TWI252478B - Optical data medium containing, in the information layer, a dye as a light-absorbing compound - Google Patents

Abstract

Optical data medium containing a preferably transparent substrate which is optionally already coated with one or more barrier layers and on the surface of which an information layer which can be recorded on using light, optionally one or more barriers, and a cover layer, have been applied, which data medium can be recorded on and read using focused blue light through the cover layer on the information layer, preferably laser light with the wavelength between 360 nm and 460 nm, the information layer containing a light-absorbing compound and optionally a binder, characterized in that at least one dye is used as the light-absorbing compound wherein the cover layer on the top of the information layer including the adhesive layer do have a total thickness of 10 mum to 170 mum and the numerical aperture NA of the focusing objective lens setup is greater or equal 0.8.

Description

1252478 at Β7 V. INSTRUCTION DESCRIPTION (1) Prior art The present invention relates to a preferred single-record optical data medium having at least one dye as a light absorbing compound in the information layer and having all of the cover layers of defined thickness and Poly 5 focal optical assembly recording and reading with defined numerical aperture, and its method of manufacture. The word "singly recordable" has the same meaning as the word "once recordable". A single-record optical data medium using a special light absorbing material or a mixture thereof is particularly suitable for blue laser diodes. In the case of high density recordable optical data media (especially for GaN or SHG 10 laser diodes (360-460 nm)), and/or for red (635-66 〇 nm) or infrared (760) -830 nm) in the case of a laser-operated dvd-R or CD-R disc, and applying the above dye to, for example, polycarbonate, by spin coating, sputtering or gas deposition Copolymerized carbonic acid 15 S, polycycloolefin or polyolefin polymer substrate. Recently, single-recorded optical discs (CD-R, 780 nm) have experienced a lot of growth and represent a technically established system. The Bureau of Staff Consumer Cooperatives printed the next generation of optical data storage - DVD - has recently been introduced to the market. By using shorter-wave laser radiation (635 to 66 〇 nm) and 20 Å numerical aperture NA, storage Density can be increased. In this case, a single recording format of DVD-R. Today 'n developed using blue laser diodes with high power of the laser (GaN-based, said jp 191 171 or the present patent iecond

Optical data storage format for Harmonic Generation SHG JP 09 050 629 (360 to 460 nm 25 m). Therefore, the writable optical data storage -3- This paper scale applies to the Chinese National Standard (CNS) A4 specification (21〇χ 297 A7 B7 1252478 V. The invention description (2) will be used for this generation. The storage density can be achieved. Depending on the focusing of the laser spot on the information plane, the spot size is commensurate with the laser wavelength λ/ΝΑ. ΝΑ is the numerical aperture of the objective used. To get the highest possible storage density, the goal is to use the smallest possible wavelength. Based on semiconductor laser diodes, 390 nm is currently possible. The patent literature discloses dye-based writable optical data storage, which is equally applicable to CD-R and DVD-R systems (Japanese Patent JP) -A H 043 481 and JP_A 1〇181 2〇6). In order to obtain the high reflectance and high modulation height of the readout signal and the sufficient sensitivity of the write to 10, the fact of use is that CD-R The 780 亳 micron IR wavelength is at the bottom of the long wavelength side of the dye absorption peak, and the 635 耄 micron or 650 nm red wavelength of DvD_r is at the bottom of the long wavelength side of the dye absorption peak. This concept extends to the length of the absorption peak. In the 450 nm working wavelength region on the long side. 15 In addition to the above optical properties, the Ministry of Economic Affairs, the Ministry of Economic Affairs, which contains light-absorbing organic substances, prints that the poor layer must be as amorphous as possible. In order to minimize the hum of the recording and the period of the item. For this purpose, it is particularly preferred by spin coating from solution, by sputtering or gas deposition and/or sublimation (continuation under reduced pressure) Applying the substance 20 during the covering of the metal or dielectric layer can avoid the crystallization of the light absorbing material. The amorphous layer containing the light absorbing material preferably has high heat distortion, otherwise by sputtering or gas deposition The application of an additional layer of organic or inorganic material to the light absorbing information layer will form an indistinguishable boundary (due to diffusion), thereby adversely affecting reactivity. Furthermore, 25 light absorptions with too low heat distortion The substance may be in the polymeric carrier boundary -4- 1252478 A7 B7 5. Inventive Note (4) 10 15 The compound is combined with the special parameters of the thickness of the cover layer accompanying NA, preferably the enemy t-green dye and The mer〇Cyanine dye is particularly successful in meeting the above requirements. In particular, phthalocyanine has a strong absorption in the wavelength range of 360-460 nm (important for lasers, ie b or Soret). The enemies have a strong absorption in the wavelength range of 420-550 nm, making them suitable for lasers. Therefore, the present invention relates to an optical data medium containing preferably one or more barrier layers coated as appropriate. a transparent substrate, on the surface of which an optically recordable information layer has been applied by an adhesive layer, and one or more barrier layers and a cover layer are optionally used, and the data medium can use a focused blue light to pass through the cover layer on the information layer. Recording and reading, preferably laser light (excellently at 360-460 亳 micron, especially at 38 〇-44 〇 nm, optimally at 395-415 亳 microns), the information layer contains light absorbing compounds And optionally using a binder, characterized in that at least one dye is used as the light absorbing compound, wherein the covering layer above the information layer containing the adhesive layer has a total thickness of 10 micrometers to 177 micrometers, and the focusing objective lens With the numerical aperture NA is greater than or equal to 2.8 billion, preferably from square to square 8〇%. It is better to use as a light absorbing compound, and it is best to print 20 Α\, (I), which is better for the compound of the Ministry of Economic Affairs of the Ministry of Economic Affairs. 25 Α represents the group with the following formula -6- 1252478 A? B7 V. INSTRUCTIONS (5) /-χ4\ 5 〇:;M (in) or R10 (IV), 10 X1 stands for CN, CO-R1, COO-R2 or CONHR3, CONR3R4, X2 Represents hydrogen, cv to c6-alkyl, c6- to c1 (r aryl, five or six member heterocyclic group, CN, CO-R1, COO-R2, CONHR3 or CONR3R4 or 15 CX!X2 represents the following formula Printed by the Intellectual Property Office of the Ministry of Economic Affairs

A7 B7 1252478 V. Description of invention (6)

(II) Printed by the Consumers' Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs

It may be fused with benzo or chin and/or substituted with a nonionic or ionic group 10, wherein the asterisk (*) represents a ring atom extending from a double bond, X3 represents N or CH, and X4 represents 〇, S, N, N-R6 or CH, wherein X3 and X4 do not simultaneously represent CH, X5 represents 〇, S or N-R6, and 15 X6 represents Ο, S, N, N-R6, CH or CH2,

Ring B of the formula (II) Οχ>~

20 together with X4, X3 and the intervening C atom and the ring of formula (V) C (V) 25 together with X5, X6 and the C atom in between r push WC' Λ / 1252478 V. Description of invention (〇 Each - independently of each other represents a five or six membered aromatic, pseudoaromatic heterocyclic ring which may contain from 1 to 4 heteroatoms and/or may be benzofused (10) _ and/or substituted with a nonionic or ionic group , σ Υ1 represents Ν or C-R7, 5 Υ2 represents Ν or C-R8, and R1 to R6 independently of each other represent hydrogen, oxime to alkyl, oxime to A. alkenyl, 〇: 5 to c7_ ring, 〇6 to Ci〇_aryl or core to c 6 aralkyl, 15 R7 and R8 independently of each other represent hydrogen, cyano or 〇1 to 匕-alkyl, 10 R9 and R1. independently of each other represents k-alkyl , C6 to aryl or C*7 to C15-aryl, or NR9R1G can form a five or six member saturated heterocyclic ring. Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative printing system (I) oligomerization or polymerization Also preferred is a partial indigo dye wherein at least one of 15 groups Ri to R10 or at least one of the nonionic groups is bridged to the bridge. The bridge can be attached to two or more indigo dyes to form oligomeric Object or polymer. It may also represent a bridge connected to a polymer chain. In this case, the indigo dye is connected in a comb-like manner to a suitable bridging of the chain, for example -(CH^S, 20 where η and m stand independently of each other The integer is 1 to 2 〇, and Z represents or -C6H4-. The polymer chain is, for example, polyacrylate, polymethacrylate, poly25 acrylamide, polymethacrylamide, polyoxyalkylene, poly-α. - Diepoxy-9- A7 B7 1252478 V. Description of the invention (8) Ethylene, polyether, polyamide, polyurethane, polyurea, polyester, polycarbonate, polystyrene or poly horse Suitable nonionic groups are, for example, <^ to (: 4-alkyl, (:1 to (:4-alkoxy, halogen, cyano, nitro, (^ to 匕-alkoxycarbonyl) ' c^c4-5 alkylthio, Cr to C4-alkanoamine, benzamidine, mono-Ci to c4- aminyl or an amine group, a slightly bite base, an n-bite group, Suitable ionic groups are, for example, ammonium groups or COO- or s〇3- groups' which can be linked via a direct bond or via -(CH2)n•, where n represents the entire 10 Numbers 1 to 6. Alkyl, alkoxy, aryl The heterocyclic group may have an additional group if necessary, such as an alkyl group, a halogen, a nitro group, a cyano group, a c〇-Nh2, an alkoxy group, a trialkylalkylene group, a trialkyldecyloxy group or a phenyl group. The alkyl and alkoxy groups may be straight or branched, and the alkyl group may be partially halogenated or fully orthodonated and the alkoxy group may be ethoxylated or propoxylated. Or a group of alkyl and/or alkoxy groups adjacent to an aryl or heterocyclic group may form a three- or four-membered bridge, and the heterocyclic group may be bonded together. And / or four levels. The Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives, printed the special ring of formula (11). The ring B represents furan-2-yl, thiophen-2-yl, pyrrol-2-yl, benzofuran-2-yl, benzo Thiophen-2-yl, thiazol-5-yl, imidazolium-5, 1,3,4-indenyl-2-yl, i,3,4-tris-2-yl, 2-σ ratio Or 4-indolyl, 2-predyl or 4-indenyl, wherein each ring may pass C! to C6-alkyl, Cl to C6-alkoxy, fluorine, gas, 25 bromine, iodine, cyanide Base, nitro, C, to C6-calcined carbonyl, q to c _ -10-

A7 B7 1252478 V. Description of the invention (9) Fragmentation, q to c6-decylamine, c6 to c1 (r aryl, c6 to Cl "aryloxy, c6 to C1G-arylcarbonylamino, mono-Ci To CV alkylamino or di-Cl to c6-alkylamino, N_Ci to c6-alkyl-N-C6 to Cl, arylamino, pyrrolidinyl, decyl or piperidinyl, and 5 Ring C of (V) represents benzotriazolyl, benzoxazolyl, benzimidazol-2-yl, thiazol-2-yl, isoisothiazol-3-yl, isoxazole-3 - base, imidazolyl-2-yl, pyridazole-5-yl, , '4 fluorene- 2 -yl-, 1,3,4-ya. 嗓咐2嗓咐_2-yl, ^,驭Thiadiazole _5_ group, arylene azole group, 3 Η 吲 吲 吲 基 、 一 一 一 一 一 一 一 一 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 二-yl or dihydroindenylene _4_ group, wherein individual rings may be via ci to c6_housing, Ci to C6_alkoxy, fluorine, chlorine, molybdenum, iodine, nitrogen, nitro, q to C6 - alkoxycarbonyl, Cl to c6-alkylthio, Cl to CV guanamine, c6 to C1 (r aryl, c6 to ClG_aryloxy-15, C6 to ClG_arylcarbonylamino, mono-Ci to (V alkylamino or di-Cl to CV amine group, N_c) to the base To q.·Aromatic amine group, acridinyl group, morpholinyl group or piperidinyl group. The Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative is printed in a special form, the department used is indigo (VI) By

A7 B7 1252478 DESCRIPTION OF THE INVENTION (H>) X2 represents hydrogen, methyl, ethyl, phenyl, 2-pyridyl or 4-pyridinyl, thiazol-2-yl, benzothiazol-2-yl, benzopyrene Zin-2-yl, CN, CO-R1 or COO-R2, or cxix2 represents a ring of the formula ο 11

, R° , R° Y V^5 Y'

Ν'

5 1X which may be selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chlorofluoro, bromo, cyano, nitro, methoxycarbonyl, ethoxycarbonylphenyl, Ministry of Economic Affairs Intellectual Property Office Consumer Cooperatives Print 20 H3C CH 3 \ /ΟΠ3/N, /+ CH3 An·

Up to three groups of groups consisting of An', so3m+ and -ch2-sc^m+ 5 2, wherein the asterisk (*) represents a ring atom extending from a double bond, -12-mouth; rAffirboeioa Shoulder 4曰4« , Ο 1 Λ OOTT /V record, A7 B7 1252478 rr^·- V. Description of invention (u)

An_ represents an anion, M+ represents a cation, X3 represents a CH, X4 represents Ο, S or N-R6, and the bad B of the formula (Π) represents a furyl group, a thienyl group, a pyrrol-2-yl group or a thiazol-5-yl group, wherein Each of the rings may be via methyl, ethyl, propyl, butyl, methoxy, ethoxy, fluoro, ethane, bromo, cyano, nitro, methoxycarbonyl, ethoxycarbonyl, Methylthio, ethylthio, dimethylamino, diethylamino, dipropylamino, II 10,052,025 Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative printed butylamine, N-methylbenzene Substituted by alkino group, pyrrolidinyl or oxime group, γί represents N or C-R7, and R scale, R and R6 independently of each other represent hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, Phenyl or benzyl, and R5 may also represent -(CH2)rN(CH3)2 or -(CH2)rN+(CH3)3An., and R7 represents hydrogen or cyano. In a particularly good form, the part used in the indigo is a formula (νπ)

Xi wherein X1 represents CN, CO-R1 or COO_R2, -13- A7 B7 1252478 V. Description of the invention (12) X2 represents hydrogen, methyl, ethyl, phenyl, 2-pyridyl or 4-pyridyl, thiazole- 2-Based, benzothiazol-2-yl, benzoxazol-2-yl, CN, CO-R1 or COO-R2, or CXiX2 represents a ring of the formula 10

R°

'N, /S

Y' 15 which may be selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chlorofluoro, bromo, cyano, nitro, methoxycarbonyl, ethoxycarbonylphenyl, Ministry of Economic Affairs Intellectual Property Bureau Employee consumption cooperative printed 20 h3cwch3/N, /+, ch3 Arr

Up to three groups of the group consisting of An- so3m+ and -ch2-so3mh are substituted for the ring atom extended from the double bond, 25 Air represents an anion, -14- wherein the asterisk (*) represents r 9ft / A7 B7 1252478 V. Invention Description (13) M+ represents a cation, X5 represents N-R6, X6 represents S, N-R6 or CH2, and ring C of formula (IV) represents benzothiazole-2-yl, benzimidazole-2-5 , thiazol-2-yl, 1,3,4-thiadiazole-2-yl, 1,3,4-tris-tris-2-yl, dihydropyridin-4-yl, dihydrogen喳咐-4-yl, or 3H-inden-2-yl, wherein each of said rings may be methyl, ethyl, propyl, butyl, methoxy, ethoxy, fluoro, chloro, Bromine, cyano, nitro, methoxycarbonyl, ethoxycarbonyl, methylthio-10, ethylthio, dimethylamino, diethylamino, dipropylamino, dibutyl Amine, N-methyl-N-phenylamino, pyrrolidinyl or decyl substituted, Y2-Y1 represents NN or (C-R8HC-R7), and R1, R2, R5 and R6 independently represent hydrogen , methyl, ethyl, propyl 15-yl, butyl 'pentyl, hexyl, phenyl or ilyl, and 5 may also represent - (< ^2)3«^((^3)2 or -((:112)3^[+(013)3八11_, R7 and R8 represent hydrogen. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed in an In the form of good, the part used in the indigo is the formula 20 (VIII) R9 ! R10 — N Art ^ 2 Χι (VIII), 25 of which -15- A7 1252478 B7 V. Description of invention (14) X1 stands for CN, CO -R1 or COO-R2, X2 represents hydrogen, methyl, ethyl, phenyl '2-pyridyl or 4-pyridyl, thiazol-2-yl, benzothiazol-2-yl, benzoxazole-2 - base, CN, CO-R1 or COO-R2, or 5 CX12 represents a ring of the following formula 10

R

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed so3m+ and -ch2-so3m+ 15 which can be selected from methyl, ethyl, methoxy, ethoxy, fluorine, bromine, cyano, nitro, methoxy Carbonyl, ethoxycarbonylphenyl, 20 H3°\ /CH3 ^ <N, ch3 /Jw

Up to three groups of Arr Arr 25 are substituted, wherein the asterisk (*) stands for -16- rm/n'KJQ\ A /1 « - 1252478 A7 B7 V. Description of invention (15) Extension from double bond Ring atom,

An_ represents an anion, M+ represents a cation, and NR9R1() represents a dimethylamino group, a diethylamino group, a dipropylamino group, a 5-dibutylamino group, an N-methylphenylamino group, a pyrrolidinyl group. Or morpholinyl, Y1 represents N or C-R7, i^, R2 and R5 independently of each other represent hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl or benzyl, and 10 R5 may also represent _(CH2)3-N(CH3)2*-(CH2)rN+(CH3)3An·. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. Suitable anions An· are all monovalent anions or one equivalent of polyvalent anions. The anion is preferably colorless. Suitable anions are, for example, chlorine, bromine, iodine, tetrafluoroborate, perotate, hexafluoroantimonate, 15 hexafluorophosphate, methionate, ethionate, (^ to sulfonate, (^ to (:1()-perfluoroalkanesulfonate, CjC1G-alkanoate (as appropriate via chlorine, hydroxyl or (^ to (: 4-alkoxy), sulfonate, naphthalenesulfonate or Benzene sulfonate (optionally nitro, cyano, hydroxy, (^ to C25-alkyl, perfluoroalkyl, (^ to (: 4-alkoxycarbonyl or chloro 20), benzenedisulfonate, Naphthalene disulfonate or diphenyl disulfonate (optionally via nitro, cyano, hydroxy, (^ to <: 4-alkyl, (^ to (: 4-alkoxy, q to C4-alkane) Oxycarbonyl or gas substituted), benzoic acid (optionally nitro, cyano, (^ to 匕-alkyl, CjC4-alkoxy, (^ to (: 4-carbooxycarbonyl, benzhydryl, Chlorobenzylidene or tolylmethyl substituted), 25 naphthalene dicarboxylic acid anion, diphenyl ether disulfonate, tetraphenylboric acid -17- 1252478

V. Description of the invention (10 15 Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printed 20 25, cyano-trisyl borate, tetra-(^ to ^ alkoxy borate, oxybutyrate, 7, 8- or 7,9-dicarba-nid(nid〇)_undecanoate (1) or (2) (optionally one or two on B and/or C atoms, as appropriate) To ^2-alkyl or phenyl group substituted), dodecahydrocarbadolium bromide (2) and heart (^ to ^ plant alkyl _c_phenyl_dodecahydrocarbazone borate (1) Bromine, iodine, tetrafluoroborate, perchlorate, methanesulfonate, benzoate, tosylate, dodecylbenzenesulfonate, tetradecanesulfonate are preferred. M+ is all monovalent cations or one equivalent of polyvalent cations. The cation is preferably colorless. Suitable cations are, for example, lithium, sodium, potassium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, trimethyl. Benzyl ammonium, trimethyl ammonium sulfhydryl and Fe(C5H5) 2+ (wherein C5H5 = cyclopentadienyl). Tetramethyl ammonium, tetraethyl ammonium, tetrabutyl ammonium is preferred. Invented with blue laser light For the preferred single-record optical data carrier to be written and read, such a phthalocyanine dye preferably has an absorption maximum in the range of 420 to 550 nm, wherein the wavelength μ 〆 is absorbed in the wavelength The extinction value of the short-wave slope of the maximum value is half of the extinction value) and the wavelength λϊ/1() (the extinction value of the short-wave slope at the wavelength Xmax2 absorbs the maximum value is one tenth of the absorbance at Xmax2). Each case is separated from each other by no more than 50 nanometers. Such a propanoid dye preferably does not exhibit a wavelength shorter than 350 nm, more preferably less than 320 Å, and most preferably less than 290 nm. The maximum value of xmaxl. The preferred part of the indigo dye is 410 to 530 microns micron absorption maximum -18- binding.

•I * 9ft ^VTC\ A / 1252478

17 10152025 The Intellectual Property Office of the Ministry of Economic Affairs, the employee consumption cooperative, prints the value Xmax2. A better part of the indigo dye is one having a maximum absorption of 420 to 5 〇 nanometers into the max2. The best part of the indigo dye is the absorption maximum value Xmax2 of 430 to 5 μm. In the case of these partial indigo dyes, M2 and λ1/10 as defined above are preferably separated from each other by no more than 4 Å, more preferably not more than 30 Å, and most preferably not more than 2 Å. . The enemy dye is at the absorption maximum, (1), with a molar extinction coefficient ε > 40,000 liters / m 2 centimeters, preferably > 6 liters / Moule cm is better > 80,000 liters / Mo Ear centimeters, the best is > 1 〇〇〇 (9) liter / Moer centimeters. The absorption spectrum is preferably determined, for example, in a solution. A suitable part of the indigo having the desired spectral properties is in particular a dipole moment change Δμ=| pg^ag| (ie a positive deviation between the ground state and the dipole moment in the first excited state) is very small (compared Good for <5D, best for <2〇). The method of determining this dipole moment change Δμ is revealed in F W (lrthner et al., Angew)

Chem. 1997, 109, 2933 and the literature cited therein. Low solvent induced wavelength shift (dioxane/DMF) is also a suitable selection criterion. The better part of the indigo is the wavelength drift of its induction from one, ^

Xdi()xanel (i.e., a positive deviation between the absorption wavelengths of the solvent dimethylformamide and dioxane) < 20 Å, more preferably 1 Å, most preferably < 5 纳米. According to the invention, the excellent part is in the form of the following formula -19- 1252478. 5. Description of the invention (18) A7 B7 (CI), where xm represents 〇 or s, X1()2 represents N or CR104, 10 R101 and R102 independently of each other represents methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, benzyl or phenyl, and R1()i additional station represents nitrogen, or NRmR1G2 represents pyroline, piperazine A dimethyl or morpholinyl group, R1G3 represents hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, 15

Cyclohexyl, phenyl, tolyl 'methoxyphenyl, thiol, NR1()1Ri〇2, and R104 represent hydrogen, methyl, ethyl, phenyl, gas, cyano, formazan Or the group of the Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, printed 20 25

(CII) wherein the alkyl group, such as propyl, butyl, etc., may have a branched oligomeric or polymeric structure bridging linkage via R101. According to the present invention, "the best material is as follows" -

^ 9ft ^XTC\ A 1252478 V. Description of invention (l9 A7 B7 p103 χ1〇3

(cm), 5 where x1Q1 represents 〇 or s and x102 represents N or CR104,

Ri〇i and Rl〇2 independently of each other represent methyl 'ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, benzyl or phenyl, and R101 additionally 10 represents hydrogen, or NRHHR1G2 represents pyrrolidine , piperidinyl or fluorenyl, R represents wind, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, phenyl, tolyl, methoxyphenyl, thiol, Chlorine or NR101R102, 15 R1G4 stands for hydrogen, methyl, ethyl, phenyl, chloro, cyano, formazan or a group of the formula: 103 \ Υ101 Ί (CIV), Ministry of Economic Affairs, Intellectual Property Office, Staff Consumption Cooperative Printed 20 Y1Q1 for N or CH, CX1G3Xi〇4 for ring 25 with the following formula

(CV), -21- 1252478 A7 B7 V. INSTRUCTIONS (20) 〇 105 10 15 N A : N , 106

105 (CVI), (CVII), (cvni), (αχ) or the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Consortium, prints 20 25 (CX), where the asterisk (*) represents the ring atom extending from the double bond, and R1G5 represents hydrogen. , methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxyethyl, methoxypropyl, cyanoethyl, hydroxyethyl, ethoxylated Base, gas ethyl, cyclohexyl, phenyl, tolyl, methoxyphenyl or a group of the formula -22- 1252478 V. Description of the invention (21 A7 B7 (CXI),

XT wherein in the formula (CX), the two R105 groups may be different, R1G6 represents hydrogen, methyl, ethyl, propyl, butyl or trifluoromethyl, and R1G7 represents cyano, methoxycarbonyl , ethoxycarbonyl, -cH2so3-ivr or a group of the formula 10

Arr (CXII) ^

An· CH, 15 (CXIH), Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed M+ stands for cation, An· stands for anion, and alkyl group, such as propyl, butyl, etc., can be branched. The connection of the bridge of the oligomeric or polymeric structure occurs via RlG1 or Rl〇5 20 25 According to the invention, it is also an excellent part of the indigo

A7 B7 1252478 V. Description of the invention (wherein X101 represents 〇 or S, X1<) 2 represents N or CR104, and R101 and R102 independently of each other represent methyl, ethyl, propyl, butyl, 5-pentyl, hexyl , cyclohexyl, benzyl or phenyl, and R1G1 additionally represents hydrogen, or NR1G1R1G2 represents pyrrolidinyl, piperidinyl or morpholinyl, R1G3 represents hydrogen, methyl, ethyl, propyl, butyl, pentyl , hexyl, cyclohexyl, phenyl, tolyl, methoxyphenyl, thiol, gas 10 or NR101R102, R1G4 represents hydrogen, methyl, ethyl, phenyl, gas, cyano, formyl or Group X103 15 (CIV), Y1Q1 stands for N or CH, X1G3 printed by the Ministry of Economic Affairs, Intellectual Property Office, and consumer cooperatives, representing cyano, ethyl methoxy, methoxycarbonyl or ethoxycarbonyl, and X represents pyridyl Bite, 3-mercapto or 4-pyridyl, oxime-2-20, benzothiazol-2-yl, carbazole-2-yl, benzoxazol-2-yl, benzopyrimidine Indole-2-yl, n-methylbenzimidazole-2-yl or N-ethylbenzimidazol-2-yl, wherein the alkyl group, such as propyl, butyl, etc., may be branched. The bridging of the oligomeric or polymeric structure occurs via RlG1 or 25 RlG3 (provided the latter represents an ester group). -24- ν /V ^ \ 1252478 A7 B7 V. Inventive Note 23 Preferably, in the indigo of formula (ci) and (cm), RlG3 represents hydrogen, methyl, isopropyl, tert-butyl Or phenyl R represents hydrogen or cyano. And according to the present invention, the excellent part of the indigo is as follows:

NC

CN (CXIV), Printed by the Consumers' Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs

Wherein X1Q5 represents S or CRu°Rin, and R1G8 represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl 15, octyl, methoxyethyl, methoxypropyl, cyano Base, hydroxyethyl, ethoxylated ethyl, gaseous ethyl, cyclohexyl, benzyl or phenethyl, R1()9 represents hydrogen, methyl, ethyl, methoxy, ethoxy, cyano , gas, trifluoromethyl, trifluoromethoxy, methoxycarbonyl or ethoxy 20 carbonyl, R11G and R111 independently of each other represent methyl or ethyl, or CRWR"1 represents a divalent group of the formula Mission (CXV), 25 -25-

10 1252478 V. Description of the invention (Μ where the two bonds are emitted by an atom with an asterisk (*), wherein the alkyl group, such as J, such as propyl, butyl, etc., may have a branch. The bridge of oligomeric or polymeric structures The connection occurs via R(10). 5 According to the invention, the excellent part is Ou Qing as the following type X103 X104 (CXVI), installed 15 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 20 25 where X105 stands for S or CR11()R111 , R108 represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxyethyl, methoxypropyl, cyanoethyl, hydroxyethyl, ethoxylated Ethyl ethyl, gaseous ethyl, cyclohexyl, benzyl or phenethyl, R109 represents hydrogen, f-group 'ethyl, methoxy, ethoxy, cyano, gas 'trifluoromethyl, trifluoroantimony a group, a methoxycarbonyl group or an ethoxycarbonyl group, R110 and R111 independently of each other represent a methyl group or an ethyl group, or a cr1 mr1 11 represents a divalent group having the formula:

(CXV) -26- ^ «^ΧΤ〇\ A / A7 B7 1252478 V. Description of invention (25) where the two bonds are issued with an asterisk (*) atom, Y1()1 represents N or CH, and CX1G3X1G4 represents Ring 10 15 〇

(CV),

R 106

NT N 105 (CVI), loaded

CH3 CH, (CVII), order -

CH. CH. (CVIII), Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, Printed 20 25 R 107 R 106

V \r105 (CIX) or -27- 1252478 —-^ V. Description of invention (26) Α7 Β7,105

105 10 (CX)? wherein the asterisk (*) represents a ring atom extending from a double bond, and R1G5 represents hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyloxy Ethyl, methoxypropyl, cyanoethyl, benzylethyl, ethoxylated ethyl, gaseous ethyl, cyclohexyl, phenyl, tolyl, methoxyphenyl or a group of the formula group

XT (CXI), 15 R represents hydrogen, methyl, ethyl, propyl, butyl or trifluoromethyl, RlG7 represents cyano, methoxycarbonyl, ethoxycarbonyl, -CH2S03-Mh or has the formula The Ministry of Economic Affairs, the Intellectual Property Bureau, the employee consumption cooperative, printed 20

An- (CXII) or

An* (cxm), 25 M+ stands for cation, and -28- A7 B7 1252478 V. Description of invention (27)

Air represents an anion wherein a alkyl group such as propyl, butyl or the like may be branched. The bridging of the oligomeric or polymeric structure occurs via the Rl〇84 Riw. 5 In accordance with the invention, it is also preferred that the indigo is of the formula: (CXVI), wherein X105 represents S or CR11GRni, and R1G8 represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl 15 , octyl, methoxyethyl, methoxypropyl, cyanoethyl, benzylethyl, ethoxylated ethyl, gaseous ethyl, cyclohexyl, pentyl or phenethyl, R1G9 represents hydrogen , methyl, ethyl, methoxy, ethoxy, cyano, printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative

-X

10 gas, trifluoromethyl, trifluoromethoxy, methoxycarbonyl or ethoxy 20 carbonyl, R110 and R111 independently of each other represent methyl or ethyl, or CR11()R(1) represents a divalent formula Group 25 (CXV), ►Who/τ"·χτο, / -29- 1252478 A7 B7 V. Description of invention (28 10 where the two bonds are emitted by an atom with an asterisk (*), Ym for N or CH, and X103 for Cyano, ethoxymethyl, methoxycarbonyl or ethoxycarbonyl, X104 represents 2-pyridyl, 3-pyridyl or 4-pyridyl, thiazol-2-yl'benzothiazol-2-yl, carbazolyl , benzoxazole-2-yl, benzimidazole-2-yl, N-methylbenzimidazole-2-yl or n-ethylbenzimidazol-2-yl, preferably 2-pyridyl, The alkyl group, such as propyl, butyl, etc., may be branched. The bridging of the oligomeric or polymeric structure occurs via r1G8 or R1G3 (provided the latter represents an ester group). It is also excellent according to the invention. Department of Indigo is bound for the following styles. 15

CN (CXVII), wherein R 2 represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methyl, ethyl, methoxypropyl, cyanoethyl, hydroxy Ethyl, ethoxylated ethyl, chloroethyl, cyclohexyl, benzyl or phenethyl, R 3 and R 114 represent hydrogen or together represent _ch=chch=ch bridging, wherein fluorenyl group 'for example propyl , butyl, etc., can be branched, oligomeric or polymeric structure bridging connections occur via R112. -30- ·: Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 20 25 ^ Ο 1 „ „ 00^7 A7 B7 1252478 V. Description of invention (29 According to the present invention

R112 I 丫1 R113 I 104 R w (CXVIII), wherein R丨丨2 represents methyl, ethyl, propyl, butyl, pentyl, hexyl, broad-based, octyl, methoxyethyl 'methoxy Propyl, cyanoethyl, 10 hydroxyethyl, ethoxylated ethyl, gaseous ethyl, cyclohexyl, benzyl or phenethyl, R and R represent hydrogen or together represent -ch^ch-ch^ Ch-bridge, wherein the courtyard group, such as propyl, butyl, etc., may have a branch, Υ1ϋ1 represents N or CH, IS CXi〇3Xi. 4 represents the ring with the following formula 0

Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

1252478 A7 B7 V. Description of invention (30) 10

(CVIII), (CIX) or (CX), Binding 15 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 20 The asterisk (*) represents a ring atom extending from a double bond, representing hydrogen, methyl, ethyl, propyl , butyl, pentyl, hexyl, heptyl, octyl, methoxyethyl, methoxypropyl, cyanoethyl, hydroxyethyl, ethoxylated ethyl, chloroethyl, cyclohexyl, Phenyl, tolyl, methoxyphenyl or a group of the formula (CXI), R106 represents hydrogen, methyl, ethyl, propyl, butyl or trifluoromethyl, 25 R1G7 represents cyano, A Oxycarbonyl, ethoxycarbonyl, -CH2S (VMh -32- ^ «//^XTC\A / [252478

V. Description of the invention or group with the following formula

An· (CXII) or ^rv Arr

CH (CXIII), 10

The Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, printed M+ for the cation, and Alr for the anion, wherein the alkyl group, for example, _, such as propyl, butyl, etc., may have a branch. The connection of a bridge or a bridge structure occurs via R112 or R105. 15 It is also known that the enemy is also X103 Ιχ1. 4 (CXVIII), R , 20 where R represents thiol, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl Base, methoxyethyl, methoxypropyl, cyanoethyl, hydroxyethyl, ethoxylated ethyl, gaseous ethyl, cyclohexyl, benzyl or phenethyl, 25 R and feet represent hydrogen Or together represent -CH=CH-CH=CH-bridge, -33- A7 B7 1252478 V. Description of the invention (32) wherein the alkyl group, such as propyl, butyl, etc., may have a branch, Y1Q1 represents N or CH, X: represents cyano, acetate, methoxy or ethoxy group, X represents 2 to thiol, 3-port specific asthma; base or 4-port ratio bite base, 嗔 -2 -2 5 phenyl thiazino-2-yl, oxazol-2-yl, benzoxazol-2-yl, benzimidazol-2-yl, N-methylbenzimidazole_2-yl or N-B Benzimidazol-2-yl, wherein an alkyl group, such as propyl, butyl, etc., may be branched. The bridging of the oligomeric or polymeric structure occurs via Rlu or 10 x 1 () 3 (provided the latter represents an ester group). According to the present invention, the excellent department of Ou Qing is the following formula

1J (CXIX), in which the Ministry of Economic Affairs' Intellectual Property Office employee consumption cooperative prints R115 and R116 independently of each other to represent thiol, ethyl, propyl, butyl, pentylhexyl, heptyl, octyl, phenyl, octyl or Phenylethyl, or NR115!^116 stands for 咬 咬 、, 咬 bite or morphine, 20 CX1G3X1G4 stands for ring

[252478 V. INSTRUCTIONS (η 〇 105

R (CVI), 106〆

10 15

>105 (CVII), (CVIII), (CIX) or

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 20 25 (CX) where the asterisk (*) represents the ring atom extending from the double bond, R1. 5 represents hydrogen, methyl, ethyl, propyl 'butyl, pentyl, Hexyl, heptyl, octyl, methoxyethyl, methoxypropyl, cyanoethyl, hydroxyethyl, ethoxylated ethyl, gaseous ethyl, cyclohexyl, benzyl, tolyl, a Oxyphenyl or a group of the formula -35-

.2%. I 1252478 A7 B7 V. INSTRUCTION DESCRIPTION (34) (CXI), ^aso: R represents hydrogen, methyl, ethyl, propyl, butyl or trifluoromethyl, and Rl()7 represents cyano , methoxycarbonyl, ethoxycarbonyl, _CH2S03-Mh or a group of the formula 10

An·(CXII) or (CXIII), 15 M+ represents a cation, and Arr represents an anion, wherein an alkyl group such as a high-loading compound such as a propyl group, a butyl group or the like may have a branch. - The connection of the bridge of the poly or poly-sigma structure is printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives. 20 25 Occurrence According to the present invention, the excellent department is also the following.

X 104 (CXIX),

1252478 A7 B7 V. INSTRUCTIONS (π 10 15 wherein R15 and R116 independently of each other represent methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, benzyl or phenylethyl Or NRll5RU6 represents pyrrolidinyl, piperidinyl or decyl, χ1 (Π represents cyano, ethyl methoxy, methoxycarbonyl or ethoxycarbonyl, X represents 2-σ ratio, 3-吼The bite group or 4-σ is more than the bite group, the 嗟a is sitting on the base, the 嗔 is 11 is sitting on the -2 - group, the β-salt-2-yl group, the benzo-statin-2-yl group, the benzimidazol-2-yl group, Ν-Methylbenzimidazol-2-yl or fluorenyl-ethylbenzimidazol-2-yl, preferably 2-pyridyl, wherein the alkyl group, such as propyl, butyl, etc., may have a branch The bridging of the oligomeric or polymeric structure is via or X1Q3 (provided the latter represents an ester group). In formulas (CIII), (CXVI) and (CXVIII), Ym preferably represents CH, and in formula (CIII) , (CXVI), (CXVIII) and (CXIX), cxlG3xlG4 is better representative of formula (CV), (CVII), (CIX) or group binding with the following formula - Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative System 20 25

(CXX), -37- 1252478 A7 B7 V. Description of invention (36

NC S (CXXI),

NC

V (CXXII),

NC

N (CXXIII), 10

(CXXIV) minus

NC N

(cxxv), 15 where the double bond is emitted from the C atom with an asterisk (*). Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 20 -(ch2)2-, -(ch2)3-, -(ch2)4-, -(ch2)2-o-(ch2)2- and -ch2-c6h4 -ch2- is a better bridge. Polyacrylates, polymethacrylates and their copolymers with acrylamide are preferred polymer chains. The above groups R1G1, R1G5, R1G8, R112 and R115 represent, for example, monomer units having the following formula

(CCXXX), 25 -38- rr*^Q\ a λ « - 1252478 V. INSTRUCTIONS (37 where R represents hydrogen or methyl, and the atom marked with a negation (a) and an atom with an asterisk (*) are emitted The single bond to the N atom of the indigo dye represents the continuity of the chain. Some parts of the formula (!) are, for example, from F Wtinhner, Synthesis 1999, 2103; F. Wttrthner, R. Sens, KH Etzbach, G. Seybold , Angew·Chem 1999, ln, l753; German Patent Lang _ OS 43 44 116 'DE-OS 44 40 066; WO 98/23688; Japanese Patent JP 52 99 379; JP 53 14 734 is known. Palladium is also preferred as the light absorbing compound. In a preferred embodiment, the phthalocyanine used is a compound of the formula 15 wherein MMR3UR4]x[R5]y[R6]z (1) is given. Property Bureau Staff Consumer Cooperative Printed 20 25

Pc stands for ouhuaqing or naphthalocyanine, wherein in both cases, the aromatic ring may also be a heterocyclic ring, such as tetrakisyl 卟咐 秦 ,, — Μ represents two independent ruthenium atoms, representing a divalent metal. An atom or a trivalent axially monosubstituted metal atom having the formula (la)

Me (la), or a tetravalent axially substituted metal atom MC of the formula (lb), / -39- 1252478 A7 V. Description of invention (38 f1 Me IX. (lb), 10 15 Ministry of Economics Intellectual Property Bureau employee consortium prints 20 25 or represents a trivalent axial monosubstituted and axial monocoordinated metal atom of formula (lc) in 1 (lc) X2 where in the case of charged ligand X2 or χι The charge is compensated by a counter ion (for example, an anion Αββ or a cation®), and the groups R3 to R6 correspond to a substituent of the phthalocyanine ring, and X1 and X2 independently represent a halogen (for example, F, Cl, Br, I), Hydroxy, oxygen, cyano, thiocyanate, cyanate, alkenyl, alkynyl, arylthio, dialkylamino, alkyl, alkoxy, decyloxy, thiol, aromatic a group of aryl, aryloxy, -〇-§[〇2118, 〇-PR10Rn, -〇-P(〇)Ri2Ri3, _〇_siR14R15Ri6, Nh2, alkylamino and heterocyclic amine, R3, R4, R5 And R6 independently of each other represent halogen (eg, F, Br, I), cyano, nitro, alkyl, aryl, alkylamino, dialkylamino, alkoxy, alkylthio, aryloxy , arylthio group, S03H, SC^NW, C02R9, CONW, NH-COR7 or a group of the formula -(B)mD, wherein B represents a straight chain, CH2, CO, CH(alkyl), C(alkyl)2, NH , S, Ο or "Η - the formation of the group of bridges, (B) m represents the bridge constitutes a chemically reasonable sequence of B (where m is 1 to -40 - 1252478

5. Description of the invention ' m is preferably i, 2, 3 or 4, D represents a monovalent group (Red) of a redox system of the formula or © ^ 0 2?=£:CH~CH:^ (〇x 10 15 or represents a metal dialhoenyl group or a metal ditenyl carbonyl group, titanium, manganese, iron, ruthenium or iron is suitable as a metal center, and Z1 and Z2 independently represent NR, R", OR "or SR", Y1 represents NR', 〇 or S, Y2 represents NR', η represents 1 to 10, and R" independently of one another represents hydrogen, alkyl, cycloalkyl, aryl or heteroaryl, or卞 or 卞H=CH 廿^ =fCH-CH^= One of the C atoms of the 20 25 chain formed by the Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative forms a straight chain or bridge, W, x, y and z stand independently of each other. To 4, wherein w+x+y + z< 16, R1 and R2 independently of each other represent hydrogen, an alkyl group, a hydroxyalkyl group or an aryl group, or R1 and R2 together with the N atom to which they are bonded form a heterocyclic ring 5-, 6 - or a 7-membered ring, optionally with additional heteroatoms from the group consisting of N and S, NW specifically representing pyrrolidinyl, lyophilized or thiol, -41- A7 B7 1252478 V. Description of invention (4〇 R7 to R16 independently of each other represent an alkyl group, an aryl group, a heteroaryl group or a hydrogen, particularly an alkyl group, an aryl group or a heteroaryl group.

Air represents an anion, particularly a halide, Cl- to C2G-alkyl COCT 'decanoate, oxalate, lactate, glycolate, lemon 5, CH3OSCV, NH2S03-, CH3S03-, 1/2S042- or 1 /3P043-. Wherein M represents a group of the formula (lc), particularly c〇(III) as a metal atom, preferably a heterocyclic amine ligand or a substituent (χι and X2 10 represent 咐, 唆唆, miso , bite, 2,2-biguanide, 4,4-bis-n-bipyridyl, anthracene, pyrimidine, piperidine, imidazole, benzimidazole, isoxazole, benzisoxazole, carbazole, benzene And carbazole, thiazole, benzothiazole, morphine, pyrene, anthracene and 3,3-dimethylhydrazine, each of which is coordinated or substituted with a metal atom in the nitrogen atom). 15 Alkyl, alkoxy, aryl and heterocyclic groups may optionally carry groups of the Ministry of Economic Affairs, the Intellectual Property Office, and the consumer cooperatives, such as alkyl, hydroxy, hydroxyalkyl, amine. , alkylamine, dialkylamine, tribasic, cyano, CO-NH2, alkoxy, alkoxy, decyl, fluorenyl, fluorenyl, hydrazine, tricarbite Xishou base, three bases dream to burn oxy or phenyl. The alkyl group and the alkoxy group may be saturated, unsaturated, linear or branched, the alkyl group may be partially halogenated or fully dentated, and the alkyl group and the oxy group may be ethoxylated. Or propoxylation or oximation. The alkyl and/or alkoxy groups adjacent to the aryl or heterocyclic group may together form a three or four member bridge. Preferred compounds of formula (1) are those wherein the following applies to the groups R1 to 25, R' and R" and to the ligand or substituents χι and X2: • 42- 1252478 at Β7

The substituent represented by "alkyl" preferably represents (: 1-(: 16-alkyl, particularly alkyl, which may optionally be halogen (e.g., gas, bromine or fluorine), thiol, cyano and/or ^ /^ alkoxy substituted; the substituent represented by "alkoxy" preferably represents c "c16-alkoxy, 5 especially G-C6-alkoxy, which may optionally be halogen (eg, gas, fill or Fluorine, hydroxy, cyano and /SCrCr alkyl substituted; the substituent represented by "cycloalkyl" preferably represents C4_C8-alkyl, especially cs- to ce-c cycloalkyl, which may optionally be halogen ( For example, a gas, a fluorine or a fluorine group, a hydroxyl group, a cyano group, and/or a CrC6-alkyl group; and 10, the substituent represented by "alkenyl group" preferably represents (6-(:8-alkenyl group), which may optionally be halogen (e.g., chlorine, bromine or fluorine), hydroxy, cyano and/or Cr c6-alkyl substituted, alkenyl specifically represents allyl; substituents represented by "heteroaryl" preferably represent 5 to 7 members The heterocyclic group of the ring 'preferably contains a heterologous 15 selected from the group consisting of N, S and/or hydrazine, and optionally fused with an aromatic chain, or optionally with additional substituents, such as a tooth. Prime Hydroxy, cyano and/or alkyl, the following are the best: hydrazine, sulfhydryl, fluorenyl, hydrazino, hydrazino, miso, fluorenyl, benzoxazolyl, Benzothiazolyl and benzimidazolyl; The Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative printed the substituent represented by "aryl" (: 6-(:1()-aryl, especially 20 phenyl) Or a naphthyl group, which may optionally be substituted by halogen (e.g., f or C1), hydroxy, (VC6-alkyl, cvcv alkoxy, νο2 and/or CN. R3, R4, R5 and R6 are preferably independently of each other. , fluorine, bromine, iodine, cyano, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, third amyl, hydroxyethyl, 3-di Methylamine 25-propyl, 3-diethylaminopropyl, phenyl, p-t-butylbenzene-43- A7 B7 1252478 V. Description of invention (4) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative Base, p-methoxyphenyl, isopropylphenyl, trifluoromethylphenyl, naphthyl, methylamino, ethylamino, propylamino, isopropylamino, butyl Amino, isobutylamino Third butylamino group, amylamino group, third amylamino group, benzylamino group, methylphenylcyclohexylamino group, hydroxyethyl 5 amine group, aminopropylamino group, amine group B Amino group, 3-dimethylaminopropylamino group, 3-diethylaminopropylamino group, diethylaminoethylamino group, dibutylaminopropylamino group, hydrazine Alkylamino group, σ butyl propylamino group, pyrrolidinyl propylamino group, pyrrolidone propylamino group, 3-(methylhydroxyethylamino)propylamino group, methoxy group Ethylamino, ethoxyl 10 ethylamino, methoxypropylamino, ethoxypropylamino, methoxyethoxypropylamino, 3-(2-ethylhexyloxy) Propylamino, isopropyloxypropylamino, dimethylamino, diethylamino, diethanolamine, dipropylamino, diisopropylamine, dibutylamine , diisobutylamino, di-tert-butylamino, dipentylamino, di-t-amyl 15 amine, bis(2-ethylhexyl)amine, bis(aminopropyl) Amino, bis(aminoethyl)amine, bis(3-dimethylaminopropyl)amine, bis (3- Ethylaminopropyl)amino, bis(diethylaminoethyl)amino, bis(dibutylaminopropyl)amino, bis(morpholinopropyl)amino, di(piperidin Octyl propyl)amino, bis(pyrrolidinopropyl)amino, bis(pyrrolidinopropyl)amine 20, bis(3-(methylhydroxyethylamino)propyl)amine, Dimethoxyethylamino, diethoxyethylamino, dimethoxypropylamino, diethoxypropylamino, bis(methoxyethoxyethyl)amine, Bis(methoxyethoxypropyl)amino, bis(3-(2-ethylhexyloxy)propyl)amino, mono(isopropyloxypropyl)amino, methoxy, Ethoxy, propoxy 25, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy-44- broad Λ 1 Λ 4 ft /r^xicx A7 B7 1252478 V. Description of the invention ( 43) benzyl, pentyloxy, methoxyethoxy, ethoxyethoxy, methoxypropoxy, ethoxypropoxy, methoxyethoxypropoxy, 3 (2-ethylhexyloxy)propoxy, methylthio, ethylthio, propylthio, isopropylthio, butyl Base, isobutylthio, tert-butylthio, pentylthio, 5th pentylthio, phenyl, methoxyphenyl, trifluoromethylphenyl, naphthyl, C02R7, CONRiR2, NH-COR7 , S03H, SC^NW or 轼佳 is a group with the following formula 10

Or (B)^

CO i〇, co 订 · where (7)乂 represents 15 r°- -CH2-〇-,^C2H4-0- . *CH(CH3)〇- -C—OCHj or jj—〇c2H4 ·! Ministry of Economic Affairs Intellectual Property Η Consumer Cooperatives Print 20 25 where the asterisk (*) represents a link to the 5-member ring,

Mi represents Μη or Fe cations, w, X, y and z independently of each other represent 〇 to 4, wherein w+x+y+z幺12, NWR2 preferably represents an amine group, a methylamino group 'ethylamino group, Propylamino, isopropylamino, butylamino, isobutylamino, tert-butylamino, pentylamino, third amylamino, benzylamino, methyl styl Cyclohexylamino, 2-ethyl-1-hexylamino, hydroxyethylamino, aminopropylamino, aminoethylamino, 3-dimethylamine-45-A7 B7 1252478 DESCRIPTION OF THE INVENTION (44) propylamino group, 3-diethylaminopropylamino group, morphinylpropylamino group, dimethyl propylamino group, 11-pyridylpropylamino group, hip hop Mercaptopropylamino, 3-(methyl-ethylethylamino)propylamino, methoxyethylamino, ethoxyethylamino, methoxypropylamine 5, B Oxypropylpropylamino, methoxyethoxypropylamino, 3-(2-ethylhexyloxy)propylamino, isopropoxyisopropylamino, dimethylamino, Diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di Butylamino, dipentylamino, di-third amylamino, bis(2-ethyl10 hexyl)amine, dihydroxyethylamino, bis(aminopropyl)amine, double ( Aminoethyl)amino, bis(3-dimethylaminopropyl)amino, bis(3-diethylaminopropyl)amino, bis(indolylpropyl)amino, two (唆 唆 propyl) amine group, di (σ ratio each mercaptopropyl) amine group, di(σ-pyrrolidinopropyl)amino group, bis(3-(methylhydroxyethylamino)propyl Base) 15 Amino, Dimethoxyethylamino, Diethoxyethyl Amine, Ericsson Intellectual Property Office Staff Consumer Cooperative Printed methoxypropylamino, diethoxypropylamine , bis(methoxyethoxypropyl)amino, bis(3-(2-ethylhexyloxy)propyl)amino, bis(isopropyloxyisopropyl)amine, aniline Base, p-toluidine, p-t-butylanilino, p-anisylamino, isopropyl 20 anilide or naphthylamino, or NW preferably represents pyrrolidinyl, piperidinyl, piperidine Or a thiol group, R and R16 independently of each other preferably represent hydrogen, methyl, and , propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, third amyl, phenyl, p-tert-butylphenyl, p-methoxyphenyl, iso 25 Propyl phenyl, p-trifluoromethylphenyl, cyanophenyl, naphthyl, 4_-46-

A7 B7 1252478 V. Description of the invention (45) Pyridyl, 2-pyridyl, 2-indenyl, 2-pyrrolyl or 2-indenyl, alkyl, alkoxy, aryl and heterocyclic groups Depending on the case, 5 may carry additional groups such as alkyl, dentate, thiol, alkyl, amine, alkylamine, dialkylamine, nitro, cyano, CO-NH2, alkane. Oxy, alkoxy k-, decyl, miso, carbyl, indolyl, trialkyldecyl, trialkyldecyloxy or phenyl. The alkyl and/or alkoxy group may be saturated, unsaturated, linear or branched, the alkyl 10 group may be partially or fully dentated, and the alkyl and/or alkoxy group It can be ethoxylated or propoxylated or decylated. The adjacent alkyl and/or alkoxy groups on the aryl or heterocyclic group may together form a three or four member bridge. In the context of this case, it is understood that the redox system representative is described in Angew Chem. 1978, page 927 and Topics Currentf Current Chemistry, Vol. 92, p. 1 (1980). Preferably, p-diphenyldiamine, phenoxypurine, dihydrogen sulfonium, diterpene salt (vi〇l〇gens) and quinodimethane are preferred. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives, in a preferred embodiment, using 具2〇花青, where Μ represents two independent H atoms, or represents Cu, Ni, Zn. , pd,

Pt, Fe, Mil, Mg, Co, Ru, Ti, Be, Ca, Ba,

a divalent metal atom of a group consisting of Cd, Hg, Pb, and Sn, or 25 Μ represents a trivalent axial monosubstituted metal atom having the formula (la), w -47- 5 invention description (46) represents Al, Ga, Ti, In, Fe, and Μη, or % represents a tetravalent axially disubstituted metal atom of the formula (ib), and the cap e represents Si, Ge, Sn, Zr, Cr, Ti, Co, and v. 5 ^ T and X 2 are particularly preferably dentate (especially chlorine), aryloxy (especially phenoxy) or alkoxy (especially methoxy R3-R6 particularly preferably represents halogen, alkyl or alkane The oxime cyanine which is represented by the formula of the formula (la) or (lb) is particularly preferred. The extremely preferred w, x, and yAz each represent 〇. In a particularly good manner, Each of (a) or (lb) and/or X2 represents a dentate. The phthalocyanine used in accordance with the invention may be prepared by known methods, for example: - oxidation of a corresponding metal, metal halide or metal In the presence of a substance, by 15 nucleation from the correspondingly substituted phthalonitrile, - by chemical modification of phthalocyanine (for example, by sulfo gasification or gasification of phthalocyanine) and The reaction (for example, a condensation reaction or a substitution reaction from a product), the axial substituents χι and X2 are usually produced by the exchange of the corresponding 20 halides. The light absorbing compound should preferably be thermally reformable. Preferably, the effect is carried out at a temperature < 700 ° C. Such modification may be, for example, in a chromophore of a light absorbing compound. Decomposition, morphological change or chemical modification 25 〇-48- A7 B7 1252478 V. Description of the invention (The light absorbing compound described in π ensures a sufficiently high reflectivity of the optical data medium in an unrecorded state, and During the point-by-point illumination of blue light (especially for laser light, preferably in the wavelength range of 360 to 460 nm), the thermal cracking of the 4 information layer has a high absorption. Since the information layer has been changed after 6 recordings Optical properties, so by comparing the amplitude of the incident light and the reflectance of the phase, it is possible to understand the contrast between the recorded and unrecorded parts of the data medium. In particular, the light absorbing compound ensures a sharply defined shape with a reflectance drop in the recorded mark. Readout signal. 10 In other words, the optical data medium is preferably capable of recording and reading laser light from 36 〇 to 46 〇 nanometers. The coating of the sapphire is preferably by spin coating, splashing or Vacuum gas deposition is carried out. By vacuum gas deposition or sputtering, it is possible to apply, in particular, phthalocyanine which is insoluble in organic or aqueous medium, preferably of formula (1), wherein w, X , y&z each represents 0, and Μ represents 15

1 or on behalf of AI

Dry 1 Si I where Xi&x2 has the above definition Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative 20 25 In particular, phthalocyanine dissolved in organic or aqueous media is also suitable for application by spin coating. Enemy cyanine can be mixed with each other or with other dyes with similar spectral properties. In addition to phthalocyanine, the information layer may contain additives (such as binders, wetting agents, stabilizers, diluents and sensitizers) as well as additional ingredients in addition to phthalocyanine. The indigo dye is preferably applied to the optical data carrier by spin coating or vacuum gas deposition. The indocyanines may be mixed with each other or with other dyes having similar spectral properties. In addition to the part of the indigo dye, the information layer can be -49- call 1252478 ----- five, invention description (48) A7 B7 5 ο 1

5 IX Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Print 20 5 2 Contains additives (such as adhesives, wetting agents, stabilizers, thinners and sensitizers) and other ingredients. In addition to the information layer, the optical data storage can have additional layers (e.g., metal layers, dielectric layers, barrier layers, and protective layers). The metal, dielectric layer and/or barrier layer are used in particular to adjust the reflectivity and heat balance. Depending on the wavelength of the laser, the metal can be gold, silver, aluminum, alloy, and the like. Examples of the dielectric layer are cerium oxide and cerium nitride. The barrier layer may be composed of a dielectric layer or a metal layer. The protective layer is, for example, a photohardenable coating, a metal adhesive layer, a pressure sensitive adhesive layer, and a protective film. The pressure-sensitive adhesive layer is mainly composed of an acrylic adhesive. Niu〇 Denko DA-8320 or DA_8310 (disclosed in Japanese Patent Jp-A 273 147) can be used, for example, for this purpose. As shown in Fig. 1, the optical data storage device preferably comprises a transparent substrate (1) 'If necessary, a barrier layer (2), an information layer (3), a barrier layer (4) is used as needed, and a binder layer is used as needed ( 5) and cover layer. Preferably, the structure of the optical data medium can be: - containing a preferably transparent substrate (1) 'the surface has been applied with at least one information layer (3) that can be recorded using light, and a barrier layer (4) is optionally used, if necessary The adhesive layer (5) and the cover layer (6) are selected. - containing a preferred transparent substrate (1), the surface of which has been applied with a barrier layer (2), at least one information layer (3) which can be optically recorded, optionally a binder layer (5) and a transparent cover layer (6). - containing a preferred transparent substrate (1), the surface of which has been applied with a barrier layer (2), at least one information layer (3) which can be recorded by light, and a barrier layer (4) if necessary, optionally using a binder Layer (5) and transparent cover layer-50- Weeping W Shishi fine by who talks about, 〇1Λ 〇fV7 eight A7 B7 1252478 V. Description of invention (49) (6) 〇 contains a better transparent substrate (1) It is located on the surface of at least one information layer (3) that can be used for optical recording, optionally with a binder layer and a transparent cover layer (6). Furthermore, the invention relates to an optical data medium according to the invention which can be recorded using blue light (especially for laser light, particularly preferably with a laser light of 36 〇 46 μm). The following examples illustrate the subject matter of the present invention. 10 Examples Example 1 15 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Print 20 25

The dye monogas-aluminum-indane cyanine (AlCIPc) is applied to the information layer. The disc structure used is shown in Figure 2a. The polycarbonate substrate was molded by injection to form a trench structure having a pitch of 64 μm and a depth of 40 nm. A 40 nm information layer was applied directly over the surface of the trench by vacuum gas deposition. For -51-

: ιύ, I A7 B7 1252478 V. INSTRUCTIONS (50 Avoiding the diffusion of the information layer into the adhesive layer, the RF layer is coated with a 25 nm thick Si〇2 buffer layer by RF reactive sputtering. A pressure sensitive adhesive (PSA; Nitto Denko DA/8320) was used as the adhesive layer and an additional cover layer (polycarbonate) on the incident light side of the medium. The total thickness of the adhesive layer and the cover layer was set to 100 μm. And the recording parameters are set as follows. The wavelength of the laser light = 405 nm The numerical aperture of the objective lens = 0.85, the two-unit lens read laser power = 0.30 mW 10 15 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 20 Write Ray Shooting power = 6.0 mW. Linear speed of disc rotation = 5.72 m/s write mark and gap length = 0.69 μm, periodic pulse wave strategy = 7 pulses per mark (with 50% mission ratio) After the groove track is recorded, as shown in Fig. 2, a square waveform can be obtained, where R represents the reflectance from the medium, and the cardiogram represents the initial reflectance. It is apparent in this figure that the recorded range is displayed as needed. Consistently lower reflectivity. At 3 The 0 kHz resolution bandwidth (RBW) carrier _ hum is 48.4 decibels (dB). Although the information layer covers only the thin Si 〇 2 buffer layer and the soft PSA layer, the read stability is shocking: The ground height is almost the same as that of a CD-R or DVD-R media containing a hard covering of UV resin. Similar results can be obtained when recording on the surface of the trench structure. 25 Example 2 -52- A7 B7 1252478 V. Description of invention (51)

Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Co., Ltd. 10 Dye dichloro-indole-cyanine (SiCl2Pc) is applied to the information layer. apart from

The Si〇2 thickness was set to 40 nm, and the disc structure used was the same as in Example 1. The recording conditions were also the same as in Example 1. The results show that the square waveform is clearly recorded in this medium with very low click and high modulation ratio (Figure 3). At a RBW of 30 kHz, the carrier-15 hum ratio is 55 decibels. The distortion of the read mark is very small, and it is apparent that the combination of the dye and the layer structure conforms to such media format and optical pickup parameters. Furthermore, 'there is also a very high read stability. The C/N level remained at this high level until the reading power of 毫·7 mW. Based on its high performance in recording and reading stability, this media shows 20 extremely high potential for high density recording. The random pattern recording with (1,7) RLL modulation was performed with a minimum mark length of 0.173 microns. The data capacity on a single 12 cm diameter disc is related to 21 GB (billion) (when it is recorded on both the surface and the slot). As shown in Fig. 4, when the surface is recorded, a conspicuous eye pattern is obtained, and the image beat level is 1%. A similar result is available in the trough, thus showing its potential on a single-sided disc -53- A7 B7 1252478 V. Description of the invention (52) at a capacity exceeding 21 GB. Example 3

The above dyes are applied to the information layer. The disc structure and recording parameters are the same as in the actual example 15. Similar to Example 1 and Example 2, it shows a square waveform with high readout stability (Fig. 5). The c/Ν level at 3 kHz resolution bandwidth is 45 dB. In a similar manner, the dyes of Examples 3-23 can be used. Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumption Cooperative, Printed -54-

A7 B7 1252478 V. Description of invention (53) Paste 3-23 (MeXiX2) PcR3R4R5R6 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 5 2 ο IX 5 IX 20 Nr· Me Xi X2 R3 R4 R5 R6 4 A1 o-c6h5 - - - - - 5 Zn - - - - - - 6 V =0 • - - - - 7 Ga Cl - - - - - 8 In Cl - - - - - 9 Ge Cl Cl - _ - 10 Si OCH2CH3 OCH2CH3 - - - - 11 Si ch3 Cl - - - - 12 Si Phenyl Cl - - - - 13 Si ch3 OCH2CH3 - - - Face 14 Si OSi(CH3)3 OSi(CH3)3 - - - - 15 Si Cl Cl C(CH3 ) 3 C(CH3)3 - - 16 Si Cl Cl C(CH3)3 C(CH3)3 C(CH3)3 C(CH3)3 17 A1 Cl - C(CH3)3 C(CH3)3 C(CH3 )3 c(ch3)3 18 A1 OH - - - - - 19 A1 Cl - Si(CH3)3 Si(CH3)3 Si(CH3)3 Si(CH3)3 20 Ti OSi(CH3)3 OSi(CH3) 3 - - - - 21 Sn OSi(CH3)3 OSi(CH3)3 - - - 22 Zr OSi(CH3)3 OSi(CH3)3 - - - - 23 Ru OCH2CH3 OCH2CH3 - - - - 8

1252478 V. DESCRIPTION OF THE INVENTION Example 24 2.1 g of 1-butyl_3-cyano-'methylhydroxy-2-pyridine_ and 2·〇克 1,3,3-trimethyl吲啐_2_仙51 Wood 2 stretched methyl-omega-aldehyde was stirred for 2 hours at 90 ° C in 5 liters of salic anhydride. After cold 铉 ^ , after the pen gambles P, pour the mixture into 100 liters of water t, filter by suction, and wash the residue with the ice of the pen. Then, the solid matter was stirred in 20 liters of water/methanol, 3 sk, 4sk K, and 3,1, and filtered by suction and dried to 3.3 g (85% of theory) of red powder of the following formula 10

(CCI) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

Mp=249-251〇C 15 UV (dioxane): Xmax=520亳micron UV (DMF): Xmax=522亳micron 8=113100 liters/mole centimeters Δλ=2 nm^1/2"^! /! 〇 (long wavelength slope) = 12 nm 20 solubility · · TFP (2, 2, 3, 3-tetrafluoropropanol) > 2%. Example 25 The same procedure was followed using 1.7 g of 1-propyl-3-cyano-methyl- 6-hydroxy-2-pyridinone and 1.7 g of N-methyl-N-(4-methoxyphenyl) > Propylene 25, 2.6 g (79% of theory) red powder with the following formula push / Λ / -56- A7 B7 1252478 V. Description of invention (55) h3c CH.

(CCII) Pack mp=206-216°C UV (dioxane): Xmax=482亳micron UV(DMF): Xmax=477nm ε=73013 liters/mole centimeters 10 Δλ=5 nm into 1/ 2-^^0 (short wavelength slope) - 33 house micrometer solubility: in TFP > 2%. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing example 26 will be 2·03 g of chlorinated 3-indolyl-4-methyl-6-pyridyl·吼唆_ and 2.〇克 1,3,3-three Methyl hydrazine-2-methyl aldehyde was stirred in 9 liters of 1 liter of acetic anhydride for 2 hours. After cooling, the mixture was poured into 2 ml of water. 2.8 g of sodium tetrafluoroborate was added to the organic solution. After stirring overnight, the mixture was filtered with suction, and the residue was washed with 20 ml of water and dried. This gives 3.3 g (74% of theory) of reddish orange powder of the following formula 15 25

-Push /r'XTC'v λ λ Shoot · (CCIII) m A7 B7 1252478 V. Description of invention (56)

Mp > 300 ° C UV (methanol): λ_χ = 513 亳 micron ε two 86,510 liters / mole centimeter λ 1/2 - λ 1 / 1 () (short wavelength slope) = 38 nm 5 Solubility: in TFP > 2%. Example 27 0. 7 g of 5-dimethylamino anthraquinone-2-carbamate and 1.5 g of N-methyl-Ν'-d-dodecyl-barbitic acid at 90 °C Stir in milliliters of 10 acetic anhydride for 30 minutes. After cooling, the mixture was poured into 1 ml of ice water, filtered with suction, and the residue was washed with water. This gives 1.7 g (79% of theory) of orange powder of the formula

Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

Mp = 118-120 〇C 20 UV (- σ smoldering) · Xmax = 483 nm ε = 53360 liters / Moen centimeters 短 (short wavelength slope) = 32 nm solubility · in benzyl alcohol > 1 %. 25 Further examples according to the present invention are shown in the following table: -58- 1252478 a7 B7 V. Description of invention (57) Table 1 (Formula (VI)) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing example d X3 Y1 = Cxlx2 Xmax 丨) /nm ε / 1/mol cm λι/2-λι/ι〇/nm △λ2) /nm 28 Η~winter h3c C-CN =C(CN)2 470 40990 323) 16 29 ” CH ch3 vVCN 〇V〇C3H7 502 62860 333) 30 CH ” 539 146480 184) 1.5 31 ” CH 〇人〇}CH3 ch3 472 70880 323) 5 32 ” CH 〇O人N人〇1 ch3 490 (DMF) 33 ” CH ch3 0 people N people 〇 1 ch3 539 106640 34 cue h3c CH ch3 0 people fjj people 0 c3h7 -59- 1252478 V. Invention description (5〇A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing example Y1 =CX!X2 λ ” /nm ε / 1/mol cm λΐ/2-λι/ι〇/nm △λ2) /nm 35 5 CH ch3 "γίγ0Ν O人0 c2h5 508 78400 36 ~Ay s CH 〒h3 0 peopleN people 0 Lo, 536 112260 37 X wide.人· CH 0 '^v^^n^C12H25 0 people N into 0 I ch3 483 53360 38 ” CH ch3 ^YCN O^N^O c6h13 535 128960 1.3 39 (y reputation CH ch3 o person rjj person o c2h5 536 ( DMF) 115603 2 40 5 CH ch3 ^ycn O^N^O c3h7 535 112260 134) 41 CH h3c D =tS=〇/Nh b^· -60-

Tfr η 1252478 V. Description of invention (59) hi B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing example Y1 =CX 丨X2 λ.") /nm ε / 1/mol cm λΐ/2-λι/ι〇/nm Δλ2) /nm 1 1 1 1 1 1 1 砸1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 t 1 1 1 1 1 1 1 η 1 1 1 1 1 1 1 1 4 1 1 1 1 1 馨·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 Value 1 1 1 1 1 42 Eight CH H3C\Factory ΤΛ ( CH, 43 N ch3 ^γ0Ν O^N^O c3h7 44 ” C-CN =c(cn)2 45 〇尽 CH ch3 0 people N people. 〇丫0 CH3 - / 46. 〇冬 CH cf3 ^YCN O^ N^O c3h7 47 ο尽 CH ch3 ^YCN 〇人νΛο (y 48 CH cm7 ^Ccn 0 people N people 0 49 ” CH ^yCN 455 -61- A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing example oV X3 Y1 = CX! X2 λ") / nm ε / I / mol cm λ ΐ / 2 - λι / ι 〇 / rim △ λ2) / nm 50 CH ch3 ^ YCN 0 people N people Ο 538 51 CH CN cold. 537 537 132860 52 X f\ CH 490 35000 403) 23 53 CH points. ~丫n * C2H,〇X[f^ 0 431 (DMF) 54 ” CH ch3 0人N丄. ^°Ύ% 〇π 1 536 (DMF) 55 CH ch3 ^yCN. Person N. k 536 (DMF 1252478 V. INSTRUCTIONS (60) 10 15 20 ” in dioxane (unless otherwise specified)

-1 into DMF- into dioxane I 3) on short-wavelength slope 25 4) on long-wavelength slope-62- A7 B7 1252478 V. Description of invention (61) Table 2 (formula (VII)) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative Printing example Y'Y1 = CX 丨X2 λ^χ1) /nm ε / 1/mol cm λΐ/2-λι/ι〇/nm △λ2) /nm 56 〇^3 ch3 CH-C(CN) =C (CN) 2 499 46470 363) 5 57 ” CH-CH CN ^Y〇, c3h7 〇 429 60390 303) 7 58 ” CH-CH 0 487 102220 353) 6 59 ” CH-CH 0 0 person — —ch3 :h3 448 76260 273) 2 60 ” CH-CH 4 —ch3 :h3 469 76130 283) 3 61 ” CH-CH gh3 ^YCN 0 people 7 people 0 c4h9 520 113100 124) 2 62 CH3 wp \ ch3 CH-C(CN) =C(CN)2 511 31345 363) 6 -63- m 0, 1252478 V. Description of invention (62 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing example • Y2-Yl ^CX^2 λ·χυ /nm ε / 1/mol cm λΐ/2·λι/ι〇/nm △λ2) /nm 63 H3 you \ ch3 CH-C(CN) ” 503 41530 363) 6 64 H3C, pu cip ch3 CH-CH NC 0 519 55910 114) 65 05= CH-CH ch3 0 people rjJ people 0 c3h7 66 ” CH-CH 〇<Y^ch3 0 people N people S 1 ch3 486 115091 67 J^CH3 0ί= CH-CH cf3 Y^ YCN 0人V人0 c3h7 68 CH-, up \ ch3 CH-CH 〇乂2h5 〇丄〒人0 ch3 69 ” CH-CH ch3 \ 473 47640 -64- 喔定 - « 1252478 V. Description of invention (63) A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing example Y2-Yl =CXlX2 Knj /nm ε / 1/mol cm λΐ/2-λι/ι〇/nm △λ2) /nm 70 CH3 CH-CH cf3 ^YCN C6h13 71 ” CH-CH cooc2h5 496 62720 72 ” CH-CH.乂0 c4h9 500 110332 73 05= CH3 CH-CH 0 ^T^f^^N+(CH3)3 0 people N into 0 + 2BfV kvs^^N(CH3)3 74 ar c2h5 CH-CH ch3 O^N^ O c4h9 490 (DMF) 109380 5 75 Ch, ch3 CH-CH c〇〇c2h5 c〇〇c2h5 450 76 \ ch3 CH-CH NKO 462 57230 343) 77 H, C CH-C(CN) =c(cn) 2 500 -65- /^XTO\ A >1 -10 -Mr ^<\Π /X Λ 1252478 V. Description of invention (64) A7 B7

In the dioxane (unless otherwise specified)

)-1 into DMF"* into dioxane I 3) on short-wavelength slope 10 4) printed on the long-wavelength slope Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative -66- A7 B7 1252478 V. Description of invention (65) Table 3 (VIII)) Printed by the Ministry of Economic Affairs' Intellectual Property Bureau employee consumption cooperative

Ex. NR9R10 Yl =CX*X2 λ") /nm ε / 1/mol cm λΐ/2-λι/ι〇/nm △λ2) /nm 79 H3C, n^^ ch3 CH ch3 0人〒人〇c3h7 462 77180 283) 8 80 ” CH 〇, Λν, η3 O^N^S 1 ch3 81 ” CH ch3 h3c dh BF, 82 ” CH cf3 ^YCN 0 people Y. c4h9 918 (DMF) 89100 83 CH ch3 ^YCN O ^N^OI 〇458 89800 283) 84 ch3 CH Φ〇〇447 84070 85 ” CH ch3 ^YCN c3h7 480 79685 1.3 -67- 1252478 a? _ B7 V. Description of invention (66

Ex. =cxlx 2 /nm ε / I/mol cm into i/τλι/ιο /nm △λ2) /nm 86 nr9r10 Y1

》in ^一 σ 烧烧 (unless otherwise specified)

453 (DMF) 2)==Ιλλ-λ 10 DMF"^dioxane · 3) On short wavelength slope 4) On long wavelength slope Example 87 Apply the dye shown in Example 76 to the information layer

The structure of the disc used by the Intellectual Property Office of the Ministry of Economic Affairs is shown in Figure 2a. The polycarbonate substrate was molded by an injection method to form a trench structure having a depth of 20 Å and a depth of 40 Å. The information layer is applied directly over the surface of the trench by spin coating. The parameters for spin coating are as follows. Solvent: tetrafluoropropanol (TFP) solution: 1 · 〇 weight % 25 disc rotation rate for coating solvent · 220 rpm, 12 sec - 68 · A7 B7 1252478 V. Description of invention (67) Throw And the rotation speed of the disc for drying: 12 rpm, 30 seconds in the groove and the thickness of the dye layer on the surface are 80 nm and 60 ns, respectively. In order to prevent the information layer from diffusing into the adhesive layer, the information layer is covered with a 40 nm thick SiN buffer layer by a 5 RF reaction method, followed by coating a pressure sensitive adhesive (PSA; Nitto Denko DA/8320). The adhesive layer and an additional cover layer (polycarbonate) are on the incident light side of the media. The total thickness of the adhesive layer and the cover layer was set to 100 μm. The reading and recording parameters are set as follows. 10 laser light wavelength = 404 nm objective lens numerical aperture = 0.85, two unit lens read laser power = 0.30 mW write laser power = 6.0 亳 watt disc rotation linear speed = 5.72 m / s 15 Write mark and gap length = 0.69 micron, periodic pulse wave strategy = 7 pulses per mark (with 50% mission ratio) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed so that after recording in the groove track, Obtain the square waveforms of the groove and the surface area respectively as shown in Fig. 61 and Fig. 61. Here, r represents the reflectance of the self-media 20, and RInit represents the initial reflectance. It is apparent in this figure that the recorded range shows a consistently lower reflectance as desired. Carrier-to-sound ratio (C/N) measurements were performed using the Takeda Riken TR4171 with a groove and surface of 57 4 and decibels and 53·0 dB at 30 kHz resolution bandwidth (RBW). These high C/Ns confirm their high efficiency for high-density recordings (since this media can be recorded simultaneously on the surface/trench), which creates a practice -69- push/v^XTcn A7

1252478 The distance between the upper and lower tracks is 〇 32 microns. Furthermore, it should be noted that the ratio (self-marking reflectance / Rlnit) is almost 80%. With this very large modulation ratio, this medium exhibits an ideal level of signal and limit. / 5 In addition, small mark recording is performed with the following parameters. Write mark and gap length = 0.17 μm, periodic pulse wave strategy = 1 pulse wave in one mark Other conditions are the same as 〇·69 μm mark record. Therefore, as shown in Fig. 7, a distinct waveform can be observed. The modulation amplitude is less than or equal to 61), however, it approaches the theoretical value of this small mark near the cutoff frequency of the readout optics. The read signal has a C/N value of 4 〇〇 decibels. The mark length is 〇·17 μm as the minimum mark of the (1,7) RLL modulation. The data capacity of the 12-mm diameter single-sided disc is 2丨. This dye shows its potential for such high density recording. 15 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 0- 1252478

V. Description of invention (69) Simple description of the printed pattern of the employee's consumer cooperative of the Intellectual Property Office of the Ministry of Economic Affairs: Figure 1: Layer structure of the optical data medium Figure 2a • • Dye single gas-aluminum-indane cyanine (AlCIPc) for information Layer disc structure / dye single gas, aluminum - phthalocyanine (AlCIPc) applied to the information layer disc after the groove track recording, the square wave dye two gas - 矽 - 酞 酞 青 (SiClje) applied to the information The waveform of the layer disc recorded on the groove track is shown in Fig. 4 · The wood pattern obtained by applying the wood-chlorine-矽_酞花青 (SiClJc) to the disc of the information layer when the surface is recorded. The waveform of the dye applied to the disc of the information layer after recording on the groove track is shown in Fig. 6a. The square waveform (groove) obtained after recording the disc made by the AK case 87 in the groove track. Figure bf Example 87 The square waveform (surface) obtained after the recording of the groove track is shown in Fig. 7. The waveform component symbol obtained after recording the other disk of the example 87 in the groove track: 20 1 transparent substrate 2 barrier layer 3 information layer 4 barrier Layer 5 adhesive layer 25 6 cover layer 5 Figure 2 Figure 3 10 15 of the 71 -

Claims (1)

1252478 槪' 丨公. A8 B8 C8 D8 烦 为 委 委 , , , , , , , , , , , , , 本 本 本 本 本 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Amend Claims in Chinese - Enel. (IV) 5 (Submitted on July, 2004) (Submitted on July, 2004) 1. An optical data medium containing a preferred transparent substrate having one or more barrier layers coated thereon, and 10 optically recordable information layers have been applied to the surface, and one or more barrier layers and cover layers are optionally used, and the data medium can be focused. The blue light is recorded and read through the cover layer on the information layer, preferably having a wavelength of between 360 nm and 460 nm, and the information layer contains a light absorbing compound and optionally a bonding agent of 15 agents. Characterized in that at least one dye is used as the light absorbing compound, wherein the covering layer above the information layer containing the adhesive layer has a total thickness of 10 micrometers to 177 micrometers, and the focusing objective lens The assembled numerical aperture NA is greater than or equal to 0.8, and wherein the barrier layer comprises a dielectric layer directly above the data layer, and the top cover layer on the dielectric layer 20 and thereon comprises a pressure sensitive adhesive layer. 2. The optical data medium of claim 1, wherein the dye used as the light absorbing compound is phthalocyanine or naphthalocyanine, and in both cases, the aromatic ring may also be a heterocyclic ring. 3. The optical data medium of claim 1, wherein the dye used as the light absorbing compound is a mercyananine dye. 4. For the optical data medium of claim 1 of the patent scope, where -72 - This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) 91124B-connected to 1252478, patent application scope A8 B8 C8 D8 5. The top cover layer is polycarbonate, copolycarbonate, polycyclic hydrocarbon or poly Hydrocarbons. An optical data medium according to claim 1, characterized in that the dye conforms to formula (I) MPc[R3]w[R4]x[R5]y[R6]z (I) wherein 10 Pc represents phthalocyanine or Naphthalocyanine, wherein in either case, the tribe may also be a heterocyclic ring, Μ representing two independent deuterium atoms, representing a divalent metal atom or representing a trivalent axial monosubstitution of formula (la) Metal atom (Ia), 15 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 20 5 2 or represented by the formula (lb) of tetravalent axially disubstituted metal atomic dry 1 T0 (lb) χ 2 or representative formula (Ic Trivalent axial single-substitution and axial mono-coordinated metal atom ί1 Me I X2 (IC) -73 - This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1252478 VI. Patent application range In the case of charged ligand or substituent X! or X2, the charge is compensated by opposite ions, and the groups R3 to R6 are equivalent to 酞花青Substituents, X1 and X2 independently of each other represent halogen, hydroxyl, oxygen, cyanide 5, thiocyanate , cyanate, alkenyl, alkynyl, arylthio, dialkylamino, alkyl, alkoxy, oxyalkylthio, aryl, aryloxy,-0-802118, a group of 0-PR10RU, -0_P(0)R12R13, -0-SiR14R15R16, nh2, an alkylamino group and a heterocyclic amine, and 10 R3, R4, R5 and R6 independently of each other represent a halogen, a cyano group, a aryl group, a Base, aryl, acrylamine, dialkylamino, alkoxy, alkylthio, aryloxy, arylthio, so3H, SC^NRiR2, C02R9, CONRi2, NH_COR7 or formula -(B) a group of mD, wherein 15 B represents a bridge composed of a group consisting of a straight chain, CH 2 , CO, CH (alkyl), C (alkyl) 2, NH, S, O or -C=CH-, B) m represents a chemically rational sequence of bridging with m=l to 10, m is preferably 1, 2, 3 or 4, 20 D represents a monovalent group Z1-^ of a redox system of the formula CH=CH^Y-—— (Red) or Θ ^ Θ. 25 Z^=^=CH-CH^~Yg— (Ox) -74 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1252478 A8 B8 C8 D8 VI. Scope of application or representative of a metal dialhoenyl group or a metal ditenyl carbonyl group, titanium, lanthanum, iron, ruthenium or iron is suitable as a metal center, Z1 and Z2 are independent of each other Represents NR'R", OR" or SR", 5 Y1 represents NR', Ο or S, Y2 represents NR', η represents 1 to 10, and R' and R" independently of each other represent hydrogen, alkyl, cycloalkyl , aryl or heteroaryl, or a straight or bridged one of the C atoms of the _|CH di CH廿 or ^ch—ch:^: 10 chain, w, x, y and z independently of each other represent 0 to 4, wherein w+x+y+z<16 5 R1 and R2 independently of each other represent an alkyl group, a hydroxyalkyl group or an aryl group, or R1 and R2 together with the N atom to which they are bonded form a heterocyclic ring 5-, 15 6- or The 7-member ring, depending on the situation, is specially occupied by another hetero atom of the group consisting of N and S. NWR2 specifically represents 吼洛唆基, BTG or 喷, R7 and R16 are independent of each other. Represents alkyl, aryl, heteroaryl or the Intellectual Property Office of the Ministry of Economic Affairs. Employees' Cooperatives Printed 20 6. The optical data media of the fifth application scope of the patent application, its characteristics In the case of Μ represents two independent Η atoms, or represents Cu, Ni, Zn, Pd, Pt, Fe, Μη, Mg, Co, Ru, Ti, Be, Ca, Ba, Cd, Hg, Pb and Sn The divalent metal atom of the group, or the trivalent axial monosubstituted formula of the formula (la) -75 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210x297 mm) 1252478 A8 B8 C8 D8 VI. Application A metal atom of the patent range, wherein Me represents Al, Ga, Ti, In, Fe or Μη, or represents a tetravalent metal atom of the formula (lb), wherein Me represents Si, Ge, Sn, Zn, Cr, Ti, Co Or V. 7. The optical data medium of claim 2, characterized in that Μ represents a group of formula (la) or (lb), wherein Me represents Α1 or Si, and X1 and X2 independently represent halogen, in particular Is a chlorine, an aryloxy group, especially a phenoxy group, or an alkoxy group, particularly a methoxy 10 group, and w, X, y and z each represent 0 〇 8. The optical of the first item of the patent application. A data medium, wherein the light absorbing compound is a part of indigo. 9. The optical data medium of claim 1, wherein the 15 light absorbing compound conforms to formula (1) is preferred Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed 20 A, representing the group with the following formula -76 - This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1252478 C8 _D8_ VI. Patent application scope R10 (iv), 5 X1 stands for CN, CO-R1, COO-R2, CONHR3 or CONR3R4, X2 represents hydrogen, c!- to C6-alkyl, (36- to c1 (r-aryl, five or six-membered heterocyclic group, CN, CO-R1, COO-R2, CONHR3 or CONR3R4 or 10 cxi2 Representative ring This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1252478 A8 B8 C8 D8 6. The scope of application for patents may be fused with benzo or naphthalene and/or substituted with nonionic or ionic groups. The asterisk (7) represents a self-double bond extended ring atom, and X3 X4 X5 xe represents N or CH, representing 0. , S, N, N-R6 or CH, wherein χ3 and χ4 do not represent CH at different times, represent 0, S or N-R6, and ring B of formula (II) represents Ο, s, Ν, N-R6, CH Or ch2, 10 (II) Together with X4, X3 and the c atom in between and the ring of formula (V) C 15 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative prints ο 2 (V) with X5, X6 and the C atom in between Parents: independently of each other representing a five or six member aromatic, pseudoaromatic heterocyclic ring which may contain from 1 to 4 heteroatoms and/or may be stupid and slightly a or negatively fused and/or nonionic Or an ionic group substitution, Y1 represents N or C-R7, Y2 represents N or C-R8, and R1 to R6 independently of each other represent hydrogen, Ci to alkyl, A-78- 1252478 VI. Patent application scope A8 B8 C8 D8 to CV alkenyl, 0:5 to c7_cycloalkyl, fluorene to Cw aryl or C7 to Ci5-aryl, 5 10 15 20 R and R 8 independently of each other represent hydrogen, cyano or q to C6-alkyl, and R and R1G independently of each other represent Ci to C6-alkyl, c6 to Cio-aryl or (^ to C15-aryl) The alkyl group, or NR9R1G, can form a five- or six-membered saturated heterocyclic ring. The method of producing an optical data medium according to the scope of the patent application is characterized in that the barrier layer is preferably transparent. The substrate is coated with a dye, and a suitable binder and additive are optionally combined, and a suitable solvent is selected as needed, and a barrier layer and a cover layer applied by the adhesive layer are provided, wherein the barrier layer contains directly above the data layer a dielectric layer, and the top cover layer on the dielectric layer and thereon comprises a pressure sensitive adhesive layer. 11. A method of manufacturing an optical data medium according to the scope of the patent application, characterized in that it is coated by spin coating. Dye coating by sputtering, sputtering or gas deposition. 12. An optical data medium having a recordable information layer by using blue light, preferably laser light, especially having a wavelength of 2 360-460 nm Laser light, recorded in Apply for the optical data media in the first paragraph of the patent. -79 - This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)