TW455853B - Optical recording media using bi-cyclic alkoxy group substitute containing cyanine dye - Google Patents

Abstract

This invention provides a cyanine dye containing bi-cyclic alkoxy group substitute to improve its solubility in common organic solvents. Moreover, this invention provides an optical recording media using the bi-cyclic alkoxy group substitute containing cyanine dye as the optical recording material.

Description

455853 A7 ______________ B7 V. Description of the Invention (I) Background of the Invention 1. Field of the Invention The present invention relates to an optical recording medium in which the recording layer contains a cyan dye, and the cyan dye is substituted with a bicycloalkoxy group to increase its solubility. 2. Description of Related Techniques The technique of using certain dyes in optical recording media has been known for many years. The physical structure of an optical recording medium includes four layers, namely a polymer substrate, a recording layer, a reflective layer, and a protective layer. A dye solution was spin-coated on a transparent substrate having a spiral groove track to form a recording layer. A gold or silver reflective layer is then sputtered on the recording layer. Next, a UV-cured protective lacquer is spin-coated on the reflective layer. Digital information can be recorded on the media thus obtained through the use of lasers. Lasers used to write information on optical recording media have wavelengths ranging from 770 to 790 nanometers (nm). Corresponding to the wavelength of the laser, the dye used in the optical recording medium preferably has a maximum absorption wavelength (Umas) between 650 and 750 nanometers and more than 1x105 cm_1 mol. Molar absorption coefficient (molar absorptivity) (e). Among the various dyes used in optical recording media, 'cyanine dye' is the most commonly used recording material. It is the most successful commercialized optical recording material and remains the most important one. The cyanine dye has the following | advantages: good optical sensitivity 'better solubility and relatively low price. The disadvantage of cyanine dyes is the lack of light and environmental stability, which affects the long-term stability of optical recording media. —, ------------------- ^ (Please read the precautions on the back before filling out this page) The paper pressure standard is applicable to the Chinese Enclosure Standard (CNS) Α4ϋ 格 （ 210 × 297 mm> ^ -'- 'f ^ v-' ^-bamboo?; T printed 5 8 5 3 A7 B7 * " '--I. I, ________ V. Description of the invention I ^) in optical data Another dye used in storage media is cyan dye = cyano dye has excellent light and environmental stability that cyanine dye lacks and its disadvantage is that it has low solubility. It is well known that turquoise dyes cannot be dissolved in common organic solvents. However, one of the requirements for any dye to be used as a recording material is that the dye must be sufficiently soluble in common organic solvents to be used in spin coating procedures. In order to solve the problem of the solubility of cyanine dyes, many structural modifications have been disclosed in many different patents. The solution most commonly used to increase the solubility of cyanine dyes is to incorporate one or more large substituents in the cyanin molecule. The combination of large-scale substituents can increase the packing distance of cyanocyanin molecules, suppress the association of cyanocyanin molecules, slow down the crystallization rate, or finally suppress the crystallization effect to obtain amorphous phthalocyanine dyes. & the modification of penicillin molecules can increase phthalocyanin in common solvents such as diacetone alcohol, n-propanol, methyl cyclohexane, dimethyl cyclohexane, methyl cellosoWe, Solubility in ethyl cellosolve, tetrafluoropropanol, di-n-butyl ether, etc., and making it suitable for spin coating procedures. The most commonly used large substituents are long-chain linear and branched alkoxy groups. Although linear and branched long-chain alkoxy substituents have a very significant effect on increasing the solubility of the halide molecule, the use of linear or branched long-chain substituents is not enough to make the perylene dye The solubility mentioned in these solvents is high enough to be used in the optical recording medium manufacturing process. This is the reason why it is necessary to incorporate other substituents into the phthalocyanin molecular structure. 3 Hiromi Zhang ruler / I ^^ l Chinese girl standard (CNS) Λ4 specification (210X297 mm) J ---_- -1---It I. i Ding ------. (Please read the precautions on the back before filling out this page) 45 585 3 A7 _________B7__ 5. Description of the Invention (Clever)

— * C (Please read the precautions on the back before filling this page) US Patent Nos. 5,280,114, 5,535,833, 5,446,142, 5,693,396 and 56 W911 disclose the simultaneous use of linear or branched alkoxy groups and bromine substituents to increase phthalocyanine dye Solubility. U.S. Patent No. 5,641,897 discloses a phthalocyanine containing a linear or branched alkoxy group 'bromine and a substituent containing a phosphorus group. Another important issue with phthalocyanine dyes is the stability of the dye solution. Most phthalocyanine dye solutions cannot be stored for too long and are best used immediately after preparation. Dyes in solution tend to associate and will precipitate out in a short period of time. In addition, when the solution flows in the pipe of the production line, due to the limited solubility of the dye in the solvent, the dye will also associate and form a precipitate in the tube. This deposit can cause major problems in production, especially it can affect the quality of optical recording media. The first item of the present invention is to propose a salty green dye which includes a bicycloalkoxy substituent to improve its solubility in a common organic solvent. This phthalocyanine dye has a maximum absorption wavelength at about 680-750 nanometers and a high absorption coefficient for near-red if :; external laser. folder

: P I The second item of the present invention is to propose an optical recording medium using I gingival dye containing a bicycloalkoxy substituent as an optical recording material. Sakusho 51 4 Paper & Standards in Sichuan S National Standard- (CNS) Λ4 Specification (210X297 mm) 455853 A7 B7 V. Description of Invention (ψ) Detailed description of the invention (please read the notes on the back before filling this page The present invention proposes a phthalocyanine dye which has a maximum absorption wavelength of about 680-750 nm and is soluble in common organic solvents. The phthalocyanin of the present invention has the following general formula (I)

This paper uses Chinese National Standards (CNS) Λ4 size (210X 297 mm) 455853

AT B7 V. Description of the invention Cu, Zn, Co, Mg and Fe or divalent oxygen metal such as VO, TiO: χ is a halogen atom such as bromine or iodine; η is 0 or an integer of 1 to 4; k is 1 to 4 Any number; R1 is an alkoxy substituent derived from a hydroxyl-containing bicycloalkyl compound. The hydroxyl-containing bicycloalkyl compound can be represented by the formulae (II) and (III): (Π)% HO—R3

(III) r —. I I ^. I. ^ N I. 1 — Later {read the precautions on the back before filling this page) λ Λ, 卬 where X, Y and Z are independently hydrogen atoms , Halogen, methyl or z. R · 3 to R8 'are independently of each other Cw linear or branched radicals, the domains of which contain no halogen substituents.皋 Paper size: Shizhou Chinese National Standard (CNS) A4 specification (21〇 < 297 mm) 45 585 3 Ατ V. Description of the invention ί R: CVm linear alkyl group with or without substituents' Yes Or unsubstituted Cm. Cmo linear alkyloxy group with or without substituents, branched alkyl ', Cuo branched alkoxy group with or without substituents, and aryloxy group with or without substituents. The substituent may be halogen, OR9, S02R1 (), OCOR12 'NR13R14', where R9, RI (), Rn, R12, R13, R14 are all < ^-12 linear or branched alkyl groups. The cyanine dyes represented by formula (I) can be used to induce ffl (compounds la and 2a) or diiminoisolines (compounds lb and 2b), where R1 and R2 The same as in formula (I), the starting materials are synthesized. Compound 1. R1 (Please read the notes on the back before filling this page) ί · Compound 2a Compound lb Compound 2b

CN R2

CN R1

CN

CN

NH

NH NH R2

NH

NH

NH

N1T Ben. Standard Fan House visits i ?; (, xsw specifications (2 丨 0 > < 29 455853 5 'invention description (9) the starting material used in the synthesis is a mixture of compound 1 and compound 2 The molar content of Compound 1 in the mixture is 25% to 100%, preferably 50% to 100%. The cyanine dye of the present invention has excellent solubility in organic solvents commonly used in CD-R manufacturing procedures. The sensitive blue dye of the present invention has better solubility than phthalocyanine dyes containing only linear or branched alkoxy substituents. After dissolution, the shelf life of the obtained solution is also much longer. ° Further explanation will be made below. Manufacture of optical recording media ° First, a polymer substrate with a spiral groove track is prepared through injection molding. The material used as the substrate can be a material with good dimensional stability, zero or very low birefringence, good heat and Any transparent amorphous polymer with mechanical properties. The best polymers are polymethyl methacrylate, polycarbonate, and amorphous polyolefins. They are then prepared by spin coating or vapor deposition procedures to contain one or more formulas ( I) Epiphthalocyanine The recording layer of a mixture of raw materials. If the recording layer is prepared by a spin coating process, the phthalocyanine dye must be dissolved in a certain solvent. The solvent may be a pure solvent or a mixture of different solvents. For a solvent or The most important requirement of a solvent mixture is that it must be able to dissolve a considerable amount of dye without damaging the surface of the substrate. Common solvents include ethanol, 1-propanol, 2-propanol 'methoxyethanol' ethoxyethanol, three Fluoropropanol, 2 8 ___________ * ______ Ding--one spring,-° (please avoid reading the notes on the back and fill in this page) The paper scale " Applicable in China_Home Materials (CNS) Λ4 Specifications (210X297 public plague) 585 3 V. Description of the invention) Acetone alcohol, n-butyl ether, n-propyl ether, methyl cyclohexane, dimethyl cyclohexane, ethyl cyclohexane, acetone, methyl ethyl ketone, Tetrahydrofuran, etc. Then, a reflective layer is deposited on the recording layer by sputtering. The reflective layer may be made of Au, Ag or A1. Finally, a protective coating is formed on the reflective layer by spin coating a UV-curable paint. The recording layer may also include the S-cyan dye and cyanine The preferred cyanine dyes include indolinoline or phenylphosphonium indolinoline and have a maximum absorption wavelength between 640-750 nm, preferably between 660-720 nm. The recording layer It may further include a mixture of a dye and a polymer. The dye is a single cyanidin component or a mixture of a phthalocyanine dye and a cyanine dye. The polymer must be transparent and amorphous. The glass transition temperature must be Above 80 ° C and must be able to dissolve in the solvents mentioned above. Preferred_Polymer includes polymethyl methacrylate, polystyrene, amorphous polyamide, novolac resin epoxy resin , Polyvinyl alcohol, polyvinyl acetate and polyvinyl ether. The present invention is further explained in detail by the following examples. It describes the synthetic procedure of the dyes of the present invention, the results of the solubility test and the results of the optical recording media. ---------- < ------ 1T ------ ¾. (Please read the notes on the back before filling out this page) The music scale of this paper is suitable. 丨 .¾¾ Jia Piquan (CNS) Λ · 4 grid (2 丨 0X297) 犮 455853 AT B7 V. Invention's description) Example A: Synthesis of starting material Example A1 m A Synthesis

il again;] ΐί-Yinxian put 9.6 grams of 60% NaH and 150 ml of anhydrous dimethylformamide (DMF) in a 500 equipped with a magnetic stirrer, reflux condenser, addition funnel and nitrogen inlet -Ml of a three-neck glass reactor to prepare a sodium alkoxide solution. The solution was stirred gently under nitrogen and cooled to a temperature below 20 ° C. 37.75 grams of Isoborneol were transferred to the addition funnel and slowly added to a 500 ml reactor. The entire solution was stirred at a temperature below 20 ° C for 3 hours. Install another 1-liter three-neck reactor with a mechanical stirrer, nitrogen inlet, and addition funnel. A 1-liter reactor under nitrogen was charged with a feed of .5 g of 3-nitrophthalphthalein and 150 ml of anhydrous DMF. The sodium alkoxide / DMF solution was transferred from the 500-ml reactor into an addition funnel connected to the Bulk reactor and added dropwise to the 1-liter reactor at room temperature for 5 hours. The reaction solution was stirred at room temperature overnight. Pour the reaction solution under slow stirring] 〇--J ------- Ά ------ 1T ------ it (Please read the precautions for backing Vg before filling in this page ) The size of this paper is ⑴ 屮 1¾¾ 家 (准 规格 4 size (converted) 455853 五) 说明] Instructions (\ 〇) In a 5-liter container with 3 liters of water. The 5-liter container was then allowed to stand for 30 minutes. The crystals formed were filtered off and dried. Recrystallization was performed using methanol as a solvent to obtain 31 g of a product (yield = 55 ° /.). mp = 1400-142 ° C, HNMR-400 (DMSO-d6): 〇7.79 (t, 1H), 7.6 (dd, 2H)? 4.38 (t; 1H), 1.96 (m, 1H), 1.75 (t , 1H), 1.65 (m, 3H), 1.53 (m, H)? 1.23 (m, 2H), 1.07 (m, 2H), 1.00 (s, 3H), 0.97 (sr 3H), 0.84 (m? 3H ). Example A2: Synthesis of phthalocyanine B

First put 9.6 grams of 60% NaH and 150 ml of anhydrous dimethylformamide (DMF) into a 500-ml three-necked glass reactor equipped with a magnetic stirrer, reflux condenser, addition funnel and nitrogen inlet. To prepare a sodium alcoholate solution. Gently stir the solution under nitrogen and cool to below 20 ° C ^ Transfer 38.4 grams of endo-i'ens〇i into the addition funnel and slowly add to 5 The entire solution was stirred in a 0.00-ml reactor for 3 hours at a temperature below 20 ° C. Install another 1-liter three-neck reactor with a mechanical stirrer, nitrogen inlet, and addition funnel. Add 34.5 grams of 11 ΐcxs) v (2H) x 297 to liters under a nitrogen reactor. ^ ^ ~. -IT .— ^ —— (4 Please read the notes on the back before filling in the transcript Page) 45585 3 Fifth, send 1⑴ instructions of 3-nitrophthalocyanine and 150 ml of anhydrous DMF. The sodium alkoxide / DMF solution was transferred from the 500 ml reactor to an addition funnel connected to the 1-liter reactor and added dropwise to the 1-liter reactor at room temperature for 5 hours. The reaction solution was stirred at room temperature overnight. The reaction solution was poured into a 5-liter container containing 3 liters of water with slow stirring. The 5-liter container was then allowed to stand for 30 minutes. The crystals formed were filtered off and dried. 34 g of the product was obtained by recrystallization from methanol with methanol as a solvent (yield = 60.7%). 0 ^ = 92-941, H'NMR ^ OOtCDCU): < 5 7.57 (t 1H); 7.28 (d; 1H)? 7.21 (d? 1H), 4.01 (d, 1H), 2.09 (mf 1H), 1.76 (m? 2H), 1.58 (m, 1H), 1.50 (m, 1H), 1.27 (m, 2H)? 1.14 (s, 3H), 1.10 (s, 3H), 0.85 (s, 3H). Implementation Example B: Dye synthesis window Example B1 A 500-ml three-necked glass reactor was equipped with a magnetic stirrer, a reflux condenser and a nitrogen inlet. The reactor was charged with 22.2 g (0.08 mol) of brewed duck A, 20 g of DBU and 80 ml of n-pentanol. Nitrogen was introduced and stirring was started and the temperature of the solution was raised to 90 ° C. 3.54 grams (0.02 moles) of palladium dichloride was added and the temperature was increased to 120-i30t. Throughout the night. To the cooled reaction solution, 100 ml of toluene was added. The entire solution was filtered to remove insoluble solids. The filtrate was passed through a column with 100 g of silica gel using toluene as the eluent. Remove the solvent and dissolve the resulting solid in the minimum amount of toluene = pour the toluene solution into a large excess of methanol. Collect the sediment and _ 12 (may read the precautions on the back before filling this page)

.1T round 丨. This paper quickly won the bidding on A scale of winter> Eight Tigger (21CU297 mm) 455853 V. Description of the invention (rx) Drying to obtain μ. 2 g palladium i cyan dye (yield = 66.〇. Ten Xma , 690 nm: e = i.8ixl05 cm mol-1 liter (toluene) C72H80N8O4Pd Element analysis: Calculate 値: C, 70.43%: Η, 6.57%; N, 9.13% Measured 値: C, 71.01%; Η , 6.40%; N, 8.91% Example B2 will be equipped with the same reactor as in Example 1. In this reactor, 22.2 g (0.08 mol) of Eye A, 20 g of DBU and 80 ml of n-pentanol were added. Nitrogen was added and the stirring was started and the temperature of the solution was raised to 90 ° C. 5.56 grams (0.02 mol) of lead dichloride was added and the temperature was raised to 120-130 ° C all night. In the cooled reaction solution 100 ml of toluene was added. The entire solution was filtered to remove insoluble solids. The filtrate was passed through a column with 100 g of silica gel using toluene as the eluent. The solvent was removed and the resulting solid was dissolved in a minimum amount of toluene. Inside. Pour the toluene solution into a large excess of methanol. Collect the precipitate and dry to obtain 13.5 g of lead cyanine dye (yield = 50.8%) .

Ama, 741 nanometers: ε = 1_3x105 cm "Mole-1 liter (toluene) C? 2H8GNs〇4Pb Element analysis and calculation 値: C, 65_09 ° / .; Η, 6.07%: N, 8.43% Measured 値: C '68.31%: Η, 6.86¾: Ν, 8.580'. Window example B3 was installed with the same reactor as in Example 1. 22.2 ---------- if-- ---- ΐτ ------ i (诮 Read the notes on the back before filling in this f) 45 58 5 3 V. Hairpin] Explanation (I 是) grams (0.08 moles), 20 g of DBU and 80 ml of n-pentanol. Nitrogen was introduced and stirring was started and the temperature of the solution was raised to 90 ° C. 3.54 g (0.02 mol) of palladium dichloride was added and the temperature was increased to 12 (M30 ° C) Throughout the night. 200 ml of ethyl acetate was added to the cooled reaction solution. The entire solution was filtered to remove insoluble solids. The filtrate was passed through a column with 100 g of silica gel using ethyl acetate as the eluent. The solvent was removed and the obtained solid was dissolved in the minimum amount of toluene. The toluene solution was poured into a large excess of methanol. The precipitate was collected and dried to obtain 17.3 g of palladium cyanine dye (yield = 70_5%) ! ^ = 691 M; ε = 1.60x105 cm -1 mole-1 liter (toluene) C72H8〇N8〇4pii Analysis of the element · Calculate 値: C, 70.43%: Η, 6.57%; N, 9.13% Measured 値: C, 71.13%; Η, 7_31%; Ν, 8.80% 眚 Example B4 The same reactor as in Example 1 was installed. 22.2 g (0.08 mol) of 醎 B, 20 g was added to the reactor. DBU and 80 ml of n-pentanol. Nitrogen was introduced and stirring was started and the temperature of the solution was raised to 9 ° C. 5.30 g (0.02 mol) of vanadylacetonylacetonate was added and the temperature was increased to 120-13 (TC all night. 100 ml of ethyl acetate was added to the cooled reaction solution. The entire solution was filtered to remove insoluble solids. The filtrate was passed through a column with 100 g of silica gel using ethyl acetate as the eluent. = Remove the solvent and dissolve the obtained solid in the minimum amount of toluene. Pour the toluene solution into a large excess of methanol. Collect the precipitate and dry to obtain 15.7 g of oxygen 14 --------- -------- KK; l Φ) ¾; Λ] (c'NS) (21〇X: 9 " ^ j |) "Read the precautions on the back 4 and fill in the '太 页 * 装-

, 1T 45 585 3 Λ 7 B7 — —-·-· »—--. ·-~ — — _ V. Description of the invention (丨) Vanadium dye (yield = 66.1%) imax = 739 nm; e = 1.56x105 cm-1 mol "L (toluene) C72H8〇Ns04VO Element analysis: Calculate 値 ·· C, 72.77. /; Η, 6.78%; N, 9.43¾ Measured 値: C, 71,71%: Rhenium, 7.26%: N, 8.44¾ Example B5 The same reactor as in Example 1 was set up. 22.2 g (0.08 mol) of phthalophthalein B, 20 g of DBU and 80 ml of n-pentanol were installed in the reactor. Feed nitrogen and start stirring and raise the solution temperature to 90t. Add 5.56 g (0.02 mol) of lead dichloride and increase the temperature to 120-130t all night. Add to the cooled reaction solution 200 ml of ethyl acetate. The entire solution was filtered to remove insoluble solids. The filtrate was passed through a column with 100 g of silica gel using ethyl acetate as the eluent. The solvent was removed and the resulting solid was dissolved in a minimum amount. The toluene solution was poured into a large excess of methanol. The precipitate was collected and dried to obtain 14.9 g of lead cyanine dye (yield = 56.1%). Λ Raa, 741 nanometers: e = 1.41xl05 cm-1 mol "liter (toluene) C72H8QNs04Pb Elemental analysis: Calculated plutonium: C, 65.09%: plutonium, 6.079 .; N, 8,43% found plutonium: C, 64.51% Η, 7.10%; Ν, 8.02¾ Example B6 The same reactor as in Example 1 was installed. 22.2 Localized scales were added to the reactor; 彳; '卜: ¾¾ 家 标 ίί-*-( ) Λ4 ^ lattice [210. ≫ < Gongchu) 45585 3

AT B7 Five 'Explanation of the invention ((¢) | g (〇watch mole) from B, 20 g DBU and 80 ml of n-pentanol.

f, please read the precautions of 1 & again, repeat the nitrogen and start stirring and raise the solution temperature to 90t. Add 2.69 g (0.02 mol) of copper dichloride and increase the temperature to 14 (M45t throughout the night. 150 ml of toluene was added to the cooled reaction solution. The entire solution was filtered to remove insoluble solids. Ethyl acetate was used The filtrate was passed through a column with 100 g of silica gel as an elution solvent. The solvent was removed and the resulting solid was dissolved in the minimum amount of toluene. The toluene solution was poured into a large excess of methanol. Collected Precipitate and dry to obtain Π.2 grams of copper cyanine dye (yield = 72.6%) ^; lmax = 708 nm; e = 2.15xl05 cm -1 mole-1 liter (toluene) C2H8 () Ns04Cu Elemental analysis: Calculated plutonium: C, 72.98%; plutonium, 6.80%: N, 9.46% found plutonium: C, 72.07%: plutonium, 6.82%; Ν, 9.19% Example B7 The same reactor as in Example 1 was installed in the line 22.2 g (0.08 mol) of 猷 嗦 B, 20 g of DBU and 80 ml of n-pentanol were added to the reactor. Nitrogen was added and stirring was started and the temperature of the solution was raised to 90 ° C. 2.73 was added G (0.02 mol) of zinc dichloride and increase the temperature to 120-13 (TC all night. To the cooled reaction solution. 200 milliliter was added. Liters of ethyl acetate. The entire solution was filtered to remove insoluble solids. Ethyl acetate was used as the eluent to dissolve the filtrate through a column with 100 g of silica gel. The solvent was removed and the resulting solution was removed. The solid was dissolved in the minimum amount of toluene. The toluene solution was poured into a large amount of excess methanol. The precipitate was collected and dried to obtain 17.5 g of zinc cyanine dye. Jiadaijiu :: Λ4 # 格 ί total) 455853 Printed by A7 B7, Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (丨 y (yield = 73.1 λ nanometers; £ = 1.83xl03 cm_1 mol_1 liter (toluene) C72H8flN804Zn elemental analysis: calculation 値: C, 72.86%; Η, 6.79%; N, 9.44% Measured 値: C, 73.10%: Η, 6.25%: Ν, 8.99% Window Example B8 The same reactor as in Example 1 was installed. The reactor was charged with grams (0,04 moles) of Xanqing B, 20 grams of DBU and 80 ml of n-pentanol. Nitrogen was added and stirring was started and the temperature of the solution was raised to 90 ° C. 3.54 grams were added (0.02 mol) of palladium dichloride and raise the temperature to 120-130 ° C all night. Add to the cooled reaction solution 100 ml of toluene. The entire solution was filtered to remove insoluble solids. The filtrate was passed through a column with 100 g of silica gel using toluene as the eluent. The solvent was removed and the resulting solid was dissolved in the minimum amount of toluene. Within that, the toluene solution was poured into a large excess of methanol. The precipitate was collected and dried to obtain gram of palladium * cyanine dye (yield = 61_1%). Nanometer: f = 1.62xl05 cm -1 mol-1 liter (toluene) C72H80〇N804Pd Elemental analysis: Calculated 値: C, 70.43 °. Η ’6.57%; N, 9, 13¾ Measured 値: C, 71.01%: 6.’ 6.43¾; N, 8.89% Window Example B9 The same reactor as in Example 1 was installed. Add Π.1 r to this reactor. This paper size is applicable to China National Standard (CNS) A4 (2⑴X 297 mm) gutter (please read the precautions on the back before filling this page) Central Bureau of Standards, Ministry of Economic Affairs Employee Consumer Cooperative Co., Ltd. 455853, A; B7 V. Description of the invention (^) grams (0.04 moles) phthalophthalate B, 9,68 grams (0.04 moles) 3- (2,4-dimethyl-3-pentane) (Oxy) Accumulate '20 g of DBU and 80 ml of n-pentanol. Nitrogen was introduced and stirring was started and the temperature of the solution was raised to 90 ° C. Add 2.69 grams (0.02 mol) of copper dichloride and increase the temperature to 140-145 ° C all night. To the cooled reaction solution, 100 ml of toluene was added. The entire solution was filtered to remove insoluble solids. The filtrate was passed through a column with 100 g of silica gel using toluene as the eluent. The solvent was removed and the resulting solid was dissolved in a minimum amount of toluene. The toluene solution was poured into a large excess of methanol. The precipitate was collected and dried to obtain 15.8 g of copper European blue dye (yield = 71.3%).窨 Example B10 Bromination of Qingxin A three-necked 300-ml reactor was equipped with a liquid addition funnel, a condenser and a mechanical stirrer. The reactor was charged with 10 grams of palladin (Example 3) and 55 grams of 1,1,2-trichloroethane. Start stirring. After 10 minutes, 20 'grams of water was added and the temperature of the solution was raised to 55 ° C. 5 grams of bromine was dissolved in 12 grams of U, 2-trichloroethane. This bromine solution was added dropwise into the reactor. After the bromine solution was added, the reaction was performed at 60 ° C for one hour. To the cooled solution was added 20 grams of a 10% aqueous NaHSO3 solution and stirring was continued until the organic phase turned dark green. The organic phase was collected and washed twice with 100 ml of water. After the organic phase was dehydrated with magnesium sulfate, it was passed through a silica gel column using toluene as an eluent. The solvent was removed and the resulting solid was dissolved in a minimum amount of toluene. The methylbenzyl solvent was poured into a large excess of methanol. Collection 18 (Please read the notes on the back before filling out this page)

Line 1T—The paper scale is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) 455853 Α7 B7 5. Description of the invention (\ parent) The precipitate is dried to obtain 8.5 g of palladium bromide. lmax = 708 nm Comparative Example 1 The same reactor as in Example 1 was installed. To this reactor was charged 19-36 g (0.08 mol) of 3- (2,4-dimethyl-3-pentoxy) H 20 g of DBU and 80 ml of n-pentanol. Nitrogen was introduced and stirring was started and the temperature of the solution was raised to 9CTC. Add 2.69 g (0.02 mol) of copper dichloride and increase the temperature to 140-H5 ° C throughout the night = > To the cooled reaction solution, 100 ml of toluene was added. The entire solution was filtered to remove insoluble solids. The filtrate was passed through a column with 100 g of silica gel using toluene as the eluent. The solvent was removed and the resulting solid was dissolved in a minimum amount of toluene. The toluene solution was poured into a large excess of methanol. The precipitate was collected and dried to obtain H.0 g of copper phthalocyanine dye (yield = 72.7%).

Ama wide 692 nanometers: ε = 1.90x105 cm "Mole" liter (toluene) C72H8〇Ns〇4Cu Elemental analysis: Calculate 値 · C, 69.77%; Η, 7.03%: N, 10.85% Measured 値: C, 70.51 %; Η, 7.65%: Ν, 10.12% Printed by the Central Bureau of Standards of the Ministry of Economic Affairs—Industrial and Consumer Cooperatives (read the notes on the back and then fill out this page) Comparative Example 2 The same reactor as in Example 1 was installed. In this reactor, 19.36 g (0.08 mol) of 3- (2,4-dimethyl I-pentyloxy, 20 g of DBU and 80 ml of n-pentanol were added. Nitrogen was added and stirring was started. And raise the solution temperature to 90 ° C. Add 3.54 g (0.02 mol) of palladium dichloride and increase the temperature to H0-145t all night. Add 19 ^ paper size General China ( CNS) A4 specifications (2〗 〇297297 公 楚 —) ~~ ^ 455853 A7 _B7___ V. Description of the invention (J) 100 ml of toluene. The entire solution was filtered to remove insoluble solids. The toluene was used as the eluent solvent to pass the filtrate through A column with 100 g of silica gel. Remove the solvent and dissolve the resulting solid in the minimum amount of toluene. Pour the toluene solution over Significant excess of β in methanol collected the precipitate and dried to obtain 14.5 g of palladium cyanine dye (yield = 67.4%); Uai = 692 nm; ε = 1.75 × 105 cm “Mole” liter (toluene) C72H8 () Ns04Pd Elemental analysis: Calculated 値: C, 66.99 ° / .; Η, 6.75%; N, 10.42% Found 値: C, 67.81 ° / .; Η, 7.02%; Ν, 9.89% Example C Solubility Test Solubility The test results are listed in the table below. The results clearly show that phthalocyanine dyes containing bicycloalkoxy substituents have better solubility than cyanine dyes containing only linear or branched substituents. (Please read the precautions on the back first and fill in this page) The paper printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives printed on this paper & the standard applies to the Chinese National Standard (CNS) Μ specifications (210 × 297 mm) 5 A 7 B7 5 2. Description of the invention) Preparation of optical recording medium 2 g of a phthalocyanine dye sample was dissolved in 100 ml of methylcyclohexane (MCH) / 1-propanol (90/10). The solution was passed through a 0.45 micron filter. Through injection Polycarbonate with a diameter of 12 cm, a depth of 160 nm and a width of 0.8 μm Ester substrate = The solution was spin-coated on the polycarbonate substrate with a programmed speed and time. The resulting picture was baked at 8VC for 90 minutes. An Ag reflective layer was formed by sputtering on the dye layer A UV curable protective lacquer (SD-17) from Dainippon Ink was spin-coated on the Ag layer and cured. A Puktec CD-R tester was used to inspect the wafer. The test results are listed in the table below. (Read the precautions on the back before you fill in this page) Samples printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs TEb IgB lib RCb 13 / Itop 111 / Itop \ Ble r Jitte r Pit 3T Jitte r Pit ΠΤ Jitter land 3T Jitter land 11T Example 0.440 0.576 0.638 0.112 0.354 0.634 2.3 22.5 24 31.7 30.5 3 Example 0.438 0.578 0.639 0.110 0.380 0.620 2.1 23.1 23.9 31.9 29 7 Example 0.430 0.586 0.725 0.116 0.401 0.705 5.1 36.3 35.4 36.2 37.5 9 Example 0.422 0.657 0.765 0.082 0.389 0.690 2.0 34.2 34.3 35 * 6 34.2 10 1

11T paper size is universal Chinese National Standard (CNS) A4 (210X 297mm)

Claims (1)

Αΐ 4 5 5 8 5 3 IL) 06. Scope of patent application: An optical recording medium includes a polymer substrate, a recording layer, a reflective layer, and a protective layer; wherein one or more of the formula ( I) The cyan dyes listed (please read the precautions on the back before filling this page) (I) Taichi scale applies to China National Standards (CNS) A4 (210 X 297 mm) X Y 45585 3 S D8 6. The scope of patent application where M is Pb 'Pd' Ni 'Cu' Zn 'Co' Mg, Fe, V0 or TiO; X is Cl, Br or I; n is an integer of 0 or 1 to 4. K is any number from 1 to 4; R1 is an alkoxy substituent derived from a hydroxyl-containing bicycloalkyl compound; the hydroxyl-containing bicycloalkyl compound can be represented by the formulae (Π) and (III): (II ) (III) 0H Z wherein X, Y and Z are each independently a hydrogen atom, halogen, methyl or ethyl; R3, R4, R5, R6, R7 and R8 are each independently Ci-4 linear or branched alkyl groups containing Or without halogen substituents; R2 is a linear alkyl group with or without substituents, 24 paper methods with or without substituents are applicable to Chinese National Standard (CNS) A4 specifications (2IOX 297 mm) -----,玎 ------ line (please read the precautions on the back before filling out this page) Printed by B8 CS Do, Employee Cooperative of the Bureau of Intellectual Property, No. 1 Bureau of the Ministry of Economic Affairs 6. Scope of Patent Application c ^. Branched alkyl, Cl_2 ° linear alkoxy 'with or without substituents, Cuo branched alkoxy with or without substituents, and aryloxy with or without substituents. 2. The optical recording medium according to item 1 of the patent application, wherein the substituent is halogen, OR9, SO # 1. 〇COR12, NR13R14 ′ wherein R9, R10, R11, R12, R13 and R14 are all Ciw linear or branched alkyl groups. ---------- Shang -------- Order ------ line (Please read the notes on the back before filling out this page. J Printed by the Employee Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy Taiji Paper's standard is applicable to China National Standard (CNS) A4 (2! 0χ 297 mm)