KR100622651B1 - Phthalocyanine derivatives and their applications in optical recording media - Google Patents

Abstract

An optical recording medium comprising a substrate, a recording layer, a reflective layer and a protective layer comprising an organic layer in which information can be recorded by a laser beam, wherein the organic dye is chemically bonded to a substituted or unsubstituted ferrocene by an anhydride group and a bridge unit G Substituted phthalocyanine compound, wherein G is -O-, -S-, -S- (CH ₂ ) _1-6 -,-(NH)-, -N (alkyl)-,-(CH ₂ )-,- CH (alkyl)-, -C (alkyl) ₂ -,-(CH ₂ -O)-, -C (= 0)-, -COC (= 0)-, -OC (= 0)-and -C ( = O) -O-.

Substrate, laser beam, recording layer, reflective layer, protective layer, optical recording medium, organic dye, phthalocyanine

Description

Phthalocyanine derivatives and their application to optical recording media {PHTHALOCYANINE DERIVATIVES AND THEIR APPLICATIONS IN OPTICAL RECORDING MEDIA}

The present invention relates to novel organic optical dyes of phthalocyanine derivatives and their applications in optical recording media, mainly for use in recordable compact discs (CD-Rs).

Organic dyes have been widely used in the field of optical recording of information. Once recorded, these recording media that can be reproduced repeatedly are abbreviated as " WORM " (write once read many). As an example of a disc format using this technique, a recordable compact disc, or so-called CD-R, is known from "Optical Data Storage 1989", Technical Digest Series, vol. 1 45 (1989).

Of all organic dyes for optical record carriers, phthalocyanine derivatives are one of the most important categories due to their high absorption in the near IR range (700-900 nm). Compared with other organic dyes such as cyanine, phthalocyanine dyes show better light resistance, temperature resistance and moisture resistance.

Early documents, such as JP-A 154888 (1986), 197280 (1986), 246091 (1986), US 4769307 (1987), and JP-A 39388 (1988), reported phthalosis as a constituent material of the recording layer of optical recording media. It is not starting. However, due to sensitivity, solubility, reflectance, recording performance and other related characteristics, the phthalocyanines described above cannot be considered as a suitable material for an optical recording medium.

In order to ameliorate the aforementioned disadvantages associated with the use of phthalocyanine as an optical recording material, JP-A 62878 (1991) provided phthalocyanine with larger (larger steric hindrance) substituents on its phenyl ring. However, these materials did not meet the recording requirements. In US 5229507 (1993), phenyl-substituted pro yrocyanine (also known as naphthalocyanine) has been proposed but the dye showed insufficient solubility. Under certain process conditions, the dye precipitated during spin coating.

Solubility issues have been described in US 5641879 (1997) by introducing various large substituents into the phenyl ring of phthalocyanine. However, inadequate reflectance was found. The isomer effect on solubility was studied in US 5663326. It has been reported that the composition of two isomers with a pair of alkoxy substituents towards each other was required to be at least 80% to obtain the desired solubility. Ensuring isomer composition for quality control is seemingly impractical and boring in dye manufacturing processes.

Another approach to address the solubility issue was taken in US 5820962 by introducing a substituted trivalent metal as the central atom of phthalocyanine. Due to the greatness of the proposed structure, the compound was well soluble in polar solvents and the resulting disk showed good reflectance. However, polar solvents inherited hydrophilic properties and had difficulty absorbing moisture during recycling. Thus, the quality is not constant and even leads to deterioration of the disk performance.

In addition to solubility, dye sensitivity is another critical factor for recording media, which in particular enables fast access to recorded information and high speed recording. The addition of the so-called "pit edge control agent" has been proposed in US 5492744 (1996) and JP-A 798887 to improve the deviation and jitter properties. Ferrocene and its derivatives (eg benzoylferrocene and n-butylferrocene) mixed with substituted phthalocyanine in certain proportions have been proposed. Fit formation has been reported to be greatly improved, but the use of materials has become an issue in real life work. Since optical dyes make up a significant proportion of the recordable disk cost structure, the dyes (and dye solutions) are designed to be designed and recycled. Phthalocyanine shows better solubility in the designated solvent (in this case ethylcyclohexane) than that of ferrocene. Thus, mixed fit edge modifiers tend to settle during spin coating and recycling and result in unwanted concentration changes in the recycled dye solution. Yield (production rate) is inferior to having a single dye. Minimal strain is shown in US Pat. No. 5,789,138 (1998), in which phthalocyanine is mixed (or dissolved) with a molten additive (eg benzimidazole) such that adjustment takes place from the additive to the central metal of phthalocyanine. The dyes thus obtained exhibit better intermolecular relationships to obtain the desired film pattern. However, the tradeoff between limited tuning chemistry and corresponding dye performance has made it difficult to optimize disk performance.

Halogenation to phthalocyanines has also been reported to improve sensitivity. US 5646273 (1997) claims that OPC (optimal power calibration, or “optimal recording power”) is effectively improved by halogenation in alkyl and / or alkoxy substituents to phthalocyanines. Halogenation in the phenyl ring of phthalocyanines has also been proposed in US 6087492 (2000). However, these producing disks still exhibited insufficient sensitivity and unsatisfactory control in the formation of information fits. Nevertheless, precise reaction control of the degree of halogenation is difficult. The resulting compound is a mixture containing various halogen atoms that exhibit disc characteristics that are inconsistent with unstable dye quality.

In US 6087492 (2000), substituted phthalocyanines having a divalent metal as the central atom were formylated, reduced and esterified. The resulting dye did not exhibit satisfactory properties when mixed in the structure as disclosed in US 5492744 (1996) or in the absence of a fit edge regulator in the structure. Improvements have been made in US 6399768 B1 (2002) and US 6790593 B2 (2004) by ferrocene chemically binding to phthalocyanine via ester linkage. These metallocenyl phthalocyanines have been halogenated (primarily brominated) to varying degrees depending on the central metal atom. This argues that the resulting dyes exhibited good optical sensitivity and solubility in solvents such as dibutyl ether (DBE) and ethylcyclohexane (ECH). Although these framings demonstrated satisfactory recording characteristics at high recording speeds, they did not show good performance at low recording speeds. Particularly in the 1X recording, the discs showed incorrect fit lengths and therefore less satisfactory deviation characteristics.

To solve the aforementioned drawbacks derived from conventional techniques, the present invention provides new optical dyes with unique chemical bonds between substituted or unsubstituted ferrocene and phthalocyanine derivatives. Discs made with these new optical dyes show excellent performance in recordings from 1X to 52X.

It is an object of the present invention to provide a novel optical dye consisting of a ferrocenyl group chemically bonded to phthalocyanine via a moiety containing anhydride group and represented by the following formula (1).

In Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ each independently contain 1-12 carbon atoms, 0-6 halogen atoms, hydroxyl groups, and 1-6 carbon atoms. An alkyl group having a substituent selected from an alkoxy group, an alkylamino group containing 1-6 carbon atoms, a dialkylamino group containing 1-6 carbon atoms, and an alkylthio group containing 1-6 carbon atoms; Alkenyl groups containing 2-12 carbon atoms; Or an alkynyl group containing 2-12 carbon atoms; M is two hydrogen atoms, a divalent metal, a monosubstituted trivalent metal, a disubstituted tetravalent metal, or an oxo metal group; G represents a bond between the phthalocyanine and the anhydride group and is -O-, -S-, -S- (CH ₂ ) _1-6 -,-(NH)-, -N (alkyl)-,- (CH ₂ )-, -CH (alkyl)-, -C (alkyl) ₂ -,-(CH ₂ -O)-, -C (= 0)-, -COC (= 0)-, -OC (= O)-and -C (= 0) -O-; R ₅ and R ₆ are each independently hydrogen, halogen (e.g., fluorine, chlorine, bromine or iodine), an alkyl group containing 1-6 carbon atoms, an alkoxy group containing 1-6 carbon atoms, An alkylamino group containing a carbon atom, an alkylthio group containing 1-6 carbon atoms, an alkenyl group containing 1-6 carbon atoms, an alkynyl group containing 1-6 carbon atoms, or an aromatic substituent; n is an integer of 1-4.

Another object of the present invention is to provide the use of the organic dye according to formula 1 as an optical dye in the recording layer of the recordable disc to give the recordable disc excellent recording characteristics.

Another object of the present invention is to provide an optical recording medium using the novel phthalocyanine derivative according to formula 1 as an optical dye in the recording layer.

The present invention provides a phthalocyanine derivative as an optical dye for use in a recording layer of an optical recording medium consisting of a pre-grooved substrate, a recording layer in which information can be recorded by a laser beam, a reflective layer and a protective layer. The optical dye is a phthalocyanine derivative (or mixture of derivatives) whose structure can be represented by the following formula:

In Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ each independently contain 1-12 carbon atoms, 0-6 halogen atoms, hydroxyl groups, and 1-6 carbon atoms. An alkyl group having a substituent selected from an alkoxy group, an alkylamino group containing 1-6 carbon atoms, a dialkylamino group containing 1-6 carbon atoms, and an alkylthio group containing 1-6 carbon atoms; Alkenyl groups containing 2-12 carbon atoms; Or an alkynyl group containing 2-12 carbon atoms; M is two hydrogen atoms, a divalent metal, a monosubstituted trivalent metal, a disubstituted tetravalent metal, or an oxo metal group; G represents a bond between the phthalocyanine and the anhydride group and is -O-, -S-, -S- (CH ₂ ) _1-6 -,-(NH)-, -N (alkyl)-,- (CH ₂ )-, -CH (alkyl)-, -C (alkyl) ₂ -,-(CH ₂ -O)-, -C (= 0)-, -COC (= 0)-, -OC (= O)-and -C (= 0) -O-; R ₅ and R ₆ are each independently hydrogen, halogen (ie fluorine, chlorine, bromine, or iodine), alkyl groups containing 1-6 carbon atoms, alkoxy groups containing 1-6 carbon atoms, An alkylamino group containing a carbon atom, an alkylthio group containing 1-6 carbon atoms, an alkenyl group containing 2-6 carbon atoms, an alkynyl group containing 2-6 carbon atoms, or an aromatic substituent; n is an integer of 1-4.

As recorded above, the phthalocyanine dye (1) provided by the present invention consists of a ferrocenyl group chemically bonded to the phthalocyanine derivative through a moiety containing an anhydride group. Phthalocyanine derivatives used in the present invention can be prepared, for example, according to the method disclosed in EP 70328, or can be obtained from commercial sources. Of those phthalocyanine derivatives, α-substituted phthalocyanine is most preferred. These phthalocyanine derivatives used in the present invention include several isomers represented by the following formulas (2) to (5):

Where R ₅ , R ₆ and G are as defined in equation 1,

R ₇ to R ₂₂ each independently contain a group containing 1-12 carbon atoms, a group containing 0-6 halogen atoms, a hydroxyl group, an alkoxy group containing 1-6 carbon atoms, and a group containing 1-6 carbon atoms An alkyl group having a substituent selected from an alkylamino group, a dialkylamino group containing 1-6 carbon atoms, and an alkylthio group containing 1-6 carbon atoms; Alkenyl groups containing 2-12 carbon atoms; Or an alkynyl group containing 2-12 carbon atoms; M is two hydrogen atoms, a divalent metal, a monosubstituted trivalent metal, a disubstituted tetravalent metal, or an oxo metal group.

The isomer composition of 4 α-substituted phthalocyanine described above may vary according to reaction conditions. Preferred substituents are secondary alkyl, alkenyl or alkynyl. Most preferred substituents are alkyl, alkenyl, or alkynyl groups containing from 2 to 4 secondary, tertiary, or quaternary carbon atoms.

As R ₁ to R ₂₀ in formulas 1 to 5, representative alkyl groups are, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl , i-pentyl, cyclopentyl, 2-methylbutyl, 1,2-dimethylpropyl, n-hexyl, cyclohexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1 , 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1- (i-propyl) propyl, n-heptyl, cycloheptyl, 2-methylhexyl, 3- Methylhexyl, 4-methylhexyl, 5-methylhexyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2, 4-dimethylpentyl, 1-ethyl-3-methylbutyl, 2- (i-propyl) butyl, 2-methyl-1- (i-isopropyl) propyl, n-octyl, cyclooctyl, 2-ethylhexyl, 3 -Methyl-1- (i-isopropyl) butyl, 2-methyl-1- (i-isopropyl) butyl, 1-t-butyl-2-methylpropyl, n-nonyl, cyclononyl, n-decyl, cyclo Decyl, undecyl, dodecyl; Preferred substituents are branched alkyl groups having from 2 to 4 secondary, tertiary or quaternary carbon atoms, for example i-propyl, i-butyl, s-butyl, t-butyl, i-pentyl, 2-methylbutyl, 1,2- Dimethylpropyl, 1,3-dimethylbutyl, 1- (i-propyl) propyl, 1,2-dimethylbutyl, 1,4-dimethylpentyl, 2-methyl-1- (i-propyl) propyl, 1-ethyl- 3-methylbutyl, 2-ethylhexyl, 3-methyl-1- (i-propyl) butyl, 2-methyl-1- (i-propyl) butyl, 1-t-butyl-2-methylpropyl, 2,4 -Dimethyl-3-pentyl; Most preferred substituents are, for example, 1-t-butyl-2-methylpropyl, 2-methyl-1-isopropylbutyl, 2,4-dimethyl-3-phenyl.

Representative halogenated alkyl groups are, for example, chloromethyl, 1,2-dichloroethyl, 1,2-dibromoethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2,2 , 2-tribromoethyl, 1,1,2,2,2-pentachloroethyl, 1,1,1,3,3,3-hexafluoro-2-propyl.

The cannonyl hydroxyalkyl groups are for example hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, 3-hydroxypropyl, 2,3-dihydroxypropyl, 3-hydroxybutyl, 4- Hydroxybutyl, 3-hydroxypentyl, 4-hydroxypentyl, 5-hydroxypentyl, 2-hydroxyhexyl, 3-hydroxyhexyl, 4-hydroxyhexyl, 5-hydroxyhexyl, 6-hydroxy Hexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl, hydroxy undecyl, hydroxydodecyl.

Representative alkoxyalkyl groups are, for example, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, 3-methoxycyclopentyl, 4-methoxycyclohexyl, ethoxyethyl, Oxypropyl, ethoxybutyl, ethoxy phenyl, ethoxyhexyl, 4-ethoxycyclohexyl, propoxyethyl, propoxypropyl, propoxybutyl, propoxypentyl, propoxyhexyl, butoxyethyl, butoxypropyl , Butoxybutyl, 1,2-dimethyloxyethyl, 1,2-diethoxyethyl, 1,2-dimethoxypropyl, 2,2-dimethoxypropyl, diethoxybutyl and butoxyhexyl; Preferred substituents are 2-10 carbon atom-containing alcoholcyalkyl groups, for example methoxymethyl, methoxyethyl, ethoxypropyl, ethoxybutyl, propoxyhexyl, 1,2-dimethoxypropyl, 2,2-dimethoxy Propyl, diethoxybutyl and butoxyhexyl; Most preferred substituents are 2-6 carbon atom containing alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxypropyl, ethoxybutyl.

Representative alkylaminoalkyl groups are, for example, methylaminomethyl, methylaminoethyl, methylaminopropyl, methylaminobutyl, ethylaminoethyl, ethylaminopropyl, ethylaminobutyl, ethylaminopentyl, ethylaminohexyl, ethylaminoheptyl, ethylamino Octyl, propylaminoethyl, propylaminopropyl, propylaminobutyl, propylaminopentyl, propylaminohexyl, i-propylaminoethyl, i-propylaminopropyl, i-propylaminobutyl, i-propylaminopentyl, i-propylamino Hexyl, butylaminoethyl, butylaminopropyl, butylaminopentyl, butylaminohexyl; Preferred substituents are alkylaminoalkyl groups containing 2-8 carbon atoms, for example methylaminomethyl, methylaminoethyl, ethylaminopropyl, ethylaminobutyl, ethylaminopentyl, ethylaminohexyl, propylaminobutyl, propylaminopentyl; Most preferred substituents are alkylaminoalkyl groups containing 2-6 carbon atoms, for example methylaminomethyl, methylaminoethyl, ethylaminopropyl, ethylaminobutyl.

Representative dialkylaminoalkyl groups are, for example, dimethylaminomethyl, dimethylaminoethyl, dimethylaminopropyl, dimethylaminobutyl, diethylaminoethyl, diethylaminopropyl, diethylaminobutyl, diethylaminopentyl, diethylaminohexyl, Diethylaminoheptyl, diethylaminooctyl, dipropylaminoethyl, dipropylaminopropyl, dipropylaminobutyl, dipropylaminopentyl, dipropylaminohexyl, di (i-propyl) aminoethyl, di (i-propyl) Aminopropyl, di (i-propyl) aminobutyl, di (i-propyl) aminopentyl, di (i-propyl) aminohexyl; Preferred substituents are dialkylaminoalkyl groups containing 2-10 carbon atoms such as dimethylaminomethyl, dimethylaminoethyl, diethylaminopropyl, diethylaminobutyl, diethylaminopentyl, diethylaminohexyl; Most preferred substituents are dialkylaminoalkyl groups containing 2-6 carbon atoms, for example dimethylaminomethyl, dimethylaminoethyl, diethylaminoethyl.

Representative alkyldioalkyl groups are, for example, methylthiomethyl, methylthioethyl, methylthiopropyl, methylthiobutyl, methylthiopentyl, methylthiohexyl, 2-methylthiocyclopentyl, 3-methylthiocyclopentyl, 4-methyl Thiocyclohexyl, ethylthioethyl, ethylthiopropyl, ethylthiobutyl, ethylthiopentyl, ethylthiohexyl, 4-ethylthiocyclohexyl, propylthiobutyl, propylthiopentyl, propylthiohexyl; Preferred substituents are 2-8 carbon atom-containing alkylthioalkyl groups such as methylthiomethyl, methylthioethyl, ethylthiopropyl, ethylthiobutyl, propylthiohexyl; Most preferred substituents are 2-6 carbon atom containing alkylthioalkyl groups such as methylthiomethyl, methylthioethyl, ethylthiopropyl, ethylthiobutyl.

Representative alkenyl groups are, for example, ethenyl, n-propenyl, i-propenyl, n-butetyl, i-butenyl, s-butetyl, n-pentenyl, i-pentenyl, cyclopentenyl, 2 Methylbutenyl, 1,2-dimethylpropenyl, n-hexenyl, cyclohexenyl, n-heptenyl, cycloheptenyl, n-octenyl, cyclooctenyl, n-nonenyl, cyclononnetyl, n -Decenyl, cyclodecenyl, undecenyl and dodecenyl; Preferred substituents are 2-6 carbon atom containing alkenyl groups such as ethenyl, n-propenyl, i-propenyl, n-butetyl, i-butenyl, s-butetyl, n-pentenyl, i-pen Tenyl, cyclopentenyl, 2-methylbutenyl, 1,2-dimethylpropenyl, n-hexenyl, cyclohexenyl; Most preferred substituents are 2-4 carbon atom containing alkenyl groups such as ethenyl, n-propenyl, i-propenyl, n-butetyl, i-butenyl, s-butetyl, t-butenyl.

Representative alkynyl groups are, for example, ethynyl, propynyl, n-butynyl, s-butynyl, n-pentynyl, i-pentynyl, cyclopentynyl, 2-methylbutynyl, n-hexynyl, cyclohex Cynyl, n-heptinyl, cycloheptinyl, n-octinyl, cyclooctynyl, n-noninyl, cyclononnityl, n-decynyl, cyclodecynyl, undecynyl and dodecynyl; Preferred substituents are 2-6 carbon atom-containing alkynyl groups such as ethynyl, propynyl, n-butythyl, s-butynyl, n-pentynyl, i-pentynyl, cyclopentynyl, 2-methylbutynyl, n-hexynyl, cyclohexynyl; Most preferred substituents are 2-4 carbon atom containing alkynyl groups, for example ethynyl, propynyl, n-butytil, s-butynyl.

Representative divalent core metals M in formulas 1 to 5 are, for example, copper, zinc, iron, cobalt, nickel, palladium, platinum, manganese, tin, ruthenium, osmium; Most preferred metals are copper, cobalt, nickel, palladium, platinum. Representative monosubstituted trivalent metals are, for example, fluorine-aluminum, chlorine-aluminum, bromine-aluminum, iodine-aluminum, fluorine-indium, chlorine-indium, bromine-indium, iodine-indium, fluorogallium, chlorogallium, bro Mogalium, iodogallium, fluorotalum, chlorotalum, bromotallium, iodotallium, hydroxyaluminum, hydroxymanganese. Representative disubstituted tetravalent metals are, for example, difluorosilicon, dichlorosilicon, dibromosilicon, diiodosilicon, difluorotin, dichlorotin, dibromotin, diiodotin, difluorogermanium, dichloro It is germanium, dibromogernium, diiodogernium, difluorotitanium, dichlorotitanium, dibromotitanium, diiodotitanium, dihydroxysilicone, dihydroxytin, dihydroxygermanium, dihydroxymanganese. . Representative oxometal groups are for example oxovanadium, oxomanganese, oxotitanium.

In order to improve the performance of the phthalocyanine during recording, the substituted or unsubstituted ferrocene group is covalently bonded to the phthalocyanine derivative through the portion containing the anhydride group. The dyes thus obtained not only meet the requirements for 1X-52X recording in various writers, but can also enable precise control in the formation of fits. This mainly improves the fit deviation characteristic.

Synthetic routes used to chemically bind substituted or unsubstituted ferrocenyl compounds to phthalocyanine derivatives via anhydride moieties include direct reactions of phthalocyanines substituted with acyl chlorides with ferrocene carboxylic acids, or with metal catalysts of ferrocene carboxylates. Acyloxylation of perester and aldehyde substituted phthalocyanine, or intermediates and hydroxyl substitutions obtained by treatment of ferrocene carboxylic acid with a third reactant (eg oxalic acid or oxalyl chloride) in the presence of a suitable catalyst (eg pyridine) There are many, including the reaction of phthalocyanines.

Another preferred embodiment of the present invention relates to an optical recording medium consisting of a substrate, a recording layer, a reflective layer and a protective layer, wherein the recording layer comprises the aforementioned phthalocyanine derivative (1) provided by the present invention as an optical dye.

In the optical recording medium provided by the present invention, the substrate is generally made of a transparent optical resin such as, for example, acrylic, polyethylene, polystyrene, or polycarbonate resin. The surface of the substrate may be treated with a thermosetting resin or UV crosslinking resin as necessary.

The recording layer can be formed by spin coating a solution of the phthalocyanine derivative (1) provided by the present invention on a substrate. The spin coating process can be carried out as follows: Dissolve the phthalocyanine derivative of the invention in a solvent at a suitable ratio, ie up to 5% wt / vol (weight / volume ratio), preferably 1.5-3%. The resulting solution can then be applied to the substrate via conventional spin coating techniques. The thickness of the recording layer is generally 50 nm-300 nm, preferably 80 nm-150 nm.

In view of the solubility of organic optical dyes in certain solvents and the corrosion of the substrate by solvents, preferred spin coating solvents are halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, trichloroethane, dichloroethane, tetra Chloroethane and dichlorodifluoroethane; Ethers such as ethyl ether, propyl ether, butyl ether and cyclohexyl ether; Alcohols such as methanol, ethanol, propanol, tetrafluoropropanol and butanol; Ketones such as acetone, trifluoroacetone, hexafluoroacetone and cyclohexanone; And hydrocarbons such as hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, octane and cyclooctane.

The reflective layer is made of metal such as copper, aluminum, gold or silver, or an alloy thereof. The reflective layer can be formed by depositing a suitable material on the recording layer by vacuum deposition or sputtering to a thickness of 1-200 nm.

The protective layer is composed of a thermosetting resin or a UV crosslinking resin, preferably a transparent resin. In general, the protective layer can be formed by spin coating a resin on the reflective layer to form a layer having a thickness of 0.1-500 micrometers, preferably 0.5-50 micrometers.

In view of practicality, polycarbonate resin is mainly used as a substrate material of an optical recording medium these days, and a spin coating method is preferentially selected to form a recording layer and a protective layer.

The main spirit of the present invention can be explained in more detail by the following examples, but is not limited thereto. Directly or indirectly related derivatives based on the main spirit of the invention are also within the scope of the invention.

EXAMPLE

Example 1

10 g tetra-α- (2,4-dimethyl-3-pentoxyl) copper phthalocyanine derivative (prepared according to EP 703280) was weighed into a 250 ml round bottom flask with nitrogen purge. Then 50 ml toluene and 5.4 g N-methylformamide were added. After complete dissolution, the temperature of the resulting solution was lowered to 0 ° C. When the temperature was stabilized, 5.6 g POCl ₃ was slowly added to the reaction solution, and the temperature was maintained not to exceed 5 ° C. After the addition of POCl ₃ the cooling system was removed and the temperature was raised to 50 ° C. The reaction solution was stirred at 50 ° C for 24 hours. Monitored by thin layer chromatography (TLC) until the reaction was complete. The reaction mixture was poured into a 200 ml solution of sodium acetate (41.5 g) covered with ice, stirred for 30 minutes, and extracted with 100 ml × 3 toluene. The combined organic layers were dried over 20 g anhydrous magnesium sulfite and the anhydrous magnesium sulfite was filtered off and concentrated to 60 ml under reduced pressure. The concentrate was poured into 1 L of methanol / water (98/2) mixed solvent and stirred vigorously for 30 minutes. The product was collected by filtration, washed with 1 L methanol and dried in a 70 ° C. vacuum oven for 2 days. The green powder thus obtained was 9.5 g (64% theory).

Basic Analysis: Experimental Value (%): C: 69.21 H: 6.79 N: 10.44

          Calculated Value (%): C: 69.06 H: 6.84 N: 10.56

UV-VIS (DBE): λ max = 710 nm

IR (KBr): Absorbed at C = O 1675 cm ^-1

Example 2

1.03 g sodium borohydride was weighed and placed in a nitrogen purge 250 ml three necked round bottom flask and 40 ml ethanol to dissolve the sodium borohydride. 10.0 g formylated tetra-α- (2,4-dimethyl-3-pentoxyl) copper phthalocyanine derivative (prepared as in Example 1) was dissolved in 40 ml tetrahydrofuran (THF) and placed in the reducing agent solution prepared above. . The resulting reaction solution was stirred vigorously at ambient temperature for 24 hours and monitored by thin layer chromatography (TLC). At the end of the reaction, the insolubles were filtered off and terminated by pouring 200 ml of 20% cell line solution. The mixture was extracted with 40 ml 3 toluene. The combined organic layer was dried over 20 g anhydrous magnesium sulfite, which was filtered off and concentrated to 40 ml under reduced pressure. The concentrate was poured into 1 L of methanol / water (98/2) mixed solvent and stirred vigorously for 30 minutes. The product was collected by filtration, washed with 1 L methanol and dried in a 70 ° C. vacuum oven for 2 days. The green powder thus obtained was 9.4 g (95% theory).

Basic analysis: Experimental value (%): C: 68.77 H: 7.20 N: 10.56

          Calculated Value (%): C: 68.93 H: 7.02 N: 10.54

UV-VIS (DBE): λ max = 713.5 nm

IR (KBr): cm ^-1 C = O absorption at 1675, OH absorption at 3210 cm ^-1

Example 3

To a 500 ml reaction flask equipped with a nitrogen purge, 4.18 g ferrocene carboxylic acid and 20 ml dichloromethane were added. At a temperature of 0-5 ° C., 2.43 g of oxalyl chloride were added slowly. After 1 hour excess (or unreacted) oxalyl chloride was removed under reduced pressure. 25 ml pyridine was added while maintaining the reaction temperature below 15 ° C. A solution containing 10 g of the compound obtained in Example 2 and 22.5 ml of dichloromethane were separately prepared and put into a 500 ml reaction flask and reacted for 3 hours. The reaction was terminated by pouring the reaction mixture into a methanol / water (75/25) mixed solvent. The green powder was collected by filtration and dried in vacuo at 70 ° C. for 2 days to give 9.7 g (78% theory) of product.

UV-VIS (DBE): λ max = 712 nm

IR (KBr): 1715, 1743, 1770 cm ^-1

TGA: Major degradation (˜34%) started around 280 ° C.

Example 4

The dye solution was prepared by dissolving the compound of Example 3 in a mixed solvent of dibutyl ether (DBE) and 2,6-dimethyl-4-heptanone (95/5, vol / vol) at 2.8% wt / vol (weight of solute / Solvent volume) to form a dye solution. After vigorous stirring for 1 hour, the solution was filtered through a 0.2 micrometer pore size Teflon filter and then 1.2 mm-thick pregrooved disc (average groove depth = 195 mm, average groove width = 600 mm, track) at an initial rotational speed of 400 rpm. Pitch = 1.7 micrometers). The rotation was raised to 3000 rpm to remove excess solution. The homogeneous recording layer thus formed was dried by circulating hot air at 60 캜 for 15 minutes. Subsequently, a 60 nm-thick silver reflective layer was sputtered onto the recording layer in a vacuum sputtering apparatus (ALCATEL, ATP150). Finally, a UV curing machine (ROHM AND HAAS DEUTSCHLAND GMBH, Rengolux 3203-031v6 clear-CD LACQUER) is spin coated onto the silver reflective layer and UV cured to form a 5 mm thick protective layer. The information was continuously recorded on a blank CD-R disc created as above at a 52X recording speed in a conventional writer (Liteon LTR-52327S). The recorded discs were tested with an automated compact disc testing system (Pulstec OMT-2000x4) to measure the signal at 1 ×. Key data was compiled in Table 1 at the 40-minute position.

Example 5

The procedure described in Example 4 was repeated. The information was continuously recorded on a blank CD-R disc created as above at a 52X recording speed on a conventional writer (Liteon LTR-52327S). The recorded discs were tested with an automated compact disc testing system (Pulstec OMT-2000x4) to measure the signal at 1 ×. Key data was compiled in Table 1 at the 75-minute location.

location BLER JitP3T JitP11T Dev.P3T Dev.P11T 40 minutes 2.0 25 27 35 14 75 minutes 3.1 28 31 -38 -38

(A) BLER: Block Error Rate

(B) JitP3T: Jitter Pit 3T (in ns)

(C) JitP11T: Jitter Pit 11T (in ns)

(D) Dev.P3T: Deviation pit 3 (in ns)

(E) Dev.P11T: Deviation pit 11T (in ns)

Example 6

The dye solution was prepared such that the compound of Example 3 was dissolved in a mixed solvent of dimethylcyclohexane and o-xylene (94/6) to form a 1.7% wt / vol (solvent weight / solvent volume) dye solution. After vigorous stirring for 1 hour, the solution was filtered through a 0.2 micrometer pore size Teflon filter and then 1.2 mm-thick pregrooved disc (average groove depth = 195 mm, average groove width = 600 mm, track) at an initial rotational speed of 400 rpm. Pitch = 1.7 micrometers). The rotation was raised to 3000 rpm to remove excess solution. The homogeneous recording layer thus formed was dried by circulating hot air at 60 캜 for 15 minutes. Subsequently, a 60 nm-thick silver reflective layer was sputtered onto the recording layer in a vacuum sputtering apparatus (ALCATEL, ATP150). Finally, a UV curing machine (ROHM AND HAAS DEUTSCHLAND GMBH, Rengolux 3203-031v6 clear-CD LACQUER) is spin coated onto the silver reflective layer and UV cured to form a 5 mm thick protective layer. The information was continuously recorded on a blank CD-R disc created as above at a 52X recording speed in a conventional writer (BenQ CD-RW 5232X). The recorded discs were tested with an automated compact disc testing system (Pulstec OMT-2000x4) to measure the signal at 1 ×. Key data was compiled in Table 2 at the 40-minute position.

Example 7

The procedure described in Example 6 was repeated. The information was continuously recorded on a blank CD-R disc created as above at a 52X recording speed on a conventional writer (Liteon LTR-52327S). The recorded discs were tested with an automated compact disc testing system (Pulstec OMT-2000x4) to measure the signal at 1 ×. Key data was compiled in Table 2 at the 75-minute location.

location BLER JitP3T JitP11T Dev.P3T Dev.P11T 40 minutes 2.0 26 28 33 18 75 minutes 3.1 27 27 -32 -33

As the data are shown in Tables 1 and 2, the optical recording medium using the invented phthalocyanine dye can obtain all good jitter and deviation performance at different recording speeds in various commercial lighters. In addition, the performance of the recorded disc conforms to the specification as defined in the Orange Book.

As described above, the present invention can impart excellent recording characteristics to a recordable disc by using the phthalocyanine derivative according to the present invention, and optical recording media using such phthalocyanine dyes have all good jitter and deviation at different recording speeds in various commercial writers. Gives the effect of getting performance.

Claims (3)

Phthalocyanine derivative having a structure represented by the following formula 1:

In Equation 1 R ₁ , R ₂ , R ₃ , and R ₄ are each independently a group containing 1-12 carbon atoms, a 0-6 halogen atom, a hydroxyl group, an alkoxy group containing 1-6 carbon atoms, An alkyl group having a substituent selected from an alkylamino group containing 1-6 carbon atoms, a dialkylamino group containing 1-6 carbon atoms, and an alkylthio group containing 1-6 carbon atoms; Alkenyl groups containing 2-12 carbon atoms; Or an alkynyl group containing 2-12 carbon atoms; M is two hydrogen atoms, a divalent metal, a monosubstituted trivalent metal, a disubstituted tetravalent metal, or an oxo metal group; G represents a bond between the phthalocyanine and the anhydride group and is -O-, -S-, -S- (CH ₂ ) _1-6 -,-(NH)-, -N (alkyl)-,- (CH ₂ )-, -CH (alkyl)-, -C (alkyl) ₂ -,-(CH ₂ -O)-, -C (= 0)-, -COC (= 0)-, -OC (= O)-and -C (= 0) -O-; R ₅ and R ₆ are each independently hydrogen, halogen (ie fluorine, chlorine, bromine, or iodine), alkyl groups containing 1-6 carbon atoms, alkoxy groups containing 1-6 carbon atoms, An alkylamino group containing a carbon atom, an alkylthio group containing 1-6 carbon atoms, an alkenyl group containing 2-6 carbon atoms, an alkynyl group containing 2-6 carbon atoms, or an aromatic substituent; n is an integer from 1-4. The phthalocyanine derivative of Claim 1 used as an optical dye for the recording layer of an optical recording medium. In the optical recording medium consisting of a substrate, a recording layer comprising an organic dye which information can be recorded by a laser beam, a reflective layer and a protective layer, the phthalocyanine derivative according to claim 1 is used for the recording layer of the optical recording medium. An optical recording medium.