KR20070000647A - Novel phthalocyanine derivatives, synthetic process thereof and their applications in optical recording media - Google Patents

Abstract

Phthalocyanine derivatives, a synthetic process thereof and their applications in optical recording media are provided to enhance recording properties of the optical recording media such as CD(compact disc)-R, and reduce the production costs of the optical recording media by using inexpensive organic dye. The phthalocyanine derivatives represented by the formula(1) are provided, wherein R1, R2, R3 and R4 are each independently C1-C12 alkyl group, hydroxyl group, C1-C6 alkoxyl group, C1-C6 alkylamino group, C1-C6 dialkylamino group, and C1-C6 alkylthio group which are optionally substituted by 0-6 halogen atoms, C2-C12 alkenyl group, or C2-C12 alkynyl group; M is two hydrogen atoms, two metals, single substituted trivalent metal, disubstituted tetravalent metal or oxometal group; S is an area containing at least one -SO3- group; and n is an integer of 1 to 4. The phthalocyanine derivatives represented by the formula(1) is prepared by reacting hydroxylated phthalocyanine with sulfonic acid anhydride or sulfonyl anhydride under the anhydrous condition.

Description

Novel phthalocyanine derivatives, synthetic process etc. and their applications in optical recording media

The present invention relates to novel phthalocyanine derivatives as organic optical dyes and their application to optical record carriers, 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).

Due to the high absorption in the near infrared range (700-900 nm), phthalocyanine derivatives are among the most important categories among all organic dyes for optical record carriers. 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), disclose phthalocyanine as a constituent material of a recording layer of an optical recording medium. Doing. However, in terms of sensitivity, solubility, reflectance, recording performance and other related characteristics, the phthalocyanines described above cannot be considered as a suitable material for an optical record carrier.

In order to ameliorate the aforementioned disadvantages associated with the use of phthalocyanine as an optical recording material, JP-A 62878 (1991) provided phthalocyanines with larger (large steric hindrance) substituents on their phenyl rings. However, these materials did not meet the recording requirements. In US 5229507 (1993) a phenyl-substituted propyocyanine (also referred to as naphthalocyanine) was proposed, but this dye exhibited insufficient solubility. Under certain process conditions, dyes often precipitate during spin coating.

Solubility issues have been described in US 5641879 (1997) by introducing various larger 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 is required to be at least 80% to achieve the desired solubility. Ensuring isomeric composition for quality control in dye manufacturing processes is obviously tedious and apparently impractical.

Another approach to account for the solubility problem was taken in US 5820962) 1998) by introducing a substituted trivalent metal as the central atom of phthalocyanine. Due to the greatness of the proposed structure, these compounds are well soluble in polar solvents, and the resulting disks showed good reflectance. However, polar solvents inherently have hydrophilic properties and have a difficulty in 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, especially for recording media which allows for high speed recording and quick access to recorded information. The addition of so-called "pit edge control agents" to improve the deviation and jitter properties has been proposed in US 5492744 (1996) and JP-A 798887. Ferrocene and its derivatives (eg, benzoylferrocene and n-butylferrocene) mixed with substituted phthalocyanine in proportions have been proposed. Although fit formation has been reported to be greatly improved, the use of materials has become a problem in real life. Because optical dyes make up a significant proportion of recordable disk cost structure, dyes (and dye solutions) have been designed and synthesized to be recyclable. Phthalocyanine shows better solubility in the designated solvent (in this case ethylcyclohexane) than that of ferrocene. Thus, mixed fit edge modifiers tend to precipitate during spin coating and recycling, resulting in unwanted concentration changes in the recovered dye solution. Yield (productivity) is inferior to that for single dyes. A secondary modification is shown in US Pat. No. 5,789,138 (1998) in which phthalocyanine is mixed (or dissolved) with a molten additive (eg benzimidazole) to cause coordination from the addition of phthalocyanine to the central metal. The dye thus obtained shows a better intermolecular relationship to obtain a desired film pattern. However, selecting limited coordination 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. On the other hand, halogenation of the phthalocyanine to the phenyl ring has also been proposed in US 6087492 (2000), however, the discs produced from them still exhibit insufficient sensitivity and unsatisfactory control in the formation of information pits. Nevertheless, precise reaction control of the degree of halogenation is difficult The resulting compound inevitably becomes a mixture containing various halogen atoms, which causes unstable dye quality and inconsistent disc properties.

In US 6087492 (2000), phthalocyanine substituted with a divalent metal as the central atom was formylated, reduced and then esterified. Without blending into the structure as disclosed in US Pat. No. 5492744 (1996) or without a fit edge regulator in the structure, the resulting dye did not exhibit satisfactory properties. Improvements by chemically bonding ferrocene to phthalocyanine via ester linkage have been made in US 6399768 B1 (2002) and US 6790593 B2 (2004). These metallocenyl phthalocyanines have been halogenated (primarily brominated) to varying degrees depending on the central metal atom. It is claimed that the resulting dyes exhibited good optical sensitivity and good solubility in solvents such as di-butyl ether (DBE) and ethylcyclohexane (ECH). Although these dyes show good recording speeds, their synthesis methods were relatively complex for industrial processes. Not to mention the high raw material (especially the metallocenes) cost. Since the CD-R market is apparently saturated, these high cost dyes may not meet the convincing demand for low cost but good CD-R production.

In order to meet the different requirements from the various recorders, and most importantly for the obviously low dye prices, the present invention is directed to the introduction of sulfonate compounds in place of traditional ferrocenyl groups in the phthalocyanine structures. Provides innovative optical dyes. Discs made with these novel optical dyes show excellent performance at recordings of 1X (1X) to 52X (52X).

One object of the present invention is to provide novel organic optical dyes comprising sulfonate groups chemically bonded to unsubstituted or substituted phthalocyanines. The resulting compound may be represented by the following formula (1).

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, 1 to 6 carbon atoms, which may be substituted with 0 to 6 halogen atoms An alkoxyl group having atoms, an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms; Alkenyl groups having 2 to 12 carbon atoms; An alkynyl group having 2 to 12 carbon atoms; M can be two hydrogen atoms, a divalent metal, a monosubstituted trivalent metal, a disubstituted tetravalent metal or an oxometal group; S is a moiety containing at least one —SO ₃ — group, and n is an integer from 1 to 4.

Another object of the present invention is to provide a method for preparing the organic dyes of the formula (1).

Another object of the present invention to provide an organic dye of the formula (2).

Wherein R ₃₀ is a trifluoromethyl group or a toryl group, and n is an integer from 1 to 4.

Yet another object of the present invention is to provide a method for preparing the organic dye of Chemical Formula 2.

It is another object of the present invention to provide the use of the organic dyes of the formula (1) or (2) as an optical dye in the recording layer of the recordable disc to impart excellent recording characteristics to the recordable disc.

It is another object of the present invention to provide an optical recording medium comprising the novel phthalocyanine derivatives of the formula (1) or (2) as the optical dye in the recording layer.

As described above, the present invention provides an optical recording medium consisting of a pre-grooved substrate, a recording layer, a reflective layer and a protective layer on which information can be recorded by means of a laser beam. A phthalocyanine derivative is provided as an optical dye used for the recording layer of the. The optical dyes are phthalocyanine derivatives (or mixtures of derivatives) whose structure can be represented by the following formula (1).

[Formula 1]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, 1 to 6 carbon atoms, which may be substituted with 0 to 6 halogen atoms An alkoxyl group having atoms, an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms; Alkenyl groups having 2 to 12 carbon atoms; An alkynyl group having 2 to 12 carbon atoms; M can be two hydrogen atoms, a divalent metal, a monosubstituted trivalent metal, a disubstituted tetravalent metal or an oxometal group; S is a moiety containing at least one —SO ₃ — group, and n is an integer from 1 to 4.

The 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 these phthalocyanine derivatives, α-substituted phthalocyanine is most preferred. These phthalocyanine derivatives used in the present invention include various isomers represented by the following Chemical Formulas 3 to 6.

In the above formulas, R ₅ to R ₂₀ are each independently an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an alkoxyl group having 1 to 6 carbon atoms, which may be substituted with halogen atoms of 0 to 6, respectively. An alkylamino group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms; Alkenyl groups having 2 to 12 carbon atoms; An alkynyl group having 2 to 12 carbon atoms; M may be two hydrogen atoms, a divalent metal, a monosubstituted trivalent metal, a disubstituted tetravalent metal or an oxometal group.

The isomeric composition of the four α-substituted phthalocyanines described above may vary depending on the reaction conditions and as desired. Preferred substituents are secondary alkyl, alkenyl or alkynyl groups. Most preferred substituents are alkyl, alkenyl or alkynyl groups containing from 2 to 4 secondary, tertiary or quaternary carbon atoms.

In Formulas 1 to 6, as R ₁ to R ₂₀ , representative alkyl groups include, 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-dimethyl Butyl, 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-ethyl Hexyl, 3-methyl-1- (i-isopropyl) butyl, 2-methyl-1- (i-isopropyl) butyl, 1-t-butyl-2-methylpropyl, n-nonyl, cyclononyl, n- Decyl, cyclodecyl, undecyl, dodecyl Be there; Preferred substituents include branched alkyl groups containing 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 include, for example, 1-t-butyl-2-methylpropyl, 2-methyl-1-isopropylbutyl, 2,4-dimethyl-3-pentyl.

Representative halogenated alkyl groups include, 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.

Representative hydroxyalkyl groups include, 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 Hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl, hydroxy undecyl, and hydroxydodecyl.

Representative alkoxyalkyl groups are, for example, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, 3-methoxycyclopentyl, 4-methoxycyclohexyl, ethoxyethyl , Ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, 4-ethoxycyclohexyl, propoxyethyl, propoxypropyl, propoxybutyl, propoxypentyl, propoxyhexyl, butoxyethyl, butoxy Propyl, butoxybutyl, 1,2-dimethoxyethyl, 1,2-diethoxyethyl, 1,2-dimethoxypropyl, 2,2-dimethoxypropyl, diethoxybutyl and butoxyhexyl; Preferred substituents include alkoxyalkyl groups containing 2 to 10 carbon atoms, for example methoxymethyl, methoxyethyl, ethoxypropyl, ethoxybutyl, propoxyhexyl, 1,2-dimethoxypropyl, 2, 2-dimethoxypropyl, diethoxybutyl and butoxyhexyl; Most preferred substituents include alkoxyalkyl groups containing 2 to 6 carbon atoms, for example methoxymethyl, methoxyethyl, ethoxypropyl, ethoxybutyl.

Representative alkylaminoalkyl groups include, for example, methylaminomethyl, methylaminoethyl, methylaminopropyl, methylaminobutyl, ethylaminoethyl, ethylaminopropyl, ethylaminobutyl, ethylaminopentyl, ethylaminohexyl, ethylaminoheptyl, Ethylaminooctyl, propylaminoethyl, propylaminopropyl, propylaminobutyl, propylaminopentyl, propylaminohexyl, i-propylaminoethyl, i-propylaminopropyl, i-propylaminobutyl, i-propylaminopentyl, i- Propylaminohexyl, butylaminoethyl, butylaminopropyl, butylaminopentyl, butylaminohexyl; Preferred substituents include alkylaminoalkyl groups containing 2 to 8 carbon atoms, for example methylaminomethyl, methylaminoethyl, ethylaminopropyl, ethylaminobutyl, ethylaminopentyl, ethylaminohexyl, propylaminobutyl, propyl Aminopentyl; Most preferred substituents include alkylaminoalkyl groups containing 2 to 6 carbon atoms, for example methylaminomethyl, methylaminoethyl, ethylaminopropyl, ethylaminobutyl.

Representative dialkylaminoalkyl groups include, for example, dimethylaminomethyl, dimethylaminoethyl, dimethylaminopropyl, dimethylaminobutyl, diethylaminoethyl, diethylaminopropyl, diethylaminobutyl, diethylaminopentyl, diethylamino Hexyl, 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 include dialkylaminoalkyl groups containing 2 to 10 carbon atoms, for example dimethylaminomethyl, dimethylaminoethyl, diethylaminopropyl, diethylaminobutyl, diethylaminopentyl, diethylaminohexyl May be mentioned; Most preferred substituents include dialkylaminoalkyl groups containing 2 to 6 carbon atoms, for example dimethylaminomethyl, dimethylaminoethyl, diethylaminoethyl.

Representative alkylthioalkyl groups include, for example, methylthiomethyl, methylthioethyl, methylthiopropyl, methylthiobutyl, methylthiopentyl, methylthiohexyl, 3-methylthiocyclopentyl, 4-methylthiocyclohexyl, ethyl Thioethyl, ethylthiopropyl, ethylthiobutyl, ethylthiopentyl, ethylthiohexyl, 4-ethylthiocyclohexyl, propylthiobutyl, propylthiopentyl and propylthiohexyl; Preferred substituents include alkylthioalkyl groups containing 2 to 8 carbon atoms, for example methylthiomethyl, methylthioethyl, ethylthiopropyl, ethylthiobutyl, propylthiohexyl; Most preferred substituents include alkylthioalkyl groups containing 2 to 6 carbon atoms, for example methylthiomethyl, methylthioethyl, ethylthiopropyl, ethylthiobutyl.

Representative alkenyl groups include, for example, ethenyl, n-propenyl, i-propenyl, n-butenyl, i-butenyl, s-butenyl, n-pentenyl, i-pentenyl, cyclopentenyl , 2-methylbutenyl, 1,2-dimethylpropenyl, n-hexenyl, cyclohexenyl, n-heptenyl, cycloheptenyl, n-octenyl, cyclooctenyl, n-nonenyl, cyclononyl , n-decenyl, cyclodecenyl, undecenyl and dodecenyl; Preferred substituents include alkenyl groups containing 2 to 6 carbon atoms, for example ethenyl, n-propenyl, i-propenyl, n-butenyl, i-butenyl, s-butenyl, n- Pentenyl, i-pentenyl, cyclopentenyl, 2-methylbutenyl, 1,2-dimethylpropenyl, n-hexenyl, cyclohexenyl; Most preferred substituents include alkenyl groups containing 2 to 4 carbon atoms, for example ethenyl, n-propenyl, i-propenyl, n-butenyl, i-butenyl, s-butenyl, t -Butenyl.

Representative alkynyl groups include, for example, ethynyl, propynyl, n-butynyl, s-butynyl, n-pentynyl, i-pentynyl, cyclopentynyl, 2-methylbutynyl, n-hexynyl, Cyclohexynyl, n-heptinyl, cycloheptinyl, n-octinyl, cyclooctynyl, n-noninyl, cyclononinyl, n-decynyl, cyclodecynyl, undecynyl and dodecynyl Can; Preferred substituents include alkynyl groups comprising 2 to 6 carbon atoms, for example ethynyl, propynyl, n-butynyl, s-butynyl, n-pentynyl, i-pentynyl, cyclopentynyl, 2-methylbutynyl, n-hexynyl, cyclohexynyl; Most preferred substituents include alkynyl groups containing 2 to 4 carbon atoms, for example ethynyl, propynyl, n-butynyl, s-butynyl.

Representative divalent core metals M in Chemical Formulas 1 to 6 include, for example, copper, zinc, iron, cobalt, nickel, palladium, platinum, manganese, tin, ruthenium, and osmium; Most preferred metals include 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 , Bromogallium, iodogallium, fluoro thallium, chloro thallium, bromo thallium, iodo thallium, hydroxyaluminum and hydroxy manganese. Representative disubstituted tetravalent metals include, for example, difluorosilicon, dichlorosilicon, dibromosilicon, diiodosilicon, difluorotin, dichlorotin, dibromotin, diiodotin, difluorogermanium , Dichlorogermanium, dibromogermanium, diiodogernium, difluorotitanium, dichlorotitanium, dibromotitanium, diiodotitanium, dihydroxysilicon, dihydroxytin, dihydroxygermanium, dihydroxy Manganese. Representative oxometal groups include, for example, oxovanadium, oxomanganese, oxotitanium.

In order to improve the performance of phthalocyanine during recording, according to the invention, the sulfonate compound is covalently bonded to a substituted or unsubstituted phthalocyanine derivative. Not only do the dyes thus obtained exhibit good reflectance and sensitivity, but they can also effectively lower the optimal recording power to satisfy the requirements for recording from 1X to 52X for various kinds of writers.

There are many routes to covalently linking sulfonate compounds to substituted or unsubstituted phthalocyanines. Typical methods include the reaction of hydroxylated phthalocyanine with trifluoromethanesulfonic anhydride under appropriate conditions or the reaction of hydroxylated phthalocyanine with p-toluenesulfonylchloride in the presence of an organic base (e.g. pyridine) as a catalyst. It is to let. The compound thus obtained may be represented by the following formula (7).

In a preferred embodiment, the phthalocyanine derivative of formula 7 is wherein R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are 2,4-dimethyl-3-pentyl, R ₂₅ is -CH ₂ -and M is copper, i.e. It includes a compound represented by the formula (2).

[Formula 2]

Wherein R ₃₀ is a trifluoromethyl group or a toryl group, n is an integer from 1 to 4.

In another preferred embodiment, the phthalocyanine derivative of Formula 8 is wherein R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are 2,4-dimethyl-3-pentyl, M is copper, and R ₂₅ is -CH _2- R ₂₆ is -CF ₃ -and can be prepared by the method described above. In particular, hydroxymethylated tetra-α- (2,4-dimethyl-3-pentoxy) copper phthalocyanine is reacted with trifluoromethanesulfonic anhydride under appropriate conditions at low temperatures to give the product of formula (8).

In another preferred embodiment, hydroxymethylated tetra-α- (2,4-dimethyl-3-pentoxy) copper phthalocyanine and p-toluenesulfonylchloride are dissolved in a suitable solvent such as dichloromethane, The resulting solution is allowed to react as a catalyst at room temperature in the presence of an organic base such as pyridine to afford the product of formula 9.

Another synthetic route to chemically link the sulfonate compound to substituted or unsubstituted phthalocyanine is to react the phthalocyanine sulfonyl chloride with an alcohol to form a sulfonate compound that can be represented by Formula 10.

R ₂₁ to R ₂₄ and M in formulas 7 and 10 are defined as R ₁ to R ₂₀ and Ms in formulas 1 to 6; R ₂₅ and R ₂₇ are independently a single bond, —CH ₂ —, —CH ₂ CH ₂ —, —CH═CH—, —CH ₂ —C (═O) —, —CH ₂ —CH ₂ —C ( ═O) —, —OR ₂₉ —, —C (═O) —OR ₂₉ — or —O— (C═O) —R ₂₉ —, where R ₂₉ is a C ₁ -C ₄ alkylene group Or a C ₂ -C ₄ alkenylene group; Preferably, R ₂₅ and R ₂₇ are —CH ₂ — and —C (═O) —OR ₂₉ — and R ₂₆ and R ₂₈ are defined as R ₁ to R ₂₀ in Formulas 1-6; And preferably a methyl or trifluoromethyl group; C ₆ -C ₁₈ aryl groups such as phenyl, naphthyl, biphenyl, anthryl, phenanthryl or terphenylyl, preferably phenyl groups and the like; Or a C ₇ -C ₁₈ aralkyl group such as-(CH ₂ ) _3-12 -phenyl group or -phenylene- (CH ₂ ) _3-11 -CH ₃ , preferably a toryl group or the like; And n is an integer from 1 to 4.

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 is the above-mentioned phthalocyanine derivative provided by the present invention as the optical dye. Include them.

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

The recording layer can form a solution of the phthalocyanine derivative provided by the present invention on the substrate by spin coating. The spin coating method can be performed as follows; The phthalocyanine derivative of the present invention is dissolved in a solvent at an appropriate ratio, preferably at most 5% by weight (% wt / vol), more preferably at 1.5 to 3% by volume. The resulting solution can then be applied onto the substrate via conventional spin coating techniques. The thickness of the recording layer is generally 50 to 300 nm, preferably 80 to 150 nm.

In consideration of the solubility of the organic optical dye in a specific solvent and corrosion of the substrate by the solvent, preferred solvents for spin coating include, for example, dichloromethane, chloroform, carbon tetrachloride, trichloroethane, dichloroethane, tetra Halogenated hydrocarbons such as chloroethane and dichlorodifluoroethane; Ethers such as, for example, ethyl ether, propyl ether, butyl ether and cyclohexyl ether; Alcohols such as, for example, methanol, ethanol, propanol, tetrafluoropropanol and butanol and the like; Ketones such as, for example, acetone, trifluoroacetone, hexafluoroacetone, cyclohexanone and the like; And hydrocarbons such as, for example, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, octane, cyclooctane and the like.

The reflective layer is mainly composed of metals such as copper, aluminum, gold or silver, or alloys thereof. The reflective layer may be formed by depositing an appropriate material on the recording layer by vacuum deposition or sputtering to a thickness of 1 to 200 nm.

The protective layer is mainly composed of a thermosetting resin or an ultraviolet crosslinking-curable resin, preferably a transparent resin. In general, the protective layer may be formed by spin coating the resin on the reflective layer to form a layer having a thickness of 0.1 to 500 μm, preferably 0.5 to 50 μm.

In view of practicality, polycarbonate resins are mainly used as substrate materials of optical recording media these days, and a spin coating method is preferentially selected to form the recording layer and the 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

10.0 g of tetra-α- (2,4-dimethyl-3-pentoxyl) copper phthalocyanine derivative (prepared according to EP 703280) was weighed and added to a 250 ml round bottom flask purged with nitrogen. Then 50 ml of toluene and 5.4 g of 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 of POCl ₃ was slowly added to the reaction solution, while maintaining the temperature not to exceed 5 ° C. After the addition of POCl ₃ was completed, 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. Subsequently, the reaction mixture was poured into a 200 ml solution of sodium acetate (41.5 g) covered with ice, stirred for 30 minutes, and then extracted three times with 100 ml of toluene. The combined organic layers after extraction were dried over 20 g of anhydrous magnesium sulfate, anhydrous magnesium sulfate 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 of methanol and dried in a 70 ° C. vacuum oven for 2 days. The green powder thus obtained was 9.5 g (64% of theory).

Elemental analysis: Experimental value (%): C: 69.21 H: 6.79 N: 10.44

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

UV-Visible Spectroscopy (DBE): λ max = 710 nm

Infrared spectroscopy (KBr): Absorption at C = O 1675 cm ⁻¹

Example 2

1.03 g of sodium borohydride was weighed and added to a 250 ml three necked round bottom flask purged with nitrogen, followed by 40 ml of ethanol to dissolve the sodium borohydride. 10.0 g of formylated tetra-α- (2,4-dimethyl-3-pentoxyl) copper phthalocyanine (prepared as in Example 1) was dissolved in 40 ml of tetrahydrofuran (THF) and prepared previously To the reduced reducing agent solution. The resulting reaction solution was stirred vigorously for 24 hours at room temperature and monitored by thin layer chromatography (TLC). At the end of the reaction, the insolubles were filtered off, and 200 ml of 20% saline solution was added thereto to terminate the reaction. Then, the mixture was extracted three times with 40 ml of toluene. The combined organic layers after extraction were dried over 20 g of anhydrous magnesium sulfate, anhydrous magnesium sulfate was filtered off and concentrated to 40 ml under reduced pressure. The concentrate was then 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 of methanol and dried in a 70 ° C. vacuum oven for 2 days. The green powder thus obtained was 9.4 g (95% of theory).

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

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

UV-Visible Spectroscopy (DBE): λ max = 713.5 nm

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

Example 3

10.0 g of hydroxymethylated tetra-α- (2,4-dimethyl-3-pentoxy) copper phthalocyanine (prepared as in Example 2) was weighed and added to a 250 ml reactor under stirring with nitrogen purge 40 ml of toluene was added to it. After complete dissolution, the temperature of the resulting solution was lowered to 0 ° C. Toluene solution (6.25%) of 48.64 ml of trifluoromethanesulfonic anhydride was slowly added to the reaction solution, while maintaining the temperature not to exceed 5 占 폚. After completion of the addition of the anhydride solution, the cooling system was removed to allow the temperature to rise to room temperature. The solution was subsequently stirred at room temperature for 2 hours and the reaction was monitored by thin layer chromatography (TLC) until completion. The reaction mixture was poured into a mixed solvent of methanol / water (80 mL / 240 mL) with stirring for 30 minutes to terminate the reaction, and then extracted three times with 100 mL of toluene. The combined organic layers after extraction were dried over 20 g of anhydrous magnesium sulfate, anhydrous magnesium sulfate was filtered off and concentrated to 60 ml under reduced pressure. The concentrate was then 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 of methanol and dried in a 70 ° C. vacuum oven for 2 days to yield 9.4 g (83% of theory) of green powder.

Elemental analysis: Experimental value (%): C: 62.50 H: 6.18 N: 9.08

          Calculated Value (%): C: 62.32 H: 6.16 N: 9.38

UV-Visible Spectroscopy (DBE): λ max = 714.5 nm

Infrared spectroscopy (KBr): SO ₃ at 1367 cm ^-1 , 1152 cm ^-1

Thermogravimetric Analysis (TGA): The main decomposition temperature starts at 253 ° C (about 37%)

Example 4

3.4 g of p-toluenesulfonylchloride was weighed and added to a 250 ml three necked round bottom flask, 10 ml of dichloromethane was added thereto under a nitrogen purge and the resulting mixture was stirred for 30 minutes. Thereafter, 20 ml of pyridine was slowly added to the reaction mixture, which was further stirred for 20 minutes. Separately, after preparing a solution containing 10.0 g of hydroxymethylated tetra-α- (2,4-dimethyl-3-pentoxy) copper phthalocyanine (prepared as in Example 2) and 15 ml of dichloromethane It was added into the 250 ml flask above, and reacted at room temperature for 12 hours. The reaction mixture was poured into 300 mL of water with stirring for 30 minutes to terminate the reaction and then extracted three times with 100 mL of toluene. The combined organic layers after extraction were dried over 20 g of anhydrous magnesium sulfate, anhydrous magnesium sulfate was filtered off and concentrated to 60 ml under reduced pressure. The concentrate was then poured into 1 liter of n-hexane and stirred vigorously for 30 minutes. The product was collected by filtration and dried for 2 days in a 70 ° C. vacuum oven to yield 9.0 g (80% of theory) of green powder.

Elemental analysis: Experimental value (%): C: 67.45 H: 6.25 N: 9.50

          Calculated Value (%): C: 67.11 H: 6.63 N: 9.21

UV-Visible Spectroscopy (DBE): λ max = 714.0 nm

Infrared spectroscopy (KBr): SO ₃ at 1367 cm ^-1 , 1152 cm ^-1

Thermogravimetric Analysis (TGA): The main decomposition temperature starts at 227 ° C (about 35%)

Example 5

The compound of Example 3 was dissolved in a mixed solvent of dibutyl ether (DBE) and 2,6-dimethyl-4-heptanone (95/5, volume / volume) to give 2.8% wt / vol (weight of solvent / volume of solvent) Dye solution was prepared by forming a solution. After vigorous stirring for 1 hour, the solution was filtered through a 0.2 μm pore size Teflon filter, followed by a 1.2 mm-thick pregrooved disc (pre-groove) at an initial rotational speed of 400 rpm. Disk formed: average groove depth = 195 mm, average groove width = 600 mm, track pitch = 1.7 mu m). The rotation was then 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 sputter deposited on the recording layer in a vacuum sputtering apparatus (ALCATEL, ATP150). Finally, an ultraviolet curing agent (ROHM AND HAAS DEUTSCHLAND GMBH, Rengolux 3203-031v6 clear-CD LACQUER) was spin coated onto the silver reflecting 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 speed (52X) recording speed in a conventional writer (Liteon LTR-52327S). The recorded disc was tested with an automated compact disc testing system (Pulstec OMT-2000x4) to measure the signal at 1X (1X). Key data at the 40-minute position was compiled in Table 1.

Example 6

The procedure described in Example 5 was repeated. The information was continuously recorded on a blank CD-R disc produced as above at a recording speed of 52 times on a conventional recording device (Liteon LTR-52327S). The recorded disc was tested with an automated compact disc testing system (Pulstec OMT-2000x4) to measure the signal at 1x speed. Key data at the 75-minute position was edited in Table 1.

location I3 I11 Rtop BLER Jit3T Jit11T 40-minute 0.31 0.69 0.63 3.1 25 27 75-minute 0.30 0.66 0.63 2.4 28 31

(A) I3: Modulation at 3T (T = 231.4ns)

(B) I11: Modulation at 11T (T = 231.4ns)

(C) Rtop: Reflectivity

(D) BLER: Block Error Rate

(E) Jit3T: Jitter value at 3T

(F) JitP11T: Jitter value at 11T

Example 7

The compound of Example 4 was dissolved in a mixed solvent (95/5, volume / volume) of 1-propanol and 4-hydroxy-4-methyl-2-pentanone to give 1.7% wt / vol (weight of solvent / volume of solvent) Dye solution was prepared by forming a solution. After vigorous stirring for 1 hour, the solution was filtered through a 0.2 μm pore size Teflon filter, followed by a 1.2 mm-thick pregrooved disc (pre-groove) at an initial rotational speed of 400 rpm. Disk formed: average groove depth = 195 mm, average groove width = 600 mm, track pitch = 1.7 mu m). The rotation was then 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 sputter deposited on the recording layer in a vacuum sputtering apparatus (ALCATEL, ATP150). Finally, an ultraviolet curing agent (ROHM AND HAAS DEUTSCHLAND GMBH, Rengolux 3203-031v6 clear-CD LACQUER) was spin coated onto the silver reflecting 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 disc was tested with an automated compact disc testing system (Pulstec OMT-2000x4) to measure the signal at 1X (1X). Key data at the 40-minute position was compiled in Table 2.

Example 8

The procedure described in Example 7 was repeated. The information was continuously recorded on a blank CD-R disc created as above at a 52x recording speed on a conventional recording device (BenQ CD-RW 5232X). The recorded disc was tested with an automated compact disc testing system (Pulstec OMT-2000x4) to measure the signal at 1x speed. Key data at the 75-minute position was edited in Table 2.

location I3 I11 Rtop BLER Jit3T Jit11T 40-minute 0.31 0.70 0.62 5.2 29 27 75-minute 0.30 0.68 0.61 4.5 30 31

As the data are shown in Tables 1 and 2, it was evident that the optical recording media using the phthalocyanine dyes invented according to the present invention could achieve all excellent performance at different recording speeds in various commercial recording devices. 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 excellent performances at different recording speeds in various commercial recording apparatuses. Give the effect you can get.

Claims (11)

A phthalocyanine derivative having a structure represented by Formula 1 below; [Formula 1]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, 1 to 6 carbon atoms, which may be substituted with 0 to 6 halogen atoms An alkoxyl group having atoms, an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms; Alkenyl groups having 2 to 12 carbon atoms; An alkynyl group having 2 to 12 carbon atoms; M can be two hydrogen atoms, a divalent metal, a monosubstituted trivalent metal, a disubstituted tetravalent metal or an oxometal group; S is a moiety containing at least one —SO ₃ — group, and n is an integer from 1 to 4. A method for producing the optical dye according to claim 1, comprising covalently bonding an sulfonate compound to an unsubstituted or substituted phthalocyanine. The method of claim 2, A method for producing an optical dye, comprising reacting hydroxylated phthalocyanine with sulfonic anhydride or sulfonyl anhydride under anhydrous conditions. The method of claim 2, A method for producing an optical dye, characterized in that a sulfonyl chloride-substituted phthalocyanine derivative is reacted with an alcohol. A phthalocyanine derivative of the formula (2); [Formula 2]

Wherein R ₃₀ is a trifluoromethyl group or a toryl group, and n is an integer from 1 to 4. A method for producing the optical dye according to claim 5, which comprises reacting hydroxylated phthalocyanine with trifluoromethanesulfonic anhydride under anhydrous conditions. A process for producing the optical dye according to claim 5, comprising reacting hydroxylated phthalocyanine with p-toluenesulfonylchloride in the presence of an organic base such as pyridine as a catalyst. Use of a phthalocyanine derivative as defined in claim 1 used as an optical dye in a recording layer of an optical recording medium. Use of a phthalocyanine derivative as defined in claim 5 used as an optical dye in a recording layer of an optical recording medium. In an optical recording medium consisting of a substrate, a recording layer comprising an organic dye on which information can be recorded by means of a laser beam, a reflective layer and a protective layer, a phthalocyanine derivative as defined in claim 1 is added to the recording layer of the optical recording medium. An optical recording medium, characterized in that used. In an optical recording medium comprising a substrate, a recording layer comprising an organic dye on which information can be recorded by means of a laser beam, a reflective layer and a protective layer, a phthalocyanine derivative as defined in claim 5 is added to the recording layer of the optical recording medium. An optical recording medium, characterized in that used.