TW200401011A - Squarylium dyes as light-absorbent compound in the information layer of optical data carriers - Google Patents

Abstract

Novel squarylium compound for optical data carriers have been found. The latter comprise a preferably transparent substrate to whose surface a light-writable information layer, if desired one or more reflection layers and a further substrate or a protective layer have been applied and can be written on and read by means of red light, preferably laser light, where the information layer comprises a light-absorbent compound and, if desired, a binder. They are characterized in that said squarylium compounds are used as light-absorbent compound.

Description

200401011 A7 B7 Scorpion V. Description of the invention 10 15 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 25 The present invention relates to a tetraaryl diamond dye, a method for preparing the same, a component based on the tetraaryl pyrene dye and a method for preparing the same, and An optical data carrier containing the tetraarylfluorene dye in the information layer. The write-once optical data carrier using a special light-absorbing substance or a mixture thereof is particularly suitable for DVD-R discs operated with a red (635_66 nm) laser diode, and is suitable for applying The above dyes are applied to polymer substrates (especially polycarbonate). Recently, single-write optical discs (CD-R, 780 nm) have undergone substantial growth 'and represent a technically established system. Optical data for the next generation Miscellaneous devices-DVDs-have now been introduced to the market. The use of shorter-wave laser radiation (635_66 nm) and higher numerical aperture NA allows higher storage density. In this case, the single-write format is DVD-R. The achievable storage density depends on the focusing effect of the laser point on the data plane. The size of the light spot is commensurate with the laser wavelength λ / NA. ^^ is the numerical aperture of the objective lens used. In order to obtain the most possible storage density, the goal is Use the smallest possible wavelength λ. Currently, '390 nm is possible based on semiconductor laser diodes. In addition to the optical properties described above, writable information containing light-absorbing organic substances Must be substantially amorphous in order to keep the noise as small as possible when writing or reading. For this reason, it is particularly preferred to spin-coat by solution, by gas deposition and / or sublimation (under pressure During the continuous covering of metal or dielectric layer) this material is applied to avoid: the crystallization of light absorbing substances. The non-crystalline layer containing no light absorbing substances is preferably highly heat resistant

200401011 A7 V. Description of the invention (2 10 15) Otherwise, it will form an indistinguishable boundary (due to diffusion) due to another organic or inorganic material layer applied to the light-absorbing information layer by subtractive plating or gas deposition. Therefore, it adversely affects the reflectance. Furthermore, the light absorber f with insufficient thermal denaturation can diffuse to the latter at the boundary of the polymer support, and at the same time, it adversely affects the reflectance again. The light absorbent material with too high vapor pressure can affect the other Sublimation (in high vacuum) during layer borrowing or depositing, thereby reducing the required layer thickness. This again has a negative effect on reflectance. The object of the present invention is therefore to provide a suitable compound ' It can meet the needs of the information layer used in single-write optical data carriers (for the southern requirements of writable optical data storage cells with laser wavelengths ranging from 600 to 6800 nanometers) (such as optical stability, suitable signal , Coating without damage to substrate materials, etc., it has been surprisingly found that a light absorbing compound selected from the group consisting of a special symmetrical tetraaryl complex can be very successfully satisfied Said request before & present invention thus provides - with one of the four kinds of aromatic compounds of general formula Bin, stapling economic need 〇- Intellectual Property Office employee consumer cooperative printed 20 R-.

-R (I) where R is a heterocyclic five-membered ring other than an amine-substituted furan ring, or a substituted 25-membered ring. Especially by taking

R2 Substituted alkyl or substituted or unprinted by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 200401011 V. Description of the invention (3) The preferred tetraaryl hydrazone compound of formula I conforms to formula Ia, (la) where R1 is hydrogen , Substituted or unsubstituted aralkyl groups, R2 = substituted or unfilament ㈣, substituted or unsubstituted = 且 and alkoxy groups, or substituted or unsubstituted 嶋 R3 and R4 each- Independent of each other are hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, an alkoxy group, or a substituted or unsubstituted alkylcarbonyl group. Formula la is one of the possible meso formulas. For the purposes of this application, "alkyl," preferably Ci_c6 alkyl 20 "'aryl", preferably C6_Ci0_aryl, ", aryl", preferably c7_c "_ar" And "alkoxy" is preferably Ci_c6_alkoxy. Possible substituents on alkyl, aryl or aralkyl are halogen (especially F), hydroxyl, nitro, cyano Groups, carboxyl groups, alkoxytrialkylsilyl groups, and trialkylsilyloxy groups. The alkyl group may be straight-chain, cyclic, or branched. It may be partially halogenated or fully halogenated.

200401011 A7 B7 V. Description of the invention G) Examples of alkyl groups of 5 10 15 are trifluoromethyl, ethyl gas, cyanoethyl, methoxyethyl. Examples of cyclic alkyl groups are examples of cyclohexylmethyl and cyclopropylmethyl knife-branched groups. Isopropyl, tert-butyl, 2-butyl, neopentyl. Examples of possible aryl groups are phenyl '4-methoxyphenyl, 4-cyanophenyl, 3,5-bis (trifluoromethyl) phenyl, 4-trifluoromethylphenyl and 4 -Ethyl benzyl. Examples of aralkyl groups are benzyl, phenethyl, benzylpropyl, 4-methoxybenzyl, 4-cyanobenzyl, 35 • bis (trifluoromethyl) benzyl, 4-trifluoro Methylbenzyl and 4-ethylbenzyl. Examples of carboxyl groups are ethoxycarbonyl, butoxycarbonyl, and trifluoromethoxycarbonyl. Examples of alkylcarbonyl are ethenyl, trifluoroethenyl, propionyl, butyryl, pentamyl, and hexamethylene. Preferred substituted or unsubstituted alkyl groups are methyl, ethyl, n-propyl, n-pentyl, isobutyl, isopropyl, perfluorinated methyl and ethyl. Preferred substituted or unsubstituted aralkyl groups are, for example, 4-trifluoromethylbenzyl, 2-trifluoromethylbenzyl, 3,5-bistrifluoromethylbenzyl, and 4-fluoro-2 -Trifluoromethylbenzyl. The preferred ethoxycarbonyl group is ethoxycarbonyl. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs' Consumer Cooperatives. 20 The best is the tetraaryl hydrazone compound of formula 1a, where R is hydrogen, methyl, ethyl, propyl, butyl, cyclohexylmethyl, benzyl, Methoxybenzyl, 4-trifluoromethylbenzyl, 3-trifluoromethylbenzyl, 2-trifluoromethylbenzyl, 3,5-bis (trifluoromethyl) benzyl, or 4-fluoro- 2-trifluorofluorenylbenzyl, 25 R2 is fluorenyl, ethyl, propyl or phenyl, and -6-200401011 A7 B7 V. Description of the invention (5) R3 and R4 are each independently hydrogen or fluorene Group, ethyl, propyl, butyl, phenyl, ethenyl or ethoxycarbonyl. Even more preferred are tetraarylphosphonium compounds of formula la, wherein R1 is 4-trifluorofluorenylbenzyl or 3,5-bis (trifluoromethyl) benzyl, especially 4-trifluoromethylbenzyl, R2 is methyl, ethyl or phenyl, especially methyl, R3 is hydrogen, ethyl, ethylfluorenyl or ethoxycarbonyl, especially ethyl, and 10% R4 is methyl 'ethyl or phenyl , Especially methyl or ethyl. The present invention further provides a method for preparing the tetraarylphosphonium compound of the present invention, which is characterized in that 3,4-dihydroxy-3-cyclobutene-1,2-dione (squaric acid) and at least one compound having formula III Reaction 15 R-R5 (III) is specifically reacted with pyrrole of the formula (Ilia) (preferably in a suitable solvent), printed by consumer cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

R is hydrogen, a hydroxy group, especially a third butoxy group or an ethoxycarbonyl group or a carboxyl group, and R and R1 to R4 are as defined above. 5 The method of the present invention is preferably carried out in an alcohol, especially in ethanol. The preferred reaction temperature is greater than 70. (:, Especially 75-85 ° C. Similarly, the method of the present invention is preferably performed in aqueous acetic acid. For example, the mixing ratio of acetic acid / water is 3: 1 to 1: 3, preferably 2: 1 to 1 · 2, preferably 1: 1. The preferred reaction temperature is in the range of room temperature to the boiling point of the medium 10. Similarly, it is preferred to use a catalytic amount of mineral acid, especially HC1. The product usually reacts by itself The solution precipitates as a pure solid and is preferably washed with ether after filtration. The present invention likewise provides a pyrrole compound of the formula (Ilia) which is preferably used to prepare the tetraaryl rust 15 compound of the invention. The invention therefore provides the formula (Nia) pyrrole (IDa), wherein R1 is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aralkyl group,

200401011

V. Description of the invention (7) Substituted or unsubstituted alkyl group is substituted or unsubstituted by aryl group and ## 乂: ¾ Said alkyl group, carbonyl group or substituted carbonyl group, and the unsubstituted β R3 and R4 each—independent of each other. Mo d, & substituted or unsubstituted ammonium, 翌 substituted or unsubstituted aryl, 浐 苴 @ wt 万 丞 alkyl carbonyl, carbonyl or substituted Or unsubstituted alkoxycarbonyl, and R5 is hydrogen, alkoxycarbonyl or carboxy. Particularly preferred are pyrrole compounds of formula IIIa, in which 10 R1 is propyl, butyl, cyclohexylmethyl, benzyl'4methoxybenzyldi4-trifluoromethylbenzyl, 3-trifluoromethyl Benzyl, 2-trifluoromethylbenzyl, 3,5-bis (trifluoromethyl) benzyl or 4-fluoro_2_trifluorofluorenylamyl, R2 is methyl'ethyl, propyl or benzene 15 R3 and R4 are each independently hydrogen, methyl, ethyl, propyl, butyl, phenyl'ethenyl, or ethoxycarbonyl, and R5 is hydrogen, a third butoxycarbonyl, or carboxyl. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics The present invention also provides a method for preparing a novel pyrrole compound of formula Ilia, which is characterized by a pyrrole compound of formula (II)

-9- 200401011 A7 ------- B7 V. Description of the invention (where R2 to R4 are as defined above with novel pyrrole of formula nia, and R5 is hydrogen, alkoxycarbonyl, especially third butoxy A carbonyl or ethoxy group, or an ethoxy group, with a halogen compound of formula IV and at least 2 equivalents R1-x (iv), 10 where R is as defined for the formula nia pyriole, X is Cl, Br or I. Specially suitable test is KOH printed by the Industrial and Commercial Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The reaction is preferably performed in a suitable solvent 15 'for example in DMSO, dimethylformamidine Amine (DMF) or a mixture thereof. The reaction is preferably carried out at a temperature of 20 rc (particularly 50-90X :, especially 65-80. 〇. If R5 in the ethoxycarbonyl group, then The ester groups are saponified to provide the corresponding alkali metal salt of pyrrole carboxylic acid. This can be precipitated from the aqueous solution by acidification and filtration. 20 In this way, the product can be obtained with satisfactory purity without the need for complex crystallization Step or similar purification step. The present invention further provides the use of the tetraarylphosphonium compound of the present invention, which is In the information layer of a single-write optical data carrier, it is used as a light absorbing compound. 25 In this application, the optical data carrier is preferably a red laser-10-200401011 A7 B7 V. Description of the invention (9) &quot; 4 It has a wavelength Laser light in the range of 600-680 nanometers) writing and reading. The present invention further provides the use of the tetraaryl compound, which is used as a light absorbing compound in the information layer of a single-write optical data carrier, which can be borrowed It is written and read by red laser light (especially laser light with a wavelength range of 600- 6805 nanometers). The present invention further provides an optical data carrier comprising a preferred transparent substrate, the surface of which has been coated A light-writable information layer is provided, and if necessary, one or more reflective layers and another substrate or a protective layer have been coated, which can pass red light (preferably with a wavelength range of 600-680 nm, preferably Write or read by laser light), wherein the information layer contains a light absorbing compound and a suitable adhesive is selected if necessary, and is characterized in that at least one tetraarylphosphonium compound according to the present invention is used as the light absorbing compound The light-absorbing compound should preferably be capable of undergoing thermal changes. The thermal change is preferably at a temperature of &lt; 600 C, particularly preferred is at a temperature of &lt; 400 ° C, and 15 is particularly preferred at &lt; At 300 ° C, especially at <20 ° C. For example, such a change could be the decomposition or chemical change of the chromophore center of a light-absorbing compound. Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printing. Similarly, it is preferred that the light-absorbing compound can be thermally changed only at more than 1000t. 20 A preferred specific example of the light-absorbing compound in the optical material storage device of the present invention is equivalent to the tetraarylfluorene compound of the present invention. A preferred specific example. In a preferred embodiment, the light-absorbing compound used is a compound of formula (la), wherein R1 is hydrogen, methyl, ethyl, propyl, butyl, cyclohexylmethyl, benzyl 25, 4-methyl Oxybenzyl, 4-trifluoromethylbenzyl, 3-trifluoromethyl-11-

〇〇〇〇〇〇〇〇

Octyl or 3,5-bis (trifluoromethyl) benzyl, R2, R3 and R4 are each independently hydrogen, methyl, ethyl, propyl, butyl, benzyl, ethenyl or ethyl Oxycarbonyl. 5 In a particularly preferred embodiment, the light-absorbing compound used is a compound of formula (la), where R1 is 4-trifluoromethylbenzyl or 3,5-bis (trifluoromethyl) benzyl, especially 4-trifluoromethylbenzyl, R2 and R4 are each independently methyl, ethyl or phenyl, especially methyl or ethyl, and R3 is hydrogen, ethyl, ethenyl or ethoxy Carbonyl, especially ethyl. Printed in the example of a single-write optical data carrier written and read by red laser light according to the present invention by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs' The preferred light-absorbing compound has an absorption maximum of 500 to 650 In the nanometer range, the wavelength λι / 2 (the absorbance at the long wavelength side of the maximum wavelength absorption is half of the absorbance value) and the wavelength λ ,,,. (The absorbance at the long wavelength side of the maximum wavelength absorption is one-tenth of the absorbance value at human ^^) It is preferably separated not more than 60 μm. Such a light absorbing compound preferably has a long wavelength maximum xmax3 up to a wavelength of 750 nm, more preferably 800 nm, and most preferably 850 nm. The preferred light-absorbing compound has an absorption maximum λ ^^ χ of 510 to 620 nanometers. The better light-absorbing compound has an absorption maximum of 25 x kax of 530 to 610 nanometers. -12- 200401011 Α7-— -__ B7. ............. 5. Explanation of the Invention-4 The best light absorbing compound has an absorption maximum of 550 to 600 nm. Among the absorption compounds, λΐ2 & λ | ι〇 as defined above is preferably separated not more than 50 nm, more preferably separated not more than 40 nm and 5 m, and most preferably separated not more than 30 nm. Moire extinction coefficient gaaoooo · / Mole • cm, preferably &gt; 80,000 liters / Mole · cm, more preferably &gt; 100,000 liters / Mole · cm, most preferably &gt; 120000L / Mole • Centimeter. 10 The suitable tetraarylpyrene compound is the change in dipole moment Δμ = | μ8-printed by M * ag 丨, the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (that is, the dipole in the ground state and the first excited state) The positive deviation between moments is not small (preferably &lt; 5D, best &lt; 2D). The method to determine this change in dipole moment Δμ is disclosed in F Wttrthner et al. '八 叫 ⑽ ^! ^ !!! · 199' 109, 2933 and the literature cited therein. The low solvent-induced 15 wavelength shift (dioxane / r) MF) is also a suitable selection criterion. The best tetraaryl fluorene compounds are the wavelength shifts Δλ = |, ... induced by dioxine I (that is, the positive deviation between the absorption wavelengths in the solvent dimethylformamide and dioxane) &lt; 20 millimeters Micron, more preferably &lt; 10 nm, most preferably &lt; 5 nm. The absorption spectrum is preferably measured in solution. The light absorbing compound used is preferably used in an unwritten optical data carrier Possibly obtained &gt; 10% reflectance, and point-by-point lighting with focused light has sufficient absorption for thermal degradation of the information layer (if the light wavelength is in the range of 600 to 680 nm). The optical properties of the layer are changed after thermal degradation.

2004010H A7 B7 V. Description of the invention (12) ~~-The reflectance change of 4 phases' can be used to obtain the contrast between the written and unwritten points. The tetraaryl compound of the present invention is preferably applied to an optical data carrier by spin coating. They can be mixed with each other or with other dyes with similar spectral properties. The information layer may contain not only the tetra-aryl rusting agent 15 of the present invention, but also additives (such as a binder, a wetting agent, a stabilizer, a diluent, and a sensitizer) and additional components. In addition to the information layer, other layers (such as a metal layer, a dielectric layer, and a protective layer) may also be present in the optical data storage device of the present invention. Metal and dielectric layers are used in particular to adjust reflectivity and heat absorption / retention. 10 Depending on the laser wavelength, the metal may be gold, silver, aluminum, or the like. Examples of the dielectric layer are silicon dioxide and silicon nitride. Protective layers are, for example, photo-hardenable surface coatings, (pressure-sensitive) adhesive layers and protective films. For example, the 'pressure-sensitive adhesive layer is mainly composed of an acrylic adhesive. Nitto Denko DA-8320 or DA-8310 (disclosed in Japanese Patent 15 JP-A U-2731471) can be used for this purpose. The optical data carrier printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has, for example, the following layer structure (refer to FIG. 2):-preferably a transparent substrate (丨), an information layer (丨 2), if necessary, one Reflective layer (13) 'If necessary, an adhesive layer (14) and another preferred transparent substrate (15) are selected. 20 In FIG. 2 ', it is preferable to replace the substrate (15) in the order of layers (13), (12), and (11). In addition, the layer structure of the 'optical data carrier' may include a plurality of information layers (preferably separated by suitable layers). The best separation layer is a photohardenable surface coating 'adhesive layer or reflective layer. 25 The arrows shown in Figures 1, 2 and 3 represent the path of incident light. -14- 200401011 A7 B7 10152025 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (13) The present invention further provides an optical data carrier according to the present invention, which has passed through red light (especially red laser light, The best is red laser light with a wavelength of 600_ 680¾ microns) for writing and reading. Similarly, the present invention provides a single-write optical data carrier, the information layer of which includes at least one cyanine dye as a light absorbing compound, and also provides a method for manufacturing the cyanine dye. Therefore, the object of the present invention is to provide a suitable compound that satisfies the information layer used in a single-write optical data carrier (especially for a high-density writable optical data storage format with a laser wavelength range of 360 to 460 nm) High requirements (such as light stability, suitable signal / noise ratio, non-destructive coating to substrate materials, etc.). Surprisingly, it has been found that special flower-moon compounds as light-absorbing compounds can very successfully satisfy the above-mentioned demand profile. Cyanine exhibits a strong absorption in the wavelength range of 36-460 nm (which is important for lasers, that is, the 8 or 801 ^ band). The present invention therefore provides an optical data carrier, which includes a preferred transparent substrate, which can be coated with one or more reflective layers in advance if necessary, and has a photo-writable information layer coated on the surface, and one or more reflective layers can be selected if necessary. Layer and, if necessary, a protective layer or another substrate or a cover layer, which can be made of blue light, preferably laser light 'preferably having a wavelength of 36 ° to 46 nm', especially 380 to 420 nm The best light is 39-40 nm, or by infrared light, preferably laser light, especially the light with a wavelength of 760-830 nm, written or read, it applies this information The layer contains a light-absorbing compound and optionally a binder, and is characterized in that at least one cyanine dye of the formula ([) is used as the light-absorbing compound -15- suspect &quot;-'XTC, Λ 200401011 A7 B7 V. Description of the invention (14) 4f1 Me Pc I (I), X25 where Me is a biaxially substituted metal atom selected from the group consisting of si, Ge, and Sn, Pc is an unsubstituted cyanine, and X1 and X2 are each independently of each other It is bromine or iodine, and χι can also be gas. 10 The best is the cyan of formula (la), (lb), (Ic), (Id), (le), (If), (Ig), and (Ih) 5 11

PC BIS'IB Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs o 2 PCnpc &gt; s—I c —sIBr slag),

Γ 6 Γ B 丨 GIB

PC

pc e XIG—I

Ie) xusnx pc BrIsn1Br χ \ / τχ / 1 *

.sn—I pc

/ IV Eight, J and (U) to (Ih) represent two halogens either above the plane of the cyan ring or one at the flower: ring system of 25 squares and one below the plane of the cyan ring. On the plane of the moon

200401011 A7 B7 V. Description of the invention (15) k The cyanine used in accordance with the present invention is from a factory, for example; ^. £ 81) 0, 0, 1_ £ ·

Sutton, M, E. Kenney, Inorg · chem. 6, 1967, 11 16 and W. J. Kroenke, M, E. Kenney, Inorg · Chem. 3, 1964, 696 are known 'or can be prepared as described therein. 5 In theory, it can be prepared by known methods, for example:-by the synthesis of a ring from phthalonitrile or amine_imino-isoindole in the presence of a suitable metal edge compound,-if necessary The product is reacted with water in a suitable solvent (eg, pyridine) to form a cyanine of formula (I), where χι = χ2 = 〇Η, 10-if necessary, substitute axial substituents with other appropriate halides X1 = rX2 = spirit,-if necessary, by replacing the axial substituent XkXkQH with a suitable halide by reaction with HXVHX2,-if necessary, by formula (Π) oxidation reaction of non-axially substituted cyanine 15

MePc (η) is performed by bromine'iodine, bromine chloride or iodine bromide. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the formula 20 (Π) cyanine, preferably Me = Sn, which is a loan-type cyanine (preferably Me Ⅱ Sn, of which the parent) and 2 are _ Element, such as gas). A suitable reducing agent is, for example, sodium tetrahydroborate (NaBh). The light-absorbing compound may be thermally changed. The thermal change preferably occurs at a temperature of <60 ° C. For example, such a change may be a decomposition or a chemical change of the chromophore center of a photoabsorptive compound. -17- 200401011 A7 B7 Description of the invention 16 10 15 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 25 The light-absorbing compound described above can be accompanied by the sufficient reflectivity of the # lie &amp;-optical data carrier, which is kept in an unwritten state, and Hit Liu Du 4 ~ ~ ,,, Yuxian (especially laser light) Che Yanjia is a laser with a wavelength range of 360 to 460 units * _ ω ,, ^ ^ Injustice laser light) point by point lighting information The thermal degradation of the layer and the thermal decomposition of the thermal layer have two absorptions. Because the information layer has changed the optical amplitude and the reflectance of the phase after the thermal degradation of the fairy, the $ _ ratio has been written and not written. The point-to-point pair means that the optical data carrier can preferably be written or read by laser light with a wavelength of _460 μm. Similarly, the optical data carrier can be &amp; 2 u, Ε Λ Bei T Ye Zhanti wrote by infrared light (especially laser light with a wavelength of 760-830 nm) Or, at this time, the groove gap and geometry are preferably commensurate with the wavelength and numerical aperture. The present invention further provides an application of formula (1) cyanine, which is used as a light absorbing compound in the information layer of the optical storage medium. The present invention similarly provides a use of the formula cyanine, and is used for manufacturing optical data carriers. The cyanine is preferably used as a light-absorbing compound in the information layer. Based on the formula (I) cyanine, it is particularly preferably used In these applications, the content of cyanine is more than 90% by weight, especially more than 5% by weight, and most preferably more than 98% by weight. The present invention further provides a particulate solid agent of formula (I) cyanine, characterized in that The average particle size is 0.5 micrometers to 10 millimeters. In the preferred specific examples of the particulate solid preparation, those having an average particle size of 0.5 to 20 micrometers (particularly 1 to 10 micrometers) are preferred. For example, this kind of fine powder can be made by grinding and binding. The flattening is 200401011 A7 B7. 5. Description of the invention (17) 4 The same is preferably a particulate with an average particle size of 50 to 300 microns. Solid preparation, hereinafter Fine crystalline form. Other preferred particulate solid formulations are agglomerates or aggregates with an average particle size of 50 to 10 mm (preferably 100 to 800 μm) and forming 5 particles as the initial particles. Particulate shaped bodies of objects. For example, such shaped bodies may have the shape of droplets, raspberries, flakes or rods (hereinafter referred to as particulate materials). For example, the particle size of fine crystalline forms may be synthesized. The parameters are set. For example, a mixture of ingredients (such as phthalonitrile or amine-imino-isoindole in a suitable solvent and appropriate Metal halide) to the reaction temperature (e.g. 16 to 220 ° C) preferably form a finely divided form "when the metal halide is added to the reaction mixture (at a suitable solvent only at the reaction temperature (e.g. 160 to 19 (TC)) In the case of phthalonitrile or amine-imino-isoindole), results similar to 15 can be obtained. For example, slowly heating a mixture of ingredients (for example, between 65 and 250 minutes) to a reaction temperature (for example, 16 to 22 (rc)) preferably forms a thick chain. Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Cooperative Print The particulate solid preparation of the invention preferably contains 80 to 100% by weight (preferably 95 to 100% by weight) of the formula cyanine, 20 ο.1-1.0% by weight (preferably 0.1). -0.5% by weight) of residual moisture, 0-10% by weight of inorganic salt, 0-10% by weight (preferably 0-5% by weight) additional additives, such as dispersants, surfactants and / or Wetting agent, in which the percentage in each case is based on the preparation, and the sum of the indicated 25 ratios is 100%. -19-

200401011 V. Description of the invention (18) 5 10 15 Printed by the Intellectual Property Office of the Ministry of Economic Affairs and Consumer Affairs Co., Ltd. 20 25 The solid-state sword of the present invention is preferably 'good storage stability. _ Dust, free-flowing and grain-pulling materials can be manufactured in many ways, such as drying, fluidized bed spray granulation, and slag agglomeration by fluidized bed. A fluidized bed to increase granulation or powder granulation is preferably performed by spray drying using a rotating disk analyzer and a single- or dual-fluid spray (= spraying device). The best is a single-fluid sprayer, especially; it is a force; at first, it is a sprayer, which is preferably dropped / checked to the inlet and outlet temperature of the spray during the spray drying under the feeding dust of 20-80 bar. Depending on the residual moisture content, the safety measures are called: specifically, ™, and two :: The granular material is usually mixed by first mixing the dye dye cake (with help 7 and additives if necessary) in the mixing container. . The crystals of the suspension are preferably broken in a mill (e.g., a bead mill) so that a finely divided sprayable suspension can be obtained. -In a preferred embodiment, the dye suspension is an aqueous suspension. Granulation is preferably carried out by spray drying. "The present invention further provides solid shaped bodies, such as granules, extrudates, etc., which contain the cyanine of formula ，. Based on the shaped bodies, the preferred amount is more than 90% by weight, especially more than 95% by weight More preferably, it is more than 98% by weight. The additional additive added to the solid molded body may be a binder. The sum of the formula cyanine and the binder is preferably more than 95% by weight. 'The best is more than 99% by weight. -20 -Λ: quasi λ / 1 «from λ 1 λ„ ^ c \ nt \ i 200401011

10 15 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 20 Such shaped bodies can be produced, for example, by pressing the cyanine of formula (1), if necessary in the presence of a binder, under a pressure of 5 to 50 bar (Preferably ⑺ to 20 bar). The present invention similarly provides a dispersion liquid (preferably an aqueous dispersion liquid) containing a metal complex of the formula (1), and based on the dispersion liquid, the preferred amount is 10 to 90% by weight. Possible dispersions are, for example, polymerized dispersions based on acrylic, urethane or long-chain polyoxyethylated compounds. Examples of suitable products are, for example: solsperse 320,000 or Solsperse 38000 (from Avecia). The present invention similarly proposes a method for coating a substrate with a cyanine of formula (1). This is preferably carried out by spin coating, sputtering or vacuum gas deposition. The flower f of the formula (Emerald Green) is particularly preferably applied by vacuum gas deposition or sputtering (especially vacuum gas deposition). By annihilation or vacuum gas deposition coating body # The starting materials for these coatings are in the form of all the above-mentioned formula cyanine, that is, fine powder, fine crystal form or granular form, particulate solid preparation, solid formed body and Dispersions. The latter is especially used to coat finely dispersed cyanine to the surface (then can be applied to the substrate by sputtering or vacuum gas deposition). For these procedures, it is better to have a flower #purity greater than the article, or And very particularly preferably greater than 90% ', especially greater than 95% of people, green can be mixed with each other or with other dyes with similar spectral properties: the layer can contain not only cyanine' but also added impurities, two. Wetting Agents, stabilizers, diluents and sensitizers) and additional -21-200401011 A7 B7 V. Description of the invention (2010 15 _ T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 25 The present invention further provides a supply for A device for depositing light-absorbing compound gas on a substrate to manufacture an optical data carrier, which is characterized in that the dye can be vaporized by heating under a low background pressure and is deposited on the substrate. The background pressure is preferably lower than 10-ι Bar, preferably less than 10-3 bar, most preferably less than 104 bar. The dye is preferably heated by resistance or by microwave absorption. In particular, the present invention provides an optical data carrier as described above. , Its towel type (I) The light-absorbing compound forms the optically amorphous information layer with the above-mentioned additives as necessary. For the purpose of the present invention, the amorphous means that microcrystals are not observed under an optical microscope and that there is no Bragg in the x-ray diffraction pattern ( Bragg) reflection, but only amorphous halo can be observed. In addition to the information layer, other layers (such as a metal layer, a dielectric layer and a protective layer) may be present in the optical data storage. Metal and dielectric ^ in particular It is used to adjust the reflectivity and heat absorption / retention. Depending on the laser wavelength, the metal can be gold, silver, metal, alloy, etc. Examples of the dielectric layer are silicon monoxide and silicon nitride. The protective layer is for example light Hardenable surface coating, adhesive layer, and protective film. The adhesive layer can be pressure sensitive. For example, the pressure sensitive adhesive layer is mainly composed of an acrylic adhesive. Nitto Denko DA-8320 or DA- 8310 (disclosed in Japanese Patent JP-A 11-273 147) can be used for this purpose. For example, the optical data carrier has the following layer structure (refer to Figure 0:-transparent substrate (1), if necessary-protective layer) (2 ), An information layer (3), if necessary, a protective layer (4), and if necessary-Adhesive-22-200401011 A7 B7 V. Description of the invention (21) 4 Agent layer (5),-Cover layer (6) The structure of the optical data carrier is preferably:-comprising a preferred transparent substrate (1), the surface of which has been coated with at least one light writable information layer (3) which can be written by light (preferably laser light) 5. When necessary, select 5-protective layer (4), if necessary, use an adhesive layer (5) and a transparent cover layer (6).-Contains a better transparent substrate (1), the surface of which has been coated with a protection Layer (2), at least one information layer (3) that can be written by light (preferably laser light), and if necessary, an adhesive layer (5) and a transparent cover layer (6). 10 _ Contains a preferred transparent substrate (1), the surface of which has been coated with a protective layer (2), if necessary, at least one information layer (3) can be written by light (preferably laser light), necessary A protective layer (4) is selected when necessary, and an adhesive layer (5) and a transparent cover layer (6) are selected when necessary. -Contains a better transparent substrate (1) 'the surface has been coated with at least one information layer that can be written by light (preferably laser light), and if necessary, an adhesive layer (5) and a transparent Overlay. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In addition, for example, the optical data carrier has the following layer structure (refer to Figure 2): — The preferred transparent substrate (11), an information layer (12), must be 20 A reflective layer (13) is selected when necessary, and an adhesive layer (14) and another preferred transparent substrate (15) are selected when necessary. In addition, for example, the optical data carrier has the following layer structure (refer to Figure 3):-preferably a transparent substrate (21), an information layer (22), and if necessary, a reflective layer (23), a protective layer ( twenty four). 25 In addition, the layer structure of the optical data carrier may contain a plurality of information -23-

2UU4U1U11

Layer (preferably separate layers). The best separation resin, adhesive layer, dielectric layer or reflective layer. ... hardenable bright-step-providing an optical data carrier according to the invention which has been written by blue light, in particular laser light, nanometer laser light. The following examples are for the purpose of illustrating the present invention with a wavelength of 360-460. Example 10 15 Example, two 5 grams of 2 · methyl_3,4_diethyl ° specific _5 · third butyl carboxylate 1.73 grams of lice potassium oxide powder suspended in 4 () ml of dimethyl ether Chia was blocked and stirred for 1 hour. Then add 3.42 grams of ammonium bromide step by step ... Baixian was stirred in the lamp for another 1 hour, and then the suspension was diluted with 50 liters of water at 7 ° C, and the product with the following formula was filtered as a white powder. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 5 2

Wash with water. Drying gave 5.5 g (84% of theory) of the product. -24- quasi / rXTC, 200401011 A7 ------ B7 V. Description of the invention (23) 瓤 M.p. = 75-77 ° C. b) 5.43 g of the compound obtained from a) and 080 g of 3 4-dihydroxy-3cyclobutane-1,2-bis- (in 20 ml of ethanol) and 0.5 ml of 37/0. Intensity of chloric acid was mixed 'and the mixture was refluxed for 4 hours. After removing the solvent 5, the residue was digested in diethyl ether, and the precipitated solid was filtered off and washed with -ethyl. Dry to obtain 2.5 g (47% of theory) of green powder with the following formula

15 mp = 203 ° C (decomposed) Intellectual Property Bureau of the Ministry of Economic Affairs Employee Co-operative Cooperative Number of Molecular Coefficients = 532.73 Xmax = 590 nm (two gas sintered) ε = 16700 liters / mole • cm 1/2 / person 1 / 10 (long wavelength side) = 21 nm 20 △ In = Δλ = 1 Dioxane '= 2 nm Example 2 a) 4.19 g of 2-methyl-3,4-diethylpyrrole-5-ethyl Carboxylic acid ester with 3.37 g of potassium hydroxide powder (in 30 ml of dimethylcarbonite) at 80. (: Stir 25 and mix for 10 minutes. After cooling, gradually add 6.14 grams of 3 5-double three -25- 200401011

The fluoromethyl group was radically stirred and the solution was stirred at rt for another ^ hours and then incubated at 70 C for 2 hours. The solution was diluted with 2 ml of water, extracted with dichloromethane, and the product was won by acidification with hydrochloric acid. Filter and wash with water. After drying, 4.29 g (53% of theory) of the product is obtained in the form of a colorless powder 10

COOH 15 M · ρ. = 126-128. . . b) Using 4.07 grams of the pyrrole compound from a) and 057 grams of 3 4-3-cyclobutene-1,2-dione, using a procedure similar to Example lb 3.29 grams (82% of theory) has the following formula Green powder f3c hydroxyl

200401011 A7 B7 V. Description of the invention (25 85 ... Molecular weight = 804.73 Xmax = 590 nm (digas methane) ε = 184652 liters per mole • cm λΐ / 2-λι / 10 (long wavelength side) = 11.9 mm Micron Example 3 10 a) Using a method similar to Example 2a, dimethylpyrrole, 2.24 g of potassium hydroxide powder and 4.78 g of 3,5-bistrifluoromethylbenzyl bromide in 20 ml of dimethylene In the reaction. After the reaction was completed, the solution was diluted with 300 ml of water, and the product was extracted with methane gas. The organic phase was dried over Na2S04 and filtered. After removing the solvent, 4.8 g (95% of theory) of the product with the following brown resin was obtained. 15 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

F, C

20 b) 1.77 g of the product from a) and 0.4 g of 3,4-dihydroxy-3-cyclobutene-1,2-dione were reacted in a similar manner to Example lb. After cooling, the product was precipitated in 400 ml of diisopropyl ether and filtered to obtain a product of the following formula: 25 -27- r + 7 I f '' Youquan / V'XTC'A / 1 4 * 〆, 1 Λ · «, 200401011 A7B7 V. Description of the invention (26 10

The lye was evaporated and chromatographed using Shixian soil (using digas methyl sintering as a separating agent. The initial purple fraction, after removing the solvent, yielded another 072 g of product. Total yield: 0 92 g ( 45% of the theoretical value). Mp = 220 ° C CF, 15 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 25 molecular weight = 584.57 into max-577 micrometers (c) ε = 139,000 liters / mole • cm λ1 / 2 入 ιηο (long wavelength side) = 20 nm Example 4 a) 4.19 g of 2-methyl-3,4-diethylpyrrole-5-ethylphosphonate and 3: g of potassium hydroxide powder (In 20 ml of dimethyl sulfoxide) mix at 8 (rc: for 10 minutes. After cooling, '4.78 g of 2-trifluorobenzyl bromide is gradually added, and the solution is stirred at RT for another 1 hour, and Stir at 70 ° C for 3 hours. Dilute the solution with 300 ml of water, extract with digas, and precipitate the product by acidification with hydrogen acid. Filter and wash with water. After drying, 380 g (Li-28- • Mouth Λ: 1 ^ 4 »9ft / r» XTC \ A / f «4 * mA ', ooi, \ Shan, 200401011 A7 B7 Invention description (56% of 27 value) has the following formula The color of the product in powder form 5

COOH M.p. = 124-126 ° C.

ο b) Use 3.39 g of the compound from a) and 0.57 g of 3,4-dihydroxy-3-cyclobutene-1,2-dione (in 20 ml of ethanol) and 0.5 ml of 37% strength hydrogen The acids were mixed and the mixture was refluxed for 4 hours. After cooling, the precipitated solid was filtered off and washed with diisopropyl ether. Dry 2.58 g (77% of theory) of green powder with the following formula 5 Ι Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ο 2 5 2

mp = 206 ° C molecular weight = 668.73 into ^^ 588nm (acetone) ε = 202000L / mole cm λ 1/21/1 () (long wavelength side) = 22nm-29- 200401011 A7 B7 V. Description of the invention (2〇Δλ = Δλ = | λ_P-λ 二 鸣 坑 | = 1nm Other suitable tetraaryl radium dyes are shown in the table. These dyes are prepared by the similarity of the ingredients and the tetraarylfluorene dye Made by law. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Ex ample Rl R2 R · 5 R4 ^ -max / nm1 * ε I l / mol cm / nm2) Δλ3 »I ch3 c2h5 c2h5 590 167 000 21 2 2 Xcf3 ch3 c2h5 c2h5 590 184652 19 3 ch3 H ch3 577 139 000 20 4 f3c ch3 c2h5 c2h5 588 202 000 22 1 4a F〆- ch3 c2h5 Ph-C6H5 4b f3c ch3 cooc2h5 ch3 583 5 c2h5 ch3 c2h5 c2h5 587 6 c5h „ch3 c2h5 c2h5 588 2 885 000 189 000 21 gh3 c2h5 c2h5 591 198 000 21 9 ch3 c2h3 c2h5 589 148 000 20 9a NC ch3 c2h5 c2H5 589 -30 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 200401011 A7 B7 V. Description of Invention (29)

Ex ample R1 R2 R · 3 R4 ^ max / nm1) ε / l / moi cm λ ^ -λι / 30 / nm: i Δλ3) 10 ch3 H C2Hj 578 11 ch3 c2h5 c2h5 588 187 000 18 1 12 ch3 coch3 c2h5 578 13 ch5 COOC2H5 ch3 577 14 cf3 ch3 H ch3 591 185 000 19 15 ^ 7 (ch3 c2h5 C2H5 589 146 000 1 16 ch3 c2h5 c2h5 599 149 000 26 0! 7 cf3 ch3 COCH3 C2H5 605 17a cf3 ch3 ch3 ch3 ch3 c2 c2h5 595 19 Η ch3 C2H5 c2h5 568 19a Η ch3 COOC2H5 ch3 563 -31-

200401011 A7 B7 V. Description of the invention (3〇) 1) In acetone (unless otherwise specified) 2) On the long wavelength side) △ in- 丨 in DMF-λdioxane 丨 5 Example 20

The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed in a high vacuum (pressure ρ «2 · 10-5 mbar) to make the dye dibromogermanium cyanine (GeBnPc) self-heat-resistant at a rate of about 5A / s at a rate of 15 A molybdenum boat-shaped container is deposited on a pre-grooved polycarbonate substrate. The layer thickness is about M nanometers. The pre-grooved polycarbonate substrate has been molded into a disc by injection molding. The diameter of the disc is 120 mm 'and its thickness is 0.6 mm. The trench structure produced in the injection molding process has a track gap of about 1 μm, a trench depth of 20 at a half height and a trench width of about 50 nm and about 260 nm, respectively. A disc having a dye layer as an information carrier is coated with 100 nm of Age by gas deposition, and then coated by a spin coating method, and UV-curable acrylic coating which is hardened by a UV lamp. By means of a dynamic writing test device (including 25 GaN diode lasers (λ = 405 nm-32-Shitian closed food mask) for linearly polarized laser light installed on an optical test bench) Λ mi octa-core, 200401011 A7 B7 V. Description of the invention (31) 4 meters), polarization-sensitive beamsplitter, λ / 4 plate, and movable suspension light collecting lens (drive lens) with numerical aperture NA = 0.65 To test the disc. The light reflected from the disc is taken out from the beam path through the polarization-sensitive beam splitter and focused on the four-quadrant detector 5 through the astigmatism lens. At a linear velocity ν = 5.0m / s and a write power Pw = 13mW, the No. 5-noise ratio C / N = 41 decibels (dB) was measured. The writing power system is a pulse wave sequence in which the disc is additionally irradiated with the above-mentioned writing power pw for 1 microsecond, and the reading power Pr = 0 44 milliwatts for 4 microseconds. The disc is illuminated with this pulse wave sequence until it rotates once. Then, the mark generated in this manner is read at a reading power Pr = 0.44 milliwatts, and the above-mentioned signal / noise ratio C / N is measured. ^ J &gt; J 21 Make 9.95 g of dichlorotin cyanine (in 25 ml of pyridine) 15

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 25 Mixed with 4.9 g of sodium tetrahydrosulfate at room temperature. Under reflux (115 ° C) make -33-

200401011

20 A7 B7 V. Description of the invention (32) 4 The mixture was stirred for 75 minutes and slowly cooled to 9 (Γ (:.) At this temperature, 100 ml of water was slowly added dropwise. Then the mixture was refluxed for another 77 in. Cool to temperature and filter with suction. Filter with 200 ml of forma = filter and cake 'with suction and wash with f alcohol until the eluate 5 regenerates. After washing with 50 ml of water, It was dried under reduced pressure at 30 ° C. This gave 4.03 g (63% of theory) of a blue powder having the following formula

15 g of this product (in 32 ml of glucose) which had been dried by a molecular engineer was mixed with 0.2 mg of bromide in 10 ml of chloronaphthalene (with stirring) at room temperature. Jieyi & Gu Zhanzhan) The recipients stirred the mixture in Sichuan-Hungry, and the temperature was in a short period of time, from $ 〇 h h to 90 c. After cooling to room temperature, the mixture was washed with a dish: main. 丨 month washed until the eluate is clear, then methanol &gt; monthly washing until the method φ and W eluate is almost colorless, and Dry at 30 ° C. This gives ^ standing under reduced pressure 46 g (74% of theory) with 4 K powder h, Buddhism blue 25 • 34-

200401011 A7 Ming Description Ming 5 5 2

The Consumer Property Cooperation Agreement of the Intellectual Property Bureau of the Ministry of Economic Affairs of Du printed passwords is accurate. A 4 4 Days of Success 0 1 Λ ,, 8 Du, 200401011 A7 B7 V. Description of the invention (34) Brief description of the diagram: Figure 1: Optical data carrier Layer Structure (First Specific Embodiment) Figure 2: Layer Structure of Optical Data Carrier (Second Embodiment) Figure 3: Layer Structure of Optical Data Carrier (Third Embodiment) 5 Code Symbol Description of the Schematic: 1 Transparent Substrate 2 Protective layer 3 Information layer 10 4 Protective layer 5 Adhesive layer 6 Cover layer 11 Transparent substrate 12 Information layer 15 13 Reflective layer Printed by the Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative 14 Adhesive layer 1 5 Transparent substrate 21 Transparent substrate 22 Information layer 20 23 Reflective layer 24 Protective layer -36- 4 · ?! Miyako BE! I® Female 4 Nishijin Λ +1 + Nikko 疒 Λ Record,

Claims (1)

200401011 1. A tetraaryl diamond compound (I) of formula I, wherein 10 R is a heterocyclic five-membered ring other than an amino-substituted furan ring. 2. For example, the compound of claim 1 is characterized in that R is a substituted or unsubstituted pyrrole. 3. For a compound in the scope of application for a patent, its characteristic name has the formula la 15 R2 (la) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 25 where R1 is hydrogen, substituted or unsubstituted alkyl or substituted or unsubstituted aralkyl, and R2 is substituted or unsubstituted Alkyl, substituted or unsubstituted aryl, alkoxycarbonyl or substituted or unsubstituted pits; carbonyl, and -37-200401011 patent application scope A8 B8 C8 D8 10 15 Consumption Cooperation by Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 25 R and R mothers-independently of each other are nitrogen, substituted or unsubstituted aryl, substituted or unsubstituted aryl, = or substituted or unsubstituted Superseded. Lactoyl 4. The compound as claimed in item 3 of the patent application, characterized in that R1 is hydrogen, methyl, ethyl, propyl, butyl, cyclohexylmethyl, octyl, "oxyoctyl, 4 -Trifluoromethyloctyl, 3-trifluoroI benzyl, 2-trifluoromethylbenzyl, 3,5-bis (trifluoromethyl) fluorenyl or 4-fluoro_2-trifluoromethyl Benzyl, R2 is methyl, ethyl, propyl or phenyl, and R and R are each, independently of one another, hydrogen, methyl, ethyl, radical, butyl, benzyl, ethenyl or ethoxy A carbonyl group. 5. The compound as claimed in claim 3, wherein R is 4-difluorofluorenylbenzyl or 3,5-bis (trifluorofluorenyl) benzyl, which is 4-trifluorofluorenyl. Benzyl, R2 is fluorenyl, ethyl or phenyl, especially fluorenyl, R3 is hydrogen, ethyl, ethenyl or ethoxycarbonyl, especially radical, and R4 is fluorenyl, ethyl or phenyl 'Especially fluorenyl or ethyl. 6. —A method for preparing a tetraarylphosphonium compound as described in item 1 of the scope of patent application', characterized by 3,4-dihydroxy-3-cyclobutene-1,2-bis ( squaric acid) is reacted with at least one compound of formula III, R-R5 (III), in particular Pyrrole of Formula (of Ilia) reacting a compound of the apparatus, especially propyl acetate Order 0 38 200 401 011 a (m 5 NIR 10 15 R5 is hydrogen, ethoxycarbonyl, or carboxyl, and R1 to R4 are as defined above. 7. —The use of a tetraarylphosphonium compound such as item 1 of the scope of patent application, which is written in a single As the light absorbing compound in the information layer of the optical data carrier. 8. For the purpose of claim 7 in the scope of the patent application, it is characterized in that the optical shell carrier can use red laser light, especially in the wavelength range of 600-680 耄 microns. Red laser writing and reading. 9 · A type (111 &amp;) of D Diao slightly printed by the Consumer Finance Cooperative of the Smart Finance Bureau of the Ministry of Economic Affairs 20 25 (D), where R1 is a substituted or unsubstituted C3-C, 2-alkyl or a substituted or unsubstituted -39 , Eight way 10 15 substituted aralkyl, R2 is a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, an oxycarbon, an n group, or a substituted or unsubstituted alkylcarbonyl , And R are independently of each other hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, alkoxycarbonyl, carbonyl, or substituted or unsubstituted alkoxycarbonyl, and R5 is hydrogen, alkoxycarbonyl or carboxy. ι〇. The pyrrole compound according to item 9 of the scope of patent application, characterized in that R1 is propyl, butyl, cyclohexylmethyl, benzyl, 4-methoxybenzyl '4-trifluoromethylbenzyl, 3-trifluoromethylbenzyl, 2-trifluoromethylbenzyl, 3,5-bis (difluoromethyl) + or 4-fluoro_2_trifluoromethylbenzyl, R2 is fluorenyl, Ethyl, propyl or phenyl, R3 and R4 are each independently hydrogen, methyl, ethyl, propyl, butyl, phenyl, ethenyl or ethoxycarbonyl, and R5 is hydrogen, Tributoxycarbonyl or carboxyl. 11. A method for preparing pyrrole of formula (III) as claimed in item 9 of the scope of patent application, characterized in that it is a pyrrole compound of formula (II) ⑼, Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 25 40-10 15 Intellectual Property Bureau, Ministry of Economic Affairs, Employee Consumption Cooperatives, number of prints 20 25 Application scope of patents A8 B8 C8 D8 Where R to R4 are as defined in the patent application, and R5 is hydrogen, alkoxycarbonyl, especially oxoyl Or several bases, reacting with a compound of formula IV and at least a z-equivalent base_ $ 9 for a pyrrole of the formula IIIa, a third butoxycarbonyl group, or R * -X (IV) where R1 is as claimed in the patent scope The ninth term refers to the definition of each of formula IIIa t, and X is Cl, Br, or I. 12. An optical data carrier comprising a preferred transparent substrate, the surface of which has been coated with an optically writable information layer and, if necessary, one or more reflective layers and another substrate or a protective layer, which can be By red light, preferably laser light writing or reading, wherein the information layer contains a light absorbing compound, which is characterized in that at least one tetraarylphosphonium compound such as any one of the claims j to 5 of the patent application is used As the light absorbing compound. 13. —A method for manufacturing optical materials and material carriers such as those in the scope of application for patent I], which is characterized in that a preferred transparent substrate is coated with the tetraaryl compound as in scope of application for patent 1 and combined as necessary Adhesives and additives, and if necessary, select a suitable solvent, and if necessary, provide a reflective layer, another intermediate layer and if necessary, a mounting tt 41 -41- 4 Cover or another substrate. 14 ·: The optical data carrier of the patent application No. 12 has been written by red light, especially red laser light. 15 'An optical data carrier comprising a preferred transparent substrate, one or more reflective layers can be coated in advance if necessary, and a photo-writable information layer has been coated on the surface, and one or more reflective layers have been selected if necessary, and When necessary, a protective layer or another substrate or a cover layer can be used, which can be blue light, preferably laser light, preferably with a wavelength of 360_460 nm 10 microns, especially 380-420 nm, the best A 39 〇41〇nm light 'or by infrared light, preferably laser light, particularly preferably with a wavelength of 760-830nm, write or read, where the information layer contains light absorbing compounds and if necessary Adhesive is selected, which is characterized in that at least one cyanine dye of formula 用作 is used as the light-absorbing compound 15 Me Pc X 1 (I), 20 where Me is a biaxially substituted metal atom selected from the group consisting of "and Sn", Pc is an unsubstituted cyanine, and X and X are each independently bromine or R, and χΐ can also be chlorine 0 -42 25 200401011 A8 B8 200401011 A8 BS C8 D8 The scope of patent application x1 and x2 are each independently bromine or iodine, and χΐ can also be 10 15 which is used as a light absorbing compound in the information layer of an optical storage medium. 18.—Use of cyanine of formula (I): 1 Me PcX. (I), where Me is a biaxially substituted metal atom selected from the group consisting of Ge, Sn, and Pc is unsubstituted Cyanine, and X1 and X2 are each independently bromine or iodine, and χ | can also be printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics. 20 It is used to manufacture optical storage media. 19. Use as claimed in claim π or 18, characterized in that, based on the cyanine of formula (I), the cyanine used has a purity of more than 90% by weight 'particularly more than 95% by weight' optimally exceeding .98 weight 20.—A method for coating a substrate, which is to make the substrate coated with a cyanine 25 -44 who A 4 + said-"1 Λ ,, 〇 (V7 200401011 A8 B8 C8 D8_ VI. Apply for a patent Range 4 f1 Me Pc I (I), χ2 where 5 Me is a biaxially substituted metal atom selected from the group consisting of Si, Ge, and Sn, Pc is an unsubstituted cyanine, and each of X1 and X2 Independently of each other, bromine or iodine, and may also be chlorine. 10 21. For example, the optical data carrier in the scope of patent application No. 15 has been made with blue light, especially laser light, preferably with a wavelength of 360-460 millimeters. Micron laser writing. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5 4 Shi Cong? E mouth office with 4 »sleeves Λ 4 4 ·· Mr 1 n ,, Road,