogenated, OR%, SR66, NR51R67, NR51COR68, NR51COOR69, NR51CONR69R70 x NR51CN x OS1R51R68R71 ^ COR$i λ 5 CR510R680R71, Ν02, CN, COOR66, CONR69R70, S02R51, SO2NR69R70, S03R69 Single or multiple substitution; Ri9, R20 and R21 are each independently hydrazine, halogen, hydrazine R66, SR66, OSiR51R68R71, CR51OR68OR71; Crc6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 ring Alkyl, 〇3-(:6-cycloalkenyl or c2-c5 10 heterocycloalkyl, each unsubstituted, or via i, OR66, SR66, NR51R67, NR5iCOR68, NR51COOR66, NR51CONR69R7〇, NR51CN, COR51, CR51OR68OR71, N02, CN, COOR66, CONR69R70 and/or S02R6 single or multiple-substituted; or c7-cn aralkyl, C6-C1G Aryl or Ci-Cs heteroaryl, each unsubstituted, or mono- or poly- to 15 C1-C4 alkyl, _, OR66, SR66, NR51R67, COR51 and/or COOC1-C4 Substituting; R22 and R23 are each independently CrC12 alkyl, c2-C12 fluorenyl, c2-c12:^, 〇7-(:12 aryl, (: 3-€12 cyclyl, c3 a -c12 cycloalkenyl group, or a C2-Cu heterocycloalkyl group, each unsubstituted, or 2 〇 halogen, 〇 66, SR%, NR51R67, NR51COR68, NR51COOR66, NR51CONR69R70, NR51CN, COR51, CR51OR68〇 R71, N02, CN, COORm, CONR69R70 and/or SO2R69 mono- or poly-substituted; or 'R22 and R23 together are C2-Ci2 alkylene, C2-C12 sub-base, C2_Ci2 cycloalkylene, or 〇2 - 〇: 12 ring alkenylene, one to five 83 200805362 discontinuous carbon atoms can be oxygen and / or sulfur atoms, and / or with nr51,. 2-〇12 alkylene group, 〇2-〇: 12 linoleylene, 〇2<12 ring alkylene group, or C2-C12 cycloalkenylene group substituted with the same or different groups, each of which is unsubstituted , or mono- or poly-substituted by halogen, OR66, SR66, NR51R67, NR51COR68, 5 NR51COOR66, NR51CONR69R7〇, NR51CN, COR51, cr51or68or71, N02, CN, COOR66, conr69r70 and/or S〇2R69; R24, R25, R27 , R28, R29, R30, R31 and R32' are each independently hydrazine, halogen, COR51, N02, CN, S03R69; or 10 Crc6 alkyl, c6-c12 aryl, c7-c12 aralkyl, each Neither is unsubstituted or mono- or poly-substituted with halogen, CrCs alkyl, and/or S03R69; R26 is halogen, COOR66, CONR69R70; or C1-C20 alkyl, C7-Ci8 aryl, each They are unsubstituted or mono- or poly-substituted by _, CrC8 alkyl, COR51, COOR66, CONR69R70, OR66, CN, and / 15 or so3r69; R33 is Ci_Ci2 alkyl, C2-C12 dilute, C2 -C12: Fe^, C7-C12 aryl, C^-Ci2 cycloalkyl, CVCu ring, or C2-Cu heterocycloalkyl, each unsubstituted, or halogen, 〇R66 , SR 66, NR51R67, nr51cor68, nr51coor66, nr51conr69r70, nr51cn, 20 cor51, CR51OR68OR71, N02, CN, C〇OR66, conr69r70, and / or S02R69 mono- or poly-substituted; or, Rh and R33 together with nitrogen and carbon atoms Forming a 5- or 6-membered ring; R34 is deuterium, CH3 or each, unsubstituted, or early- or poly-substituted by _84 200805362, OR60, SR60 or NR41R55; each of R36 and R37 All of them are independently Cr; CrC12 alkyl, c2-c12 alkenyl, C2-C12 alkynyl, 0:3 <12 cycloalkyl, C3-C12 cycloalkenyl, or CVCn heterocycloalkyl, each Unsubstituted, or mono- or poly-substituted by halogen, hydrazine, R6Q, SR6Q 5 or NR41R55; or CVCid alkyl, c6-c10 aryl or Crc8 heteroaryl, each unsubstituted, or crc4 alkane a group of halogen, OR60, SR60, NR41R55, COR55, N02, CN, and/or C00CrC4 alkyl mono- or poly-substituted; R4I, R63, 64, R67, R69 and R70 are each independently hydrazine; Ίο Ci-c6 alkyl, C2-C6 alkenyl, C2-C6 fast radical, C3-C6 cycloalkyl, C3-C6 % fine radical or C2-C5 heterocyclic alkyl radical, each unsubstituted, Or halogen OR72, SR72, NR55R62, CN and/or COOR55 mono- or poly-substituted; or (36<1() aryl, C7-Cu aralkyl or ^-indole aryl, each unsubstituted, Or a mono- or poly-substituted group of CrC4 alkyl, halogen, OR72, sr72, 15 nr55r61, cor55, CR55OR61OR62, N02, CN and/or COOR62; or NR63R64 and/or NR69R7G is a five- or six-membered heterocyclic ring More preferably, it may contain an N or a ruthenium atom, and it may be mono- or poly-substituted via a methyl group and/or an ethyl group; 20 R42, R43 and R56 are each independently η, halogen, OR60, SR6〇, NR41R55 , NR55COR6i, NR55COOR63, NR55CONR63R64, NR55CN, OSiR55R61R62, COR55, CR55OR61OR62, N02, CN, COOR60, CONR63R64, S02R55, S02NR63R64, S03R63, PO(OR55)(OR61); cvc6 alkyl, c2-c6 85 200805362 sulfhydryl, CrC6 Alkynyl, CrC6 cycloalkyl, crC6 cycloalkenyl, or c2_c5 heterocycloalkyl, each unsubstituted, or via IS, 0R6Q, SR6Q, NR41R55, NR55COR61, NR55COOR60, NR55CONR63R64, nr55cn, COR55, CR55OR61OR62 , N02, CN, COOR60, 5 CONR63R64, and / or S02R63 single- or multi-substituted; 4C7-Cu Fang An alkyl group, a C6-C1()aryl group or a CrC8 heteroaryl group, each of which is unsubstituted or has a (^-(:4 alkyl group, halogen, hydrazine R60, SR60, NR4iR55, cor55, N〇2) CN and/or C〇OCrC4 alkyl mono- or poly-substituted; or one or more pairs R9 and Ri〇, Rw and Ru, R" and R12, R14 10 and rule 15, Rm and R20, R14 and R21, R15 and Rl6, R15 and Rl9, Rl5 and R20, Rl6 and Rl7, R16 and R52, R17 and Rl8, Rn and R20, Rl7 and R21, Ri8 and R33, R18 and R52, R2〇 and R52, R21 and R52, R24 And R25, R27 and R28, R29 and R30, R3〇 and H31, R31 and R32, R39 and R4G, R42 and R43, R42 and R56, R44 and R59' and/or R47 and R48' These pairs are independently linked to the lower valence group Therefore, two adjacent carbon atoms bonded thereto form benzene, cyclohexene, cyclohexadiene, cyclopentadiene, or cyclopentene ring; Rsl, Rs5, ', Han 62, 'and r71 are independent of each other. The ground is hydrogen, benzyl; or sulphate, cvc4 alkenyl, crc4 alkynyl, [c2-c3 sub 86 20 200805362 alkyl 〇ϋ 81, or [C2-C3 alkylene-NR82-] k_R81, Each of which is unsubstituted or substituted with a single or multiple _; or nr51r67, Nr51r68, Nr41r55, and/or NR55R61 is a five or six fluorene heterocycle, which further comprises an N or a ruthenium atom, which may Methyl and/or 5 ethyl mono- or poly-substituted; R53, R54, H57 and each of them are independently Ci_Ci2 alkyl, c2-c12 alkenyl, c2_c12 alkynyl, C7-Ci2 arylalkyl , C3-Ci^alkyl, C3-Cl2 cycloalkenyl or C2-Cn heterocycloalkyl, each unsubstituted, or via lS, 〇r6. , Sr6. , NR41R55, NR55COR61, 10 NR55COOR6〇, NR55CONR63R64, NR55CN, COR55, CR55〇R61〇R62, N02, CN, COOR6〇, CONR63R64 and/or S02R63 single- or multi-substituted; or R53 and R54, and/or R57 R58 together form C2_Cl2 alkylene, CVC 2 alkenylene, c2_Cl2 cycloalkylene or C2-Ci2 cycloalkenylene with 15 pairs, one to five discontinuous carbon atoms may be substituted by oxygen and/or sulfur atoms, and / or substituted with the same or different groups of the service 55, CVC12S alkyl, C2-C12S alkenyl, c2-c12 cycloalkylene, or C2_C12 cycloalkenylene, each unsubstituted, or halogen, 〇R60, SR60, NR41R55, NR55COR61, NR55COOR60, NR55CONR63R64, NR55CN, 20 COR55, CR55OR61〇R62, N02, CN, coor60, conr63r64 and/or so2r63 single- or multi-substituted; each R6G or R66, independent of any other R6G or r66, R41 or R65; r65 is (3)r41, coor41, conr63r64, cn, so2nr63r64 87 200805362 or SO2R63; R72, independent of any other R72, each independently CVC6 alkyl, c2-6 alkenyl , c2-c6 alkynyl, c3-c6 cycloalkyl, c3-c6 cycloalkenyl, or c2-c5 Alkyl groups, each unsubstituted, or mono- or poly-substituted with halogen, 5 nr55r62, cn and/or COOR55; or c6-c10 aryl, c7-cu aralkyl or crc5 heteroaryl, each Neither is unsubstituted or independently by CrC4 alkyl, halogen, NR55R61, COR55, CR55OR61OR62, N02, CN and/or (: 001162 mono- or poly-substituted; R73, R74, R75 and R76 are each independently Is hydrazine, CrC4 alkane 10, halogen, OR66, SR66, NR51R67, COR51, N〇2, CN, or COOCVC4 alkyl; or R73 and R74, R74 and R75 ' and/or one or more of R75 and R76 The pair is independently bonded to R86, R86, R86 or R86, so that two adjacent carbon atoms bonded to it form a benzene, or a partially 15 or fully saturated 6-membered ring; R77, R78, 1179 and 1180 each Independently ruthenium, CrC4 alkyl, halogen, OR66 or SR66, R73 can form a 3-, 4-, 5- or 6-membered ring with R77, and R74 can form 3-, 4-, 5- or 6 with R78. - a ring, R75 can form a 3-, 4-, 5- or 6-membered bad with Rso or R76 can form a 3-, 4-, 20 5- or 6-member with R79, or R73 and R77, R74 and R78, R75 and R79' or R76 and 118() may be combined with NR51, 0 or S; each of feet 81 and 1182 is independently fluorenyl, ethyl, vinyl, 88 200805362 and/or alkene Propyl; R83, R84, R85 and R86 are each independently H, C1_C4 alkyl, halogen, OR66, SR66, NR51R67, c〇R5, N〇2, CN, or COOCVC4 alkyl; l, R3, R4, R5, r7, r8, R9, Rn, R13, R14, R15, R16, Ri7, Ri8, Ri9, R2. , R21, R22, R23, R24, R25, R26, R27, R28, R29, R3G, R3, R32, R34, R35, R38, r39, R4〇, R41, R42, R43, R44, R45, R46, R47, R48, r49, Rs. , Rsi, R53, R55, R56, 10 15 , R59, R6G, R61, r62, R63, R65, R66, R67, R68, R69, R72, R73, r74, R75, R76, Rsi, Rs3 ϋ and Rs6 Each of the same or different substituents may have one or more radicals that may be paired with the other, selectively bonded by direct bonding, or via U- or -N(R82) bridges. a compound comprising two or three identical or different fragments of formula (I); k being an integer of 1, 2, 3 or 4; 4 integers 2 or 3. 2. For example, the optical disc /C::<1 recording media of the scope of the patent application, where N_• and / or di-c-N G Independently Or R43, preferably 89 200805362 3. An optical recording medium according to claim 1 or 2, wherein R2 and/or R6 are Ο, S, N-CN or N_S02CF3, preferably Ο. 4. An optical recording medium as claimed in claim 1, 2 or 3, wherein R3 and/or R7 are hydrazine, halogen, N02, CN, COR55, COOR60, SO3R60, 5 NCO or SCN, preferably Η. 5. The optical recording medium of claim 1, 2, 3 or 4, wherein the heterocyclic ring comprises G14G2, at least one R42 and R56, especially R42 is CF3, N02, CN, COR55, coor6〇, CR55OR61OR62, CONR63R64, so2r55, so3r6〇, so2nr63r64, preferably CF3, N02, CN, 10 COR55, coor60, so2r55, and/or SO3R60, or R42 and R56 together are unsubstituted or substituted butadiene, preferably It is unsubstituted or substituted by CF3, N02, CN, COR55, COOR60, and/or SO3R60. 6. The optical recording medium of claim 1, 2, 3, 4 or 5, wherein the heterocyclic ring comprises G3, R58 is Η or F, or together with R44 forms an unsubstituted or substituted diced An alkene, preferably unsubstituted, or via one or more Ci-C* alkyl, halogen, 〇6〇, sr60, NR55R61, CF3, N02, CN, cor55, coor6〇, so2r55, and/or S03R6〇 replaced. 7. For optical recording media of the scope of patent application No. 2, 3, 4, 5 or 6, 20 of which are As3+, Au3+, Bi3+, Ce3+, Co3+, Cr3+, Dy3+, Er3+, Eu3+, Fe3+, Gd3+, Ho3+, Ir3+, La3+, Lu3+, Mn3+, Mo3+, Nb3+, Nd3+, Pm3+, Pr3+, Rh3+, Ru3+, Sb3+, Sc3+, Sm3+, Ta3+, Tb3+, Ti3+, [TiCl]3+, [TiOH]3+, Tm3+, V3+, [VO]3+, W3+, Y3+, Yb3+, [ZrCl]3+ or [ZrOH]3+, 90 200805362 is preferably Co3+ or Cr3+, and η is 1 or 2. 8. A compound of formula (I) wherein the cation Ζ! comprises one of the following groups 91 200805362 9. The use of a compound of formula (I) according to any one of claims 1, 2, 3, 4, 5, 6, 7 or 8 for optical recording, the record being at a wavelength below 600 nm, A laser from 350 to 500 nm is performed. 5 10·—A method of optically recording or broadcasting information, wherein a laser beam having a wavelength of less than 600 nm, preferably from 350 to 500 nm, is focused on, for example, patent claims 1, 2, 3, 4, 5, 6 Or the recording of any of the seven recording media. 11. The method of claim 10, wherein at least 0.30, preferably 0.38 to 0.60, of the modulation channel (pits 〇f 10 modulation) is written. 12. If the optical recording medium of the patent scope 1, 2, 3, 4, 5, 6 or 7 is applied, the maximum reflection after the illumination of the record is 14 to 28%, and the track is on the track. Pits) can be written with a power of 7 ohms and 5 mW of 405 士 5 nm laser light, and a cavity modulation system with a power of 〇.4 ± 〇 2 mW 15 of 405 ± 5 nm laser measurement, at least 〇.30, It is preferably from 0.38 to 0.60. 13. If the optical recording medium of claim 1, 2, 3, 4, 5, 6 or 7 is applied for, the reflection before the illumination of the record is 10 to 30%, preferably 12 to 25%. The tunnel can be written with a laser of 405±5 nm with a power of 5 m 4 mW. The cavity modulation is measured with a power of 0.35 m 0.15 mW 20 405 士 5 laser, at least 0.30, preferably 0.38 to 0.60. R. For example, the optical recording medium of the first, second, third, fourth, fifth, sixth or seventh aspect of the patent application has a pre-reflection of 10 to 30%, preferably 12 to 25%, and 92. Up to 20%, preferably 1 to 15%, using a laser light of 350-500 nm with a power of 5 ± 4 mW, the reflectance after illumination is lower than 0 93 before illumination