TW200540860A - High-performance optical storage media - Google Patents

Abstract

The invention relates to an optical recording medium comprising a substrate, a reflecting layer and a recording layer, wherein the recording layer comprises a compound of formula, , or a mesomeric or tautomeric form thereof, wherein Zn+ is a proton or an n-valent ammonium, phosphonium, metal complex or alkali metal cation and n is a number 1, 2 or 3; it being possible, where appropriate, for Zn+ to be linked to R1, R2, R3 or R4 by a direct bond or by way of an O, S or NR8 bridge. R1 to R7 are hydrogen or hydrocarbon radicals defined in the description and claims; R2 and R6 can additionally be halogen or nitro. Novel compounds of formula (I) are also claimed, these being compounds in which Zn+ is a phosphonium, metal complex or alkali metal cation or which are asymmetrical.

Description

200540860 IX. Description of the invention: I: The technical field of the inventors] The field of the present invention is an optical storage device in which information is optically stored in a single-write storage medium. The optical properties of the toner in position 5 are distinguished. This technology is commonly referred to as "WORM" (such as "CD-R", "DVD-R", or "DVD + R," etc.) These terms are reserved here. [Prior Art 3 Uses compact high-power diode mines The laser can emit a laser with a range of 63 to 690 nanometers and a range of 10. Using the pit trajectory distance (the distance between two resistance information holders) and the pit size can be reduced to about half of the conventional CD. In principle, comparison can be achieved The information storage density of blue-layer or green-layer media is improved by 4 to 5 times, and the storage capacity is increased by 6 to 8 times. 15

However, there are special requirements for the recording layer used, such as high refractive index, uniform handwriting width at different pulse durations, high light stability to daylight, and high sensitivity to high-energy thunderbolting. . Known recording layers can only possess these properties to an unsatisfactory level. FR 2019 ·, BE 7682M, and DD are as high as μ revealing that there are one or two cyanine dyes with a shed end group (the so-called "difluorene", also known as boryloxy groups depending on the author) ..., dioxyborane ... or dioxyboronic acid) can be used as a sensitizer for photographic materials. The & DE UH529 body is disclosed in the electronic semiconductor composition using a symmetrical bis-dihumorene compound having an unsaturated bond member containing an even number of carbon atoms or an odd number of carbon atoms. 20 200540860 Other symmetric and asymmetric difluorene borene complexes are disclosed in Dyes and Pigments Zhao, 41-46 (2003) (but no mention of their intended use) includes the following formula

JP-A Sho 60-71294 discloses a writable optical information medium, which can be written at 632 nanometers, which contains a difluorene borene end group and a heterocyclic end group neutral cyanine dye, and contains The quencher, for example, the mixture has the formula:

10 However, this system is not compatible with today's standards (such as DVD-R or DVD + R), because at most only a partial reflective layer is preferred, and the preferred method does not use a reflective layer at all. In addition, it is found that those who use the finished product of the laser with a wavelength of about 658 ± 5 nm still need to be improved. As a result, the object of the present invention is to provide an optical recording medium having a storage capacity of 15 COSCO Brothers along with excellent other properties. The recording medium can also be read and written in the same range of 630 to 690 nm (preferably 640 to 680 nm). The main feature of the recording layer according to the present invention is that the laser diode has a very high initial reflectance in the wavelength range, and the reflectance can be modified with a high sensitivity of 200540860; a high refractive index; the solid-state absorption band is steep at the color depth end For different pulse durations, the uniformity of handwriting width is good; light stability is good; good solubility in polar solvents; and excellent compatibility with laser light sources of different wavelengths for recording and playback. 5 Unexpectedly, excellent results are obtained through the use of specific ionic compounds in which the anion contains boron and the cation contains protons, ammonium, scales, metal complex ions, or alkali metal ions. Unexpectedly, the refractive index in the solid layer was significantly higher than in the previous comparative system. Compounds in which the cation is a colorant cation are of particular interest. [Summary of the Invention] Thus, the present invention relates to an optical recording medium including a substrate, a reflective layer, and a recording layer, wherein the recording layer includes a compound of the following formula

15 or its tautomeric or tautomeric form, wherein

Zn + is a proton or η-valent ammonium, scale, metal complex cation or alkali metal cation, and η is the number 1, 2 or 3; where appropriate, if possible, Zη + is via a direct bond or via a 0, S or NR8 bridge And bonded to R !, R2, R3 or R4; 1 and 117 are each CN; CONR8R9; or CrC6 alkyl, C2-C6 20 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3 -C6 cycloalkenyl, or C3-C6 heterocyclic alkyl, each of which is unsubstituted or substituted with a halogen atom, ORig, SR10, 200540860 NR8R9, OSiRnRnRu, CORn, CRnORR12OR] 3, N02, CN, C. NR8R9, COOR13, S02R13, S02NR8R9, S03R13 or p〇 (〇R12) (〇R13) substituted one or more times; or phenyl, benzyl, phenethyl, styryl, or CrC5 heteroaryl, each of which is unsubstituted Substituted or replaced by r13, halogen 5 atom, 〇R10, SR10, NR8R9, OSiRnR12R13, CORu, CRnOR12 〇R13, N02, CN, CONR8R9, COOR13, S02R13, so2nr8r9, so3r13, P0 (〇R12) (〇R13) , NR8S02R13,

SiRuR ^ Rn or SiORnOR ^ OR ^ substituted one or more times; R2 and R6 are each hydrogen, _ prime, N02, CN, CONR8R9; 10 or xin alkyl, c2-c6 alkenyl, c2-c6 alkynyl , C3-c6 cycloalkyl, c3-c6 cycloalkenyl, or C ^ C: 6 heterocycloalkyl, each of which is unsubstituted, or is halogenated, 〇R1 (), SR1 (), NR8R9, 〇SiRuR12R13, COR ", CRuORuORn, N02, CN, CONR8R9, COOR13, S02R13, S02NR8R9, S03R13, or POCORuXORn) or one or more substitutions; or phenyl, benzyl, phenethyl, 15styryl, C] -C5 Aryl, phenyl-N = N- or C2-C5 heteroaryl-N = N-each of which is unsubstituted, or is R] 3, halogen, 〇Ri〇, SRI〇, NR8R9, 〇SiRuR12R13, CORn, CRn〇R12〇R13, No2, CN, coon8R9, CO0R13, S02R13, S02NR8R9, so3R13, p0 (〇r12) (〇r13), NR8S02R] 3, SiRnRuR ^ siORnOj ^ oRu Replaced one or more times 20 times; In addition, 1 ^ and 112 and / or in addition, the heart and the heart may borrow a linking group selected from the group consisting of a single bond direct bond and a double bond direct bond and 0, s, and nr8 bridge groups Group bonding to form a 5-membered or 6-membered ring; R4 and R5 respectively Is hydrogen; or Crc6 alkyl, c2-c6 alkenyl, 200540860 CVC6 alkynyl, CrC6 cycloalkenyl, C3-C6 cycloalkenyl, or c3-C6 heterocycloalkyl, each of which is unsubstituted or a functional atom , 〇Riq, SR1Q, NR8R9, OSiRnR ^ R ^, CORn, CRn〇R12〇R13, No2, CN, c〇Nr8R9, COOR13, S02R13, S02NR8R9, so3R13 or P〇 (〇r12) (〇r13 ) Take 5 generations one or more times; or phenyl, benzyl, phenethyl, styryl, or crc5 heteroaryl, each of which is unsubstituted or substituted by r13, letter atom, 0RW, SR10, NR8R9, OSiRuR12R13 , CORn, CRnORuORu, no2, CN, CONR8R9, COOR13, S02R13, so2NR8R9, SO3R13, P0 (0R12) (0R13). NR8S02R13 ^ SiR11R12R13 ^ Si0Rn0R120R13 10 replaced one or more times; R8R1 and R9 respectively [C2_C3 alkylene-O + Rm or [C2_C3 alkylene-NUk-R] 4, k is an integer from 1 to 3; 4NR8r9 is a 5- or 6-membered heterocyclic ring that optionally contains a nitrogen or oxygen atom The heterocyclic ring may be substituted one or more times with Ci_C6 alkyl; 15 each is Rh, CORn, COOR13, CONRnR12, CN or S02R13;

Rn & R12 are each hydrogen or heart 3 respectively; or NRnRi2 is a 5- or 6-membered heterocyclic ring optionally containing a nitrogen or oxygen atom, and the heterocyclic ring may be fluorene. -. An alkyl group is substituted one or more times;! 0 Each Rl3 is respectively a CrC6 alkyl group, a C2-C6 alkenyl group, (: 2-(: 6 alkynyl group, CrC6 cycloalkyl group, cvC6 cycloalkenyl group or heterocycloalkyl group) Each is unsubstituted, or after halogen, 〇Ri4, SRI4, NRhRi5, NRi4CX) Ri5, nr14coor16. Nhconr14r15, nr16conr14r15, OSiR14R16R17, C0R] 4, CRi4〇Ri6〇R] 7, No. 2, CN, ⑺〇 r] 6, 200540860 CONR14R15, S02Rl4Rl5, S02Rl6, or S03Ri6 substituted one or more times; or benzyl, phenyl, or C2-C5 heteroaryl, each of which is unsubstituted, or OR14, SRI4, nr14r15, NR14COR15, NR14COOR] 6, NHCONR14R15, NR16CONR14R15, OSiR14R16R17, c〇R14, 5 CRi4〇R16OR17, NO2, CN, COOR16, CONR14R15, SO2R14R15, S02R16, or SO3 ) (〇Ri7), SiR14R16R17 or SiOR14OR16OR17 replaced one or more times; In addition, R12 and r13 can be connected via a link member selected from the group consisting of single bond direct and double bond direct bonds and 0, S and NRM bridge groups Bond to form a 5, 6, 7, or 8-membered ring; 10 and each are hydrogen, Rl6 Ri7; or a 5- or 6-membered heterocyclic ring optionally containing a nitrogen or oxygen atom, the heterocyclic ring may be substituted one or more times with a C1-C4 alkyl group; each of core 6 and R17 is a CVC6 alkyl group, and c2 -c6 alkenyl, c2_C6 ^, alkynyl, C3-C6% dilute, C3-C6% dilute, C3-C6 heterocycloalkyl, benzyl, 15phenyl or CyC5 heteroaryl, preferably methyl , Ethyl, vinyl, or ethynyl, each of which is substituted one or more times with halogen, OR18, SR18, NR18R19, COR18, No2, CN, or COOR] 8; In addition, Ri6 & R〗 7 can be selected by one Free single-bond and double-bonds directly link to 0, S, NH, and N (C ^ C4 alkyl) bridge members to form a 5, 6, 7, or 8-member 20 ring ;as well as

Ri8 & R] 9 are each hydrogen, methyl or ethyl. In the case of multiple substitutions, it is obvious that substituents such as 丨, 2, 3, 4 < 5 substitutions may be the same or different based on some or all cases, such as trifluorofluorenyl, 3. · bromo-4,4 -Dimethoxy, 2-cyclohexenyl, or 2-nitro ^^-center 10 200540860 methyl-phenyl. When Zn is η-valent ammonium, scale or metal complex cation, the preferred formula is N + R8R9RuR12, P + R8R9RnR12, R8R9N, CR2OR21, R8nLRi, ρζ 11 4 [Ll-M-L2] n + 'or two of them Binary 5 bodies of the same or different groups, where < L is r々 :, '☆, preparation :, yt ^ 25 Μ is a metal, and Li & L2 is a ligand, respectively; or Q6?

R 25 QAO, S, NR10 or Q4 = Q7; Q2 is Cr24N; q3 is 0, s, NRhSQpQ ?; Q4 is Cr244N; q5 is cr23 or N; QA〇, s, 10 NR11 or Q5 = Q7; and Q4CR26 or N; Q7 at Q4 = Q7, Q5 = QAq2 = q7 is preferably located at β position relative to N of ^^^; νν · * R2〇 and R21 are Rio, OR13 or NRuRn, respectively; and R22 are C =? -R2 ^ n = N-R27; R12, R23, R24, R2iR26 are H, halogen, OR10, SR, respectively. , Cn, CONR8R9, C00R] 3, so2R] 3, so2nr8r9, S03R13; or Cl-C6 alkyl, C2-C6 alkenyl, CyQ fast group, C3-C6 cyclohexyl or c3-c6 cycloalkenyl Is unsubstituted 'or substituted one or more times with halogen, ORH or CN; 200540860 and

Rn is phenyl, benzyl, phenethyl, styryl, or Cl_c5 heteroaryl, each of which is unsubstituted or substituted by R] 3, a halogen atom, 〇R] 0, SR1〇, NR8R9, 〇SlRllRl2Ri3, COR ", CRnOR12R13, N02, CN, CONR8R9, 5 C00R13, S02Ri3, so2nr8r9, so3r13, p0 (〇r12) (〇r13), NR8so2R13, SiRllRi2Ri3 or Si〇Rii〇Ri2Ri3 substituted once Or multiple times 0 Q2 == Q7, Q4 = Q7 and Q5 = Q7 In each case two atoms and two groups defined by Q2, Q4, q5 and Q7 are joined by a double bond. Among them, zn + gn valence metal complex cation, particularly preferred is the formula [LrM-L2] n +

Qi to Q6 and R23 to Rh are as defined previously; 15 G2 is 0C0, OS〇2, N (R1 ()) or particularly preferably · 〇 or · N (δ〇2κ13); Μ is a transition metal or η +2 positive valent Group 13 metal cations; QACR30 or N′qacr—n; preferably q ^ CR3〇 and 仏 is CR3]; or Qs and Q9 are both N; R28SH, halogen, 0R], SR10, NR8R9, 〇SiRnR12R13, 20 C0R11, cRii〇R12OR13, No2, CN, CONR8R9, COOR13, 12 200540860 SO2R13, SC ^ NRsRg, SO3R13; or Ci_C6 alkyl group, C2-C6 dilute group, CrC6 fast group, 〇3 < 6 ring Alkyl or c3-C6 cycloalkenyl are each unsubstituted or substituted one or more times with halogen, OR144CN; and R29, R30, and R3 are each Η, halogen, OR] 0, SRio, NR8R9 , 5 SiRnRi2Rn, CORn, CRu0R12〇RI3, no2, CN, CONR8R9, COOR13, S02R13, so2NR8R9 or S03R13. Transition metal or Group 13 metal cations are, for example, co2 +, Co3 +, Cu +,

Cn2, Zn2 +, Cr3 + ,, Fe2 +, Fe 'A1' Ce2 +, Ce3 +,

Mn2 +, Mn3 +, or V3 +, and preferably cO3 +, Cr3 +, Fe3 +, Ce3 + 4Mn3 +. 10 ammonium or scale cations are, for example, ammonium ammonium, ethyl ammonium, pentadecyl ammonium, isopropyl ammonium, dicyclohexyl ammonium, tetramethyl ammonium, tetraethyl ammonium, tetrabutyl ammonium, benzyl diammonium Ammonium ammonium, benzyltriethylammonium, methyltrioctylammonium, tri-dodecylammonium ammonium, tetrabutylammonium, tetraphenylammonium, butyltriphenylammonium, or ethyltribenzyl The scale may also be protonated Prime 81R or rosinamine D. However, 15 is preferably a cationic chromophore. ^ For the positron organic chromophore, any cation that can absorb 300 to 1500 nanometers, especially 300 to _ nanometers can be used. It ’s better to be familiar with the technology. Those skilled in the art have specifically selected the chromophore 20 group ions previously suggested for optical information media, such as cyanine, xanthan onion, dihalomethylene, stylyl, and stupid. Alkyloxane, azo metal complex, quinonediammonium, bipyridine and its cation. It is better to use cyanine, oxazine, two mouthfuls thinner than beetle, and azo gold. And stupid ethyl cations. These chromophores and other chromophores suitable for use in cationic form are disclosed, for example, in dyes and pigments! 69 (2003), EP 1 125 987, EP 1 130 063, EP 1 152 038, 13 200540860 EP 1 156 084, EP 1 170 339, EP 1 174 472, JP-A-ll / 28 865, JP-A- 11/170695, JP-A-2003 / 119 404, WO2002 / 34 841, WO 2002/50210 or WO 01/75 873, but these examples are by no means considered restrictive options. Particularly noteworthy are the following chromophore cations:

14 200540860

200540860 and also include paraquat and diquat categories, such as alkyl and benzyl viologen or

Quinone diimmonium cations 〇 or group cations such as Kayasorb IRG 022, Kayasorb IRG 040, NC CN

Q d ^ b d

NC (〉 CN

NC CN alkyl, alkenyl or alkynyl can be straight chain or branched. The alkenyl group is a single unsaturated alkyl group or a polyunsaturated alkyl group, and may be separated or conjugated by two or more double bonds if appropriate. An alkynyl is an alkyl or alkenyl group having one or more double unsaturated bonds', if appropriate, the reference bond may be separated or conjugated with other such reference bonds, and the 10 or reference bond may be conjugated with a double bond. Cycloalkyl and cycloalkenyl are monocyclic or polycyclic alkyl and dilute, respectively. As such, the CrC6 alkyl group is, for example, fluorenyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, third butyl, 1methyl-butyl, n-fluorenyl, 2-pentyl, 3-pentyl, 2,2-diamidylpropyl, 3,3-dimethylpropyl or n-hexyl. C ^ -C] 2 cycloalkyl is, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl or cyclohexyl. 16 200540860 C2-C6 diluent is, for example, vinyl,

C, Sai Qi, A U

1 isomer, 2-pentenyl, 3-pentyl, 2-fluorenyl-3-butene_2-yl, 3-diene-3-yl or hexenyl, any isomeric fluorenyl-2-butene- 1-based, 1,4-pentane-5. C3_C6 cycloalkenyl is, for example, 2-cyclobuten-1-yl, 2-cyclopentenyl, 2

10-2-pentane-4-yn-1-yl or 1,3-hexadiyne-5-yl. Halogen is chlorine, bromine, fluorine, or iodine, preferably fluorine is alkyl, cycloalkyl, alkylene, or cycloalkyl; and odor is preferred over aryl, heteroaryl, and aralkyl. C1-C5 heteroaryl is an unsaturated group or aromatic 15 group having a total of 4n + 2 π electrons, such as tetrazolyl, thiadiazolyl, thiaimidazolyl, 2-thienyl, 2-furanyl ,; U-pyrazolyl, 2-pyridyl, 2-thiazolyl, 2-oxazolyl, 2-methylsigma group, isolazyl group, or trivalyl group. In addition, 'aryl groups and aralkyl groups may also be aromatic groups bonded to a metal', for example, in the form of a known metal's metallocene (meta-ocenes) of the transition metal, 20 is more particularly, ~ CH2- ^ Ip > Or -cH0 ^ rr >, ^^ Cll > ^ R32 where R32 is ch2oh, ch2or16, or coor16. 17 200540860 c3-c6 heterocycloalkyl is an unsaturated or partially unsaturated ring system group, such as epoxide, monooxy Butanyl, aziridine, aziridinyl, .pyridinyl, .pyridyl, imidazolinyl, pyrazolidyl, pyrazolinyl, morpholinyl, or other CrC5 heterocycles that are hydrogenated one or more times Aryl. 5 5 to 8 membered rings are, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, preferably cyclopentyl and especially cyclohexyl. Particularly noteworthy are the following as R23 to R26 And as substituents of R28: -CH2-CH2-OH, _CH2-0-CH3 ·, -CH2-0- (CH2) 7-CH3, -CHrCHrO-CH2_CH3, _CHrCH (OCH3) 2, -CH2-CH2- CH (OCH3) 2, 10 -ch2-c (och3) 2-ch3, -ch2-ch2-o-ch2-ch2-o-ch3,-(CH2) 3-OH,-(CH2) 6-OH,- (CH2) 7-OH,-(CH2) 8-OH,-(CH2) 9-OH,-(CH2) 1 (rOH,-(CH2) n-OH,-(CH2) 12-OH, -CH2- Si (C H3) 3, -CH2-CH2-0-Si (CH3) 2_C (CH3) 3,-(CH2) rO-Si (CH3) rC (CH3) 3,-(CH2) 4-0-Si (C6H5) 2 -C (CH3) 3, 15 -CH2-CH2_CH (CH3) -CH2-CH2-CH (OH) -C (CH3) 2-OH,-(CH2) 5-0-Si (CH (CH3) 2) 3 , -CH2-CH (CH3) -CH2-OH, -CH2-C (CH3) 2-CH2-OH, -CH2-C (CH2-OH) 3, -CH2-CH (OH) -CH3, -CH2- CH (OH) -CH2-OH, -ch2ch2o · ^}, _ (ch2) 3o- ^},

H3 a ch2ci <

ch2 {], -ch2ch2 {],

One (CH2) 3〇 {18 200540860 _ (ch2) 2. And _ (CH2) 2_CH = N_R33, in which R_Ci C6 is aryl, 10 15 c2-c6 alkenyl, c2_c6 alkynyl, dagger ring alkyl, c5_C6 ring dilute group, benzyl, phenyl, c2-c5 heteroaryl The stilbene heterocyclic alkyl groups are each unsubstituted or substituted with one or more of the same or different groups according to the definitions listed above, or metal complexes. When R33 is the base, R33 can be unbroken or free! One or two oxygen atoms and / or osmium. Unsubstituted silk or a substituted group substituted with a 1 or 2 group or with a metallocene group or an azo metal complex group is particularly preferred, especially methyl, ethyl, n-fluorene, propyl , N-butyl, 2-butyl, isobutyl, third butyl, 3-pentyl, n-pentyl, third pentyl, neopentyl, 2,2-dimethyl-butyryl, 2, 2,4_trifluorenyl_pent_5_yl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl or cyclopentylfluorenyl. R28 is preferably nr8r9, 0r1g, or SRI0. + Is preferably a compound of formula VII whose center, 仏 and / or heart are chlorine and / or zn + is K + or a special metal complex cation. When R1 and R2 and / or R6AR7 are connected by direct bond or mNR8 bridge base if appropriate, it is difficult to connect member rings to each other. Particularly preferred are compounds of formula (I) wherein R4 is hydrogen. The preferred cations and scale cations are the third or fourth order cations, particularly preferred are the third and fourth Qianyang materials with double bonds to N + atoms (such as Nitto iron or N-burning ratio). ). For example, the compound of formula ⑴ may contain xanthium secondary structure as a cation 'patent or disclosure US_5, ⑸' M Betjia is 19 20 200540860 peroxanthracene cation, which is claimed or disclosed in ⑽ and W〇. 3 / 〇98618, incorporated herein by reference. The 4-inch oligocyanine cation also includes cations according to the formula (i) to formula (iv) (the counter ion X is not included in each example), and according to the formula 03/007296 ( I) Basic structural formula of the left half

Cations, and cations of formula (II) according to WO 04/088649 (p = q = 0), where M1 * is a transition metal in oxidation state III (e.g., co3 +). Particularly interesting metal complex cations have a chemical formula

/ = \ 丨 ',, and {{—Co—〇 \ = J Μ-// and a cation having the following formula according to WO 04/088649 20 200540860

Preference is also given to using metal complex cations of the formula (η) in which the two ligands Li and / or L2 are, for example, directly bonded or bridged by any substituent between -O-, -S- or -NR8_. Under 50 h conditions, the 'bridged ligands L1 and L2 may be mismatched with the same gold cations; if they are mismatched with different metal cations, oligomers may be generated in the following cases. The bridge via the N atom of 1 ^ and / or L2 (either in the chromophore or in the substituent) is particularly preferred. This form of agglomeration is exemplified (but not limited) by the following examples, where X may be (purely for illustration) -CH2-, -CH2-CH2-, -CH2-0-CH2 •, or -CH2- NH-CH2-:

(H5c2) N (h5c2) n (h5c2) n (H5c2) N The preparation of these oligomers and similar oligomers is common. These preferences can be applied to any secondary structure contained in formula (I), in each case independent of other secondary structures that may be present. Of course these preferences are better combined with each other. 15 Compounds of formula (I) of interest, in particular those listed in the examples below. 21 200540860 Several compounds of formula (i) are known compounds. Novel compounds can be prepared in a manner similar to known compounds by known methods. Of particular interest are asymmetric compounds of formula (I) which also include their tautomeric and slowly isomeric forms, in other words, 仏 is different from heart, I is different from heart, and / or R3 is different from Rs5. Compounds. Of particular interest are compounds obtained by concentrating the solution by evaporation, but not crystalline but amorphous. The substrate that can be used as a support for each layer is preferably translucent (Cmo%), or preferably transparent (1 ^ 90%). The thickness of the support is from 0.01 to 10 mm, and preferably from 0.1 to 5 mm. 10 The recording layer is preferably applied between the transparent substrate and the reflective layer. The thickness of the recording layer is 10 to 1,000 nm, preferably 30 to 300 nm, and particularly a thickness of about 80 nm ', such as 60 to 120 nm. The light absorption ratio of the recording layer is particularly 0.1 to 1.0 at the maximum absorption value. The thickness of the layer is very specifically selected in a known manner, and the thickness is selected remotely based on the refraction index 15 of the unwritten state and the written state individually. Therefore, constructive interference is obtained in the unwritten state, but The write state gets destructive interference, or vice versa. The thickness of the reflective layer may be from 10 nm to 150 nm, preferably having a high reflectance (R245%, especially RMO%) plus a low transparency (TS10%). In other specific examples, for example, in a medium with multiple recording layers, the reflective layer may also be translucent. In other words, the reflective layer may have higher transparency (such as T250%) and low reflectivity (such as RS30%). The uppermost layer (for example, a reflective layer or a recording layer depending on the layer structure) is preferably additionally provided with a protective layer, which may have a thickness of 0.1 to 1000 μm, preferably 0.1 to 50 μm, and particularly 0.5 to 15 μm. If necessary, this protective layer 22 200540860 can also be used as an adhesion promoter for the second substrate applied thereon. The thickness of the second substrate is preferably from 0.1 to 5 mm, and is made of the building substrate. Made of the same material. The reflectance of the entire recording medium is preferably at least 15%, and particularly at least 5 is 40%.

The main feature of the recording layer according to the present invention is that the wavelength range of the laser diode has a very high initial reflectance, which can be modified and has high sensitivity; a high refractive index; at the deep end of the color of the solid-state absorption band Has a very particularly steep edge (even in the case of a mixture of multiple compounds according to the present invention 10); the width of the handwritings with different pulse durations and durations is uniform; the light% is good, and Excellent solubility in polar solvents. Further advantages are high light stability under sunlight and laser radiation with low power density, and high sensitivity, uniform handwriting width, high contrast under high power density laser radiation, and good thermal stability and storage. Stability. The recording medium according to the present invention cannot be read or written using an infrared light laser diode of a conventional CD device according to the requirements of the Orange Book standard. As a result, the risk of damage when erroneously attempting to write to a device that is not capable of high resolution can be greatly reduced. As a result of using the formula VII dye, a homogeneous amorphous low-scattering recording layer having a high refractive index was obtained, and even in the case of a solid phase, the absorption edge was still extremely steep%. 20 At relatively high recording speeds, the results are unexpectedly better than previously known recording media. This mark is more accurately defined relative to the surrounding media and will not appear thermally induced deformation. The statistical change (jitter) of the error rate (BLER) and mark length is low at both the normal recording speed and the relatively high recording speed. Therefore, error-free recording and playback can be achieved in a wide range of speeds. Even in high-speed recording, it is rare to have any rejection, and the speed of the written media will not be slowed down due to error correction during reading. This advantage can be obtained in the entire range of 630 to 690 nanometers (preferably 650 to 680 nanometers), but the advantage is most significant in the range of 650 to 670 nanometers 5 meters, and more particularly 658 ± 5 nanometers. Suitable substrates are, for example, glass, minerals, ceramics and thermosetting plastics or thermoplastics. Preferred supports are glass and homopolymer plastic or copolymer plastic. Suitable plastics are, for example, thermoplastic polycarbonates, polyamides, polyesters, polyacrylates and polymethacrylates, polyurethanes, poly10 olefins, polyvinyl chloride, polyvinylidene fluoride Ethylene, polyimide, thermosetting polyacetate and epoxy resin. The substrate may be in a pure form, and the substrate may also contain conventional additives such as an ultraviolet light absorber or a dye, such as a light stabilizer proposed in jP-A_04 / 167239 as a recording layer. In the case described later, it is preferred that the dye added to the support substrate has the highest relative absorption of the dye of the recording layer. High color 15 High displacement 15 at least 10 nm, and preferably at least 20 nm. The substrate is preferably transparent in at least a part of the range of 630 to 690 nanometers (preferably as indicated above), so that at least 90% of the writing or reading wavelength of incident light is allowed to penetrate. The substrate preferably has a spiral guide groove on the coating side, a groove depth of 50 to 500 nanometers, a groove width of 0.2 to 0.8 micron, and a track interval between 2 turns of 20 to 4 to 6 Micrometers; especially having a groove depth of 100 to 200 nanometers, a groove width yield of 0.3 micrometers, and a 2-turn interval of 0.6 to 0.8 micrometers. Depending on the depth of the groove, the recording layer is preferably different in thickness from the inside and outside of the groove; usually inside the groove ^ The thickness of the recording layer is about 2 to 20 times larger than the outside, and the inside of a typical groove is 5 to 10 times larger than the outside. The recording layer may be present in the groove alone. 24 200540860 The storage medium according to the present invention is particularly suitable for optical recording media having a conventionally known minimum pit length of 0.4 U meters and a track interval of ^^ 0 礅 or 0 乂 〇 + &. Compared with known media, the recording speed is high, allowing synchronization or even for special effects, allowing the video sequence to be recorded at an accelerated speed, with the best image quality. Instead of a single compound of the formula (I), the recording layer may also contain a mixture of these compounds and diboranes such as those according to the embodiment 2, 3, 4, 5, 6, 7, or 8 of the present invention. The use of mixtures, such as mixtures of isomers or homologues, but also including the use of mixtures of different structural formulas, often results in increased solubility and / or improved amorphousness. If desired, the ion-pair compound mixture may have different anions, different cations, or different anions and different cations. In order to further improve the stability, known stabilizers may be added in conventional amounts if necessary. For example, nickel dithiolate described in JP-A-04 / 025493 is used as a light stabilizer. 15 The recording layer contains a compound of formula (I) or a mixture of these compounds, preferably in an amount sufficient to substantially affect the refractive index, such as at least 10% by weight, preferably at least 30 to 70% by weight, and particularly at least 4%. To 60% by weight. The recording layer particularly preferably contains a compound of formula (I), or a mixture of a plurality of these compounds as a main ingredient, or the recording layer consists exclusively or substantially of only one or more compounds of formula (I). Other conventional ingredients are also possible, such as other chromophores (for example, chromophores with a maximum absorption of 300 to 1000 nanometers), ultraviolet light absorbers and / or other stabilizers,] 02-floating agents, Ternary quenchers or luminescent quenchers, dazzling point reducers, decomposition accelerators, or any other additives already described in Optical Recording Media 25 200540860, such as film generators. When the recording layer contains other chromophores, it can be any dye that can be inactive during recording. During the modification, the decomposition of the t, gray: /, dimmer chromophore can be easily performed by laser, or can be directly induced indirectly by absorbing laser radiation according to the invention. Decomposition of industrial compounds, such as thermal decomposition, and the light of the daughter-in-law d ~ e recording layer 10 15 cations, other chromophoric groups, cut: two 'preferred use of colorants to humanize & sub-colored female tinctures The optical properties should be as close as possible to the properties of the oral fluorene compound or the amount of chromophores should be maintained to maintain A / I, ι — ^ other gastric α '”, ri. Right to maintain the amount of other coloring ions to Xiaoli Λ Jia line borrowed Equivalent molar scales, or specifically ranging from nanometers to 90 nanometers, can be achieved by replacing ammonium cations with appreciable absorption. When using other chromophores, it has optical properties as much as possible. When conforming to the optical properties of the compound of formula ⑴, it is preferably in the range of the longest wavelength absorption side branch. The other chromophore inflection points and the inflection points of the compound of formula (I) are preferably separated by a maximum of 40 nm, especially 20 nm Meters, more particularly with a maximum interval of 10 nm. In these 20 cases, 'other chromophores and compounds of formula (I) must have similar performance in terms of laser radiation, so they can be used as known records of other chromophores Agent, and its effect can be obtained by the compound of formula 协Increase or increase the homogeneity. When using other chromophores or color stabilizers whose optical properties are as different as possible from those of the compound of formula (I), it is preferred to have a maximum absorption relative to the maximum absorption of 26 200540860 to the dye of formula (I) Under colored conditions, the maximum absorption is preferably at least 50 or 7 'shifts. In this case, this is the case,', especially at least 100 nanometers. "The offense is 1 external light absorber which has a formula ⑴ Dyeing color stability stabilizer, 2_ color of the material 'or NIR or IR range. You can also add shirt absorption, such as tied to the code mark ("diamond dye") or to enhance the record; ^ into the color code identification, color reduction-to find 々 * 卞 layer beauty and other purposes. All of these October conditions are as inert as possible in terms of their chromophores or pigmented shots. Shell has light and laser radiation. 10 When another dye is added to modify the optical properties of the compound of formula VII, the other dye is based on the optical properties of red mosquitoes. Those skilled in the art can change other without any difficulty. The ratio of dye to compound of formula VII until the desired result is obtained. When a chromophore or a color stabilizer is used for other purposes, it is preferably used in a low amount, letting it total the recording layer in the range of 640 to 680 nanometers. The contribution of light absorption 15 is at most 20%, preferably at 658 ± 5 nm and at most 10%. In this case, based on the recording layer, the amount of additional dye or stabilizer is preferably at most 50% by weight, and more preferably Up to 10% by weight. In addition to the compound of formula (I), other chromophore groups that can be used in the recording layer include, for example, cyanines and cyanine metal complexes (US-A-5,958,650), styrene 20-based compounds (US-A-6, 103,331), with oxonol dyes (EP 833 314), azo dyes and azo metal complexes (JP-A-11 / 028 865), phthalocyanines (EP 232 427, EP 337 209, EP 373 643, EP 463 550, EP 492 508, EP 509 423, EP 511 590, EP 513 370, E P 514 799, EP 518 213, EP 519 419, EP 519 423, EP 575 816, 27 200540860 EP 600 427, EP 676 751, EP 712 904, WO98 / 14520, WO / 09 522, WO 02/083 796 ), Turin and aza and forest (ep 822 546, US 5,998,093), dipyrrolene dyes and their metal chelate compounds (EP822 544, EP 903 733), xanthan dyes and their metal complexes Salt 5 (US 5,851,621) or a quadratic acid compound (EP 568 877), which also includes aquatic, aquatic, diazastyrene, formazans, onion quinone This form is not exclusive, and those skilled in the art can interpret this form to include other known dyes. Other excellent chromophores are cyanine, xanthan, and 0 biloba. Class 10 also includes squalium salts and neutral metal azo complexes. Preferred are cyanine to benzoindocarbocyanines; oxonium to special rhodan Rhodamines; neutral metal azo complexes are particularly heterocyclic compounds, especially corresponding to compounds of formula (II) where n = 0. Then others Color group (15 may be charged or uncharged), in particular in the form of lines and the metal complex counterion. However, unless it is a color stabilizer, it is very preferable that no other chromophore is added. Stabilizers or fluorescent quenchers such as metal complexes of N- or S-containing enolates, phosphonates, bisphenolates, thiolates or bisthiolates; 20 or even Metal complexes of nitrogen, azo-loweryl, or Fuzan dyes, such as Irgalan Bordeaux EL (ciba Spezialitatenchemie AG), Cibafast N3 (Cibamate Chemicals) and other compounds; blocked phenols and their derivatives (optionally also anionic X) such as Cibafast A0 (Cibamate Chemical Company 28 200540860 Division) ; Λ7,, 8,8, -tetracyanoquinone dioxane (TCNQ) and its compound (selectively anion of charge transfer complex); via phenylphenyl trisigma or- Base-three crops or other ultraviolet light absorbers, such as Cibafast W or Cibafast P (Cibabat Chemicals); or blocked amines 5 (TEMPO or HALS, also Nitrous oxides or NOR-HALS, the selectivity is also an anion X ·). A variety of these structural formulas are known, some of which are related to optical recording media , For example, from US-5,219,707, JP-A-06 / 199 045, JP-A-07 / 76 169 or JP-A-07 / 262 604. It can be, for example, the 10 metal complex anion disclosed previously and any The desired cations are the salts of the cations disclosed above. In addition, neutral metal complexes must be considered, such as disclosed in EP 0 822 544, EP 0 844 243, EP 0 903 733, EP 0 996 123, EP 1 056 078 , EP 1 130 584 or US 6,162,520, such as

29 200540860

CH, ncvn 3. Or F3CS (^ N_ ^ Factory

Cn-〇 " Nn ^ nYCN

Nacn hue or other known metal complexes such as those illustrated by compounds of the formula «5 分 〇 s〇2cf3

CF3S〇, NJN: j_W CN ^ N ^ NrCH3

S_N / = 1 ^, N = \ / = K .N = \ H〇 " (^ 〇 / Cg〇 \ ^ 〇H C / 〇 / Cy〇v)

Those skilled in the art will understand from other optical information media or easily identify additives whose concentration is particularly suitable for this purpose. The appropriate additive concentration is, for example, 0.001 to 1000% by weight, and preferably 1 to 50% by weight based on the recording medium of formula (I). 10 In addition to the compound of formula (I), the recording medium according to the present invention may additionally contain salts such as ammonium vapor, pentadecyl ammonium chloride, cobalt (II) vapor, sodium vapor, sodium sulfate, The ions of sodium methanesulfonate or sodium methylsulfate can be derived, for example, from the constituents used. If other salts are present, they are preferably present in an amount up to 20% by weight. Reflective materials suitable for use in the reflective layer include, in particular, metals, which can provide good reflections for recording and playback to laser radiation, such as periodic table element groups III, IV and V and subgroup metals. A, In, Sn, Pb, Sb, 5 Bi, Cu, Ag, Au, Zn, Cd, Hg, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and their alloys are special suitable. Considering its high reflectivity and ease of manufacture, it is particularly preferred to use a reflective layer of Ming, silver, copper, gold or its alloy. Suitable materials for the protective layer mainly include plastic, which is applied to the support in a thin layer or to the top layer directly or by means of an adhesive layer. It is better to choose a plastic that is mechanically stable and thermally stable. It has good properties. This property can be further modified, such as writing on the top. The plastic can be a thermoset 15 plastic or a thermoplastic. It is preferred to use a radiation-curable (such as UV-curable) protective layer, which is particularly simple and economical to manufacture. A wide variety of radiation curable materials are known. Radiation-curable monomers and oligomers are, for example, acrylates and methacrylates of diols, triols, and tetraols; aromatic tetracarboxylic acids and aromatic diamines (with crc4 alkyl groups in the amine group) Ortho to 20 or less) polyimides; and agglomerates having a dialkyl cis butene diimide group such as dimethyl cis butene diimide group. The recording medium according to the present invention also has additional layers, such as an interference layer. A recording medium having multiple (for example, two, three, four, or five) recording layers can also be constructed. The structure and use of such materials are known to those skilled in the art. When present, the dry layer is preferably disposed between the recording layer and the reflective layer, and / or the recording layer and the substrate interference layer are composed of a dielectric material, for example, as described in £ 353,393, by , Si3N4, ZnS or polylithic resin. The recording medium according to the present invention can also be manufactured by a known method, and various coating methods can be used depending on the sealing material and the operation mode thereof. Suitable coating methods are, for example, the dip coating method, the tilt coating method, the brush coating method, the doctor blade method and the spin coating method, and the vapor deposition performed under a high vacuum condition. For example, when the tilt coating method is used, it is generally used in The solution of the organic solvent is static; v * 10 15 2 0 is called Yu Ji. When solvents are used, the supports that must be used with care are not sensitive to these solvents. Suitable coating methods and solvents are described, for example, in EP 401 791. The application of the recording layer is preferably performed by spin coating application of the dye solution or dye matter; the solvents proved to be satisfactory are especially alcohols such as 2-methoxyhexanol, τ-propanol, isopropyl Alcohol, isobutanol, n-butanol, 1-methoxy-2-propanol, Λβ, A alcohol or 3-methyl-1-butanol; or preferably a fluorinated alcohol such as 2, 2, 2-trifluoro ^ or 2,3,3-tetrafluoro + propanol and mixtures thereof. It is of course also possible to use other or solvent mixtures, such as those described in EP 511 598 and EP 833 316. It is also possible to use ethers (dibutyl ether), ketones (2,6-difluorenylheptane, 5-field, methyl-2-hexanone), esters (for example, lactic acid known as WO 03/098617) Saki) or saturated or unsaturated hydrocarbons (toluene, xylene or compounds such as WO03 / 034, disclosed by tertiary butadiene, etc.), if appropriate, can be in the form of a mixture (such as dibutyl ether / 2,6 Dimethylheptanone) or individual components in a mixture. Ground spin coating technicians routinely try all known solvents. For mixtures and ternary mixtures, they will find a solvent or solvent mixture that can obtain good quality. 32 200540860 Cost-effective recording layer for solids. In such an optimization process, known process technology methods can also be used, which can reduce the number of experiments performed. Therefore, the present invention also relates to a method for manufacturing an optical recording medium, in which a solution of a compound of the formula (I) in an organic solvent is applied to a substrate having a concave portion. Its application is preferably performed by a spin coating method. The metal reflective layer is preferably applied by sputtering, vacuum vapor deposition, or CVD. Considering that the metal reflective layer has a high degree of adhesion to the building, it is particularly good to use the Qianboat technology to apply the metal reflective layer. This type of 10 technique is known and described in expert references (e.g. JL

Kem ’" Thin Film Method ", Academic Press, 1978). The structure of the recording medium according to the present invention is mainly controlled by the reading method. Known principles include measuring changes in transmission or changes in better reflections. 2 For example, it is also known to measure fluorescence instead of measuring transmission or reflection. 15 * The recording material is determined by the structure of the reflection. For example, a transparent structure / recording layer (optionally multilayer) / reflection layer and a protective layer (if not necessary, transparent) if it is favorable; Or a support (not necessarily transparent) / reflective layer / δ-recorded layer and a transparent protective layer if it is advantageous. In the first case, light is incident from the support side, and in the case described below, the incident light is incident from the recording layer side, =; when applicable, the radiation is incident from the protective layer side. In both cases, the light detection is white on the same side of the light source. The first recording layer structure is usually preferably used in the present invention. & When the structure of the recording material is determined based on the change in light transmission, for example, consider the following different structures: transparent support / recording layer (selective multilayer), and 33 200540860 if it is advantageous, a transparent protective layer. Recording light and reading light can be shot by the target side 'or by the recording layer side' or, if applicable, by the protective layer side. The light detector in this case is often located on the opposite side. Suitable lasers are lasers with a wavelength of 630 to 690 nanometers, for example, 隹 5 lasers with a wavelength of 633, 635, 647, 650, 670, or 680 nanometers, especially semiconductor lasers, such as those with a wavelength of particularly about 635. GaAsA, InGaAlP or GaAs laser diodes of nanometers, 650 nanometers or 658 nanometers. Recording is usually performed, for example, point-to-point in a known manner, by modulating the laser according to the length of the mark, and focusing the laser radiation on the recording layer. References from experts 10 It is known that other methods currently under development can also be used. The method according to the present invention allows storing information with high reliability and stability, which is characterized by excellent mechanical and thermal stability, as well as sharpening of the boundary section with steam stability and pits. The special advantages of the present invention include high contrast and low jitter, which can achieve an unexpectedly high signal / noise ratio of 15 and thus can be read without problems. High storage capacity in video and multimedia fields is particularly good. The reading of the information is performed according to known methods, using laser radiation to register changes in absorption or reflection, such as described in "CD Player and R-DAT Recorder" (Claus Biaesch_Wiepke, v〇gel is so good, 20 Wiirzburg 1992). The information-containing medium according to the present invention is particularly a WORM type optical recording material. For example, it can be used as a playback DVD (digital video disc), as a storage material for a computer, or as an identification card or a security card, or used to make diffractive optical elements such as holograms. 34 200540860 Thus, the present invention also relates to a method for optical recording, storage, and playback, wherein a recording medium according to the present invention is used. Recording and / or playback is preferably performed in the wavelength range of 630nm to 69Gnm, and is preferably performed as previously indicated. '5 Shuming also refers to compounds used according to the present invention' but must be new social compounds. Thus, the present invention also relates to a compound of formula (I) or an inter-isomeric or slowly isomeric form, in which Zn + is a scale, a metal complex ion, or an alkali metal cation. [Embodiment 3] The following examples illustrate further details of the present invention (Shan Fei otherwise-indicates, otherwise all percentages are by weight): Yuejie: 16_22 g 4-Dissolved in base coumarin To be used as a catalyst. H.4 ml of "gas" was slowly added dropwise to the general color solution, cooled in an ice bath, and the color of the solution slowly turned to a reddish color. The product was produced. After the addition was completed, it was heated to 3 generations and maintained at the same temperature for an hour. The suspension was then stirred into 300 grams of ice, and hydrochloric acid (concentrated) was added until all the products were released from the temple. The temple was decanted, washed with water, and dried at c / i04 bar for 18 hours. Known 29.55 Grams of light brown powder 'powder mixed with 54 6 ml trifluoric acid salt. After heating at reflux for 1 hour and cooling, extract the transition sediment 20, wash with ether and dry at 80/10/10 bar for 18 hours. Obtained 34 3 chess 1 solid, the solid was dropped into U.6 ml of triethyl orthoformate§ Purpose: a mixture of diamine and 340 ml of acetic anhydride. The reaction mixture was heated at 6 (TC for 30 minutes. Cooled to 23 C, again after After 90 minutes, it was filtered and washed out. The solid was dried at 80 ° C / 104 bar for 18 hours. 105 g of dark solid of the following formula were obtained. 35 200540860

UV / VIS (DMF): λ max = 576 nm; ε = 207 000 〇 Example 2-7: The procedure is similar to that of Example 1, but other amines of equal molar amount are used instead of triethylamine. Corresponding ammonium salts were obtained with the UV / VIS spectrum of dimethylphosphonium amine 5 as follows: Example cation λ max [nm] ε 2 2-methylpyridine fluorene 576 124 300 3 pyridine fluorene 576 135 200 4 4-methyl Pyridinium 576 174 900 5 N, N-diethylaniline 576 169 700 6 Tetrabutylammonium 576 192 500 7 Ethyl-diisopropyl-Sy 576 205 000 Example 8: 8.11 g of benzamidine Acetone was mixed with 18.85 ml of boron trifluoride etherate in an ice bath, and then cooled with ice and stirred for 40 minutes. The colorless precipitate was removed by suction filtration, washed with ether, and dried at 80 ° C. and 804 bar for 18 hours. The colorless powder 10 is further processed in a manner similar to that of Example 1 to obtain a colored product having the following main components:

36 200540860 Example 9: In a manner similar to the previous example (but adding 120 ml of diethyl ether in the final step for easy stirring), a light yellow product with the following main components was obtained:

5 Example 10: 34.2 g of dehydroacetic acid was stirred at 23 ° C into 100 ml of ethyl acetate.

anhydride. 104 ml of boron trifluoride etherate was added dropwise to the serge color suspension over a period of 30 minutes. The mixture was then heated at 85 ° C for 1½ hours to make a yellow suspension. After cooling to 25 ° C, the suspension was filtered, washed with 200 ml of ether and dried at 60 ° C / 104 bar for 18 hours. A light yellow product of the following formula was obtained: F F w

17.0 g of this pale yellow product was stirred into 150 ml of acetic anhydride, 15.5 g of diphenylphosphonium was added, and the mixture was heated at 65 ° C for 2½ hours. The resulting yellow suspension was filtered, washed with 100 ml of ether, and dried at 60 ° C / 104 bar, and the residue was filtered for 18 hours. A yellow product of the following formula was obtained (cis isomerization of enamine 15 unproven):

37 200540860 2.55 g of this yellow product together with ι7 g of the intermediate product of Example 8 (the reaction of benzamidine acetone with boron trifluoride etherate) was stirred into 20 ml of dichloromethane. Then 2 ml of acetic anhydride was added and the mixture was heated at reflux (40 ° C). Then 2.2 ml of triethylamine was added and the mixture turned red immediately. After refluxing for 2 hours, the mixture was allowed to cool to 20 ° C. The separated precipitate was filtered off; 50 ml of ether was added to the filtrate, and the newly formed precipitate was filtered off. The two residues were combined, washed with 50 ml of ether and dried at 60 ° C / 104 bar for 18 hours. A blue product of the following formula was obtained:

10 Example 11: The dark blue product of the following structural formula is obtained in a similar manner to Example 10:

— F'F-15 UV / VIS (DMF): λ max = 589 nm; ε = 206 700 〇 f Example 12 • The dark blue product with the following structural formula is obtained in a similar manner to Example 11:

UV / VIS (DMF): λ max = 589 nm; ε = 205 300. 38 200540860 Example 13: The dark blue product of the following structural formula is obtained in a similar manner to the previous example:

UV / VIS (DMF): λ max = 587 nm; ε = 147 000. Example 14: The dark blue product of the following structural formula was obtained in a manner similar to the previous example:

UV / VIS (DMF): λ max = 584 nm; ε = 166 000. Example 15: The dark blue product of the following structural formula was obtained in a manner similar to the previous example:

UV / VIS (DMF): λ max = 558 nm; ε = 197 600. Example 16: The dark blue product of the following structural formula was obtained in a manner similar to the previous example:

UV / VIS (DMF): λ plane = 574 nm; ε = 167 600. 39 15 200540860 Example 17: The dark blue product of the following structural formula is obtained in a similar manner to the previous example:

UV / VIS (DMF): λ max = 557 nm; ε = 161 300. Embodiment 18: The dark blue product of the following structural formula is obtained in a similar manner to the previous embodiment:

UV / VIS (DMF):; lmax = 554 nm; £ = 179 500. Example 19 The dark blue product of the following structural formula was obtained in a manner similar to the previous example:

UV / VIS (DMF): again max = 573 nm; ε = 194 700. Example 20: 1.0 ° /. The weight ratio of the compound according to Example 1 was dissolved in 2-butanone and applied to a flat glass substrate by a spin coating method. Charm Example 21: 1.0% by weight The extremely finely ground compound according to Example 7 was suspended in 2,2,3,3-tetrafluoro-1-propanol and applied to a flat glass substrate by a spin coating method. Examples 22-23: The optical parameters of the solid layers according to Examples 20 and 21 40 200540860 were measured at 658 nm using an ETA spectral reflectance and transmittance tester (Steag ETA_〇ptik GmbH): Recording layer: ^ 658 n658 Example 20 0.039 2.53 Example 21 0.038 2.44 Repeat Examples 24-38: The solids according to Examples 2 to 6 and 10 to 19 were coated on glass in a similar manner to Examples 20 and 21, and their optical parameters were It measured according to Examples 22 and 23. Example 39: 1 gram of compound of formula

A solution of 90 g of 1-methoxy-2-propanol and 3 g of 2-butanone was filtered through a Teflon filter membrane having a pore size of 10 · 2 micrometers, at 1800 revolutions per minute by spin coating method & It is applied to the surface of a grooved polycarbonate disc with a diameter of 120 mm and a thickness of 0.6 mm (the groove width is 170 nm, the groove width is 330 nm, and the spacing is 0.74 microns). The excess solution was removed by centrifugation by increasing the speed. When the solvent was removed by evaporation, the dye remained as a uniform amorphous solid layer. The phases were dried at 20 ° C in circulating air 15 (20 minutes). The optical data were good (η658 = 2.4 · / <: 658 == 0.05). In a vacuum coating device (Twister, Balzers Unaxis), a 120-nm-thick silver layer was applied to the recording layer by spraying. A UV-curable photopolymerizable protective layer (TM650-020, DSM) was then applied by spin coating. The recording support 200540860 has a reflectance at 658 nanometers that conforms to the specifications of DVD-R and DVD + R. In a commercial test device (DDU-1000, pulstec, Japan), a laser diode with a wavelength of 658 nm was used to write a mark to the active layer at a speed of 3.5 m / s and a power of 7.5 mW. Dynamic parameters were then established on a commercial test device (DVD Pro, Audio 5 Dev). The media is highly sensitive. Example 40: The procedure is similar to Example 39, but using a compound of the formula

Examples 41-57: Similar to Examples 39 and 40 'using the solid recording medium according to Examples 1 to 7 and 10 to 19 to manufacture optical recording media' using a laser diode with a wavelength of 10 658 nm above the mark . fExamples 58-94: Compounds of the following formula were prepared similarly to Examples 1 to 57 and used for recording materials ·

42 200540860

43 200540860 Example Structural formula ^ max [nm] 4 6

K 573 83 300 5 6

567 156 900 6 6

FwF one

570 123 700 7 6

〇CH 3 574 48600 8 6

HO f ^ OH

HCT 570 126 500 9 6

HX 〇 '〇 570 116800 44 200540860

Example structural formula ^ max [nm] ε 70 FF FF σΒ, 〇〇, 'Β: 〇 ^ 590 125 700 71 σΒ'〇crB'〇κ + ay ^^ o 587 152 800 72 7 π σΒ, ρ 〇 / B' 〇K + 73 FFFF o ^ o (Λο H? F0H h? 538 26 300 74 7 F'F- j 〇 ^ B'〇crB'〇-\ _ u 〇y ^^ 〇587 132 800 75 FWF F \ F crB, 〇crB 〇γ ay ^ x- 76 FWF F'F σΒ, 〇crB, 〇K + h3c 〇〇ch3 558 61300 45 200540860

Example structural formula ^ max [nm] ε 77 FF FF 558 89500 78 FF FF 79 FF FF crB, 〇〇, B, 〇 80 FWF F \ F 〇B'p crB'0 HO f ^ OH Oi ^ 0. 〕 81 Ϊ F'F J crB'〇crB'〇-λ f χΥ ^ όι Eight eat. Enter 〇々〇, ^ 〇ch3 Γ 558 59500 82 7 F'F σΒ, 〇 〇 』, 〇 ^ force human h3 578 25200 46 200540860 ❿ Example 83 84 85 86 87 Formula Structure

JI Λ / rL

FwFσΒ, ο ο ο

κ 581 26500

cr〇 κ 591 107400

CT〇

CH.O

CT〇 Κ 591 569 113900 92400 FF \ ι σΒ, 〇

γΤήνΊ 567 ch3〇

cr〇 569 72000 47 200540860

Example structural formula ^ max [nm] 8 89 588 195000 90 FF FF 588 44900 91 FF FF o ^ o crB, 〇 \ ccy ^ to ^ 546 32200 92 A meaning ^ 〇y ^ x) 589 104400 93 x 0¾ v / 〇y ^ 0〇 / '588 68800 94 FF FF 〇; ^ 〇cAo 丨 + 〇y ^ t〇_r 547 44000 48 200540860 The compound of Example 66 was in the form of a solid layer and had the following optical data: n = 2.11; k = 0.02. The compound of Example 69 was in the form of a solid layer and had the following optical data: n = 1.82; k = 0.01. The compound of Example 74 was in the form of a solid layer and had the following optical data: n = 2.37; k = 0.02. The compound of Example 85 5 was in the form of a solid layer and had the following optical data: n = 1.84; k = 0.03. I: Schematic description 3 (none) ® [Description of main component symbols] (none) 49

Claims (1)

200540860 10. Scope of patent application: 1. An optical recording medium comprising a substrate, a reflective layer and a recording layer, wherein the recording layer comprises a compound of the following formula Zn + (I), or its slowly isomeric or tautomeric form, where Zn + is a proton or η-valent ammonium, scale, metal complex cation, or alkali metal cation, and η is the number 1, 2 or 3; where appropriate, Where possible, ζη + is linked to Ri, r2, R3, or R4 via a direct bond or via a 0, S, or NR8 bridge group; RJR7 is each CN; conr8r9; or crc6 alkyl, c2-c6 alkenyl, cvc6 fast group, 〇3 <: 6 cycloalkyl, C3-C6 cycloalkenyl or CrC6 heterocycloalkyl, each of which is an unsubstituted or letter atom, 〇R〗 0, SR10, Nr8r9, osiRnRi2Ru, c 〇Ru, CRn〇Ri2OR13 ^ N02 ^ CN > CONR8R9 ^ CO〇R13 > S〇2R13. So2nr8r9, so3r13 or PO (ORl2) (ORl3) substituted one or more times; or benzyl, benzyl, phenethyl , Styryl, or crc5 heteroaryl are each unsubstituted or substituted by R13, halogen atom, 〇Ri〇, NR8R9, 〇SiRnR12R13, CORn, CRn〇Ri2〇Ri3, No2, CN, CONR8R9, coor13, so2r] 3, so2nr8r9, so3R13, PO (OR12) (OR13), Nr8s〇2R13, SiRuR12R13 or SiORn〇Ri2〇Ru substituted one or more times; 50 200540860 R2 and R6 are each hydrogen, valenin, N02, CN, CONR8R9; or crc6 alkyl, c2-c6 alkenyl, c2-c6 alkynyl, c3-c6 cycloalkyl, c3-c6 cycloalkenyl, or c3-c6 hetero Cycloalkyl groups are each unsubstituted, or are substituted with OR, OR10, SRI〇, NR8R9, 〇SiRi] Ri2Ri3, CORn, 5 CRnORnOR ^ 'NC ^, CN, CONR8R9, COOR13, S02R13, 10 15 SC ^ NRsR9, S03R13 or P〇 (〇R12) (〇R13) substituted one or more times; or phenyl, benzyl, phenethyl, styryl, crc5 heteroaryl, phenyl-NN- or C2_C5 heterosquare -N = N- each is unsubstituted, or passed R13, halogen, OR10, SR10, NR8R9, 〇SiRnR12R13, COR ", CRnORnOR ", N02, CN, CONR8R9, COOR13, S02R13, so2nr8r9, so3r13, p0 (〇r12) (〇Ri3), Nr8so2r13, SiR " R12R13 or SiORn〇R12〇R13 replaced one or more times; In addition, the heart and / or in addition, the heart can be selected from a single bond directly Bonds and double bonds are directly bonded and the bonding groups of groups consisting of 0, S and NR8 bridge groups are bonded to form a 5-membered or 6-membered ring; r3, r4, and r5 are each hydrogen; 4C, c6 alkyl, c2_c ^, C2-C6 fastyl, C3; cycloalkyl, C3-C6 dilute alkyl, or (: 3-(: 6 heterocycloalkyl) , Which are each unsubstituted or substituted with a halogen atom, 〇Riq, sr ^, NR8R9 ^ OSiRhR12R13 > c〇Rn. CRnOR12〇R13 ^ N02, 20 CN > CONR8R9 ^ CO〇R13. S〇2R13. S02NR8R9 & gt so3r13 or POCORnXOR ^) substituted one or more times; or phenyl, benzyl, benzyl, phenethyl, or Cl-c5 heteroaryl, each of which is unsubstituted or substituted with Rn, _ atom, OR10 , SRI〇, NRsR9, 〇SiRnRi CORn, CRn〇R12〇R13, n〇2, CN, CONR8R9, C00R13 51 200540860 S〇2R! J, he 8s〇2r13 multiple times; S02nr8r9 ^ s〇3R | j PO (OR ] 2) (〇r | 3), SlRnRl2Rl3 or SiORnORuORu replace once or 10 15 20 R8 and R9 are each an integer of [CVC3alkylene-〇_] kR] 4 or [C2_C3alkylene · NRlQ_] k_Ri4; or it is said that 9 is a selective content—the atomic money source is only 5 Or a 6-heterocyclic ring, which may be substituted one or more times by a WCrC6 alkyl group; each Rio is respectively R] 1, C0Rii, c〇〇Ru, C〇NRnR12, C > ^ S〇2Ri3; Rn and R 〖2 is hydrogen or heart 3 respectively; 4NRiiR】 24 optionally contains a 5- or 6-membered heterocyclic ring of a nitrogen atom or an oxygen atom, and the heterocyclic ring may be substituted one or more times by a C] -C6 alkyl group; Each Ri3 is respectively a crc6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C ^ C6 cycloalkyl group, or a c ^ c: 6 cycloalkenyl group. ^^ Heterocycloalkyl groups are each unsubstituted, or by halogen, 〇Ri4, SR 丨 4, NR14R ", NR] 4COR15, NR14C00R〗 6, NHCONR14R15, NR16CONR14R15, OSiR 丨 4R16Rn, c〇R] 4, CR] 4〇R] 6〇Ri7, no2, cn, coor16, conr] 4r15, so2R14R15, so2r16, or SC ^ R] 6 substituted one or more times; or benzyl, phenyl, or c2_c5 heteroaryl each Is unsubstituted, or is halogen, R16, 〇Ri4, SRU, nr14r15, nr14cor15, nr] 4coor16, NHCONR14R15, NR16CONR14R15, 〇SiR14R16R17, cor14, CR14OR16OR17, n〇2, CN, coor16, conr14r15, so2rhr15, so2rhr15, S03R16, PO (OR16) (〇R17), SiR14R16R17 or 52 200540860 Si0R140R160R17 replaced one or more times; In addition, R〗 2 and R] 3 can be selected through a direct bond from a single bond and a direct bond with a double bond and 0, S & NRi4 bridge group consisting of members of the linkage group to form a 5, 6, 7 or 8-membered ring; 5 Rl4 and Rl5 are each hydrogen, R16 or R17; or NR14R15 is optionally containing a nitrogen atom or 5- or 6-membered heterocycle of oxygen atom, the heterocycle may be substituted by Ci_C4 One or more times; _R! 6 and Rl7 are each Cl-C6 alkyl, C2-C6 alkenyl, c2_c6 alkynyl, CVC6 cycloalkyl, CVC6 cycloalkenyl, C3-C6 heterocycloalkyl, benzyl 10-based, phenyl, or C ^ C5 heteroaryl, preferably fluorenyl, ethyl, vinyl, or ethynyl, each of which is substituted once with halogen, 〇RU, SR18, NRMR19, ⑺R18, N02, CN, or C00R18 Or multiple times; in addition, R! 6 and Rn can borrow 15 bonds from a link member selected from the group consisting of single bond direct and double bond direct bonds and 0, s, NH and N (CrC4 alkyl) bridge groups To form a 5, 6, 7, or 8-membered ring; and «^ and Xin 9 are each hydrogen, fluorenyl, or ethyl. 53 200540860 M is a metal and 1 ^ and 1 ^ are ligands, respectively; Qi is 0, S, NR1 (^ Q4 = Q7; q ^ CR25 or N · 仏 is 0, 5 S, NRn, or Q2 = Q7; Q4 is CR24 or Ν; Q5 is CR23 or Ν; QA 0, S, NRu4Q5: = q7; and q ^ CR26 or N; 仏 仏 化 仏, Q5-Q7 or Q2 = q? Is preferably located relative to (^ of N Β position; NR *-R20 and R21 are respectively R10, 〇Ri ^ NRiiRi2;, R22 is 0 = (| > ^ or > ^, -1127; 10 R23, R24, R25 and R26 respectively Η, halogen, 〇10, SR10, NR8R9 > OSiRnR12R13 > CORn > CRnOR12〇R13 > No 〇2 > CN, CONR8R9, CO〇R13, SO2R13, S02NR8R9, S03R13; or (^-( : 6-alkyl, c2-C6 alkenyl, C2-C6 alkynyl, c3-c6 cycloalkyl, or C ^ -C: 6-cycloalkenyl are each unsubstituted or substituted by halogen, 〇Ri4 or CN for 15 times One or more times; and R27 is phenyl, benzyl, phenethyl, styryl, or Crc5 heteroaryl, each of which is unsubstituted or substituted with R13, a halogen atom, 0Rig, SRI0, NR8R9, OSiRnR12R13, c〇Rn, CRn〇Ri2〇Ri3, No2, 54 200540860 CN, CONR8R9 'COOR ", so2Rl3, s 2NR8R9, so3R 3 or P0 (〇R12) (〇R13), nr8so2Ri3, SiRiiRi2R ", or SiORnOR12OR13 replaced one or more times. 4. For the optical recording medium of item 1, 2 or 3 of the scope of patent application, where zn + Co2 +, Co3 +, Cu +, Cn2 +, Zn2 +, Cr3 +, Ni2 +, Fe2 +, Fe3 +, V, Ce \ Ce >, 2+, Mn, v3 +, and preferably ~ 3 +, Cr3 +, Fe3 +, Ce3 +, or Mn3 +. 5. For example, the optical recording medium of the fourth item of the patent application, wherein z „+ is the formula 10 15 20 [1 ^ Μ {2 广 ⑻ 的 nvalent metal complex cation, in which μ ^ 〇3 +, Cr3 +, Fe3 +, Ce3 + or Μη3, 6 ·-A method for optically recording, storing, or playing back information, using a recording medium such as the scope of patent application No. 1, 2, 3, 4 or 5. 7. Method such as the scope of patent application No. 6. The recording and / or playback is performed in a wavelength range of 630 to 690 nanometers, preferably 640 to _ nanometers, and more particularly 658 ± 5 nanometers. 8. = manufacturing method of an optical recording medium, in which a solution of a compound of the formula (I) in an organic solvent in a patent range of 1, 2, 3, 4 or 5 is applied to a substrate having a recessed portion. 9 ^ = _ 利范 _, formula (1) contained in item 2, 2, 3, 4 or 5; or its tautomeric or slowly isomeric form, where ζη + is a scale, a metal complex cation, or a base Metal cation. ^ In the patent, please refer to the erbium compound contained in item 2, 2, 3, 4 or 5 of the patent scope, or 1 _ s π, the weight of the formula (I), the isomerized form of the inter-ceramic or the gradual change system and R7 is different, the formula is, in which R1 and 2 、 are different from I, and / or I is different from R5. 55 200540860 VII. Designated Representative Map: (1) The designated representative map in this case is: (). (2) Brief description of the component symbols in this representative picture: 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: 4