EP1377973A1

EP1377973A1 - Optical data memories containing an axially substituted co-phthalocyanine in the information layer that can be written with light

Info

Publication number: EP1377973A1
Application number: EP02719993A
Authority: EP
Inventors: Horst Berneth; Friedrich-Karl Bruder; Wilfried Haese; Rainer Hagen; Karin HASSENRÜCK; Serguei Kostromine; Peter Landenberger; Rafael Oser; Thomas Sommermann; Josef-Walter Stawitz; Thomas Bieringer
Original assignee: Bayer Chemicals AG
Current assignee: Lanxess Deutschland GmbH
Priority date: 2001-03-28
Filing date: 2002-03-20
Publication date: 2004-01-07
Also published as: WO2002080162A1; US6737142B2; JP2004524194A; TWI227486B; US20020172793A1; CN1513174A

Abstract

The invention relates to optical data memories containing a preferably transparent substrate that is optionally already coated with one or more reflective layers. An information layer that can be written with light, optionally, one or more reflective layers and, optionally, a protective layer or another substrate or a covering layer are applied to the surface of the preferably transparent substrate. The inventive data memory can be written and read with infrared light, preferably laser light, especially preferred, with light having a wavelength ranging from 750 to 800 nm, particularly from 770 to 790 nm. In addition, the information layer contains a light-absorbing compound and, optionally, a binding agent. The data memory is characterized in that at least one Co(III) phthalocyanine is used as a light-absorbing compound, whereby the Co metal center carries two axial substituents R?1 and R2¿ that, independent of one another, represent CN, SCN, alkoxy or alkylthio.

Description

Optical data storage media containing an axially substituted Co-phthalocyanine in the information layer which can be written on with light

The present invention relates to the use of axially substituted Co-

Phthalocyanine as a light-absorbing compound in the light-writable information layer of write-once optical data carriers, optical data carriers and a process for their production.

The once writable compact disk (CD-R) has been experiencing an enormous leap lately

Volume growth. The light-absorbing connection of the information layer represents an essential component of the optical data carrier, to which correspondingly high and diverse requirements are made. It is not uncommon for the production of such compounds to be correspondingly complex (cf. WO-A-00/09522).

The object of the invention is accordingly to provide an easy-to-synthesize phthalocyanine dye which meets the high requirements (such as light stability, favorable signal-to-noise ratio, high writing sensitivity, damage-free application to the substrate material, etc.) for use as a light-absorbing material

Connection in the as an information layer of a write-once optical data carrier (primarily CD-R) fulfilled.

Surprisingly, it was found that axially substituted Co-phthalocyanines are well suited for the purpose mentioned.

The present invention therefore relates to an optical data carrier, comprising a preferably transparent substrate, possibly already coated with one or more reflection layers, on the surface of which an information layer which can be written on with light, optionally one or more reflection layers and optionally a protective layer or a further substrate or one Cover layer are applied, which can be written and read with infrared light, preferably laser light, particularly preferably light with a wavelength in the range of 750-800 nm, in particular 770-790 nm, the information layer containing a light-absorbing compound and optionally a binder, characterized in that at least one Co (III) phthalocyanine is used as the light-absorbing compound, the Co metal center carrying two axial substituents R ¹ and R ² which independently of one another represent CN, SCN, alkoxy or alkylthio.

A Co-phthalocyanine is preferred as the light-absorbing compound

Formula (I) used

Kat Θ (I), wherein

CoPc stands for cobalt (III) phthalocyanine, where R ¹ and R ^{2 are} axial residues of cobalt, and the residues R ³ to R ⁶ correspond to substituents on the phthalocyanine, in which

R ¹ and R ² independently of one another represent CN, SCN, alkoxy or alkylthio,

R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another for halogen, cyano, alkyl, aryl, alkylamino, dialkylamino, alkoxy, alkylthio, aryloxy, arylthio, SO ₃ H, SO ₂ NR ⁷ R ⁸ , CO ₂ R ¹² , CONR ⁷ R ⁸ , NH-COR ¹² or a radical - (B) _m -D stand,

B is a bridge member from the group direct bond, CH ₂ , CO, CH (alkyl), C (alkyl) ₂ , NH, S, O or -CH = CH-, where (B) _{m is} a chemical meaningful order of bridge members B means with m = 1 to 10, preferably m = 1, 2, 3 or 4,

D for the monovalent residue of a redox system of the formula

X ¹ - ^ CH: = CH ^ Y- (Red) or

or represents a metallocenyl radical or metallocenylcarbonyl radical, titanium, manganese, iron, ruthenium or osmium being suitable as the metal center,

X ¹ and X ² independently of one another represent NR'R ", OR" or SR ",

Y ^{1 represents} NR ', O or S, Y ^{2 represents} NR',

n stands for 1 to 10 and

R 'and R "independently of one another are hydrogen, alkyl, cycloalkyl, aryl or

Hetaryl, or a direct bond or bridge to one of the C-

Atoms of the Forming a chain,

w, x, y and z are, independently of one another, 0 to 4 and w + x + y + z <12,

R ⁷ and R ⁸ independently of one another for alkylamino, hydroxyalkylamino, dialkylamino, bishydroxyalkylamino, arylamino or R ⁷ and R ⁸ together with the N atom to which they are attached form a heterocyclic 5-, 6- or 7- form a membered ring, optionally with the participation of further heteroatoms, in particular from the group O, N and S, where NR R, in particular pyrrolidino, piperidino or morpholino,

R ^{12 represents} alkyl, aryl, hetaryl or hydrogen,

Kat ^{+ stands} for a cation, in particular for an alkali application, ammonium cation,

Trialkylammonium cation, trialkyloxonium cation, triphenylcarbonium cation, diphenyliodonium cation, N-alkyl-pyridinium cation or stands for a metallocene cation, titanium, manganese, iron being the metal center,

Ruthenium or osmium comes into question.

The alkyl, alkoxy, aryl and heterocyclic radicals can optionally further radicals such as alkyl, halogen, hydroxy, hydroxyalkyl, amino, alkylamino, dialkylamino, nitro, cyano, CO-NH ₂ , alkoxy, alkoxycarbonyl, morpholino, piperidino,

Wear pyrrolidino, pyrrolidono, trialkylsilyl, trialkylsiloxy or phenyl. The alkyl and alkoxy radicals can be saturated, unsaturated, straight-chain or branched, the alkyl radicals can be partially or perhalogenated, the alkyl and alkoxy radicals can be ethoxylated or propoxylated or silylated. Adjacent alkyl and / or alkoxy radicals on aryl or heterocyclic radicals can together form a three- or four-membered bridge.

Preferred compounds of the formula (I) are those in which for the radicals R ¹ to R ⁸ and R, R \ R "and R ¹² :

Substituents with the designation "alkyl" are preferably C 1 -C ₁₆ -alkyl, in particular C ₁ -C ₆ -alkyl, which are optionally substituted by halogen, such as chlorine, bromine, fluorine, hydroxy, cyano and / or CrCβ-alkoxy; Substituents with the designation "alkoxy" preferably mean dC ^ -alkoxy, in particular d-Cβ-alkoxy, which are optionally substituted by halogen, such as chlorine, bromine, fluorine, hydroxy, cyano and / or C ₁ -C ₆ -alkyl;

Substituents with the designation "cycloalkyl" preferably mean C ₄ -C ₈ cycloalkyl, in particular C ₅ to C _ö cycloalkyl, which may be replaced by halogen, such as chlorine, bromine or fluorine, hydroxy, cyano and / or CI-C _Ö alkyl are substituted.

Substituents with the designation "alkenyl" preferably denote C ₆ -C ₈ alkenyl, which are optionally substituted by halogen, such as chlorine, bromine or fluorine, hydroxy, cyano and / or Cj-C ₆ alkyl, in particular alkenyl means allyl,

Substituents with the meaning "hetaryl" preferably for heterocyclic radicals with 5- to 7-membered rings, which preferably contain heteroatoms from the group N, S and / or O and are optionally fused with aromatic rings or optionally carry further substituents, for example halogen, hydroxy , Cyano and / or alkyl, with particular preference being given to: pyridyl, furyl, thienyl, oxazolyl, thiazolyl, imidazolyl, quinolyl, benzoxazolyl, benzthiazolyl and benzimidazolyl,

The substituents with the term "aryl" preferably C _ö -Cio--aryl, in particular phenyl or naphthyl, optionally substituted by halogen, such as F, Cl, hydroxy, CC ₆ - alkyl, Ci-Cβ- alkoxy, NO ₂ and / or CN are substituted.

Co-phthalocyanines of the formula (I) are preferred in which

R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another for chlorine, fluorine, bromine, iodine, cyano,

Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert. Butyl, pentyl, tert.

Amyl, hydroxyethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, phenyl, p-tert-butylphenyl, p-methoxyphenyl, isopropylphenyl, trifluoromethylphenyl, naphthyl, methylamino, ethylamino, propylamino, Isopropylamino, butylamino, isobutylamino, tert. Butylamino, pentylamino, tert. Amylamino, benzylamino, methylphenylhexylamino, hydroxyethylamino, aminopropylamino, aminoethylamino, 3-dimethylamino-propylamino, 3-diethylaminopropylarnino, diethylaminoethylamino, dibutylamino propylamino, morpholinopropylamino, piperidinopropylamino,

Pyrrolidinopropylamino, pyrrolidonopropylamino, 3 - (methyl-hydroxyethylamino) propylamino, methoxyethylamino, ethoxyethylamino, methoxypropylamino, ethoxypropylamino, methoxyethoxypropylamino, 3- (2-ethylhexyloxy) propylamino, isopropyloxamino, dimethylamino, dimethylamino, dimethylamino, dimethylamino, dimethyl Diisopropylamino, dibu ylamino,

Diisobutylamino, di-tert. butylamino, dipentylamino, di-tert. amylamino, bis (2-ethylhexyl) amino, bis (aminopropyl) amino, bis (aminoethyl) amino, bis (3-dimethylaminopropyl) amino, bis (3-diethylaminopropyl) amino, bis (diethylaminoethyl) amino, bis (dibutylamine propyl) amino , Di (morpholino-propyl) amino, di (piperidinopropyl) amino, di (pyrrolidinopropyl) amino, di-

(pyrrolidonopropyl) amino, bis (3- (methyl-hydroxyethylamino) propyl) amino, dimethoxyethylamino, diethoxyethylamino, dimethoxypropylamino, diethoxypropylamino, di (methoxyethoxyethyl) amino, di (methoxyethoxypropyl) amino, bis (3 - (2-ethylhexyloxy ) propyl) amino, di (isopropyloxy-isopropyl) amino, methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy,

Isobutyloxy, tert. Butyloxy, pentyloxy, tert. Amyloxy, methoxyethoxy, ethoxyethoxy, methoxypropyloxy, ethoxypropyloxy, methoxyethoxypropyloxy, 3- (2-ethylhexyloxy) propyloxy, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, tert.-butylthio, phenyl, methyl, pentylthio, tert , Trifluoroethylphenyl, naphthyl, CO ₂ R ¹² ,

CONR ⁷ R ⁸ , NH-CORl ² , SO ₃ H, SO ₂ NR ⁷ R ⁸ , or for a radical of the formula

wherein

_ _c _0 -, -CH ₂ -O-, * -C ₂ H ₄ -O-, ± CH (CH ₃ ) O-

O

(B) _m for

^ C- -OCH: or -C - OC, H, stands, II II ^{2 4} OO

where the asterisk (*) indicates the connection with the 5-ring,

M represents an Mn or Fe,

w, x, y and z are independently 0 to 4 and w + x + y + z <12,

Kat ⁺ for lithium cation, sodium cation, potassium cation, tetrabutylammonium cation, tetrapropylammonium cation, tetraethylarnmonium cation, tetramethylammonium cation, triethyloxonium cation, triphenylcarbonium cation, diphenyliodonium cation, N-ethylpyridinium cation, or ferroc

NR ⁷ R ⁸ for amino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, tert. Butylamino, pentylamino, tert. Amylamino, benzylamino, methylphenylhexylamino, 2-ethyl-l-hexylamino, hydroxyethylamino, aminopropylamino, aminoethylamino, 3-dimethylaminopropylamino, 3-diethylaminopropylamino, morpholinopropylamino, piperidino-propylamino, pyrrolidinopropylamino, pyrrolidinopropylamino, (3) ) propylamino, methoxyethylamino, ethoxyethylamino, methoxypropylamino, ethoxypropylamino, methoxyethoxypropylamino, 3- (2-ethylhexyloxy) propylamino, isopropyloxyisopropylamino, dimethylamino, diethylamino, dipropylamino, diisopropylamino, di-butylamino, diibutylamino. butylamino, dipentylamino, di-tert. amylamino, Bis (2-ethylhexyl) amino, dihydroxyethylamino, bis (aminopropyl) amino, bis (aminoethyl) amino, bis (3-dimethylaminopropyl) amino, bis (3-diethylaminopropyl) amino, di (morpholinopropyl) amino, di (piperidinopropyl ) amino, di (pyrrolidinopropyl) amino, di (pyrrolidonopropyl) amino, bis (3 - (methyl - hydroxyethylamino) propyl) amino, dimethoxyethylamino, diethoxyethylamino, dimethoxypropylamino, diethoxypropylamino, di (methoxyethoxypropyl) amino, bis ( 3 - (2-ethylhexyloxy) propyl) amino, di (isopropyloxyisopropyl) amino, anilino, p-toluidino, p-tert. Butylanilino, p-anisidino, isopropylanilino or naphthylamino or NR R stands for pyrrolidino, pipidino, piperazino or morpholino,

R ¹² for hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert.-butyl, pentyl, tert.-amyl, phenyl, p-tert.-butylphenyl, p-methoxyphenyl, isopropylphenyl, p-trifluoromethylphenyl, Cyanophenyl, naphthyl, 4-pyridinyl, 2-pyridinyl, 2-quinolinyl, 2-pyrrolyl or 2-indolyl,

in which

the alkyl, alkoxy, aryl and heterocyclic radicals, optionally further radicals such as alkyl, halogen, hydroxy, hydroxyalkyl, amino, alkylamino, dialkylamino,

Nitro, cyano, CO-NH ₂ , alkoxy, alkoxycarbonyl, morpholino, piperidino, pyrrolidino, pyrrolidono, trialkylsilyl, trialkylsiloxy or phenyl, which alkyl, and / or alkoxy radicals can be saturated, unsaturated, straight-chain or branched, the alkyl radicals partially or may be perhalogenated, the alkyl and / or alkoxy radicals may be ethoxylated or propoxylated or silylated, adjacent alkyl and / or

Alkoxy residues on aryl or heterocyclic residues can jointly form a three- or four-membered bridge.

Redox systems in the context of this application include in particular those described in Angew. Chem. 1978, p. 927 and in Topics of Current Chemistry, Vol. 92, p. 1

(1980), described redox systems. P-Phenylenediamines, phenothiazines, dihydrophenazines, bipyridinium salts (viologens), quinodimethanes are preferred.

Those co-phthalocyanines of the formula I which correspond to the formula (Ic) are particularly preferred.

The invention also relates to Co (III) phthalocyanines, the co-metal center of which carries two axial substituents R ¹ and R ² , which independently of one another represent CN, SCN, alkoxy or alkylthio and whose phthalocyanine radical is substituted.

These are preferably co-phthalocyanines of the formula (I), in which the sum of w, x, y and z is greater than zero, preferably a number from 1 to 12.

Compounds of the formula Ic according to the invention are very particularly preferred

R '

Co ° Pc (SO ₂ NR ⁷ R ⁸ ) _a (halogen) _b (alkoxy) _c Kat® R ²

(Ic) where

Halogen represents chlorine, bromine or fluorine,

Alkoxy is Cj-Cg-alkoxy, which is optionally substituted, and a a

Number from 0 to 4, b is a number from 0 to 10, c is a number from 0 to 8, the sum of a, b and c being <12 and

R ¹ , R ² , R, R ⁸ , Kat + and CoPc have the above meaning. The invention also relates to a process for the preparation of compounds of the formula (Ic), which is characterized in that one with sulfonamide groups 7 R 7 R of the formula SO ₂ NR R, where R and R have the abovementioned meaning, and optionally halogen - and / or alkoxy-substituted Co-phthalocyanine oxidized and reacted with KatCN, KatSCN, Katalkoxy or Katalkylthio.

The preparation is preferably carried out starting from a co-phthalocyanine optionally substituted with halogen and / or alkoxy by sulfochlorination with chlorosulfonic acid and thionyl chloride at 50-130 ° C. and reaction with the corresponding amine to give the amide in water at pH 8-12 Room temperature up to 100 ° C. The subsequent introduction of the axial amine substituents is preferably carried out in a known manner under oxidative conditions, e.g. Chlorine or air, preferably air, in the case of air in the presence of excess KatCN, KatSCN, Katalkoxy or Katalkylthio

Particularly preferably, the information layer which can be written on with light contains, as light-absorbing compounds, in addition to a Co (III) phthalocyanine compound as described above, in particular one of the formula I, additionally at least one other optionally substituted phthalocyanine in component b) below, with or without a central atom. For example, one of the groups Si, Zn, Al, Cu, Pd, Pt, Au and Ag, in particular Cu and Pd, can be used as the central atom.

The invention therefore also relates to mixtures

a) a Co (III) phthalocyanine, whose Co metal center has two axial substituents

R ¹ and R ² , which independently of one another represent CN, SCN, alkoxy or alkylthio and

b) a phthalocyanine different from a), in particular from Co-free phthalocyanine. For components a) and b), the preferred embodiments specified above are preferred.

Particularly preferred as component b) are, for example, the sulfonamide-substituted Cu-phthalocyanines known from DE-A 19 925 712. Those of the formula II are particularly preferred

wherein

CuPc stands for a copper phthalocyanine residue,

A for an optionally substituted straight-chain or branched

C ₂ -C ₆ alkylene such as ethylene, propylene, butylene, pentylene, hexylene,

R ⁹ and R ¹⁰ independently of one another for hydrogen or in each case optionally substituted straight-chain or branched C ₁ -C ₆ -alkyl such as, for example

Are methyl, ethyl, propyl, butyl, pentyl, hexyl, in particular for substituted CrCe-hydroxyalkyl and for unsubstituted CrCβ-alkyl,

or R ¹ and R ² together with the N atom to which they are attached form a heterocyclic 5- or 6-ring which optionally contains a further hetero atom, for example S, N or O,

x stands for 2.0 to 4.0,

v represents 0 to 1.5 and the sum of x and y is 2.0 to 4.0, preferably 2.5 to 4.0.

Particularly preferred mixture components b) are those compounds of the formula (II) which correspond to the formula (Ha)

CuPc - [SO ₂ NH-CH ₂ CH ₂ CH ₂ N (CH ₂ ) ₃ (Ha), wherein

CuPc means copper phthalocyanine.

Other preferred additional light-absorbing compounds are the sulfonamide- or amido-substituted phthalocyanines as are known, for example, from EP-A-519 395.

In the case of mixtures of different light-absorbing compounds, the proportion of the compounds of the formula (I) thereof is preferably 10 to 90% by weight.

A mixture of the formulas (I) and (II) in a weight ratio of 10:90 to 90:10, preferably 20:80 to 80:20, particularly preferably of is particularly preferred

40:60 to 60:40.

In addition to the light-absorbing compound, the information layer can also contain binders, wetting agents, stabilizers, thinners and sensitizers and other constituents.

The substrates can be made of optically transparent plastics which, if necessary, have undergone a surface treatment. Preferred plastics are polycarbonates and polyacrylates, as well as polycycloolefins or polyolefins. The reflection layer can be made of any metal or metal alloy that is usually used for recordable optical data carriers. Suitable metals or metal alloys can be evaporated and sputtered and contain, for example, gold, silver, copper, aluminum and their alloys with one another or with other metals.

The possible protective layer over the reflective layer can consist of UV-curing acrylates.

A possible intermediate layer, which protects the reflection layer from oxidation, for example, may also be present.

The invention further relates to a method for producing the optical data carrier according to the invention, which is characterized in that the information layer which can be written on with light is passed through onto a transparent substrate

Coating with at least one co-phthalocyanine complex of the formula I, optionally in combination with other light-absorbing compounds, in particular those of component b), applying suitable binders, additives and solvents and, if appropriate, providing a reflection layer, optionally further intermediate layers and optionally a protective layer.

The coating of the substrate with the light-absorbing compound of the formula I, if appropriate in combination with other dyes, binders and / or solvents, is preferably carried out by spin coating or sputtering.

For the coating, the light-absorbing compound of the formula I is preferably dissolved with or without additives in a suitable solvent or solvent mixture, so that the compound of the formula I is 100 or less, for example 10 to 20 parts by weight to 100 parts by weight of solvent. The recordable information layer is then preferably metallized at reduced pressure by sputtering or vapor deposition (reflection layer) and possibly then provided with a protective lacquer (protective layer) or another substrate or a cover layer. Multi-layer arrangements with a partially transparent reflection layer are also possible.

Solvents or solvent mixtures for coating the light-absorbing compounds of the formula I or their mixtures with additives and / or binders and other light-absorbing compounds are determined on the one hand by their solvency for the light-absorbing compound of the formula I and the other additives and on the other hand by a minimal influence on the Substrate selected. Suitable solvents that have a minor impact on the

Have substrate are, for example, alcohols, ethers, hydrocarbons, halogenated hydrocarbons, alkoxy alcohols, ketones. Examples of such solvents are methanol, ethanol, propanol, 2,2,3,3-tetrafluoropropanol, butanol, diacetone alcohol, benzyl alcohol, tetrachloroethane, dichloromethane, diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, methoxyethanol, ethoxyethanol , 1-

Methyl 2-propanol, methyl ethyl ketone, 4-hydroxy-4-methyl-2-pentanone, hexane, cyclohexane, ethylcyclohexane, octane, benzene, toluene, xylene. Preferred solvents are hydrocarbons and alcohols because they have the least influence on the substrate.

Suitable additives for the recordable information layer are stabilizers, wetting agents, binders, thinners and sensitizers.

The light-absorbing compound should preferably be thermally changeable. The thermal change preferably takes place at a temperature <600 ° C.

Such a change can be, for example, a decomposition or chemical change in the chromophoric center of the light-absorbing compound.

In addition to the information layer, the optical data storage device can carry further layers such as metal layers, dielectric layers and protective layers. Metals and dielectric layers serve, among other things, to adjust the reflectivity and the Heat balance. Depending on the laser wavelength, metals can be gold, silver, aluminum and others. Dielectric layers are, for example, silicon dioxide and silicon nitride. Protective layers are, for example, photocurable lacquers, (pressure-sensitive) adhesive layers and protective films.

Dirt sensitive adhesive layers mainly consist of acrylic glue. Nitto Denko DA-8320 or DA-8310, disclosed in patent JP-A 11-273147, for example, can be used for this purpose.

The optical data carrier has, for example, the following layer structure (cf.

1): a transparent substrate (1), optionally a protective layer (2), an information layer (3), optionally a protective layer (4), optionally an adhesive layer (5), a cover layer (6).

The structure of the optical data carrier can preferably:

contain a preferably transparent substrate (1), on the surface of which at least one information layer (3) which can be written on with light and which can be written on with light, preferably laser light, optionally a protective layer (4), optionally an adhesive layer (5), and a transparent cover layer (6) are applied.

contain a preferably transparent substrate (1), on the surface of which a protective layer (2), at least one information layer (3) which can be written on with light, preferably laser light, optionally an adhesive layer (5), and a transparent cover layer (6) are applied.

contain a preferably transparent substrate (1), on the surface of which there is optionally a protective layer (2), at least one information layer (3) that can be written on with light, preferably laser light, and optionally one Protective layer (4), optionally an adhesive layer (5), and a transparent cover layer (6) are applied.

contain a preferably transparent substrate (1), on the surface of which at least one information layer (3) which can be written on with light, preferably laser light, optionally an adhesive layer (5) and a transparent cover layer (6) are applied.

Alternatively, the optical data carrier has, for example, the following layer structure (cf. FIG. 2): a preferably transparent substrate (11), an information layer

(12), optionally a reflection layer (13), optionally an adhesive layer (14), another preferably transparent substrate (15).

Alternatively, the optical data carrier has, for example, the following layer structure (cf. FIG. 3): a preferably transparent substrate (21), an information layer

(22), optionally a reflection layer (23), a protective layer (24).

The invention further relates to optical data carriers according to the invention described with blue, red or infrared light, in particular laser light, in particular infrared laser light.

The following examples illustrate the subject matter of the invention.

Examples:

The following preparative examples show the preparation of the dyes to be used according to the invention.

example 1

11.5 g of Co-phthalocyanine were introduced into 700 ml of dry ethanol at room temperature. 19.5 g of KCN were added and the mixture was heated to reflux for 6 hours. After cooling to RT, the product is filtered off with suction and washed with water and ethanol.

The dye obtained is dried in vacuo.

12.5 g of dye of the formula were obtained

λ _max 689nm (NMP).

The following compounds were prepared analogously by using other Co-phthalocyanines in the same molar amount.

Fe = ferrocenyl Example 17

11.5 g of Co-phthalocyanine were introduced into 700 ml of dry ethanol at room temperature. 29.5 g of KSCN were added and the mixture was heated to reflux for 10 h. After cooling to RT, the product is filtered off with suction and washed with water and ethanol. The dye obtained is dried in vacuo.

10.5 g of dye of the formula SCN were obtained

Co ° Pc K ^e

^SCN λ _max 687nm (NMP).

Example 18

11.5 g of Co-phthalocyanine were introduced into 700 ml of dry ethanol at room temperature. 31 g of K tert-butoxide were added and the mixture was heated to reflux for 10 h. After cooling to RT, the product is filtered off with suction and washed with water and ethanol. The dye obtained is dried in vacuo.

8.5 g of dye of the formula were obtained

λ _max 685 nm (NMP). Example 19

5 g of dye from Example 6 were introduced into 700 ml of dry ethanol at room temperature. 0.5 g of lithium perchlorate was added and the mixture was stirred at RT for 12 h. After cooling to 5 ° C is suctioned off. The solution is evaporated to dryness on a rotary evaporator. The residue is suspended in water, suction filtered and washed with water. The dye obtained is dried in vacuo.

4.1 g of dye of the formula were obtained

λ _m ax 709nm (NMP).

Example 20

11 g of dye from Example 6 were introduced into 1 1 of dry ethanol at room temperature. 3 g of ferrocentetrafluoroborate were added and the mixture was stirred at RT for 12 h. The precipitated dye is suctioned off. The dye obtained is dried in vacuo.

4.1 g of dye of the formula were obtained

) 4 Ferrocen®

Example 21

10 g of tetra-α- (2,4-dimethyl-3-pentoxy) -co-phthalocyanine were introduced into 500 ml of dry ethanol at room temperature. 3.6 g of tetraethylammonium cyanide were added and the mixture was heated to reflux for 8 h. After cooling it will turn on

Water discharged and suctioned off. The residue is washed with water. The dye obtained is dried in vacuo.

11 g of dye of the formula were obtained

N (ethyl) 4 ©

λ _max 707nm (NMP).

Example 22

10 g of tetra-α- (2,4-dimethyl-3-pentoxy) -co-phthalocyanine were introduced into 500 ml of dry ethanol at room temperature. 4.5 g of tetrabutylammonium cyanide were added and the mixture was heated to reflux for 8 h. After cooling, it is discharged onto water and suction filtered. The residue is washed with water. The dye obtained is dried in vacuo.

11 g of dye of the formula were obtained

N (butyl) ₄ ®

Example 23

10 g of tetra-α- (2-butylthio) co-phthalocyanine were introduced into 500 ml of dry ethanol at room temperature. 4.5 g of tetraethylammonium cyanide were added and the mixture was heated to reflux for 8 h. After cooling, it is discharged onto water and suction filtered. The residue is washed with water. The dye obtained is dried in vacuo.

12 g of dye of the formula were obtained

λ _max 711nm (NMP).

Example 24

A 3.8% solution of the dye from Example 6 in 2,2,3,3-tetrafluoropropanol was prepared at room temperature. This solution was applied to a pregrooved polycarbonate substrate using spin coating. The pre-grooved polycarbonate was produced as a disk using injection molding. The dimensions of the disc and the groove structure corresponded to those which are usually used for CD-R. The disk with the dye layer as the information carrier was sputtered with 100 nm Ag. A UV-curable acrylic lacquer was then applied by spin coating and cured using a UV lamp. With a commercial test writer for CD-R (Pulstec OMT 2000 x 4) at 6m W writing power and simple writing speed (l. Am / s) when reading the information a modulation height of 75% (> 60% is CD-R specification) for received the 1 IT signal. Example 25

A 3.8% solution of the dye from Example 19 in 2,2,3,3-tetrafluoropropanol was prepared at room temperature. This solution was applied to a pregrooved polycarbonate substrate using spin coating. The pre-grooved polycarbonate was produced as a disk using injection molding. The dimensions of the disc and the groove structure corresponded to those which are usually used for CD-R. The disk with the dye layer as the information carrier was sputtered with 100 nm Ag. A UV-curable acrylic lacquer was then applied by spin coating and cured using a UV lamp. With a commercial test writer for CD-R (Pulstec OMT 2000 x 4) writing power at 6m W became easier and easier

Write speed (l.Am/s) when reading the information received a modulation level of 73% (> 60% is CD-R specification) for the 1 IT signal.

Claims

claims

1. Optical data carrier, comprising a preferably transparent substrate, optionally already coated with one or more reflective layers, on the surface of which an information layer which can be written on with light, optionally one or more reflective layers and optionally a protective layer or a further substrate or a covering layer, which are applied with Infrared light, preferably laser light, particularly preferably light with a wavelength in the range of 750-800 nm, in particular 770-790 nm, can be described and read, the information layer containing a light-absorbing compound and optionally a binder, characterized in that as the light-absorbing Compound at least one Co (III) phthalocyanine is used, wherein the Co metal center carries two axial substituents R ¹ and R ² , which independently of one another are CN, SCN, alkoxy or alkylthio.

2. Optical data carrier containing a phthalocyanine of the general formula I as light-absorbing compound

Kat® wherein

CoPc stands for cobalt (III) phthalocyanine, where R ¹ and R ² correspond to axial radicals, and the radicals R ³ to R ⁶ correspond to substituents on the phthalocyanine, wherein R ¹ and R ^{2 are} independently CN, SCN, alkoxy or alkylthio

R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another are halogen, cyano, alkyl, aryl, alkylamino, dialkylamino, alkoxy, aryloxy, arylthio, alkylthio,

SO ₃ H, SO ₂ NR ⁷ R ⁸ CO ₂ Rl ² , CONR7R ⁰ -, NH-COR12 or a radical - (B) _m -D,

B is a bridge member from the group direct bond, CH ₂ , CO, CH (alkyl), C (alkyl) ₂ , NH, S, O or -CH = CH-, where (B) _{m is} a chemically sensible combination of bridge members B means and m stands for 1 to 10, preferably m = 1,

D for the monovalent residue of a redox system of the formula

X ^ CH ^ CH ^ -Y (ed) or

X ¹ and X ² independently of one another represent NR'R ", OR" or SR ",

Y ^{1 represents} NR ', O or S,

Y ^{2 stands} for NR ', n stands for 1 to 10 and

R 'and R "independently of one another represent hydrogen, alkyl, cycloalkyl, aryl or hetaryl or a direct bond or a bridge

one of the C atoms of the [^ ^" ^ TiT ^DZW - ^^ H ^ T ^*

Forming a chain,

w, x, y and z are independently 0 to 4 and w + x + y + z <12,

1 row

R and R independently of one another for alkylamino, hydroxyalkylamine, dialkylamino, bishydroxyalkylamino, arylamino or R ⁷ and R ⁸ together with the N atom to which they are attached form a heterocyclic 5-, 6- or 7-membered ring, optionally under Defense of further heteroatoms, in particular from the group O, N and S, where NR ⁷ R is in particular pyrrolidino, piperidino or morpholino, and

Kat ^{+ stands} for a cation, and

R ^{12 represents} alkyl, aryl, hetaryl or hydrogen.

3. Optical data carrier according to at least one of claims 1 or 2, characterized in that the light-writable information layer contains at least one co-phthalocyanine of the formula I, in which for the radicals R ¹ to R ^s , R, R, R ", R * ² :

Substituents with the designation "alkyl" mean CrC ^ alkyl, in particular C ₁ -C ₆ alkyl, which are optionally substituted by halogen, such as chlorine, bromine, fluorine, hydroxy, cyano and / or C ₁ -C ₆ alkoxy, the substituent of the term "alkoxy" Q-D.beta-alkoxy, in particular dC ₆ - alkoxy, which is optionally substituted by halogen, such as chlorine, bromine, fluorine, hydroxy, cyano and / or _C-C6 - alkyl _substituted!

Substituents with the designation "cycloalkyl" are preferably C ₄ -C ₈ cycloalkyl, in particular C ₅ to C ₆ cycloalkyl, which may be replaced by halogen, such as chlorine, bromine or fluorine, hydroxy, cyano and / or C ₁ -C ₆ Alkyl are substituted,

Substituents with the designation "alkenyl" preferably denote C ₆ -C ₈ alkenyl, which are optionally substituted by halogen, such as chlorine, bromine or fluorine, hydroxy, cyano and / or dC ₆ alkyl, in particular alkenyl means allyl,

are the substituents with the designation "aryl" C ₆ -do-aryl, preferably phenyl or naphthyl, which are optionally substituted by halogen, such as F, Cl,

Hydroxy, dC ₆ alkyl, dC ₆ alkoxy, NO ₂ and / or CN are substituted.

4. Optical data carrier according spoke 1, characterized in that the co-phthalocyanine corresponds to the formula Ic Optical data carrier according spoke 1, characterized in that at least one Co-phthalocyanine of the formula I is contained in the information layer which can be written on with light, in which

R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another for chlorine, fluorine, bromine, iodine,

Cyano, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert. Butyl, pentyl, tert. Amyl, hydroxyethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, phenyl, p-tert-butylphenyl, p-methoxyphenyl, isopropylphenyl, trifluoromethylphenyl, naphthyl, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, tert. Butylamino, pentylamino, tert. Amylamino, Benzylamino, Methylphenylhexylamino, Hydroxyethylamino, Aminoethylamino, 3-Dimethylaminopropylamino, 3-Diethylamino-propylamino, Diethylaminoethylamino, Dibutylaminpropylamino, Morpholinopropylamino, Piperidinopropylamino, Methylrolidinethylamino, Pyrrolidinomethyl Mefhoxypropylamino, ethoxypropylamino, methoxyethoxypropylamino, 3- (2-ethylhexyloxy) propylamino, isopropyloxypropylamino, dimethylamino, diethylamino, diethanolamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di-tert. butylamino, dipentylamino, di-tert. amylamino, bis (2-ethylhexyl) amino, bis (aminopropyl) amino, bis (aminoethyl) amino, bis (3-dimethylamino propyl) amino, bis (3-diethylaminopropyl) amino, bis (diethylaminoethyl) amino, bis (dibutylamine propyl) amino, di (morpholinopropyl) amino, di (piperidinopropyl) amino, di (pyrrolidinopropyl) amino, di (pyrrolidonopropyl) amino, bis (3 - (methyl-hydroxyethylamino) propyl) amino, dimethoxyethylamino, diethoxyethylamino, dimeth oxypropylamino, diethoxypropylamino, di (methoxyethoxyefhyl) amino, di (methoxyethoxypropyl) amino, bis (3- (2-ethylhexyloxy) propyl) amino, di (isopropyloxyisopropyl) amino, methoxy, ethoxy, Propyloxy, isopropyloxy, butyloxy, isobutyloxy, tert-butyloxy, pentyloxy, tert. Amyloxy, methoxyethoxy, ethoxyethoxy, methoxypropyloxy, ethoxypropyloxy, methoxyethoxypropyloxy, 3- (2-ethylhexyloxy) propyloxy, phenyl, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, tert.-butylthio, pentylthio Methoxyphenyl, trifluoromethylphenyl, naphthyl, CO R ¹² , CONR ⁷ R ⁸ , NH-COR ¹² , SO ₃ H, SO ₂ NR ⁷ R ⁸ or for a radical of the formula

or

wherein

for - CO—. -CH ₂ -O-, -C ₂ H ₄ -0-, -CH (CH ₃ ) O- II O

(B); m

- C - OCH— or ^~ G - OC ₂ H ₄ ,

O O

where the asterisk (*) indicates the connection with the 5-ring,

w, x, y and z are independently 0 to 4 and w + x + y + z <12,

Kat ⁺ for lithium cation, sodium cation, potassium cation, tetrabutylammonium cation, tetrapropylammonium cation, tetraethylammonium cation, tetramethylammonium cation, triethyloxonium cation, triphe- nylcarbonic cation, diphenyliodonium cation, N-ethylpyridinium cation or ferrocene cation,

7 rows

NR R for amino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, tert. Butylamino, pentylamino, tert.

Amylamino, benzylamino, methylphenylhexylamino, 2-ethyl-1-hexylamino, hydroxyethylamino, aminopropylamino, aminoethylamino, 3-dimethylaminopropylamino, 3-diethylaminopropylamino, morpholinopropylamino, piperidinopropylamino, pyrrolidinopropylamino-hydroxylamino, hydroxylamino, pyrrolidino pylamino, methoxyethylamino, ethoxyethylamino, methoxypropylamino, ethoxypropylamino, methoxyethoxypropylamino, 3- (2-ethylhexyloxy) propylamino, isopropyloxyisopropylamino, dimethylamino, diethylamino, dipropylamino, diisopropylamino, di-butylamino, diibutylamino. butylamino, dipentylamino, di-tert. amylamino, bis (2-ethylhexyl) amino, dihydroxyethylamino, bis (aminopropyl) amino, bis (aminoethyl) amino, bis (3-dimethylaminopropyl) amino, bis (3-diethylaminopropyl) amino, di (morpholinopropyl) amino, di (piperidinopropyl) amino, di (pyrrolidinopropyl) amino, di (pyrrolidonopropyl) amino, bis (3 - (methyl-hydroxyethylamino) propyl) amino,

Dimethoxyethylamino, diethoxyethylamino, dimethoxypropylamino, diethoxypropylamino, di (methoxyethoxypropyl) amino, bis (3- (2-ethylhexyloxy) propyl) amino, di (isopropyloxyisoρropyl) amino,

Anilino, p-toluidino, p-tert. Butylanilino, p-anisidino, iso-

7 R are propylanilino, naphthylamino or NR R are, in particular pyrrolidino, piperidino, piperazino or morpholino,

R12 for hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, tert-amyl, phenyl, p-tert. -Butylphenyl, p-

Methoxyphenyl, isopropylphenyl, p-trifluoromethylphenyl, cyano- phenyl, naphthyl, 4-pyridinyl, 2-pyridinyl, 2-quinolinyl, 2-pyrrolyl or 2-indolyl,

in which

the alkyl, alkoxy, aryl and heterocyclic radicals, optionally further radicals such as alkyl, halogen, hydroxy, hydroxyalkyl, amino, alkylamino, dialkylamino, nitro, cyano, CO-NH, alkoxy, alkoxycarbonyl, morpholino, piperidino, pyrrolidino, pyrrolidono, Can carry trialkylsilyl, trialkylsiloxy or phenyl, the alkyl and / or alkoxy radicals can be saturated, unsaturated, straight-chain or branched, the alkyl radicals can be partially or perhalogenated, the alkyl and / or alkoxy radicals can be ethoxylated or propoxylated or silylated, neighboring ones Alkyl and / or alkoxy radicals on aryl or heterocyclic radicals can together form a three- or four-membered bridge.

6. Optical data carrier according to claim 1, characterized in that the information layer which can be written on with light additionally contains a metal-containing or metal-free phthalocyanine different from (I), the central atom being selected from the groups: Si, Zn, Al, Cu, Pd, Pt , Au and

Ag, especially Cu or Pd.

7. Optical data carrier with a described information layer, obtainable in that the optical data carrier according to spoke 1 was written with light with a wavelength of 700 to 830 nm, preferably from 750 to 800 nm.

8. A process for producing the optical data carrier according to claim 1, characterized in that the information layer which can be written on by light is coated onto a transparent substrate by coating with the co-phthalocyanine of the formula I, if appropriate in combination with suitable binders, Additives and suitable solvents, and optionally provided with a reflection layer, optionally further intermediate layers and optionally a protective layer.

9. Use of Co-phthalocyanines of the formula (I) as light-absorbing compounds in the light-writable information layer of optical data memories.

10. Compounds of formula Ic

wherein

Halogen represents chlorine, bromine or fluorine,

Alkoxy stands for dC ₈ -alkoxy, which is optionally substituted, and a denotes a number from 0 to 4, b a number from 0 to 10, c a number from 0 to 8, the sum of a, b and c <12 is and

R ¹ , R ² , R ⁷ , R ⁸ , Kat ⁺ and CoPc have the above meaning.

11. A method for producing the connection according to spoke 10, characterized

7 R characterized in that one substituted with sulfonamide groups of the formula SO ₂ NR R, where R ⁷ and R ^{8 have} the meaning given above, and optionally halogen and / or alkoxy-substituted Co-phthalocyanine and oxidized with KatCN, KatSCN, Katalkoxy or catalkylthio.

2. Containing mixtures

a) a Co (III) phthalocyanine, whose Co metal center bears two oxial substituents R ¹ and R ² , which independently of one another represent CN, SCN, alkoxy or alkylthio and

b) a phthalocyanine different from a), in particular from Co-free phthalocyanine.