Patent Application
20060276651
The present invention relates to metal complexes of formula (I), to recording media comprising the metal complexes and to the use of the metal complexes in the production of optical recording media. Use of the metal complexes of formula (I) In combination with, for example, oxonol dyes results, surprisingly, in a comparatively weak tendency of the oxonol dyes to aggregate in the solid state so that the absorption curve remains advantageously narrow even in the solid state, as a result of which recording media having high reflectivity as well as high sensitivity and good playback characteristics in the desired spectral region are made available.
Lacroix et al., describe in Chem. Mater. 8 (1996), 541 to 545 the synthesis and second order nonlinear optical properties of the following metal complexes:
JP60-44390A discloses colorless metal complexes (stabilizer), which do not contribute to the refractive index at 658 nm.
WO03/042989, which forms state of the art according to Article 54(3) EPC, discloses compositions comprising at least one oxonol dye and at least one metal complex and recording media comprising the compositions. The following metal complex is explicitly mentioned in WO03/042989.
The present invention relates to metal complexes of the following formula
wherein
Me is a transition metal of Sub-Group 7, 8, 9, 10, 11 or 12, preferably 9, 10 or 11,
D1 and D2 are each independently of the other a carbocyclic or heterocylic ring or ring system, which may be unsubstituted or substituted by one or more groups R5 and R6,
R1 and R4 are each independently of the other a hydrogen atom, a perfluoroalkyl radical, an unsubstituted or substituted alkyl radical, an aryl radical or an aralkyl radical,
R2 and R3 are a cyano group, or
R2 and R3 together form a five to seven membered heterocylic ring, or
R2 and R3 together form an aromatic carbocyclic ring, which is substituted by at least one electron accepting substituent, or which is substituted by at least one electron donating substituent,
R5 and R6 being a halogen atom, such as fluorine, chlorine or bromine, a group —NR8R9, a group —SO2NR8R9, wherein
R8 and R9are each independently of the other a hydrogen atom, an alkyl group, a C1- C24alkylcarbonyl group, an alkyl group which is substituted by E and/or interrupted by D, a C8-24aryl-carbonyl radical or C7-24aralkyl-carbonyl radical, an aryl group, or an aralkyl group, or R8 and R9together form a five- to seven-membered heterocylic ring, which optionally can be interrupted by D,
a nitro group, a cyano group, a hydroxy group, an alkyl group, an alkyl group which is substituted by E and/or interrupted by D, an alkoxy group which is substituted by E and/or interrupted by D, an aryloxy group, an aralkyloxy group, an alkylthio group which is substituted by E and/or interrupted by D, an arylthio group, an aralkylthio group, an acyl radical, a phenyl group, an ester group, such as a phosphonic acid, phosphoric acid or carboxylic acid ester group, a carboxamide group, a sulfamide group, an ammonium group, a carboxylic acid, sulfonic acid, phosphonic acid or phosphoric acid group or a salt thereof, wherein at least one of the substituents R5 and at least one of the substituents R8 is an electron donating group, if R2 and R3 together form an aromatic carbocyclic ring, which is substituted by at least one electron accepting substituent, or at least one of the substituents R5 and at least one of the substituents R8 is an electron accepting group, if R2 and R3 together form an aromatic carbocyclic ring, which is substituted by at least one electron donating substituent, wherein
D is —CO—; —S—; —SO—; —SO2—; —O—; —NR10; and
E is —OR11; —SR11; —NR12R13; —COR14; —COOR15; —CONR12R13; —CN; or halogen; wherein
R10, R12 and R13 are each independently of the other a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group,
R11 is a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group,
R14 is an alkyl group, an aryl group, or an aralkyl group, and
R15 is a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, with the proviso that the following compounds are excluded:
The use of the metal complexes of formula (I) in combination with, for example, oxonol dyes results, surprisingly, in a comparatively weak tendency of the oxonol dyes to aggregate in the solid state so that the absorption curve remains advantageously narrow even in the solid state, as a result of which recording media having high reflectivity as well as high sensitivity and good playback characteristics in the desired spectral ranged are made available. In addition, the metal complexes of formula (I) do not only function as stabilizer, but also as absorber, i.e. contribute to the refractive index at 658 nm.
In accordance with the invention, an alkyl radical is understood to be a straight-chain or branched C1-24alkyl radical, preferably C1-8alkyl radical, which may be unsubstituted or substituted, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl or octyl, ethoxycarbonylethyl, cyanoethyl, diethylamino-ethyl, chloroethyl, acetoxyethyl, and partially or fully halogenated C1-8-alkyl radicals.
Examples of a halogen atom are fluorine, chlorine or bromine.
In accordance with the invention, a perfluoroalkyl radical is understood to be a straight-chain or branched C1-C24perfluoroalkyl, such as for example —CF3, —CF2CF3, —CF2CF2CF3 —CF(CF3)2, —(CF2)3CF3, and —C(CF3)3.
In accordance with the invention, an alkoxy radical is understood to be a straight-chain or branched C1-24alkoxy radical, that is to say O—C1-24alkyl, preferably O—C1-8alkyl, such as, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-otyloxy, 1,1,3,3-tetramethylbutoxy or 2-ethylhexyloxy.
In accordance with the invention, an aromatic carbocyclic ring or an aryl radical is understood to be a C6-24aryl radical, preferably C6-12aryl radical, which may be unsubstituted or substituted, such as, for example, phenyl, 4methylphenyl, 4methoxyphenyl, naphthyl, biphenylyl, 2-fluorenyl, phenanthryl, anthryl or terphenylyl.
In accordance with the invention, an aralkyl radical is understood to be a C7-24aralkyl radical, preferably C7-12aralkyl radical, which may be unsubstituted or substituted, such as, for example, benzyl, 2-benzyl-2-propyl, β-phenethyl, 9-fluorenyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω-phenyl-octyl, ω-phenyl-dodecyl or 3-methyl-5-(1′, 1′,3′,3′-tetramethyl-butyl)-benzyl.
As described above, the aforementioned radicals may be substituted by E and/or, if desired, interrupted by D. Interruptions are of course possible only in the case of radicals containing at least 2 carbon atoms connected to one another by single bonds; C6-C18aryl is not interrupted; interrupted arylalkyl or alkylaryl contains the unit D in the alkyl moiety. C1-C18alkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (CH2CH2O)n—Rx, where n is a number from the range 1-9 and Rx is H or C1-C10alkyl or C2-C10alkanoyl (e.g. CO—CH(C2H5)C4H9), CH2—CH(ORy′)—CH2—O—Ry, where Ry is C1-C18alkyl, C5-C12cycloalkyl, phenyl, C7-C15phenylalkyl, and Ry′ embraces the same definitions as Ry or is H; C1-C8alkylene-COO—Rz, e.g. CH2COORz. CH(CH3)COORz, C(CH3)2COORz, where Rz is H, C1-C18alkyl, (CH2CH2O)1-9—Rx, and Rx embraces the definitions indicated above; such as, for example, CH2CH2—O—CO—CH═CH2−; CH2CH(OH)CH2—O—CO—C(CH3)═CH2.
—(CH2)2OCH3, —(CH2CH2O)2CH2—CH3, —CH2—O—CH3, —CH2CH2—O—CH2CH3, —CH2CH2CH2—O—CH(CH3)2, —[CH2CH2O]Y1—CH3 wherein Y1=1-3, —CH2CH(CH3)—O—CH2—CH2CH3 and —CH2—CH(CH3)—O—CH2—CH3.
In accordance with the present invention, the expression “a salt thereof” means the combination of an anion, such as —O−, —COO− etc., and a metal cation, such as a sodium, potassium, lithium, calcium, a metal complex cation, or an ammonium cation.
In accordance with the present invention, the expression “ester group” encompasses carboxylic acid esters —C(O)OR101, phosphonic acid esters —P(O)OR102OR103 and phosphoric acid esters —OP(O)OR102OR103, wherein R101 is an unsubstituted or substituted alkyl, aryl or aralkyl radical or is an alkyl radical which is interrupted one or more times by —O— or by —S— and which is unsubstituted or substituted by a hydroxy group, R102 and R103 are a hydrogen atom, an unsubstituted or substituted alkyl, aryl or aralkyl radical or are an alkyl radical which is interrupted one or more times by —O— or by —S— and which is unsubstituted or substituted by a hydroxy group, such as, for example, —C(O)OCH2CH2OCH2CH2OCH(CH3)2 and —C(O)OCH2CH2OCH2CH2OH.
The expression “sulfamide group” indicates a group —SO2NR8R9 wherein R8 and R9 are as defined above.
Examples of an amino group —NR8R9 are amino, methylamino, ethylamino, dimethylamino, diethylamino, phenylamino, methoxycarbonylamino, acetylamino, ethylcarbonylamino, cyclohexylcarbonylamino, benzoylamino or chloroacetylamino, morpholino, piperidino or pyrrolidino.
A C1-24alkoxycarbonyl radical is understood to be a straight-chain or branched.
C(O)O—C1-24alkyl radical, preferably C(O)O—C1-8alkyl radical, such as, for example, methoxy-, ethoxy-, n-propoxy-, isopropoxy-, n-butoxy-, sec-butoxy-, isobutoxy- or tertbutoxy-carbonyl.
Examples of a C6-24aryl- or C7-24aralkyl-carbonyl radical are a phenylcarbonyl group and a benzylcarbonyl group, respectively.
In accordance with the invention, an “ammonium group” is understood to be a group —NR106R107R108 wherein R106, R107 and R108 are a hydrogen atom or an unsubstituted or substituted alkyl, aryl or aralkyl radical.
Examples of an (aromatic) heterocylic ring (or ring system) are heterocycles having from 3 to 12 carbon atoms, for example 2-thienyl, 2-furyl, 1-pyrazolyl, 2-pyridyl, 2-thiazolyl, 2-oxazolyl, 2-imidazolyl, isothiazolyl, triazolyl or any other ring system consisting of thiophene, furan, pyrazole, thiazole, oxazole, imidazole, isothiazole, thiadiazole, triazole, pyridine or benzene rings unsubstituted or substituted by from 1 to 6 ethyl, methyl, ethylene and/or methylene substituents.
Examples of a saturated heterocylic ring are heterocycloalkanes having from 4 to 6 carbon atoms which have one or two hetero atom(s) selected from nitrogen, oxygen and sulfur, for example tetrahydrofuran, tetrahydropyran, 1,4-dioxane, thiolane, piperidine, γ-butyrolactone, 5-aminopentanoic acid lactam or pyrrolidine.
Examples of an aromatic carbocyclic ring or ring system are aromatic rings having from 6 to 24 carbon atoms, such as phenyl or naphthyl.
The definitions given hereinbefore for the radicals in formula (I) apply to the entire invention, unless otherwise specified.
If R2 and R3 together form a five to seven membered heterocylic ring, metal complexes represented by formula
are preferred, wherein X is >O, >S, >S═O, or >S)2, and R1, R4, Me, D1, D2, R5 and R6 are defined as above.
In one aspect, the present invention relates to metal complexes of formula I, wherein at least one of the substituents R5 and at least one of the substituents R6 is an electron accepting group and R2 and R3 together form an aromatic carbocyclic ring, which is substituted by at least one electron donating substituent. An example of such a compound is given below:
wherein
A2 and A3 are an electron donating substituent, especially a hydroxy group, an C1-C18alkoxy group, an C8-C24aryloxy group, an C7-C24aralkyloxy group, or a group —NR8R9,
R53 and R63 are an electron accepting substituent, especially —NO2, a halogen atom, especially a chlorine or a bromine atom, a group —SO2—NR8R9, wherein R1, R4, R8 and R9 are defined as above.
In a further more preferred aspect, the present invention relates to metal complexes of formula I, especially III, wherein at least one of the substituents R5 and at least one of the substituents R6 is an electron donating group and R2 and R3 together form an aromatic carbocyclic ring, which is substituted by at least one electron accepting substituent.
Me is preferably a transition metal of Sub-Group 9, 10 or 11, especially Co3+, very especially Cu2+, Ni2+, Pd2+, Pt2+, Co2+, or Zn2+, R1 and R4 preferably are a hydrogen atom, a C1-4perfluoroalkyl radical, especially —CF3 or —C2F5, or a C1-4alkyl radical, especially a methyl or ethyl group.
R2 and R3 are preferably a cyano group, or a group of formula
(N and Me are added for clarity reasons; the formed ring is highlighted in boldface), wherein X is >O, >S, >S═O, or >SO2, A1 and A4 are each independently of the other a hydrogen atom, an alkoxy radical, an alkyl radical, an alkyl radical which is interrupted one or more times by —O— or by —S—, at least one of A2 and A3, preferably A2 and A3, are an electron accepting substituent, especially —NO2, a halogen atom, especially a chlorine or a bromine atom, a group —SO2—NR8R9 and the other is a hydrogen atom.
Examples of groups D1 and D2 are:
wherein X1, X2, X3 are a group ═CH—, —O—, —S—, or —NR200—, wherein R200 is a hydrogen atom, or an alkyl group. R55 is a hydrogen atom, or a C1-C18alkyl group, R56, R57, R58 and R59 are each independently of the other a hydrogen atom, a C1-C18alkyl group, or a C1-C18alkyl group, which is interrupted by one or more oxygen atoms, X4 and X5 are each independently of the other a sulfur; or oxygen atom and R5 is as defined above.
Preferred groups D1 and D2 have the following structures:
wherein
R53 is OH, —OC1-C24alkyl, such as CH3O—, C2H5O—, C4H9O—, C8H17O—, C12H25O—,3,5,5-trimethylhexyloxy-, or C18H37O—, RxO—[CH2CH2—O—]x wherein Rx is a methyl group and x is 1, or Rx is an ethyl group and x is 2, or Rx is a butyl group and x is 2, or Rx is a methyl group and x is 3, —NR8R9, wherein R8 and R9 are C1-C24alkyl, or (CH2)y—OH, wherein y is 1 to 24; or
The metal complexes of formula (I) are coloured and make a contribution to the refractive index. The present invention accordingly relates also to the use, in the optical storage of information, of a metal complex of formula (I).
According to the present invention metal complexes having the following formula
wherein
Me is Cu2+, Ni2+, Pd2+, Pt2+, Co2+, Co3+ or Zn2+,
X is >O, >S, >S═O, or >SO2,
A1, A4, A5 and A6 are each independently of the other a hydrogen atom, an alkoxy radical, an alkyl radical, an alkyl radical which is interrupted one or more times by —O— or by —S—,
at least one of A2 and A3, preferably A2 and A3, are an electron accepting substituent, especially —NO2, a halogen atom, especially a chlorine or a bromine atom, a group —SO2— NR8R9 and the other is a hydrogen atom,
R1 and R4 are defined as in claim 1,
R51, R52, R54, R61, R62 and R64 are each independently of the other a hydrogen atom, or an C1-C18alkyl group,
R53 and R63 are each independently of the other a hydroxy group, an C1-C18alkoxy group, an C8-C24aryloxy group, an C7-C24aralkyloxy group, or a group —NR8R9, wherein R8 and R9 are each independently of the other a hydrogen atom, an C1-C18alkyl group, an C1-C18alkyl group which is substituted by E and/or interrupted by D, an C6-C24aryl group, an C7-C24aralkyl group, wherein D and E are as defined in claim 1, or a salt thereof, or
R53 and R52, R53 and R54, R63 and R62, and/or R63 and R64 are each independently of the other
wherein A10, A10′, A11, A11′, A12 and A12′ are each independently of the other a hydrogen atom, or a C1-C6alkyl group, or
A10′ and A11′ together, form a double bond, and
A13 is a hydrogen atom or a C1-C8alkyl group, or
R53 and R52 and R54, and/or R63 and R62 and R64 are
wherein A14, A14′, A15, A15′, A17, A17′, A18, A18′, A19, A19′, A20 and A20′ are each independently of the other a hydrogen atom, or a C1-C8alkyl group,
R55 and R65 are each independently of the other a hydrogen atom, or a C1-C18alkyl group,
R58, R57, R58, R59, R66, R67, R68 and R69 are each independently of the other a hydrogen atom, a C1-C18alkyl group, or a C1-C18alkyl group, which is interrupted by one or more oxygen atoms, and
X4 and X5 are each independently of the other a sulfur, or oxygen atom.
In formula II, III, or III the substituents have the following preferred meanings:
Me is Co3+, especially Cu2+, Ni2+, Pd2+, Pt2+, Co2+, or Zn2+,
X is >O, >S, >S═O, or >SO2,
A1, A4, A5 and A6 are a hydrogen atom,
A2 and A3 are —NO2,
R1 and R4 are each independently of the other a hydrogen atom, a perfluoro C1-C8alkyl radical or a C1-C6alkyl radical,
R51, R52, R54, R61, R62 and R64 are a hydrogen atom, or
R51 and R52 together, and/or R61 and R62 together, form an unsubstituted or substituted phenyl ring,
R53 and R63 are each independently of the other a hydroxy group, an C1-C18alkoxy group, a group —NR8R9, wherein R8 and R9 are each independently of the other a hydrogen atom, an C1-C18alkyl group, a group —(CH2)n—OH, a group —(CH2CH2O)R16, where n is a number from the range 1-9 and R16 is H or C1-C10alkyl, or a salt thereof, or
R53 and R52, R53 and R54, R63 and R62, and/or R63 and R64are each independently of the other
wherein A10, A10′, A11, A11′, A12 and A12′ are each independently of the other a hydrogen atom, or a C1-C8alkyl group, or
A10′ and A11′ together, form a double bond,
A13 is a hydrogen atom or a C1-C6alkyl group, or
R53 and R52 and R54, and/or R63 and R62 and R64 are
wherein A14, A14′, A15, A15′, A17, A17′, A18, A18′, A19, A19′, A20 and A20′ are each independently of the other a hydrogen atom, or a C1-C8alkyl group.
More preferred are metal complexes having the formula
wherein X1 is a group —O—, —S—, or —NR200—, wherein R200 is a hydrogen atom, or an alkyl group, R55 and R65 are each independently of the other a hydrogen atom, or a C1-C18alkyl group,
R56, R57, R58, R59, R66, R67, R68 and R69 are each independently of the other a hydrogen atom,
a C1-C18alkyl group, or a C1-C18alkyl group, which is interrupted by one or more oxygen atoms,
wherein
Me is Co3+, especially Cu2+, Ni2+, Pd2+, Pt2+, Co2+, or Zn2+,
R1 is hydrogen and R4 is C1-C4perfluoroalkyl,
R52, R54, R62 and R64 are a hydrogen atom, or
R53 and R63 are each independently of the other a hydroxy group, an C1-C18alkoxy group, a group —NR8R9, wherein R8 and R9 are each independently of the other a hydrogen atom, an C1-C18alkyl group, a group —(CH2)n—OH, a group (CH2CH2O)n—R16, where n is a number from the range 1-9 and R18 is H or C1-C10alkyl, or a salt thereof, or
R53 and R52, R53 and R54, R63 and R62, and/or R63 and R64 are each independently of the other a group of formula
wherein
A13 a hydrogen atom or a C1-C8alkyl group, or
R53 and R52 and R54, and/or R63 and R62 and R64 are a group of formula
Most preferred are the metal complexes listed below:
The metal complexes described hereinbefore can be prepared in accordance with, or in analogy to, methods described in WO03/042989, EP-A-200 843, EP-A-162 811, EP-A-362 139 and EP-A-436 470.
In a further aspect, the present invention relates to compositions, comprising
(a) a metal complex according to the present invention, including
(b) a dye.
Further chromophores (dyes) that can be used in the recording layer in addition to the compounds of formula I, II, III or IV are, for example, cyanines and cyanine metal complexes (U.S. Pat. No. 5,958,650), styryl compounds (U.S. Pat. No. 6,103,331), oxonol dyes (EP-A-833 314, U.S. Pat. No. 6,225,024), azo dyes and azo metal complexes (JP-A-11/028865), phthalocyanines (EP-A-232 427, EP-A-337 209, EP-A-373 643, EP-A-463 550, EP-A-492 508, EP-A-509 423, EP-A-511 590, EP-A-513 370, EP-A-514 799, EP-A-518 213, EP-A-519 419, EP-A-519 423, EP-A-575 816, EP-A-600 427, EP-A-676 751, EP-A-712 904, WO-98/14520, WO-00/09522, CH-693/01), porphyrins and azaporphyrins (EP-A-822 546, U.S. Pat. No. 5,998,093), dipyrromethene dyes and metal chelate compounds thereof (EP-A-822 544, EP-A-903 733), xanthene dyes and metal complex salts thereof (U.S. Pat. No. 5,851,621) or quadratic acid compounds (EP-A-568 877 ), or oxazines, dioxazines, diazastyryls, formmazans, anthraquinones or phenothiazines; as well as the rhodamines and rhodamine/quencher mixtures described in WO03/098617, especially examples 1 to 75 of WO03/098617, and WO03/098618, especially examples 1 to 48 of WO03/098618.
Examples of suitable dyes are non-charged diaza-styrylium chromophores, where quaternization is achieved by complexation of the heterocyclic nitrogen by a heavy metal cation instead of an alkyl group, especially
or a mixture of the above chromophore with the below quenchers or a mixture of the below quenchers,
squarylium dyes and optionally a 1:2 nickel formazane dye as a quencher, especially
SQ=SQUARYLIUM CHROMOPHORE
an anionic oxonol dye (or mixture of oxonol dyes) is combined with a cationic quencher (paraquat type), especially
dipyrromethene chromophores, especially
cyanine dyes, especially
or cyanine dyes in combination with quenchers of the quinone-diammonium (Kayasorb) type or metal azo complexes, especially
or cyanine dyes combined with an azo cobalt complex (in part as ion-pair), especially
or mixtures of cyanine dyes, especially
Preferably, the compositions comprise a metal complex of formula I, II, III or IV, wherein Me is Ni2+, Cu2+, or Co2+, and an oxonol dye of formula
described in WO03/042989,
wherein D1, D2, B1 and B2 are in each case a substituent; Y3 and Z1 are in each case a group of atoms necessary for the formation of a carbocyclic or heterocylic ring; G1 and G2 are in each case a group of atoms necessary for the formation of a chain having conjugated double bonds; Y1 is ═O, ═NR109 or ═C(CN)2, R109 being a substituent; Y2 is —O, —NR109 or —C(CN)2, R109 being a substituent; L is a methine group, which may be substituted, or a group by means of which a polymethine group is completed, it being possible for 3, 5 or 7 methine groups to be connected in order to form a chain having conjugated double bonds, which chain may be substituted, x and y are 0 or 1, Mk+ is an organic or inorganic cation, and k is an integer from 1 to 10.
Oxonois having formula
wherein R130, R131, R132, R133, R134, R135 and R136, p, q and r are as defined below and R141 and R141′ are each independently of the other a hydrogen atom, an unsubstituted or substituted C1-12alkyl radical, C5-7cycloalkyl, C6-12aryl, C7-12aralkyl radical or heterocylic radical,
R142 and R142′ are each independently of the other a hydrogen atom, a cyano group, a group C(O)OR146, C(O)NR146R147 or C(O)R147, an unsubstituted or substituted C1-12alkyl radical, C5-7Cycloalkyl, C6-12aryl, C7-12aralkyl radical or heterocylic radical, R148 and R147 being an unsubstituted or substituted C1-12alkyl radical, C5-7cycloalkyl, C6-12aryl, C7-12aralkyl radical or heterocyclic radical, or R146 and R147, together with the nitrogen atom to which they are bonded, forming a five- or six-membered ring, and
R143 and R143′ are each independently of the other a hydrogen atom, a carboxylic acid group or an alkyl radical; especially oxonol dyes of the following general formula
wherein
R141 and R141′ are each independently of the other a hydrogen atom, a C1-4alkyl radical, such as methyl or ethyl, or a perfluoro-C1-4alkyl radical, such as trifluoromethyl, a hydroxy-C1-4alkyl radical, or a C1-8alkyl radical interrupted one or more times by —O—, such as CH2CH2CH2—O—CH(CH3)2, a C6-10aryl radical, such as phenyl, or a C7-12aralkyl radical such as benzyl,
R142 and R142′ are each independently of the other a hydrogen atom, a cyano or carboxamide group.
R143 and R143′ are each independently of the other a hydrogen atom, a carboxylic acid group or a salt thereof or a C1-4alkyl radical,
R144 and R144′ are each independently of the other a hydrogen atom, a C1-4alkyl radical, a C6-12aryl or C7-12aralkyl radical, or
R144 and R144′ together form a five-membered or six-membered ring, such as a cyclohexenyl or cyclopentenyl ring, and
R145 is a hydrogen atom, a halogen atom, especially a chlorine atom, an unsubstituted or C1-4alkyl- or C1-4alkoxy-substituted C6-12aryl radical, such as phenyl or p-methylphenyl, or C7-12aralkyl radical, such as benzyl, or
oxonol dyes of the following general formula
wherein Ra, Rb, Ra′ and Rb′ are each independently of the other a hydrogen atom, a C1-8alkyl radical, in particular a C1-4alkyl radical, a hydroxy-C1-8alkyl radical, a C1-8alkenyl radical, such as —CH2—CH═CH2, an unsubstituted or C1-4alkyl- or C1-4alkoxy-substituted C6-12aryl, such as phenyl, or C7-12aralkyl radical, such as benzyl,
R144 and R144′ are each independently of the other a hydrogen atom, a C1-4alkyl radical, a C6-12aryl or C7-12aralkyl radical, or
R144 and R144′ together form a five-membered or six-membered ring, such as a cyclohexenyl or cyclopentenyl ring, and
R145 is a hydrogen atom, a halogen atom, especially a chlorine atom, an unsubstituted or C1-4alkyl- or C1-4alkoxy-substituted C6-12aryl radical, such as phenyl or p-methylphenyl, or C7-12aralkyl radical, such as benzyl.
Special preference is given to ion pairs of a metal complex of formula I, II, III or IV, wherein Me is Co2+, Ni2+ or Cu2+ and an oxonol dye of formula
described in
U.S. Pat. No 6,225,024, wherein R121, R122, R123 and R124 are each independently of the others a hydrogen atom, a substituted or unsubstituted alkyl radical, a substituted or unsubstituted aryl radical, a substituted or unsubstituted aralkyl radical or a substituted or unsubstituted heterocylic radical, L21, L22 and L23 are each independently of the others a methine group which may have a substituent, m is an integer 0, 1, 2 or 3, provided that when m is 2 or 3 the groups L22 and L23 may be the same or different, k and Mk+ are as defined above.
Special preference is given to oxonol compounds of formula
wherein R121, R122, R123 and R124 are each independently of the others a hydrogen atom, a C1-8alkyl radical, a C1-8perfluoroalkyl radical, such as trifluoromethyl, a C1-8alkenyl radical, a C1-4alkoxy-C1-4alkyl radical, a hydroxy-C1-4alkyl radical, a R8R9N—C1-4alkyl radical, R8 and R9 being as defined hereinbefore, a C6-10aryl radical, such as phenyl, a C7-10aralkyl radical, such as benzyl, or a heterocyclic ring having from 2 to 10 carbon atoms, or
R121and R122 together, and/or R123 and R124 together, form an unsubstituted or substituted carbocyclic ring, preferably having from 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, cycloheptyl or cyclooctyl, or an unsubstituted or substituted heterocylic ring, preferably having from 2 to 10 carbon atoms, such as piperidyl, chromanyl or morpholyl, which rings may be unsubstituted or substituted by one or more C1-4alkyl and/or C1-4alkoxy radicals,
R130, R131, R132, R133, R134, R135 and R136 are each independently of the others a hydrogen atom, a halogen atom, such as chlorine or bromine, a C1-8-alkyl radical, a C1-8perfluoroalkyl radical, such as trifluoromethyl, a C6-10aryl radical, such as phenyl, a C7-10aralkyl radical, such as benzyl, or a heterocylic ring having from 2 to 10 carbon atoms, or
two substituents R130, R131, R132, R133, R134, R135 and R136, which are located in 1,3-positions relative to one another, together form an unsubstituted or substituted carbocyclic ring having 5 or 6 carbon atoms, such as cyclohexenyl or cyclopentenyl, which may be unsubstituted or substituted by one or more C1-4alkyl and/or C1-4alkoxy radicals, and p, q and r are 0 or 1.
If Me is Cu2+, Ni2+, Pd2+, Pt2+, Co2+, or Zn2+, i.e. the metal complex is neutral, the oxonols of formula V are used in combination with an organic or inorganic cation. Examples of cations are hydrogen cations, metal cations, such as a sodium, potassium, lithium, calcium, iron and copper ion, a metal complex cation, an ammonium cation, including cationic dyes and a pyridinium cation, an oxonium, sulfonium, phosphonium, selenium and iodonium ion. In accordance with the invention, the cation is generally selected from ammonium cations, and cationic dyes as described in WO03/042989.
A further aspect of the present invention is directed to an optical recording medium comprising a substrate and at least one recording layer, wherein the recording layer comprises a metal complex according to the present invention, including
a composition according to the present invention.
Accordingly, the present invention also relates to the use of a metal complex according to the present invention or a composition according to the present invention in the production of optical recording media.
The recording layer may also comprise, instead of a single oxonol dye, a mixture of such compounds with, for example, 2, 3, 4 or 5 oxonol dyes. The use of mixtures, for example mixtures of isomers or homologues but also mixtures of differing structures, can often result in an increase in solubility and/or a reduction in the tendency to aggregate. Where appropriate, mixtures of ion-pair compounds may have differing anions, differing cations or both differing anions and differing cations.
The oxonol dyes used in accordance with the invention have, in combination with the metal complexes of formula (I), a narrow absorption band whose maximum is located at from 540 to 640 nm or in the range lower than 450 nm. The use of metal complexes of formula (I) results, surprisingly, in a comparatively weak tendency of the oxonol dyes to aggregate in the solid state so that the absorption curve remains advantageously narrow even in the solid state.
The metal complexes or compositions used in accordance with the invention, in the form of a solid film, as used in optical storage media, have, on the longer-wavelength flank of the absorption band, a high refractive index which reaches a peak value of from 2.0 to 3.0 in the range from 600 to 700 nm and more than 1.9 in the range from 390 to 430 nm, so that a medium having high reflectivity as well as high sensitivity and good playback characteristics in the desired spectral range can be achieved.
The substrate, which functions as support for the layers applied thereto, is advantageously semi-transparent (T≧10%) or, preferably, transparent (T≧90%). The support generally has a thickness of from 0.01 to 10 mm, preferably from 0.1 to 5 mm.
The recording layer Is located preferably between the transparent substrate and the reflecting layer. The thickness of the recording layer is from 10 to 1000 nm, preferably from 30 to 300 nm, especially from 60 to 120 nm. The absorption of the recording layer is generally from 0.1 to 1.0 at the absorption maximum. The layer thickness is very especially so selected in dependence upon the respective refractive indices in the non-written state and in the written state at the reading wavelength that, in the non-written state, constructive interference is obtained but, in the written state, destructive interference is obtained, or vice versa.
The reflecting layer, the thickness of which can be from 10 to 150 nm, preferably has high reflectivity (R≧45%, especially R≧60%), coupled with low transparency (T≦10%). In further embodiments, for example in media having a plurality of recording layers, the reflector layer may likewise be semi-transparent, that is to say may have comparatively high transparency (for example T≧50%) and low reflectivity (for example R≦45%).
The uppermost layer, for example the reflective layer or the recording layer, depending upon the layer structure, is advantageously additionally provided with a protective layer having a thickness of generally from 0.1 to 1000 μm, preferably from 0.1 to 50 μm and especially from 0.5 to 15 μm. Such a protective layer can, if desired, serve also as adhesion promoter for a second substrate layer applied thereto, which is preferably from 0.1 to 5 mm thick and consists of the same material as the support substrate.
The reflectivity of the entire recording medium is preferably at least 15%, especially at least 40% (for example 45% for DVD-R).
The main features of the recording layer according to the invention are the very high initial reflectivity in the said wavelength range of the laser diodes, which reflectivity can be modified with especially high sensitivity: the high refractive index; the narrow absorption band in the solid state; the good uniformity of the script width at different pulse durations; the good light-stability; and the good solubility In non-halogenated solvents, especially alcohols.
The use of the metal complexes or compositions according to the Invention results in advantageously homogeneous, amorphous and low-scatter recording layers having a high refractive index, and the absorption edge is surprisingly especially steep even in the solid phase. Further advantages are high light-stability in daylight and under laser radiation of low power density with, at the same time, high sensitivity under laser radiation of high power density, uniform script width, high contrast, and also good thermal stability and storage stability.
At a relatively high recording speed, the results obtained are surprisingly better than with previously known recording media. The marks are more precisely defined relative to the surrounding medium and thermally induced deformations do not occur. The error rate (BLER or Pi Sim 8) and the statistical variations in mark length (jitter) are also low both at normal and at relatively high recording speed, so that error-free recording and playback can be achieved over a large speed range. The advantages are obtained in the entire range from 600 to 700 nm (preferably from 630 to 690 nm), but are especially pronounced at 640-680 nm, more especially at from 650 to 670 nm, very especially at 658±5 nm.
Suitable substrates are, for example, glass, minerals, ceramics and thermosetting or thermoplastic plastics. Preferred supports are glass and homo- or co-polymeric plastics. Suitable plastics are, for example, thermoplastic polycarbonates, polyamides, polyesters, polyacrylates and polymethacrylates, polyurethanes, polyolefins, polyvinyl chloride, polyvinylidene fluoride, polyimides, thermosetting polyesters and epoxy resins. The substrate can be in pure form or may also comprise customary additives, for example UV absorbers or dyes, as proposed, for example, in JP 04/167239 as light-stabilisers for the recording layer. In the latter case it may be advantageous for the dye added to the support substrate to have an absorption maximum hypsochromically shifted relative to the dye of the recording layer by at least 10 nm, preferably by at least 20 nm.
The substrate is advantageously transparent over at least a portion of the range from 600 to 700 nm so that it is permeable to at least 90% of the incident light of the writing or readout wavelength. The substrate has preferably on the coating side a spiral guide groove having a groove depth of from 50 to 500 nm, a groove width of from 0.2 to 0.8 μm and a track spacing between two turns of from 0.4 to 1.6 μm, especially having a groove depth of from 100 to 200 nm, a groove width of 0.3 μm and a spacing between two turns of from 0.6 to 0.8 μm. The compositions according to the invention are therefore suitable especially advantageously for use in DVD media having the currently customary pit width of 0.4 μm and track spacing of 0.74 μm.
For a further increase in stability it is also possible, if desired, to add known stabilisers in customary amounts, such as, for example, a nickel dithiolate described in JP 04/025 493 as light-stabiliser.
If an oxonol dye Is used in combination with a metal complex of formula I, the recording layer comprises an oxonol dye or a mixture of such compounds advantageously in an amount sufficient to have a substantial influence on the refractive index. Such an amount is generally at least 30% by weight, preferably at least 60% by weight, especially at least 80% by weight.
Suitable concentrations of metal complex oompound(s) of formula (I) are generally from 1 to 1000% by weight, preferably from 30 to 60% by weight, based on the oxonol compound(s). The recording media may comprise customary additives, for example film-formers, further customary constituents, such as, for example, other chromophores (for example those having an absorption maximum at from 300 to 1000 nm), UV absorbers and/or other stabilisers, quenchers, such as, for example, fluorescence quenchers, melting-point depressants and decomposition accelerators.
Besides the metal complexes of formula I, further stabilisers or fluorescence quenchers may be used, for example metal complexes of nitrogen- or sulfur-containing enolates, phenolates, bisphenolates, thiolates, bisthiolates or of azo, azomethine or formazan dyes, e.g. ®Irgalan Bordeaux EL (Ciba Spezialitätenchemie AG) or similar compounds, hindered phenols and derivatives thereof (where appropriate also as anions X−), e.g. ®Cibafast AO (Ciba Spezlalitätenchemle AG), hydroxyphenyl-triazoles, -triazines or other UV absorbers, e.g. ®Cibafast W or ®Cibafast P (Ciba Spezialitätenchemie AG) or hindered amines (TEMPO or HALS, also in the form of nitroxides or NOR-HALS, where appropriate also as anions X−). Many such structures are known, some of them also in connection with optical recording media, for example from U.S. Pat. No. 5,219,707, JP-A-06/199045, JP-A-07176169 or JP-A-07/262604.
The recording medium according to the invention, in addition to comprising the compounds of formula (I), may additionally comprise salts, for example ammonium chloride, pentadecylammonium chloride, sodium chloride, sodium sulfate, sodium methyl sulfonate or sodium methyl sulfate, the ions of which may originate, for example, from the components used. The additional salts, if present, may be present preferably in amounts of up to 20% by weight, based on the total weight of the recording layer.
Reflecting materials suitable for the reflective layer include especially metals, which provide good reflection of the laser radiation used for recording and playback, for example the metals of Main Groups III, IV and V and of the Sub-Groups of the Periodic Table of the Elements. Al, In, Sn, Pb, Sb, Bi, Cu, Ag, Au, Zn, Cd, Hg, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb and Lu, and alloys thereof are especially suitable. Special preference is given to a reflective layer of aluminum, silver, copper, gold or an alloy thereof, on account of their high reflectivity and ease of production.
Materials suitable for the protective layer include chiefly plastics, which are applied in a thin layer to the support or to the uppermost layer either directly or with the aid of adhesive layers. It is advantageous to select mechanically and thermally stable plastics having good surface properties, which may be modified further, for example written. The plastics may be thermosetting plastics or thermoplastic plastics. Preference is given to radiation-curable (for example by means of UV radiation) protective layers, which are particularly simple and economical to produce. A wide variety of radiation-curable materials are known. Examples of radiation-curable monomers and oligomers are acrylates and methacrylates of diols, triols and tetrols, polyimides of aromatic tetracarboxylic acids and aromatic diamines having C1-C4alkyl groups in at least two ortho-positions to the amino groups, and oligomers with dialkylmaleimidyl groups, e.g. dimethylmaleimidyl groups.
The recording media according to the invention may have additional layers, for example interference layers. It is also possible to construct recording media having a plurality of (for example two) recording layers. The structure and the use of such materials are known to the person skilled in the art. Preference is given to interference layers that are arranged between the recording layer and the reflecting layer and/or between the recording layer and the substrate and consist of a dielectric material, for example as described in EP-A-353 393 of TiO2, Si3N4, ZnS or silicone resins.
The recording media according to the invention can be produced by processes known per se, it being possible for various methods of coating to be employed depending upon the materials used and their function.
Suitable coating methods are, for example, immersion, pouring, brush-coating, blade-application and spin-coating, as well as vapour-deposition methods carried out under a high vacuum. When, for example, pouring methods are used, solutions in organic solvents are generally employed. Suitable coating methods and solvents are described, for example, in EP-A-401 791.
The recording layer is applied preferably by spin-coating with a dye solution, solvents that have proved satisfactory being especially alcohols, such as, for example, 2-methoxyethanol, n-propanol, isopropanol, isobutanol, n-butanol, amyl alcohol or 3-methyl-1-butanol and mixtures thereof. Ethers (dibutyl ether), ketones (2,6-dimethyl-4-heptanone, 5-methyl-2-hexanone) or saturated or unsaturated hydrocarbons (toluene, xylene) can also be used, for example in the form of mixtures (e.g. dibutyl ether/2,6-dimethylheptanone) or mixed components.
The invention therefore relates also to a method of producing an optical recording medium, wherein a solution of a compound of formula (I) in an organic solvent, especially a non-halogenated organic solvent is applied to a substrate having depressions. The application is preferably carried out by spin-coating.
The application of the metallic reflective layer is preferably effected by sputtering, vapour-deposition in vacuo or by chemical vapour deposition (CVD). The sputtering technique is especially preferred for the application of the metallic reflective layer on account of the high degree of adhesion to the support. Such techniques are known and are described in specialist literature (e.g. J. L. Vossen and W. Kern, “Thin Film Processes”, Academic Press, 1978).
The structure of the recording medium according to the invention is governed primarily by the readout method; known function principles include the measurement of the change in transmission or, preferably, reflection, but it is also known to measure the fluorescence instead of the transmission or reflection.
When the recording medium operates on the basis of a change in reflection, the recording medium may be structured, for example, as follows: transparent support/recording layer (optionally multilayered)/reflective layer and, if expedient, protective layer (not necessarily transparent); or support (not necessarily transparent)/reflective layer/recording layer and, if expedient, transparent protective layer. In the first case, the light is incident from the support side, whereas in the latter case the radiation is incident from the recording layer side or, where applicable, from the protective layer side. In both cases the light detector is located on the same side as the light source. The first-mentioned structure of the recording medium is generally preferred for DVD-R, the latter-mentioned structure (inverse structure) is desirable especially for recording systems in the blue-violet range (DVR; EP-A-822 546 and EP-A-1 103 962).
When the recording medium operates on the principle of a change in light transmission, the following structure, for example, comes into consideration: transparent support/recording layer (optionally multilayered) and, if expedient, transparent protective layer. The light for recording and for readout can be incident either from the support side or from the recording layer side or, where applicable, from the protective layer side, the light detector in this case always being located on the opposite side.
Suitable lasers are those having a wavelength of 600-700 nm, for example commercially available lasers having a wavelength of 602, 612, 633, 635, 647, 650, 658, 670 or 680 nm, especially semiconductor lasers, such as GaAsAl, InGaAlP or GaAs laser diodes having a wavelength especially of about 635, 650 or 658 nm. The recording is generally effected point for point, by modulating the laser in accordance with the mark lengths and focusing its radiation onto the recording layer.
The method according to the invention allows the storage of information with great reliability and stability, distinguished by very good mechanical and thermal stability and by high light-stability and by sharp boundary zones of the pits. Special advantages include the high contrast, the low jitter and the surprisingly high signal/noise ratio, so that problem-free readout is achieved.
The readout of information is carried out according to methods known per so by registering the change in absorption or reflection using laser radiation, for example as described in “CD-Player und R-DAT Recorder” (Claus Biaesch-Wiepke, Vogel Buchverlag, Würzburg 1992).
The information-containing medium according to the invention is especially an optical information material of the WORM type. It can be used, for example, as a playable DVD (digital versatile disk), as storage material for a computer or as an identification and security card or for the production of diffractive optical elements, for example holograms.
The invention accordingly relates also to a method for the optical recording, storage and playback of information, wherein a recording medium according to the invention is used. The recording and the playback advantageously take place in a wavelength range of from 600 to 700 nm.
The compositions according to the invention are, moreover, suitable for the production of printing inks having excellent application properties for various uses such as intaglio/flexo-graphic printing, sheet offset printing and sheet-metal printing, and for the production of colour filters that have an advantageously narrow absorption curve. The invention accordingly relates also to a printing ink or colour filter (optical filter) comprising a composition according to the invention, wherein oxonols are particularly preferred. The invention relates especially to an optical filter comprising a support layer and a filter layer, wherein the filter layer comprises a composition according to the invention. The optical filters can themselves be used for example in electroptical systems such as TV screens, liquid crystal displays, charge coupled devices, plasma displays or electraluminescent displays and the like.
The filter layer contains from 1 to 75% by weight, preferably from 5 to 50% by weight, most preferably from 25 to 40% by weight, of the composition according to the invention, based on the total weight of the filter layer, dispersed in a high-molecular-weight organic material.
The support layer is preferably substantially colourless (T≧95% in the entire visible range from 400 to 700 nm). Further details relating to the production of colour filters and the high molecular-weight materials used in the production of colour filters are described, for example, in High-Technology Applications of Organic Colorants, Peter Gregory, Plenum Press, New York and London 1991, p. 15 to 25, WO01/04215 and WO02/10288. Optical filters having an absorption maximum in the range from 560 to 620 nm are, for example, suitable as very-narrow-band optical filters for plasma displays (see, for example, EP-A-1 124 144).
The printing inks of the invention contain the compositions of the invention judiciously in a concentration of from 0.01 to 40% by weight, preferably from 1 to 25% by weight, with particular preference from 5 to 10% by weight, based on the overall weight of the printing ink, and may be used, for example, for gravure printing, flexographic printing, screen printing, offset printing, or continuous or dropwise inkjet printing on paper, board, metal, wood, leather, plastic or textiles, or else in special applications in accordance with formulations which are general knowledge, for example in publishing, packaging or freight, in logistics, in advertising, in security printing or else in the office sector for ballpoint pens, felt-tip pens, fibre-tip pens, inking pads, ink ribbons or inkjet printer cartridges.
The Examples that follow illustrate the invention. Unless otherwise indicated, figures in percent and in parts are percent by weight and parts by weight, respectively.
The metal complex is prepared according to Lacroix et al., Chem. Mater. 8 (1996). 541 to 545.
A solution of diaminomaleonitrile (5.41 g, 50 mmol), nickel (II)chloride (11.89 g, 50 mmol) and absolute ethanol (950 ml) is stirred at 70-72° C. A solution of 4-diethylamino-I-salicaldehyde (19.33 g, 100 mmol) in hot ethanol (575 ml) is added during 1 hour, upon which a crystalline precipitate gradually forms. Heating is continued for a further 1 hour, then the mixture is left to cool to 25° C. during 4 hours. The precipitate is filtered off, washed with ethanol and then dried in vacuo at 60° C. Yield 25.3 g (98%).
1 % by weight of the compound of example 1 is dissolved in chloroform and filtered through a 0.2 μm teflon filter. The dye solution is then applied onto a 1.2 mm thick flat glass substrate (diameter 120 mm) at 250 revs/min and spin coating is subsequently carried out at 600 revs/min. A uniform solid layer is obtained which, after drying 15 minutes at 70° C., has an absorbance of 0.30 at λmax 594 nm. The refractive index n and the extinction coefficient k of the so-formed layer are determined by using an optical measurement system (ETA-RT, ETA-Optik). The values at 658 nm are: n(658 nm)=2.33, k(658 nm)=0.084.
| Number | Date | Country | Kind |
|---|---|---|---|
| 03405336.3 | May 2003 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP04/50706 | 5/5/2004 | WO | 10/20/2005 |
