TWI297350B - - Google Patents

Description

1297350 IX. Description of the Invention: [Technical Field] The present invention relates to a novel organic dye of phthalphthalein (Cyan ines) and derivatives, a preparation method thereof and application thereof in an optical recording medium, Especially in the one-time recording disc application. [Prior Art] Organic dyes are widely used in the field of optical recording. Although these recording media can only be recorded once, they can be read and played repeatedly. • 4 is called “irite gnce nead niany”, abbreviated as WORM. Recordable Compact Discs or CD-Rs are CD formats that utilize this technology and were first published in Optical Data Storage 1989, Technical Digest Series, v〇l· 1,45 (1989). / All organic dyes used in optical recording media, phthalocyanine derivatives are one of the most important items, mostly because they are in the near-infrared range (7〇〇~9〇) 〇Nami) has a high degree of reincarnation. Compared with other organic dyes such as Cyanines

Under the conditions, the anthraquinone dye and the manufactured disc can exhibit better light stability φ and good temperature and humidity resistance. U • Earlier technical documents JP-A 154888 (1986), 197280 (1986), 246091 (1986), US 4769307 (1987), JP-A 39388 (1988) • Both describe anthraquinone as an optical recording layer material. Applied to optical recording media. However, the above-mentioned anthraquinones are not sufficient as good optical recording media materials in terms of sensitivity, solubility, refractive index, burning characteristics and other related physical properties. In order to improve the disadvantages of the above-mentioned phthalocyanine as an optical recording layer material, JP-A 62878 (1991) proposes an anthocyanin having a large steric hindrance group on a benzene ring, so that the above disadvantages are improved, however, this Material & burnt, 1297350 does not meet the requirements. In addition, the disadvantages of coating on us 52295G7 (i993). In some specific cases, τ, the dye will be rotated by the introduction of a variety of larger substituents to the phthalocyanine ili 6/1997), then the isomer composition is studied for solubility ίίίϊϋ must be greater than _ to obtain appropriate (4) Solubility. For goods

The transport of the isomer composition is clearly cumbersome and seems impractical for dye manufacturing (4). Another approach to solving the solubility problem is described in US Pat. No. 582,096 (1998), which is based on a trivalent metal with a substituent as a central atom. Due to the steric hindrance of the proposed chemical structure, the compound can be dissolved in a polar solvent, and the resulting optical disk exhibits good reflectance. However, the hydrophilic nature of polar solvents inevitably causes the dye solution to absorb moisture during recycling, which makes it difficult to vary the quality of the disc or even the quality. In addition to solubility, dye sensitivity is another key factor in good recording media, especially in high-speed recording and fast reading. The so-called "Pit edge control agent" is proposed in US Pat. No. 5,492,744 (1996) and JP-A 798,887 to improve the pit pit and jiter properties of the pit. It is proposed that ferrocenes and derivatives thereof (such as benzoylferrocene and /7-buty 1 f errocene) are blended in a certain ratio. Qingsu can greatly improve the formation of signal pits, but the material utilization rate is tested in practical operation. Since optical dyes occupy a significant proportion in the cost structure of optical discs, the design and synthesis of dyes must be considered. Recycling of dye and dye 6 1297350 solution. Anthraquinone has better solubility than ferrocene in the specified solvent (ethyl cyclohexane in this case); therefore, the pit is incorporated The edge control agent tends to smother in the spin coating and recovery process, which makes it difficult to control the concentration change of the recovered dye solution. The yield (the number of discs that can be produced per unit of dye) is also higher than that of the single dye. In us 5789138 (1998), an additive that incorporates chlorophyll in a molten state (eg, benzimidazole), thereby facilitating the coordination of the additive with the central metal of the anthraquinone. It is said that a satisfactory dye film pattern can be obtained after coating due to better intermolecular associations. However, there is a trade-off between the limited coordination and the corresponding dye properties. It is difficult to optimize the performance of the disc.

There are also reports mentioning halogenation on anthracycline to improve sensitivity. US 5,646,273 (1997) teaches that the optimum burning power (〇pc, gptimal and ower calibration or optimal recording power) can be effectively improved by halogenation on a substituent such as an alkyl group and/or an alkoxy group of anthraquinone. Us 6087492 (2000) also proposed direct halogenation on the phenyl ring of anthracycline. However, the resulting disc still shows insufficient sensitivity and cannot effectively control the pit length. In addition, precise control of the degree of halogenation in chemical reactions is still difficult. The resulting compound is inevitably a mixture of a plurality of compounds containing different numbers of halogen atoms, resulting in dye quality instability and inconsistent disc properties. In US 6087492 (2000), an ugly-green pigment having a central atom of a divalent metal is thiolated, then reduced, and finally esterified. However, the dye structure thus formed does not have satisfactory properties because it does not have a pit edge control agent as described in U.S. Patent 5,492,744 (1996). In US 6,399,768 B1 (2002) and US 6,790,593 B2 (2004), ferrocenecarboxylic acid is esterified with a hydroxyl group on uglyan to produce a stable chemical bond. These dyes are also toothed (mainly brominated), and the degree of toothing depends on the atomic weight of the central gold 1297350. The resulting dye is said to exhibit good optical properties and good solubility to solvents such as dibutyl ether (DBE) and ethylcyclohexane (ECH). Although this dye has good characteristics at high-speed burning, it is difficult to synthesize, and the raw materials are expensive (especially metallocene), and it cannot satisfy the increasingly saturated CD-R market. The urgent need for cheap and quality products. In order to meet the burning requirements of different burning machines, and to achieve a significant reduction in the cost of the dye, the present invention replaces the ferrocene compound with a sulfonate compound and bonds with the anthraquinone through a covalent bond. A novel optical dye is produced. The optical discs using this novel optical dye have good characteristics for burning from IX to 52X. SUMMARY OF THE INVENTION The primary object of the present invention is to provide a novel optical dye which is formed by chemically bonding a sulfonate-based compound to a substituted phthalocyanine, and has the structure of formula (I) _· 1297350

'Sn (I) Another object of the present invention is to provide a method for synthesizing an organic dye of the formula (I). Another object of the present invention is to provide an organic dye of the formula (II):

N N N

i? CH2 - 〇 - S - R30 ο ' - [OCH(CHMe2) 2] 4 Another object of the present invention is to provide a method for synthesizing an organic dye of the formula (II). 9 1297350 Another object of the present invention is to provide an organic dye of the formula (1) or (11) as an optical dye in a recording layer contained in a secondary recording optical disc having good burning characteristics. Another object of the present invention is to provide an optical recording medium using the novel anthraquinone derivative of the formula (11) as a recording layer dye. [Embodiment] 1. The invention relates to a phthalocyanine dye for use in an optical recording medium, the optical recording comprising a substrate having a groove

a recording layer material on which the recording layer material is recorded by laser illumination; wherein the recording layer material comprises an anthraquinone derivative represented by the formula (1):

"Sn (I) 二中^'匕^匕 and 匕 can represent an alkyl group having a carbon atom to a carbon atom, and can be cleaved to 6 halogen atoms, a base group, 1 to β carbon atoms. An alkylamine group of from 6 to 5 carbon atoms, two = 1 to 6 carbon atoms = earth, or an alkylthio group of 1 to θ carbon atoms; 2 to 12 carbons, an alkenyl group a chain; or an alkynyl chain of 2 to 12 carbon atoms; M is two hydrogen 1297350 atoms, a divalent metal, a monovalently substituted trivalent metal, a disubstituted tetravalent metal, or an oxidized metal group; S represents a molecular moiety having a sulfonate group; and n is an integer between 1 and 4. The anthraquinone starting material used in the present invention is prepared according to the prior art ΕΡ 703280; the most preferred one is a-substituted phthalocyanine, and its possible isomers are as shown in formula (2) to (5) ··

11 1297350

(5) wherein R5 to R2G represent an alkyl chain of 1 to 12 carbon atoms, respectively, which may be 0 to 6 halogen atoms, a hydroxyl group, an alkoxy group of 1 to 6 carbon atoms, 1 to 6 carbons An alkylamino group of an atom, a dialkylamine group of 1 to 6 carbon atoms, or an alkylthio group of 1 to 6 carbon atoms; an alkenyl chain of 2 to 12 carbon atoms; or 2 to 12 carbon atoms An alkynyl chain; hydrazine is two hydrogen atoms, a divalent metal, a monovalently substituted trivalent metal, a disubstituted tetravalent metal, or an oxidized metal group. The isomer composition of the above four ortho-substituted phthalocyanins varies depending on the reaction strip 12 1297350 U. The preferred substituent is a secondary (se(7)ndary) alkyl, alkenyl, or alkynyl group; the most preferred substituent It is an alkyl, alkenyl, or alkynyl group having 2 to 4 secondary, tertiary, or quaternary carbon atoms. ' . ΐ Π Π ) ^ (5) in & to R2D, a representative of the base is - D: base enough ethyl 'n-propyl, isopropyl 'n-butyl, isobutyl, the first Base, tert-butyl, n-pentyl, isopentyl, cyclopentyl, 2-methylbutytidine; 1-dimethylpropanyl-n-hexyl, cyclohexyl, "ylpentyl, 3- Methylpentyl, 4-methylpentyl, i,2-dimethylbutyl, 13-dimethylbutanf Λ2: dimethylbutyl, 2,3-dimethylbutyl, 3, 3 - dimethylbutyl, 1-isopropylpropyl, n-heptyl, cycloheptyl, 2-methylhexyl, 3 methylhexyl 4;:hexyl group '5-methylhexyl, dimethylpentyl , 1,3-di: 2 pentyl, 1,4-dimethylpentyl, 2, 2-dimethylpentyl, 2,3-dimethylmethyl, 2,4-dimethylpentyl , 丨-ethyl_3_methylbutyl, 2 isopropylbutyl, 2-methyl-1-isopropylpropyl, n-octyl, cyclooctyl, 2-ethylamine, 3-methyl Base-1 monoisopropylbutyl, 2-methyl-anthracene-isopropylbutyl, tert.: yl-2-methylpropyl, n-decyl, cyclodecyl, n-decyl, fluorenyl Base, eleven base and dodecyl; preferred substituents are from 2 to 4 ;" tertiary, or a branched alkyl group of a quaternary carbon atom such as isopropyl, isobutyl, butyl, tert-butyl, isopentyl, 2-methylbutyl, hydrazine ,2-bi-propenyl propylate, 1"3-dimethylbutyl, isopropylidenepropyl, l-2-didecylbutyl, 1,4-dimethylpentyl, 2-methyl-one丨-isopropylpropyl, fluorenylethyl 3-methylbutyl, 2-ethylhexyl, 3-methyl-1-isopropylbutyl, 2-methylisopropyl isopropyl butyl, Tert-butyl-2-methylpropyl and 2,4-didecyl-3-&base; the most preferred substituent is 丨-t-butyl-2-methylpropyl, 2-methyl Base mono-isopropyl butyl, and 2,4-dimethyl-3-pentyl. The halogen-substituted alkyl group is, for example, a gas methyl group, a hydrazine, a dioxoethyl group, an anthracene, a 2-dibromoethyl group, a 2,2,2-trifluoroethyl group, a 2,2,2-trigas. Ethyl, 2,2,2^tribromoethyl, 1,1,2, 2, 2-pentaethyl, and m3,3,3-hexafluoro-2-dipropyl. 13 1297350 A hydroxy-substituted alkyl group is, for example, a hydroxyindenyl group, a 2-hydroxyethyl group, a 1,2-di-diethylethyl 3-cyanopropyl 2,3-dipropylpropyl ' 3 - Butyl, 4-hydroxybutyl, 3-hydroxypentyl, 4-pyridylpentyl, 5-pyridylpentyl, 2-ylhexyl, 3-perylhexyl, 4-ylhexyl, 5- By a hexyl group, 6-ylhexyl, via hexyl heptyl, via octyl, via fluorenyl, hydrazino, hydroxy undecyl, hydroxydodecyl. The alkoxyalkyl group is, for example, an anthranyloxy group, a decyloxyethyl group, a decyloxypropyl group, a methoxybutyl group, a decyloxypentyl group, a methoxyhexyl group, a 3-decyloxycyclopentyl group. , 4-decyloxycyclohexyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, 4-ethoxycyclohexyl, propoxy Base, propoxypropyl, propoxybutyl, propoxypentyl, propoxyhexyl 'butoxyethyl' butoxypropyl'butoxybutyl, 1,2-dioxyloxy Ethyl ethyl, 1,2-diethoxyethyl, 1,2-dimethoxypropyl, 2,2-dimethoxypropyl, diethoxybutyl and butoxyhexyl; Preferably, the substituent is an alkoxyalkyl group of 2 to 10 carbon atoms, for example: anthracenyloxy, methoxyethyl, ethoxypropyl, ethoxybutyl, propoxyhexyl, 1,2 - Dimethoxypropyl, 2,2-dimethoxypropyl, diethoxybutyl and butoxyhexyl; most preferred are alkoxyalkyl groups of 2 to 6 carbon atoms, for example : decyloxymethyl, decyloxyethyl, ethoxypropyl, ethoxybutyl. The alkylaminoalkyl group is, for example, amidinoindolyl, decylaminoethyl, nonylaminopropyl, nonylaminobutyl, ethylaminoethyl, ethylaminopropyl, ethylaminobutyl, ethyl Aminopentyl, ethylaminohexyl, ethylaminoheptyl, ethylaminooctyl, propylaminoethyl, propylaminopropyl, propylaminobutyl, propylaminopentyl, propylaminohexyl, isopropylaminoethyl Base, isopropylaminopropyl, isopropylaminobutyl, isopropylaminopentyl, isopropylaminohexyl, butylaminoethyl, butylaminopropylbutylamylpentyl, butylaminohexyl; preferred substitution An alkylamino group having 2 to 8 carbon atoms such as: fluorenyl fluorenyl, decylaminoethyl, ethylaminopropyl, ethylaminobutyl, ethylaminopentyl, ethylaminohexyl , propylaminobutyl, propylaminopentyl; the most preferred alkylaminoalkyl group of 2 to 6 carbon atoms 14 1297350 such as methylamino thiol, methylaminoethyl, ethylaminopropyl , ethylaminobutyl.

The dihydrogen amine group is, for example, dimethylaminomethyl, dimethylaminoethyl, dimethylaminopropyl, dimethylaminobutyl, diethylaminoethyl, diethylaminopropyl Diethylaminobutyl, diethylaminopentyl, diethylaminohexyl, diethylaminoheptyl'-ethylaminooctyl'dipropylaminoethyl, dipropylaminopropyl'-propylaminobutyrate Base, dipropylaminopentyl, dipropylaminohexyl, diisopropylaminoethyl, diisopropylaminopropyl, diisopropylaminobutyl, diisopropylaminopentyl, diisopropylaminohexyl; preferred substitution An alkylamine alkyl group having 2 to 1 ring carbon atoms such as dimethylaminomethyl, dimethylaminoethyl, diethylaminopropyl, diethylaminobutyl, diethylaminopenta The group is a diethylaminohexyl group; the alkoxy group having 2 to 6 carbon atoms is preferably a dimethylaminomethyl group, a dimethylaminoethyl group or a diethylaminoethyl group. The soil sulphur-burning group is, for example, methylthiomethyl, sulfonylethyl, methylthiopropyl, methylthiobutyl, methylthiopentyl, decylthiohexyl, 3-terpene cyclopentyl , 4-indolethiocyclohexyl, ethylthioethyl, ethylthiopropyl: ^ thiobutyl 'ethylthiopentyl 'ethylthiohexyl' 4 -ethylthiocyclohexyl, propylthiobutyrate a group, a propylthiopentyl group, a propylthiohexyl group; preferably an alkylthioalkyl group having a substituent of 2 to 8 carbon atoms, such as: sulfonylthio group, methylthioethyl 1, ethylthiopropyl, ethyl Thiobutyl, propylthiohexyl; the most preferred alkylthioalkyl group of 2 to 6 carbon atoms such as sulfonylthio, methylthioethyl & diethylthiopropyl, Thiobutyl. The alkenyl group represented by the earth is, for example, a vinyl group, a n-propenyl group, a ruthenyl group: a second butenyl group, a n-pentenyl group, an isopentenyl i: : 'cycloheptanyl group, a n-octyl group' ring octane Alkenyl=mercapto-N-alkenyl, n-decenyl, cycloalkenyl, eleven::alkenyl; preferred substituent is 2 to 6 carbons; fluorenyl-n-propenyl, isopropyl <Return to base, π m · „································ Dilute 'n-pentyl' isopentenyl-based, one ring 15. 15 1297350 • 1,2-dimethylpropenyl, euhexenyl, cyclohexenyl; the most preferred substituent is 2 to 4 The base of a carbon atom such as ethylidene, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, ί; Ethyl group, propyl block, n-butan group, second butyl group, n-pentyl group, isopentenyl group, cyclopentyl group, 2-mercaptobutyl group, n-hexynyl group, cyclohexynyl group, positive Hepynyl, cycloheptynyl, n-octyl, cyclooctynyl, positive Alkynyl, cyclodecynyl, n-decynyl, cyclodecyl, undecynyl and dodecynyl, and the like; preferably a substituent of 2 to 6 carbon atoms, such as an ethynyl group , propyl group, n-butynyl, second butynyl, n-pentynyl, isethynyl, cyclopentynyl, 2-methylbutynyl, n-hexynyl, cyclohexynyl; most Preferred are alkynyl groups of 2 to 4 carbon atoms such as ethynyl, propynyl, n-butynyl and second butynyl. Intermediate metal iridium in formula (1) to formula (5) , representative of divalent metals such as: copper, zinc, iron, cobalt, nickel 'Ji, I from, short, tin, Shu and 锇; the best metals are copper, Ming, nickel, put and platinum; representative Monosubstituted trivalent metals such as · · fluorine - Shao, gas - Ming, bromine - aluminum, iodine - Ming, fluorine - indium, gas - indium, bromine - indium, moth - indium, fluorine - gallium, chlorine - gallium, bromine - Gallium, bismuth-gallium, fluorine-Ming, Qi Yiqi, Bromine-Ming, Iodine-Ming, Jingji-Ming, Jingji-Meng; representative double-substituted tetravalent metals such as: difluoroanthracene, dioxane, Dibromofluorene, diiodofluorene, difluorotin, bismuth dichloride, dibromotin, tin iodide Difluoroanthracene, dioxon, dibromofluorene, diiodofluorene, difluorotitanium, di-titanium, dibromotitanium, diiodotitanium, dihydroxy-hydrazine, di-hydroxy-tin, dihydroxy-hydrazine, dihydroxy - Manganese; representative oxidized metal base such as: . vanadium oxide, manganese oxide, titanium oxide. " ΐ ΐ ΐ ΐ ΐ 之 之 之 ΐ ΐ ΐ ΐ 醋 醋 醋 醋 醋 醋 醋 醋 醋 醋 ί ί ί ί ί ί ί ί ί J J J J J J , , , , , , , , Good effect to reduce the burning power 'conforms to different burners (4) ί ίm base or unsubstituted 仏 夕 ,, representative methods include · take hydroxyl with 16 1297350 generation of ruthenium and trifluoroanthryl acid anhydride (trifluoromethanesu 1 fonic anhydride) is reacted under appropriate conditions, or the hydroxy-substituted anthraquinone is reacted with p-non-phenylene sulfonium chloride (/?-toluenesulfonyl chloride) under an organic test (such as biting); The compound is represented by the formula of formula (6):

(6) In a preferred embodiment, in the formula (6) anthraquinone derivative, R21, R22, R23 and R24 are all 2,4-dimercapto-3-pentyloxy compounds, R25= -CH2, M=Cu, ie the compound as shown in formula (II): 1297350

N 'n

O; CH2-〇-|-R30)n -[OCH(CHMe2)2]4 wherein R3G may be trifluoromethyl or fluorenylphenyl, and n is an integer of from 1 to 4. In another embodiment, the compound of the formula (6) is wherein R21 to R24 are 2,4-dimercapto-3-pentyloxy, the central metal is Cu, R25 is -CH2-, and R26 is -CF3. It can be prepared by the above method. Specifically, the use of hydroxy-thiolated tetra-α-(2,4-dimercapto-3-pentyloxy) copper phthalocyanin derivatives and trifene lucinum anhydride (if if luoromethanesu If on ic anhydride) The low temperature reaction is carried out under anhydrous conditions to obtain the product of formula (7): 1297350

In another embodiment, the hydroxymethylated tetra-α-(2,4-dimercapto-3-pentyloxy)copper isponic acid derivative and p-toluenesulfonyl (p-toluenesulfonyl) Chloride) is dissolved in methylene chloride, added with an organic base (such as pyridine) catalyst, and reacted at room temperature to obtain the product of formula (8):

(8) Another way to covalently bond a sulfonate-based compound to a synthetic route with a substituent of 1297350 or unsubstituted isocyanin, which is an anthocyanin substituted with a sulfonyl chloride The alcohol compound is reacted to obtain a sulfonate-based compound, and the obtained product can be expressed by the formula of the formula (9):

〇

^ II R27—s—〇—r28 The definitions of R2丨~I and Μ in the above formulas (6) and (9) are as defined in R丨~r20 and Μ in equations (1) to (5); KM And I7 can be a single bond, -CH2-, -CH2CH2 - , _CH=CH-, -CH2-C(=0)-, -CH2-CH2-C(=0)-, a 0-r29-, - c(=o)—0—r29- or —(KOO)-R29-, wherein R29 is a C—α alkyl group or a C 2 -C 4 alkylene group; preferably -CH 2 and -C (=0)- 0-r29— ; r26 and r28 are like υ2. In the formula (1), the definition in the formula (5) is preferably a methyl group and a trifluoromethyl group; or a c6-Ci8 group such as a phenyl group, a naphthyl group, a biphenyl group, or a fluorene group. Anthryl, phenanthryl, tert-triphenyl^terphe+nylyl), preferably phenyl; or C?-Ci8 aromatic alkyl such as: phenyl, benzyl, ethylphenyl, Phenylethyl, -(CH2)3^phenyl or phenyl-(CHOmCH3, preferably tolyl; η is an integer from 1 to 4. The present invention also relates to an optical recording medium comprising a substrate, recording 20 '1297350 layer, reflective layer, protective layer, wherein the recording layer uses the ugly pigment derivative of the present invention as a recording layer material. θ The substrate is generally made of an optically transparent tree, such as an acrylic resin. , polyethylene resin, polystyrene resin or polycarbonate resin, and if necessary, the surface of the substrate can also pass through the thermosetting tree g uv uv cross-linking tree vinegar. The recording layer can be coated by spin coating The indigo distribution of the present invention is distributed on a substrate as needed; the method of coating is as described: the indocyanin derivative of the present invention Appropriate proportion is dissolved in the solvent, and 〆舣 is not more than 5% wt/vol (weight by volume), especially 丨. 5~3%, and then the above solution is applied to the substrate by spin coating. The thickness of the layer is between 50 and 300 nanometers, preferably between 8 and 15 nanometers. Solubility of the material on the substrate and the invasion of the substrate. Sex, suitable for rotary coating solvent, as follows: more suitable solvents include toothed hydrocarbons, such as dioxane, gas, four gasified carbon, tri-ethane, gas-fired four Fluoride and difluoroethylene bromide; ethers, such as diethyl hydrazine, propyl scales, dibutyr and cyclohexane; alcohols such as decyl alcohol, ethanol, propanol, tetraamyl alcohol and butanol Ketones such as propyl ketone, trifluoroacetone, hexafluoroacetone and cyclohexanone; hydrocarbons such as hexane, cyclohexane, nonylcyclohexane, dimercaptocyclohexyl, octyl and cyclooctane The reflective layer is mainly composed of a metal material or an alloy material such as copper, aluminum, gold or silver. The reflective layer can be coated on the recording layer via vacuum distillation or antimony ore. Generally, the thickness of the reflective layer is between 丨 and 2 〇〇 nanometer. The protective layer is mainly composed of thermosetting resin or UV cross-linking resin, especially transparent, and when used, the resin is A spin coating method is applied over the radiant layer to form a protective layer. Generally, the thickness is between 〇·丨 and 500 μm; preferably between 5 and 50 μm. Based on ease of use, Nowadays, the manufacture of optical recording media is mostly based on a polycarbonate resin plate, and the spin coating method is a method of supporting the recording layer 21 1297350 and the protective layer. 0 i ΐ ΐ ϊ Illustrated by the following non-limiting examples Any related bamboo organisms based on the basic spirit of the present invention will be encompassed within the scope of the present invention. EXAMPLES Example 1 EP 703280 (2tJf 圆 round bottom bottle, followed by the addition of 50 ml of hydrazine and 54 g of N-mercaptoguanamine, after dissolving, the temperature of the solution was lowered to &£> Then, "*5.6 grams of phosphorus J chlorine (P0C13) is slowly added to the reaction solution to control the feed rate to maintain the temperature of the reaction solution does not exceed. After the addition is completed, the cooling system is removed and the temperature of the reaction solution is raised to 5 ( Rc, the reaction solution was stirred at 50 ° C for 24 N· and the reaction was monitored by thin layer chromatography. After the reaction was completed, the reaction mash was poured into 200 ml of sodium acetate (415 g) ice-water mixture. The mixture was stirred for 30 minutes, and then the mixture was extracted with 1 mL of hydrazine (3 g of benzene). The organic layer was collected in a separate portion, and dried over 2 g of anhydrous magnesium sulfate. ML, then the concentrate was poured into 1 liter of a methanol/water (98/2) mixed solvent and stirred vigorously for 30 minutes. The product was collected by filtration, and the product was washed with 1 liter of methanol, and the product was dried under vacuum at 7 ° C for two days. The green powder product was obtained in 9.5 g (94% of theory). Analysis: Found value (%): C··69· 21 Η: 6· 79 Ν··10· 44 Theoretical value (%): C: 69. 06 H: 6. 84 N: 10. 56 UV-VIS ( DBE):;lmax=710 nm. IR (KBr): C=0 band, at 1675 CHT1. Example 2 Weighing 1.03 g of sodium borohydride to a nitrogen-filled 250 ml round bottom three neck In the bottle, 40 ml of ethanol 22 1297350 was then added and mixed to dissolve most of it. Derivatized with 1G·G gram of 4,22 dimethyl-3-pentyloxy)copper phthalocyanine The product (known in Example 1) Luo;, 0 halo THF solution, and then added to the above reducing agent solution, the reaction solution was vigorously stirred at room temperature for 24 hours and by thin layer chromatography (TLC^ The reaction was monitored. After the reaction was completed, the reaction mixture was filtered to remove the mixture and poured into 2 mL of 2% aqueous saline to terminate the reaction, and the mixture was extracted with 40 ml of x 3 benzene. The organic layer was uniformly collected, dried over 20 g of anhydrous magnesium sulfate, filtered to remove aqueous magnesium sulfate, and concentrated to 40 ml under reduced pressure. The concentrate was poured into 1 liter of methanol/water (98/2) mixed solvent. After mixing for 30 minutes, the product was collected by filtration, and the product was washed with i liter of decyl alcohol, and the product was dried under vacuum for 7 days to obtain a green powder product 9.4 g (95% of theory). Elemental analysis: found value (%) :C:68,77 Η·7 20 Ν·10 56 ^«): C:68.93 H;?:〇2 !;! ί:54 UV-VIS (DBE): Amax=713.5 nm. IR (KBr): 〇0 with 1675cm1 disappeared, 〇H with 3210cm1. Example j: A hydroxymethylated tetra-a-(2,4-dimercapto-3-pentyloxy) copper phthalocyanine derivative (prepared in Example 2) was weighed and weighed in 250 ml. In the reactor, 40 ml of toluene was then added under nitrogen and stirred. To dissolve it _ reduce the temperature of the solution to 〇 ° C, then add 48.64 ml of 6.25% - trifluoromethanesulfonic anhydride 曱 stupid solution, slowly added to the reaction solution, and maintain the temperature of the reaction solution More than 5 ° C. After the addition was completed, the cooling system was removed and the reaction solution was allowed to warm to room temperature, and the reaction solution was stirred at room temperature for 2 hours and the reaction was monitored by thin = chromatography. After the reaction was over, the reaction solution was poured into a 80/240 ml sterol/water mixture to terminate the reaction, and then the mixture was mixed for 30 minutes, followed by extraction of the mixture with 1 liter of x 3 of the broth, 23.1297350

N: 9.08 N: 9.38 Found value (%): C: 62.50 H: 6. 18 N; 9 > 〇 8 Theoretical value (%): C: 62. 32 H: 6. 16 〇〇 UV-VIS (DBE) : Amax = 714·5 nm. IR (KBr): S〇3 at 1367, 1152 cm 1. TGA: The main cracking temperature starts at 253t: (~37%). Example 4 Weighing p-phenylenesulfonate (??-t〇luenesulf〇nyi chloride) 3·4 g in a 250 ml round bottom three-necked flask, followed by adding 1 ml of dioxane under nitrogen And gave a drop of 30 minutes. Thereafter, 20 ml of IT was added to the reaction solution at a room temperature ratio of σ. The addition was completed, and the mixing was continued for 20 minutes. 15 ml of a two-gas bismuth solution containing 10· gram of hydroxy thiolated tetra-α-(2,4-dimethyl-1,3-pentyloxy) copper phthalocyanin derivative (prepared in Example 2) The reaction solution was added to the above reaction solution, and the reaction solution was maintained at room temperature for 12 hours. After the reaction was completed, the reaction solution was poured into 300 ml of water to terminate the reaction and stirred for 30 minutes, then the mixture was extracted with 1 ml of hydrazine 3, and the organic layer was uniformly collected, dried over 20 g of anhydrous magnesium sulfate, and filtered to remove water. Magnesium sulphate was concentrated to 60 ml under reduced pressure. The concentrate was poured into 1 liter of n-hexane and stirred vigorously for 30 minutes. The product was collected by filtration. The product was dried under vacuum at 70 ° C for 24 hours to give a green powder product. (80% of theory). Elemental analysis: Found value (%)··〇·67· 45 Η··6· 25 Ν··9· 50 Theoretical value (%): C:67· 11 Η··6· 63 Ν: 9. 21 24 1297350 UV-VIS (DBE): λΐΜΧ=714· 0 nm. iR (KBr): S〇3 at 1367, 1152 cm 1. TGA: The main cracking temperature starts at 227 ° C (~35%). Rabbit Example 5 The metered Example 3 compound was dissolved in a mixed solvent of dibutyl ether (dbe) and 2,6-dimercapto-4-heptanone (95:5) to form 2.8 ° / ^ 1 : / ^〇1 (solute-weight/solvent volume percentage) of the recording layer dye solution, after stirring for 1 hour to be fully dissolved, and then filtering the solution through a 0.2 micron pore size Teflon filter and by spin coating method The dye was applied to a 1.2 cm thick grooved disc surface at a speed of 4 rpm (the groove depth was 195 KN, the groove width was 600 nm, and the track pitch was 1.7 μm). The coating rotation speed was gradually increased to 3,000 rpm to thereby remove excess solution, and then the formed uniform recording layer was dried in a circulating hot air of 60 C for 15 minutes. A 60 nm thick silver reflective layer was then sputter deposited onto the recording layer in a vacuum sputtering apparatus (ALCATEL, ATP150). Finally, a UV hardener (ROHM AND HAAS DEUTSCHLAND GMBH, Rengolux 3203-03lv6 clear-CD LACQUER) was applied by spin coating on a silver reflective layer to form a 5 mm thick protective layer, which was hardened by UV light. . The above-mentioned CD-R blank sheets were sequentially written on the commercial burner (Liteon LTR-52327S) at a recording speed of 52 times, and then passed through a fully automated optical disc test system (PulstecOMT). -2000x4), read w test dynamic signal parameters at IX speed 'measured 40 minutes position signal and listed in the table below, (1). Example 6 By repeating Example 5, the prepared CD_R blank sheet was sequentially written on a commercial burner (Liteon LTR-52327S) at a recording speed of 52 times, and then passed through a fully automatic optical disc. The test system (Pulstec 0MT-2000x4) reads the test dynamic signal parameters at IX speed and measures the signal at the 75-minute position and is listed in the following table (1). 25 1297350 Table (1) Position 13 111 Rtop BLER Jit3T JitllT 40 minutes 0.31 0. 69 0. 63 3· 1 25 27 75 minutes 0.30 0.66 0.63 2.4 28 31 (A) I3 value at 3Τ (Τ=231· 4ns) signal pit Signal strength • (B) I11 value at 11 Τ (Τ = 231 · 4 ns) signal etch pit signal strength. (C) Rtop reflectivity (D) BLER (Block Error Rate) sector error rate (E) Jit3T at 3T #坑的坑坑跳 (in ns) (F) JitPllT jumps in the pit of the 11T etch pit (in ns) Example 7 The metered compound of Example 4 is dissolved in n-propanol and 4-hydroxy-4- In a mixed solvent of mercapto-2-pentanone (95:5), a recording layer dye solution of L7% (wt/vol) was formed. After being scrambled for 1 hour to be sufficiently dissolved, the solution was then passed through a 0.2 μm aperture. The Teflon filter was filtered and the dye was applied to a surface of a 1.2 cm thick grooved disk by a spin coating method at a speed of 400 rpm (the groove depth was 195 nm, and the groove width was 600 Å. Meter, track pitch 1 · 7 microns). The coating speed was gradually increased to 3 rpm per minute. φ This excess solution was removed, and then the formed uniform recording layer was dried in a circulating hot air at 60 ° C for 15 minutes. Next, a 60 nm thick silver reflective layer was sputter deposited onto the recording layer in a vacuum sputtering apparatus (alcatel, * ρτρ150). Finally, a UV hardener (ROHM AND HAAS DEUTSCHLAND GMBH, Rengolux 3203-031v6 clear-CD LACQUER) was applied by spin coating on a silver reflective layer to form a 5 mm thick protective layer which was hardened by light irradiation. The above-mentioned CD-R blanks were sequentially written on a commercial burner (BenQ CD-RW 5232X) at a recording speed of 52 times, and then the dynamic signal parameters were passed through a fully automated optical disc test system. (Pulstec OMT-2000x4), read the test at IX speed, and measure the signal at 4 〇 26 1297350 minutes and list it in the following table (2). Example 8 By repeating Example 7, the prepared CD-R blank sheet was sequentially written on a commercial burner (BenQ CD-RW 5232X) at a recording speed of 52 times, and then passed through a completely automatic Optical Disc Test System (Pulstec OMT-2000x4) 'Read the test dynamic signal parameters at 1X speed and measure the signal at 75 • minute position and list it in the following table (2). Table (2) Position 13 - 111 Rtop BLER Jit3T JitllT 40 minutes 0.31 0. 70 0.62 5.2 29 27 75 minutes 0. 30 0.68 0.61 4.5 30 31 From Tables (1) and (2), it can be seen that 'the use of the invention 酜The optical recording medium of the blue pigment derivative optical dye can obtain good burning characteristics at different burning speeds of different commercial burners, and meets the specifications of the Orange Book. Sentence [simplified description] no picture

27

Claims (1)

1297350 _________ % Year of the month t (吏) is replacing page X. Patent application scope: J 1 · A novel phthalocyanine derivative whose structure is as shown in formula (1): (I) wherein Ri, R2, R3 and R4 each independently represent an alkyl group having 1 to 12 carbon atoms, which may be 0 to 6 halogen atoms, a hydroxyl group, an alkoxy group of 1 to 6 carbon atoms, 1 Alkenylamino group to 6 carbon atoms, dialkylamino group of 1 to 6 carbon atoms, or alkylthio group of 1 to 6 carbon atoms; alkenyl group of 2 to 12 carbon atoms; or 2 to 12 Alkynyl group of one carbon atom; Μ is two argon atoms, one divalent metal, one monovalent metal having a monosubstituted group, one tetravalent metal having a double substitution, or an oxidized metal group; S represents a group having -S〇3 a molecular moiety of the base; and η is an integer between 1 and 4. 2. A method for synthesizing an anthraquinone derivative according to item 1 of the scope of the patent application, comprising covalently bonding a sulfonate-based compound to a substituted or unsubstituted anthraquinone. 28 1297350 令月 KB修 (more) replacement page 3 · According to the patent application, the phthalocyanine derivative containing a sulfhydryl group is reacted with a sulfonic anhydride or a sulfonium chloride compound under anhydrous conditions. 4 • According to the method of claim 2, including replacing the anthraquinone derivative with an alcohol and reacting with the alcohol. , 5·-a novel phthalocyanine derivative, its structure • as in formula (II): 〃 ' Wherein R 3 is a trifluoromethyl or tolyl group, and n is an integer of 1 to 4. Spring 6 - a method for synthesizing an anthraquinone derivative according to item 5 of the patent application scope, comprising reacting a hydroxy-substituted anthraquinone with trif loromethanesulfonic anhydride under anhydrous conditions . 7. The method for synthesizing an anthraquinone derivative according to item 5 of the scope of the patent application includes the use of a hydroxyl-substituted anthocyanin and p-toluenesulfonyl chloride under organic catalysis. reaction. 8 - The use of an anthraquinone derivative as an optical dye in a recording layer contained in an optical recording medium, which is an optical dye in the recording layer according to the anthraquinone derivative described in claim 1 or 5. 29 1297350月< 曰 ( (i) is being replaced page 4 _ . 9 · An optical recording medium comprising a substrate, a recording layer containing an organic dye and illuminating recordable data by laser light, a reflective layer, and a protective layer Wherein the recording layer comprises the anthraquinone derivative according to claim 1 or 5 of the patent application as the optical dye.