# Patent

## Title
Photopolymer formulations for producing holographic media having highly crosslinked matrix polymers

## Abstract

The invention relates to a photopolymer formulation comprising a polyol component, a polyisocyanate component, a writing monomer, and a photoinitiator, containing a coinitiator and a dye having the formula F An, where F stands for a cationic dye and An′′ stands for an anion, wherein the dye having the formula F An comprises a water absorption of =5%. The invention further relates to a holographic medium, in particular in the form of a film, containing a photopolymer formulation according to the invention, to the use of such a medium for recording holograms, and to a special dye that can be used in the photopolymer formulation according to the invention.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional application of U.S. patent application Ser. No. 13/883,008 now U.S. Pat. No. 9,146,456, filed May 2, 2013, which national stage application (under 35 U.S.C. §371) of PCT/EP2011/069389, filed Nov. 4, 2011, which claims benefit of European application 10190324.3, filed Nov. 8, 2010.


BACKGROUND OF THE INVENTION
The invention relates to a photopolymer formulation comprising a polyol component, a polyisocyanate component, a writing monomer and a photoinitiator containing a coinitiator and a dye of formula F+An−, where F+ represents a cationic dye and An− represents an anion. The invention further relates to a holographic medium, particularly in the form of a film, containing a photopolymer formulation according to the invention, to the use of such a medium for recording of holograms, and also to a specific dye usable in the photopolymer formulations according to the invention.
Photopolymer formulations of the type mentioned at the beginning are known in the prior art. WO 2008/125229 A1, for instance, describes a photopolymer formulation comprising a polyol component, a polyisocyanate component, a writing monomer based on acrylate and also photoinitiators containing a coinitiator and a dye. In the cured state, the writing monomer and the photoinitiators form a spatially isotropic distribution embedded in the polyurethane matrix formed from polyol and polyisocyanate components.
The uses of photopolymer formulations are decisively determined by the refractive index modulation Δn produced in the photopolymer by holographic exposure. In holographic exposure, the interference field of signal light beam and reference light beam (in the simplest case, that of two plane waves) is mapped into a refractive index grating by the local photopolymerization of, for example, high refractive index acrylates at loci of high intensity in the interference field. The refractive index grating in the photopolymer (the hologram) contains all the information of the signal light beam. Illuminating the hologram with only the reference light beam will then reconstruct the signal. The strength of the signal thus reconstructed relative to the strength of the incident reference light is diffraction efficiency, DE in what follows.
In the simplest case of a hologram resulting from the superposition of two plane waves, the DE is the ratio of the intensity of the light diffracted on reconstruction to the sum total of the intensities of the incident reference light and the diffracted light. The higher the DE, the greater the efficiency of a hologram with regard to the amount of reference light needed to visualize the signal with a fixed brightness.
When the hologram is illuminated with white light, for example, the width of the spectral range which can contribute to reconstructing the hologram is likewise only dependent on the layer thickness d. The relationship which holds is that the smaller the d, the greater the particular acceptance widths. Therefore, to produce bright and easily visible holograms, it is generally desirable to seek a high Δn and a low thickness d while maximizing DE. That is, increasing Δn increases the latitude to engineer the layer thickness d without loss of DE for bright holograms. Therefore, the optimization of Δn is of outstanding importance in the optimization of photopolymer formulations (P. Hariharan, Optical Holography, 2nd Edition, Cambridge University Press, 1996).
In order that a very high Δn and DE may be realized for holograms, the matrix polymers and writing monomers of a photopolymer formulation should in principle be chosen such that there is a very large difference in their refractive indices. One possible method of realization is to use matrix polymers having a very low refractive index and writing monomers having a very high refractive index. Suitable matrix polymers of low refractive index are for example polyurethanes obtainable by reaction of a polyol component with a polyisocyanate component.
In addition to high DE and Δn values, however, another important requirement for holographic media from photopolymer formulations is that the matrix polymers be highly crosslinked in the final medium. When the degree of crosslinking is too low, the medium will lack adequate stability. One consequence of this is to appreciably reduce the quality of holograms inscribed in the media. In the worst case, the holograms may subsequently even be destroyed.
It is further very important for the large scale industrial production of holographic media from photopolymer formulations in particular that the matrix polymers crosslink quickly. Short cure times to blocking resistance are very important here, since this parameter determines the processing speed and/or the length of any curing sector needed.
However, it has been determined that media obtained from the known photopolymer formulations are frequently devoid of adequate crosslinking. Moreover, reaching an even just adequate crosslink density requires long cure times in many cases. This means that media obtained from the known photopolymer formulations may have quality issues and the prolonged cure time is associated with appreciable cost and inconvenience in large scale industrial manufacture.
The problem addressed by the present invention was therefore that of providing a photopolymer formulation of the type mentioned at the beginning, from which stable holographic media for bright holograms are obtainable quickly and at low cost and inconvenience.
BRIEF SUMMARY OF THE INVENTION
This problem is solved by the photopolymer formulation according to the invention when the dye has a water imbibition of ≦5%.
Water imbibition is apparent from formula (F-1)

W=(mf/mt−1)*100%  (F-1),

where mf is the mass of the dye after water saturation and mt is the mass of the dried dye. mt is ascertained by drying a particular quantity of dye to constant mass, for example at elevated temperature in vacuo. mf is determined by letting a particular quantity of dye stand in air at a defined humidity to constant weight.

Surprisingly, fast-curing holographic media are found to be obtainable from photopolymer formulations containing a dye of formula F+An− with a water imbibition of ≦5%. The media exhibit fast and high crosslinking of the matrix polymer and make it possible for bright holograms to be exposed in them.



A BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 shows the measured transmitted power PT (right y axis) as a solid line plotted against the angle detuning ΔΩ, the measured diffraction efficiency η (left y axis) as solid circles plotted against the angle detuning ΔΩ (if permitted by the finite size of the detector) and the adaptation of the Kogelnik theory as a dashed line (left y axis).
FIG. 2 shows the plot of the Bragg curve η according to the Coupled Wave Theory (dashed line), the measured diffraction efficiency (solid circles) and the transmitted power (black solid line) against the angle detuning ΔΩ.
FIG. 3 shows the course of curing the matrix network as a plot of storage modulus G′ against curing time.
FIG. 4 shows the comparison of modulus build-up over the curing time between Example Formulation 1 and Comparative Formulation 1.
FIG. 5 shows the comparison of modulus build-up over the curing time between Example Formulation 2 and Comparative Formulation 2.
FIG. 6 shows the comparison of modulus build-up over the curing time between Example Formulation 3 and Comparative Formulation 3 and Example Formulation 4.
FIG. 7 plots the n achieved versus the exposure dose E, holographic writing ensues in Example Medium 1 at lower doses E than in Comparative Medium 1.



A DETAILED DESCRIPTION OF THE INVENTION
In a first preferred embodiment of the invention, the dye has a water imbibition of ≦3% and preferably of ≦2%. It is very particularly preferable for the dye to imbibe only traces of water, if any.
Cationic dyes of formula F+ is to be understood in the context of the present invention as referring to dyes as described for example in H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Cationic Dyes, Wiley-VCH Verlag, 2008.
Cationic dyes of formula F+ is preferably to be understood as meaning cationic dyes of the following classes: acridine dyes, xanthene dyes, thioxanthene dyes, phenazine dyes, phenoxazine dyes, phenothiazine dyes, tri(het)arylmethane dyes, particularly diamino- and triamino(het)arylmethane dyes, mono-, di- and trimethinecyanine dyes, hemicyanine dyes, externally cationic merocyanine dyes, externally cationic neutrocyanine dyes, nullmethine dyes—particularly naphtholactam dyes, streptocyanine dyes. Dyes of this type are described for example in H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Azine Dyes, Wiley-VCH Verlag, 2008, H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Methine Dyes and Pigments, Wiley-VCH Verlag, 2008, T. Gessner, U. Mayer in Ullmann's Encyclopedia of Industrial Chemistry, Triarylmethane and Diarylmethane Dyes, Wiley-VCH Verlag, 2000.
It is also preferable for the anion An− of the dye to have an AC log P in the range of 1-30, preferably in the range of 1-12, more preferably in the range of 1-6.5 and even more preferably in the range 1-4.
AC log P is computed as described in J. Comput. Aid. Mol. Des. 2005, 19, 453; Virtual Computational Chemistry Laboratory, http://www.vcclab.org.
In a further preferred embodiment of the invention, the anion An− has a molar mass >150 g/mol and more preferably >250 g/mol.
The anion of formula An− can comprise at least a phosphorus, boron or sulphur atom, preferably at least a boron or sulphur atom and more preferably at least a sulphur atom particularly a sulphur atom in an SO3 moiety.
It is likewise preferable for the anion An− to have one or more than one linear or branched aliphatic moiety and preferably one linear or branched aliphatic C8 to C18 moiety. If the anion contains more than one linear or branched aliphatic moiety, these together contain 8 to 36 and preferably 8 to 24 carbon atoms. This aliphatic moiety may bear substituents such as fluorine, methoxy or ethoxy.
Outstandingly preferred anions of formula An− have, therefore, a molar mass >250 g/mol and contain an SO3− grouping and also at least one alkyl group of 8 or more carbon atoms and have an AC log P in the range 1-6.5.
The formula An− anions according to the invention also subsume in particular:
C8- to C25-alkanesulphonate, preferably C13- to C25-alkanesulphonate, C3- to C18-perfluoroalkanesulphonate, preferably C4- to C18-perfluoroalkanesulphonate, C9- to C25-alkanoate, C9- to C25-alkenoate, C8- to C25-alkyl sulphate, preferably C13- to C25-alkyl sulphate, C8- to C25-alkenyl sulphate, preferably C13- to C25-alkenyl sulphate, C3- to C18-perfluoroalkyl sulphate, preferably C4- to C18-perfluoroalkyl sulphate, polyether sulphates based on 4 or more equivalents of ethylene oxide and/or propylene oxide, bis-C4- to C25-alkyl, C5- to C7-cycloalkyl, C3- to C8-alkenyl or C7- to C11-aralkyl sulphosuccinate, bis-C2- to C10-alkyl sulphosuccinate substituted by 8 or more fluorine atoms, C8- to C25-alkyl sulphoacetates, benzenesulphonate substituted by at least one moiety from the group halogen, C4- to C25-alkyl, perfluoro-C1- to C8-alkyl and/or C1- to C12-alkoxycarbonyl, optionally nitro-, cyano-, hydroxyl-, C1- to C25-alkyl-, C1- to C12-alkoxy-, amino-, C1- to C12-alkoxycarbonyl- or chlorine-substituted naphthalene- or biphenylsulphonate, optionally nitro-, cyano-, hydroxyl-, C1- to C25-alkyl-, C1- to C12-alkoxy-, C1- to C12-alkoxycarbonyl- or chlorine-substituted benzene-, naphthalene- or biphenyldisulphonate, dinitro-, C6- to C25-alkyl-, C4- to C12-alkoxycarbonyl-, benzoyl-, chlorobenzoyl- or toluoyl-substituted benzoate, the anion of naphthalenedicarboxylic acid, diphenyl ether disulphonate, sulphonated or sulphated, optionally mono- or polyunsaturated C8- to C25-fatty acid esters of aliphatic C1- to C8-alcohols or glycerol, bis(sulpho-C2- to C6-alkyl) C3- to C12-alkanedicarboxylic esters, bis(sulpho-C2- to C6-alkyl) itaconic acid esters, (sulpho-C2- to C6-alkyl) C6- to C18-alkanecarboxylic esters, (sulpho-C2- to C6-alkyl) acrylic or methacrylic acid esters, triscatechol phosphate optionally substituted by up to 12 halogen moieties, an anion from the group tetraphenyl borate, cyanotriphenyl borate, tetraphenoxyborate, C4- to C12-alkyltriphenyl borate, the phenyl or phenoxy moieties of which may be halogen, C1- to C4-alkyl and/or C1- to C4-alkoxy substituted, C4- to C12-alkyltrinaphthyl borate, tetra-C1- to C20-alkoxyborate, 7,8- or 7,9-dicarbanidoundecaborate(1-) or (2-), which optionally bear on the B and/or C atoms one or two C1- to C12-alkyl or phenyl substituents, dodecahydrodicarbadodecaborate(2-) or B—C1- to C12-alkyl-C-phenyldodecahydrodicarbadodecaborate(1-), where An− in multivalent anions such as naphthalenedisulphonate represents one equivalent of this anion, and where the alkane and alkyl groups may be branched and/or may be halogen, cyano, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl substituted.
Particular preference is given to:
sec-C11- to C18-alkanesulphonate, C13- to C25-alkyl sulphate, branched C8- to C25-alkyl sulphate, optionally branched bis-C6- to C25-alkyl sulphosuccinate, sec- or tert-C4- to C25-alkylbenzenesulphonate, sulphonated or sulphated, optionally mono- or polyunsaturated C8- to C25-fatty acid esters of aliphatic C1- to C8-alcohols or glycerol, bis(sulpho-C2- to C6-alkyl) C3- to C12-alkanedicarboxylic esters, (sulpho-C2- to C6-alkyl) C6- to C18-alkanecarboxylic esters, triscatechol phosphate substituted by up to 12 halogen moieties, cyanotriphenyl borate, tetraphenoxyborate.
Examples are:







AC log P values of various anions are collated in the following Table 1:







TABLE 1







AClogP values of selected anions








Anion
AClogP









−1.50


 






−0.11


 






0.23


 






0.76


 






0.76


 






1.07


 






1.84


 






1.96


 






3.05


 






3.32


 






3.45


 






3.62


 






3.67


 






4.85


 






5.78


 






5.81


 






6.34


 






6.86


 






7.55


 






8.76


 






8.99


 






9.16


 






12.49


 






17.49









It is likewise particularly preferable for

    An− to represent a 4-(sec-alkyl)benzenesulphonate of formula (LI)






where

    a and b independently of each other represent an integer from 0 to 20 subject to the proviso that a+b is ≧3.
    a+b here is preferably ≧5, more preferably ≧7 and even more preferably ≧9.


The formula (LI) also subsumes mixtures of anions with various values of a and b where a+b is the same. However, the formula (LI) also subsumes mixtures of anions with different values of a and b.
Examples of anions of formula (LI) are:




and also as mixture of all five conceivable isomers.

It is likewise particularly preferable for

    An− to represent a sec-alkylsulphonate of formula (LII)






where

    c and d independently of each other represent an integer from 0 to 20 subject to the proviso that c+d is ≧5.
    c+d is preferably ≧7, more preferably ≧9 and even more preferably ≧11.


The formula (LII) also subsumes mixtures of anions with various values of c and d where c+d is the same. However, the formula (LII) also subsumes mixtures of anions with different values of c and d.
Examples of anions of formula (LII) are:




and also as mixture of all conceivable isomers.

It is likewise particularly preferable for

    An− to represent a secondary or branched alkyl sulphate of formula (LIII)






where

    e represents an integer from 0 to 5,
    f and g independently of each other represent an integer from 0 to 15 subject to the proviso that e+f+g is ≧5 and
    
        the CH2 groups may additionally be substituted by further methyl or ethyl groups.
    
    
    e+f+g is preferably ≧7, more preferably ≧9 and even more preferably ≧11.
    e preferably represents 0 or 1.


It is preferable for two CH2 groups to be methyl and/or ethyl substituted.
The formula (LIII) also subsumes mixtures of anions with various values of e, f and g where e+f+g is the same. However, the formula (LIII) also subsumes mixtures of anions with different values of e, f and g.
Examples of anions of formula (LIII) are:




It is likewise particularly preferable for

    An− to represent a branched phosphate of formula (LIV)






where

    R200 represents hydrogen or halogen,
    h represents an integer from 1 to 4.


Preferably, R200 represents chlorine or bromine and h represents 4.
Examples of anions of formula (LIV) are:




It is likewise particularly preferable for

    An− to represent an alkyl sulphate of formula (LV)






where

    i represents an integer from 12 to 25.


Preferably, i represents an integer from 18 to 25.
Examples of anions of formula (LV) are:




It is likewise particularly preferable for

    An− to represent a sulphosuccinate of formula (LVI)






where

    R201 and R202 independently of each other represents a C4- to C16-alkyl moiety, which may be branched, a C2- to C12-alkyl moiety substituted by 4 or more fluorine atoms, a C5- to C7-cycloalkyl moiety or a C7- to C10-aralkyl moiety.


Preferably R201 and R202 are the same.
It is particularly preferable for R201 and R202 to represent a C6- to C12-alkyl moiety, which may be branched, a C4- to C8-alkyl moiety substituted by 6 or more fluorine atoms, cyclohexyl or benzyl. It is very particularly preferable for R201 and R202 to represent n-hexyl, n-octyl, 2-ethylhexyl or 1H,1H,7H-dodecafluoroheptyl.
Examples of anions of formula (LVI) are:




It is likewise particularly preferable for

    An− to represent an ester sulphonate of formula (LVII)






where

    R203 represents a C2- to C22-alkyl or alkenyl moiety, which may be branched or substituted, and
    u represents an integer from 2 to 4.


Preferably, R203 represents a branched or unbranched C6- to C17-alkyl or alkenyl radical or represents —CH═CH2 or —C(CH3)═CH2, and more preferably represents a branched or unbranched C6- to C17-alkyl or alkenyl radical.
Preferably, u represents 3 or 4.
Examples of anions of formula (LVII) are:




It is likewise particularly preferable for

    An− to represent an ester sulphonate or ester sulphates of formula (LVIII)






where

    v represents 0 or 1,
    R204 represents C1- to C18-alkyl, which may be branched and/or substituted,
    R205 represents hydrogen or C1- to C8-alkyl, and
    Y201 represents a direct bond, an aliphatic C1 to C22 bridge or an olefinic C2 to C22 bridge,
    subject to the proviso that Y201 and R204 together have 7 or more carbon atoms.


Examples of anions of formula (LVIII) are:




It is likewise particularly preferable for

    An− to represent a borate of formula (LIX)






where

    R206 represents cyano, C1- to C12-alkyl, C7- to C10-aralkyl or a moiety of formula






    R207 and R208 independently of each other represents hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, halogen, cyano or nitro, or
    two adjacent R207 and R208 form a —CH═CH—CH═CH— bridge.


It is particularly preferable for

    R206 to represent cyano, butyl, pentyl, hexyl, benzyl or a moiety of formula






    R207 and R208 independently of each other to represent hydrogen, methyl, methoxy, fluorine, chlorine or cyano or
    two adjacent R207 and R208 to form a —CH═CH—CH═CH— bridge.


Examples of examples of anions of formula (LIX) are:




It is likewise particularly preferable for

    An− to represent a fluorinated alkyl sulphate of formula (LX)






where

    R209 represents a C4- to C18-alkyl radical bearing 4 or more fluorine atoms.


Preferably, R209 represents a C8- to C18-alkyl moiety bearing 6 or more fluorine atoms. It is likewise preferable for R209 to represent a perfluorinated C6- to C12-alkyl moiety.
Examples of anions of formula (LX) are:




The cationic dyes and anions are either known or obtainable similarly to known processes.
Cationic dyes of formula F+ are preferably those of the following formulae:




where

    X1 represents O, S, N—R6 or CR6aR6b,
    X2 represents N or C—R5,
    R5 represents hydrogen, cyano, C1- to C4-alkyl, C4- to C7-cycloalkyl, an optionally C1- to C4-alkoxycarbonyl- or NR7R8-substituted C6- to C10-aryl or a heterocyclic moiety,
    R6 represents hydrogen, C1- to C16-alkyl, C4- to C7-cycloalkyl, C7- to C16-aralkyl, C6- to C10-aryl or a heterocyclic radical,
    R6a and R6b are the same and represent methyl, ethyl or conjointly a —CH2—CH2—CH2— or —CH2—CH2—CH2—CH2— bridge,
    R1 to R4, R7 and R8 independently of each other represent hydrogen, C1- to C16-alkyl, C4- to C7-cycloalkyl, C7- to C16-aralkyl, C6- to C10-aryl or a heterocyclic moiety, or
    NR1R2, NR3R4 and NR7R8 independently of each other represent a five- or six-membered saturated ring which is attached via N and which may additionally contain an N or O and/or may be substituted by nonionic moieties, or
    R1 to R4, R7 and R8 independently of each other combine with a benzene ring carbon atom adjacent to the nitrogen atom to form a two- or three-membered bridge, which may contain an O or N and/or may be substituted by nonionic moieties,
    R9, R9a, R9b, R10, R10a and R10b independently of each other represent hydrogen, halogen or C1- to C4-alkyl,






where

    R15 represents hydrogen, halogen, C1- to C4-alkyl, C1- to C4-alkoxy or NR18R19,
    R11 to R14, R18 and R19 independently of each other represent hydrogen, C1- to C16-alkyl, C4- to C7-cycloalkyl, C7- to C16-aralkyl, C6- to C10-aryl or a heterocyclic moiety, or
    NR11R12, NR13R14 and NR18R19 independently of each other represent a five- or six-membered saturated ring which is attached via N and which may additionally contain an N or O and/or may be substituted by nonionic moieties, or
    R12; R17b, R13; R17c and R18; R17a independently of each other form a two- or three-membered bridge, which may contain an O or N and/or may be substituted by nonionic moieties,
    R16 represents hydrogen, chlorine, methyl, methoxycarbonyl or ethoxycarbonyl,
    R16a represents hydrogen, chlorine or methyl,
    R17a, R17b and R17c independently of each other represent hydrogen, chlorine, methyl or methoxy,






where

    A and B together with X21 to X24 and the atoms connecting them independently of each other represent a five- or six-membered aromatic or quasiaromatic or partially hydrogenated heterocyclic ring, which may each contain 1 to 4 heteroatoms and/or be benzo- or naphtho-fused and/or be substituted by nonionic moieties, in which case the chain attaches to the respective ring in position 2 or 4 relative to X21 and X22 respectively,
    X21 and X22 represent nitrogen, or
    X21—R21 and X22—R22 independently of each other represent O or S,
    X23 and X24 independently of each other represent O, S, N—R23, CR24 or CR25R26,
    Y21 represents N or C—R27,
    w represents 0 or 1,
    R21, R22 and R23 independently of each other represent C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl,
    R27, R28 and R29 independently of each other represent hydrogen, C1- to C16-alkyl or cyano,
    R24 represents hydrogen or C1- to C4-alkyl,
    R25 and R26 independently of each other represent C1- to C16-alkyl or C7- to C10-aralkyl or conjointly form a —CH2—CH2—CH2— or —CH2—CH2—CH2—CH2— bridge,






where

    C together with X31 and X32 and the atoms connecting them independently of each other represent a five- or six-membered aromatic or quasiaromatic or partially hydrogenated heterocyclic ring which may each contain 1 to 4 heteroatoms and/or be benzo- or naphtho-fused and/or be substituted by nonionic moieties, in which case the chain attaches to the ring in position 2 or 4 relative to X31,
    X31 represents nitrogen, or
    X31—R31 represents O or S,
    X32 represent O, S, N—R37, CR38 or CR39R40,
    R31 and R37 independently of each other represent C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl,
    R38 represents hydrogen or C1- to C4-alkyl,
    R39 and R40 independently of each other represent C1- to C4-alkyl, C3- to C6-alkenyl, C4- to C7-cycloalkyl or C7- to C10-aralkyl or conjointly form a —CH2—CH2—CH2— or —CH2—CH2—CH2—CH2— bridge,
    R32 and R33 independently of each other represent hydrogen, C1- to C16-alkyl, C4- to C7-cycloalkyl, C7- to C16-aralkyl, C6- to C10-aryl or a heterocyclic moiety, or
    NR32R33 represent a five- or six-membered saturated ring which is attached via N and which may additionally contain an N or O and/or be substituted by nonionic moieties,
    R34 represents hydrogen, C1- to C16-alkyl, C1- to C16-alkoxy or halogen, or
    R34 combines with R32 to form a two- or three-membered bridge which may contain an O or N and/or be substituted by nonionic moieties,
    R35 represents hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, halogen, cyano, C1- to C4-alkoxycarbonyl, O—CO—C1- to C4-alkyl, NH—CO—C1- to C4-alkyl, O—SO2—C1- to C4-alkyl or NH—SO2—C1- to C4-alkyl,
    R36 represents hydrogen, C1- to C4-alkyl or cyano,
    x represents 0 or 1,






where

    Y42 represents a moiety of formulae (Va) or (Vb)






    R41, R41a and R41b independently of each other represent C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl or C6- to C10-aryl,
    R42 and R42a independently of each other represent hydrogen, C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl, C6- to C10-aryl or hetaryl,
    R43 and R43a independently of each other represents hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, halogen, cyano, nitro or C1- to C4-alkoxycarbonyl or two adjacent R43 or R43a represent —CH═CH—CH═CH—,
    n and o independently of each other represent an integer from 0 to 4,
    Y41 represents CR44, ═CR45a—CR46═CR45b— or N,
    Y43 represents CH or N,
    R44, R45a, R45b and R46 independently of each other represent hydrogen, C1- to C4-alkyl, C5- to C6-cycloalkyl, C6-aryl, hetaryl, halogen or cyano,
    D together with X41, X42 and the carbon atom connected therebetween represents a five- or six-membered aromatic or quasiaromatic or partially hydrogenated heterocyclic ring which may contain 1 to 4 heteroatoms and/or be benzo- or naphtho-fused and/or be substituted by nonionic moieties, in which case the chain attaches to the ring in position 2 or 4 relative to X41,
    X41 represents N, or
    X41—R41b represents O or S,
    X42 represents O, S, CR47R48 or —CH═CH—,
    R47 and R48 independently of each other represent C1- to C4-alkyl, C3- to C6-alkenyl, C4- to C7-cycloalkyl, C7- to C10-aralkyl or C6-aryl or conjointly form a —CH2—CH2—CH2— or —CH2—CH2—CH2—CH2— bridge,






where

    Y52 represents a radical of formulae (VIa), (VIb) or (VIc)






    R51, R51a, R51b and R51c independently of each other represent C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl or C6- to C10-aryl,
    R52 and R52a independently of each other represent C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl or C6- to C10-aryl,
    R53 and R53a independently of each other represent C1- to C4-alkyl, halogen, cyano, nitro or C1- to C4-alkoxycarbonyl,
    R53d represents hydrogen, C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl, C6- to C10-aryl or hetaryl,
    R53b represents hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, halogen, cyano, nitro or C1- to C4-alkoxycarbonyl or two adjacent R53b or R53c represent —CH═CH—CH═CH—,
    m represents an integer from 0 to 4,
    Y51 represents CR54, ═CR51a—CR56═CR55b— or N,
    Y53 represents CH or N,
    R54, R55a, R55b and R56 independently of each other represent hydrogen, C1- to C4-alkyl, C5- to C6-cycloalkyl, C6-aryl, hetaryl, halogen or cyano,
    E together with X51, X52 and the carbon atom connected therebetween represents a five- or six-membered aromatic or quasiaromatic or partially hydrogenated heterocyclic ring which may contain 1 to 4 heteroatoms and/or be benzo- or naphtho-fused and/or be substituted by nonionic moieties, in which case the chain attaches to the ring in position 2 or 4 relative to X51,
    X51 represents N, or
    X51—R51c represents O or S,
    X52 represents O, S, CR57R58 or —CH═CH—,
    R57 and R58 independently of each other represent C1- to C4-alkyl, C3- to C6-alkenyl, C4- to C7-cycloalkyl, C7- to C10-aralkyl or C6-aryl or conjointly form a —CH2—CH2—CH2— or —CH2—CH2—CH2—CH2— bridge,






where

    Y62 represents a radical of formulae






    X61 and X61a independently of each other represent O or S,
    X62 and X62a independently of each other represent CR66 or N,
    R63 and R63a independently of each other represent hydrogen, C1- to C6-alkyl, halogen, hydroxyl, C6- to C10-aryl or NR64R65 or R63 and R63a together represent a —C(CH3)2— bridge when Y61 represents CH and Y62 represents a moiety of formula (VIIa),
    R61, R61a, R62, R62a, R64 and R65 independently of each other represent hydrogen, C1- to C6-alkyl, C5- to C7-cycloalkyl, C6- to C10-aryl or C7- to C15-aralkyl, or
    NR61R62 and NR64R65 independently of each other represent pyrrolidino, morpholino, piperazino or piperidino,
    R66 represents hydrogen, cyano, C1- to C6-alkyl, halogen or C6- to C10-aryl,
    Y61 represents ═Y63—(Y64═Y65)p—,
    Y63 to Y65 independently of each other represent N or C—R67,
    P represents 0 or 1,
    R67 represents hydrogen, cyano or C1- to C3-alkyl, or
    R67 represents a radical of formula (VIIa), when p represents 1,
    G together with X63, X64 and the carbon atom connected therebetween represents a five- or six-membered aromatic or quasiaromatic or partially hydrogenated heterocyclic ring which may contain 1 to 4 heteroatoms and/or be benzo- or naphtho-fused and/or be substituted by nonionic moieties, in which case the chain attaches to the ring in position 2 or 4 relative to X63,
    X63 represents nitrogen, or
    X63—R68 represents O or S,
    X64 represents O, S, N—R69 or CR70R71,
    X65 represents N or C—R67,
    R68 and R69 independently of each other represent C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl,
    R70 and R71 independently of each other represent C1- to C4-alkyl or C7- to C10-aralkyl or conjointly form a —CH2—CH2—CH2— or —CH2—CH2—CH2—CH2— bridge,
    R72 and R73 independently of each other represent hydrogen, C1- to C16-alkyl, C4- to C7-cycloalkyl, C7- to C16-aralkyl, C6- to C10-aryl or a heterocyclic radical, or
    NR72R73 represent a five- or six-membered saturated ring which is attached via N which may additionally contain an N or O and/or be substituted by nonionic moieties,
    R74 and R74a independently of each other represent hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy or halogen, or
    R74; R73 and/or R74a; R72 form a two- or three-membered bridge which may contain an O or N and/or be substituted by nonionic moieties,
    R75 represents hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, halogen, cyano, C1- to C4-alkoxycarbonyl, O—CO—C1- to C4-alkyl, NH—CO—C1- to C4-alkyl, O—SO2—C1- to C4-alkyl or NH—SO2—C1- to C4-alkyl,






where

    R81 and R82 independently of each other represent hydrogen, C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl or C6- to C10-aryl,
    R83 and R84 independently of each other represents hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, halogen, cyano, nitro or C1- to C4-alkoxycarbonyl or two adjacent R83 or R84 represent —CH═CH—CH═CH—, or
    R83; R81 and/or R84; R82 form a two- or three-membered bridge which may be substituted by nonionic moieties,
    q and r independently of each other represent an integer from 0 to 4,






where

    Y91 represents a moiety of formulae (IXa) or (IXb)






    R91 represent C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl,
    R92 and R93 independently of each other represent hydrogen, C1- to C16-alkyl, C4- to C7-cycloalkyl, C7- to C16-aralkyl, C6- to C10-aryl or a heterocyclic radical, or
    NR92R93 represent a five- or six-membered saturated ring which is attached via nitrogen and which may additionally contain an N or O and/or be substituted by nonionic moieties,
    R94 and R94a independently of each other represent hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy or halogen, or
    R94; R93 and/or R94a; R92 form a two- or three-membered bridge which may contain an O or N and/or be substituted by nonionic moieties,
    R95 represents hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, halogen, cyano, C1- to C4-alkoxycarbonyl, O—CO—C1- to C4-alkyl, NH—CO—C1- to C4-alkyl, O—SO2—C1- to C4-alkyl or NH—SO2—C1- to C4-alkyl,
    R96 represents hydrogen, halogen, O—C1- to C4-alkyl or S—C1- to C4-alkyl,
    j represents 0 or 1,
    R97 represents C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl or C6- to C10-aryl,
    R98 represents hydrogen, C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl, C6- to C10-aryl or hetaryl,
    R99 represents hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, halogen, cyano, nitro or C1- to C4-alkoxycarbonyl or two adjacent R99 represent —CH═CH—CH═CH—,
    l represents an integer from 0 to 4,






where

    Y101 represents a radical of formulae






    X101 represents O or S,
    X102 represents CR107 or N,
    R103 represents hydrogen, C1- to C6-alkyl, halogen, hydroxyl, C6- to C10-aryl or
    R101a, R102, R101a, and R102a independently of each other represent hydrogen, C1- to C6-alkyl, C5- to C7-cycloalkyl, C6- to C10-aryl or C7- to C15-aralkyl, or
    NR101R102 and/or NR101aR102a represent pyrrolidino, morpholino, piperazino or piperidino,
    R107 represents hydrogen, cyano, C1- to C6-alkyl, halogen or C6- to C10-aryl,
    H together with X103, X104 and the carbon atom connected therebetween represents a five- or six-membered aromatic or quasiaromatic or partially hydrogenated heterocyclic ring which may contain 1 to 4 heteroatoms and/or be benzo- or naphtho-fused and/or be substituted by nonionic moieties, in which case the chain attaches to the ring in position 2 or 4 relative to X103,
    X103 represents N, or
    X103—R104 represents O or S,
    X104 represents O, S, CR115R116 or —CH═CH—,
    R115 and R116 independently of each other represent C1- to C4-alkyl, C3- to C6-alkenyl, C4- to C7-cycloalkyl, C7- to C10-aralkyl or C6-aryl or conjointly form a —CH2—CH2—CH2— or —CH2—CH2—CH2—CH2— bridge,
    R104 represents C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl or C6- to C10-aryl,
    R105 and R106 independently of each other represent hydrogen, C1- to C16-alkyl, C4- to C7-cycloalkyl, C7- to C16-aralkyl, C6- to C10-aryl or a heterocyclic moiety, or
    NR105R106 represent a five- or six-membered saturated ring which is attached via N and which may additionally contain an N or O and/or be substituted by nonionic moieties,
    Y102 and Y105 independently of each other represent N or CR108,
    R108 represents hydrogen, cyano or C1- to C4-alkyl,
    Y103 represents CN, CO—R109, COO—R110, CONHR110 or CONR110R111,
    Y104 represents a cationic moiety of formula






or

    CY103Y104 together represents a moiety of formulae






    where the asterisk (*) indicates the ring atom from which the double bond emanates,
    R109 to R112 independently of each other represent hydrogen, C1- to C6-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl, C6- to C10-aryl or C7- to C15-aralkyl,
    R113 represents hydrogen, cyano, COO—R110 or C1- to C4-alkyl,
    J, K and L independently of each other combine with the nitrogen atom to represent a five- or six-membered aromatic or quasiaromatic or partially hydrogenated heterocyclic ring which may contain 1 to 4 heteroatoms and/or benzo- or naphtho-fused and/or be substituted by nonionic moieties,
    M combines with the nitrogen atom to represent a five- or six-membered aromatic or quasiaromatic or partially hydrogenated heterocyclic ring which may contain 1 to 4 heteroatoms and/or benzo- or naphtho-fused and/or be substituted by nonionic moieties, in which case the chain attaches to the ring in position 2 or 4 relative to the N atom,
    R114 represents C1- to C6-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl, C6- to C10-aryl or C7- to C15-aralkyl,
    wherein two or more of these dye formulae (I) to (X) may be connected via a bridge and this bridge takes the place of R21, R22, R31, R32, R41, R41a, R41b, R51b, R51c, R61, R61a, R66, R72, R91, R92, R101, R104 and/or R105.


Cationic dyes of formula F+ preferably also include those of the following formula:




where

    Y62 represents a moiety of the formulae






    X61 and X61a independently of each other represent O or S,
    X62 and X62a independently of each other represent CR66 or N,
    R63 and R63a independently of each other represent hydrogen, C1- to C6-alkyl, halogen, hydroxyl, C6- to C10-aryl or NR64R65 or R63 and R63a together represent a —C(CH3)2 bridge when Y61 represents CH and Y62 represents a moiety of formula (VIIa),
    R61, R61a, R62, R62a, R64 and R65 independently of each other represent hydrogen, C1- to C6-alkyl, C5- to C7-cycloalkyl, C6- to C10-aryl or C7- to C15-aralkyl, or
    NR61R62 and NR64R65 independently of each other represent pyrrolidino, morpholino, piperazino or piperidino,
    R66 represents hydrogen, cyano, C1- to C6-alkyl, halogen or C6- to C10-aryl,
    Y61 represents ═Y63—(Y64═Y65)p—,
    Y63 to Y65 independently of each other represent N or C—R67,
    p represents 0 or 1,
    R67 represents hydrogen, cyano or C1- to C3-alkyl, or
    R67 represents a moiety of formulae (VIIa), (VIIc) or represents in the case of p representing 1 a phenyl moiety optionally substituted by one or more C1- to C4-alkyl, halogen, C1- to C4-alkoxy, cyano, nitro or C1- to C4-alkoxycarbonyl,
    G together with X63, X64 and the carbon atom bound therebetween represents a five- or six-membered aromatic or quasiaromatic or partially hydrogenated heterocyclic ring which may contain 1 to 4 heteroatoms and/or may be benzo- or naphtho-fused and/or be substituted by nonionic moieties, in which case the chain attaches to the ring in position 2 or 4 relative to X63,
    X63 represents nitrogen, or
    X63—R68 represents O or S,
    X64 represents O, S, N—R69 or CR70R71,
    X65 represents N or C—R67,
    R68 and R69 independently of each other represent C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl,
    R70 and R71 independently of each other represent C1- to C4-alkyl or C7- to C10-aralkyl or together form a —CH2—CH2—CH2— or —CH2—CH2—CH2—CH2— bridge,
    R72 and R73 independently of each other represent hydrogen, C1- to C16-alkyl, C4- to C7-cycloalkyl, C7- to C16-aralkyl, C6- to C10-aryl or a heterocyclic moiety, or
    NR72R73 represents a five- or six-membered saturated ring which is attached via N and which may additionally contain an N or O and/or be substituted by nonionic moieties,
    R74 and R74a independently of each other represent hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy or halogen, or
    R74; R73 and/or R74a; R72 form a two- or three-membered bridge which may contain an O or N and/or be substituted by nonionic moieties,
    R76a, R76b and R79 independently of each other represent C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl, C7- to C16-aralkyl or C6- to C10-aryl,
    R77a represents hydrogen, C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl, C7- to C16-aralkyl, C6- to C10-aryl or hetaryl,
    R77b represents C1- to C4-alkyl, halogen, cyano, nitro or C1- to C4-alkoxycarbonyl,
    R78 represents hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, halogen, cyano, nitro or C1- to C4-alkoxycarbonyl or two adjacent R78 moieties represent —CH═CH—CH═CH—,
    m1 represents an integer from 0 to 4.


Cationic dyes of formula F+ preferably also include those of the following formula:




where

    Y91 represents a moiety of formulae (IXc)






    R91 represents C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl,
    j represents 0 or 1,
    R97a and R97b independently of each other represent C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl, C7- to C16-aralkyl or C6- to C10-aryl,
    R98a represents C1- to C4-alkyl, halogen, cyano, nitro or C1- to C4-alkoxycarbonyl.


Suitable bridges are for example those of formulae:

—CH2—CH2—CH2—, —CH2—CH2—CH2—CH2—, —CH2—CH2—O—CH2—CH2—,





Nonionic moieties are C1- to C4-alkyl, C1- to C4-alkoxy, halogen, cyano, nitro, C1- to C4-alkoxycarbonyl, C1- to C4-alkylthio, C1- to C4-alkanoylamino, benzoylamino, mono- or di-C1- to C4-alkylamino.
Alkyl, alkoxy, cycloalkyl, aryl and heterocyclic moieties may optionally bear further moieties such as alkyl, halogen, nitro, cyano, CO—NH2, alkoxy, trialkylsilyl, trialkylsiloxy or phenyl, the alkyl and alkoxy moieties may be straight-chain or branched, the alkyl moieties may be partially halogenated or perhalogenated, the alkyl and alkoxy moieties may be ethoxylated or propoxylated or silylated, adjacent alkyl and/or alkoxy moieties on aryl or heterocyclic moieties may conjointly form a three- or four-membered bridge, and the heterocyclic moieties may be benzo-fused and/or quaternized.
Halogen is to be understood as meaning fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
Examples of substituted alkyl moieties are trifluoromethyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl. Examples of branched alkyl moieties are isopropyl, tert-butyl, 2-butyl, neopentyl. Examples of alkoxy moieties are methoxy, ethoxy, methoxyethoxy.
Preferred optionally substituted C1- to C4-alkyl moieties are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, perfluorinated methyl, perfluorinated ethyl, 2,2-trifluoroethyl, 3,3,3-trifluoroethyl, perfluorobutyl, cyanoethyl, methoxyethyl, chloroethyl.
Preferred aralkyl may be for example benzyl, phenethyl or phenylpropyl.
Examples of C6- to C10-aryl are phenyl and naphthyl. Examples of substituted aryl moieties are tolyl, chlorophenyl, dichlorophenyl, methoxyphenyl, nitrophenyl, cyanophenyl, dimethylaminophenyl, diethylaminophenyl.
Examples of hetaryl moieties, particularly of five- or six-membered heterocyclic moieties, are indolyl, pyridyl, quinolyl, benzothiazolyl. Examples of substituted heterocyclic moieties are 1,2-dimethylindol-3-yl, 1-methyl-2-phenylindol-3-yl.
Examples of the rings A and C of formulae




respectively

are: 2- or 4-pyridyl, 2- or 4-quinolyl, 2- or 4-pyrimidyl, pyrimid-2-on-4-yl, 2-pyrazinyl, 1,3-thiazol-2-yl, 1,3-thiazolin-2-yl, benzothiazol-2-yl, 1,3-oxazol-2-yl, 1,3-oxazolin-2-yl, benzoxazol-2-yl, imidazol-2-yl, imidazolin-2-yl, benzimidazol-2-yl, pyrrolin-2-yl, pyrrol-2-yl, 3-H-indol-2-yl, 3-H-benzindol-2-yl, 1,3,4-thiadiazol-2-yl, 1,2,4-thiadiazol-3-yl, benz-1,4-thiazin-3-yl, quinoxalin-2-yl or quinoxalin-3-on-2-yl, which may each be substituted by C1- to C6-alkyl, C1- to C6-alkoxy, fluorine, chlorine, bromine, iodine, cyano, nitro, C1- to C6-alkoxycarbonyl, C1- to C6-alkylthio, C1- to C6-acylamino, C6- to C10-aryl, C6- to C10-aryloxy, C6- to C10-arylcarbonylamino, mono- or di-C1- to C6-alkylamino, N—C1- to C6-alkyl-N—C6- to C10-arylamino, pyrrolidino, morpholino, piperidino or piperazino.

3-H-Indol-2-yl is to be understood as meaning particularly the 3,3-dialkyl derivatives, for example those of formulae




Examples of the rings A and C of formulae




respectively

are: pyrylium-2- or -4-yl, thiopyrylium-2- or -4-yl, which may each be substituted by C1- to C6-alkyl or C6- to C10-aryl.

Examples of the rings B, D, E, G and H of formulae




respectively

are: pyridin-2- or -4-ylene, quinolin-2- or -4-ylene, pyrimidin-2- or -4-ylene, pyrimid-2-on-4-ylene, pyrazin-2-ylene, 1,3-thiazol-2-ylene, 1,3-thiazolin-2-ylene, benzothiazol-2-ylene, 1,3-oxazol-2-ylene, 1,3-oxazolin-2-ylene, benzoxazol-2-ylene, imidazol-2-ylene, imidazolin-2-ylene, benzimidazol-2-ylene, pyrrolin-2-ylene, pyrrol-2-ylene, 3-H-indol-2-ylene, 3-H-benzindol-2-ylene, benz[c,d]indol-2-ylene, 1,3,4-thiadiazol-2-ylene, 1,2,4-thiadiazol-3-ylene, benz-1,4-thiazin-3-ylene, quinoxalin-2-ylene or quinoxalin-3-on-2-ylene, which may each be substituted by C1- to C6-alkyl, C1- to C6-alkoxy, fluorine, chlorine, bromine, iodine, cyano, nitro, C1- to C6-alkoxycarbonyl, C1- to C6-alkylthio, C1- to C6-acylamino, C6- to C10-aryl, C6- to C10-aryloxy, C6- to C10-arylcarbonylamino, mono- or di-C1- to C6-alkylamino, N—C1- to C6-alkyl-N—C6- to C10-arylamino, pyrrolidino, morpholino, piperidino or piperazino.

3-H-Indol-2-ylene is to be understood as meaning particularly the 3,3-dialkyl derivatives, for example, those of formulae




Examples of the rings B, D, E, G and H of formulae




respectively

are: 2H-pyran-2-ylene, 4H-pyran-4-ylene, 2H-thiopyran-2-ylene, 4H-thiopyran-4-ylene, which may each be substituted by C1- to C6-alkyl or C6- to C10-aryl.

It is also possible for two or more, preferably two, dyes of formulae (I) to (X) to be connected via a bridge. Preferably, two identical dyes are connected to each other. Such a bridge may have, for example, one of the formulae

—CH2—[CH2]k—CH2— or





where

    k represents an integer from 0 to 4, and

the two methylene groups on the benzene ring are disposed in o-, m- or p-position relative to each other.



Very particular preference is given to cationic dyes of formula (I)




where

    X1 represents O, S or CR6aR6b,
    X2 represents C—R5,
    R5 represents hydrogen, cyano, methyl, ethyl, cyclohexyl, phenyl, 2-methoxycarbonylphenyl, 2-ethoxycarbonylphenyl or 4-(R7R8N)-phenyl,
    R6a and R6b represent methyl,
    R1 to R4, R7 and R8 independently of each other represent hydrogen, methyl, ethyl, propyl, butyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, benzyl, phenyl, tolyl, anisyl or chlorophenyl, or
    NR1R2, NR3R4 and NR7R8 independently of each other represent pyrrolidino, piperidino, morpholino or N-methylpiperazino,
    R9, R9a, R9b, R10, R10a and R10b represent hydrogen or in each case one of R9, R9a, R9b and/or one of R10, R10a and R10b represents methyl, or
    R1; R9, R2; R9a, R3; R10 and R4; R10a independently of each other form a —CH2CH2—, —CH2CH2CH2— or —CH2CH2—O— bridge which may bear up to three methyl groups.


Of outstanding preference are cationic dyes of formula (I),
where


    X1 represents O, S or CR6aR6b,
    X2 represents C—R5,
    R5 represents hydrogen, cyano, phenyl, 2-methoxycarbonylphenyl, 2-ethoxycarbonylphenyl or 4-(R7R8N)-phenyl,
    R6a and R6b represent methyl,
    R1 to R4, R7 and R8 independently of each other represent methyl, ethyl, cyanoethyl, benzyl or phenyl, and
    R1, R3 and R7 may additionally represent hydrogen, or
    NR1R2, NR3R4 and NR7R8 independently of each other represent pyrrolidino, piperidino or morpholino,
    R9, R9a, R9b, R10, R10a and R10b represent hydrogen or in each case one of R9, R9a, R9b and/or one of R10, R10a and R10b represents methyl.


Very particular preference is likewise given to cationic dyes of formula (I)




where

    X1 represents O, S or N—R6,
    X2 represents N,
    R6 represents hydrogen, methyl, ethyl, propyl, butyl, cyclohexyl, benzyl, phenyl, tolyl, anisyl or chlorophenyl,
    R1 to R4 independently of each other represent hydrogen, methyl, ethyl, propyl, butyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, benzyl, phenyl, tolyl, anisyl or chlorophenyl, or
    NR1R2 and NR3R4 independently of each other represent pyrrolidino, piperidino, morpholino or N-methylpiperazino,
    R9, R9a, R9b, R10, R10a and R10b represent hydrogen or in each case one of R9, R9a, R9b and/or one of R10, R10a and R10b represents methyl, or
    R1; R9, R2; R9a, R3; R10 and R4; R10a independently of each other form a —CH2CH2—, —CH2CH2CH2— or —CH2CH2—O— bridge which may bear up to three methyl groups.


Of outstanding preference are cationic dyes of formula (I),
where


    X1 represents O, S or N—R6,
    X2 represents N,
    R6 represents phenyl,
    R1 to R4 independently of each other represent hydrogen, methyl, ethyl, cyanoethyl or phenyl,
    R9, R9a, R9b, R10, R10a and R10b represent hydrogen or in each case one of R9, R9a, R9b and/or one of R10, R10a and R10b represents methyl.


Likewise of outstanding preference are cationic dyes of formula (I),
where


    X1 represents O,
    X2 represents N,
    NR1R2 represents dimethylamino or diethylamino,
    NR3R4 represents dimethylamino, diethylamino, N-methyl-N-(2-cyanoethyl)amino, bis(2-cyanoethyl)amino or anilino,
    R9 represents hydrogen or methyl, and
    R9a, R9b, R10, R10a and R10b represent hydrogen.


Preference is likewise given to mixtures of dyes of formula (I) where X2 represents N.
Particular preference is given to those mixtures of dyes of formula (I)
where


    X1 represents S or N—R6,
    X2 represents N,
    R6 represents phenyl or tolyl,
    R1 to R4 independently of each other represent hydrogen, methyl, ethyl, cyanoethyl or phenyl, or
    NR1R2 and NR3R4 independently of each other represent pyrrolidino, piperidino or morpholino or N-methylpiperazino, and in each case one of the moieties of the groups
    R9, R9a, R9b and R10, R10a, R10b represents methyl and the other two represent hydrogen.


Particular preference is likewise given to those mixtures of dyes of formula (I)
where


    X1 represents S or N—R6,
    X2 represents N,
    R6 represents phenyl or tolyl,
    R1 and R3 independently of each other represent hydrogen, methyl, ethyl, cyanoethyl or phenyl,
    R2 and R4 independently of each other represent hydrogen, methyl or ethyl,
    R9 and R10 represent hydrogen or methyl and are identical to each other, and
    R9a, R9b, R10a and R10b represent hydrogen.


Examples of such mixtures are:




Very particular preference is likewise given to cationic dyes of formula (II)




where

    R15 represents hydrogen, chlorine, methyl, methoxy, NR18R19 or N+R18R19N20 An−,
    R11 to R14, R18, R19 and R20 independently of each other represent hydrogen, methyl, ethyl, propyl, butyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, benzyl, phenyl, tolyl, anisyl or chlorophenyl, or
    NR11R12, NR13R14 and NR18R19 independently of each other represent pyrrolidino, piperidino, morpholino or N-methylpiperazino, or
    R12; R17b, R13; R17c and R18; R17a independently of each other form a —CH2CH2—, —CH2CH2CH2— or —CH2CH2—O— bridge which may bear up to three methyl groups,
    An− represents an anion,
    R16 represents hydrogen, chlorine, methoxycarbonyl or ethoxycarbonyl,
    R16a represents hydrogen or chlorine, and
    R17a, R17b and R17c independently of each other represent hydrogen or methyl.


Of outstanding preference are cationic dyes of formula (II),
where


    R15 represents hydrogen or NR18R19,
    NR11R12, NR13R14 and NR18R19 independently of each other represent amino, methylamino, ethylamino, cyanoethylamino, dimethylamino, diethylamino, bis(2-cyanoethyl)amino or anilino,
    R16 and R16a represent hydrogen, or
    R16 may additionally represent chlorine when R15 represents hydrogen,
    R17a, R17b and R17c represent hydrogen, or
    R17a, R17b and R17c independently of each other may additionally represent methyl when the respective adjacent group NR11R12, NR13R14 or NR18R19 represents amino, methylamino, ethylamino or cyanoethylamino.


Very particular preference is likewise given to cationic dyes of formula (III)




where

    A together with X21 and X23 and the atoms connecting them represents 2- or 4-quinolyl, 1,3-thiazol-2-yl, 1,3-thiazolin-2-yl, benzothiazol-2-yl, 1,3-oxazolin-2-yl, benzoxazol-2-yl, imidazol-2-yl, imidazolin-2-yl, benzimidazol-2-yl, pyrrolin-2-yl, 3H-indol-2-yl or quinoxalin-2-yl, which may each be substituted by methyl, ethyl, benzyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl, while in the case of imidazol-2-yl, imidazolin-2-yl and benzimidazol-2-yl both the nitrogen atoms are substituted by R21, or
    A together with X21—R21 and X23 and the atoms connecting them represents pyrylium-2- or -4-yl, thiopyrylium-2- or -4-yl which are substituted by 2 moieties from the group phenyl, tolyl or anisyl,
    B together with X22 and X24 and the atoms connecting them represents pyridin-2- or -4-ylene, quinolin-2- or -4-ylene, 1,3-thiazol-2-ylene, 1,3-thiazolin-2-ylene, benzothiazol-2-ylene, 1,3-oxazolin-2-ylene, benzoxazol-2-ylene, imidazol-2-ylene, imidazolin-2-ylene, benzimidazol-2-ylene, pyrrolin-2-ylene, 3-H-indol-2-ylene, 1,3,4-thiadiazol-2-ylene, 1,2,4-thiadiazol-3-ylene or quinoxalin-2-ylene, which may each be substituted by methyl, ethyl, benzyl, methoxy, chlorine, cyano, nitro, methoxycarbonyl, dimethylamino, diethylamino, dipropylamino, dibutylamino, pyrrolidino, morpholino or piperidino, while in the case of imidazol-2-ylene, imidazolin-2-ylene and benzimidazol-2-ylene both the nitrogen atoms are substituted by R22,
    Y21 represents N or C—R27,
    w represents 0 or 1,
    R21 and R22 independently of each other represent methyl, ethyl, propyl, butyl, benzyl or phenethyl,
    R27 and R28 independently of each other represent hydrogen or cyano, and
    R29 represents hydrogen.


Of outstanding preference are cationic dyes of formula (III),
where


    A together with X21 and X23 and the atoms connecting them represents 2- or 4-quinolyl, 1,3-thiazol-2-yl, 1,3-thiazolin-2-yl, benzothiazol-2-yl, imidazol-2-yl, imidazolin-2-yl, benzimidazol-2-yl, pyrrolin-2-yl or 3H-indol-2-yl, which may each be substituted by methyl, methoxy, chlorine, nitro or methoxycarbonyl, while in the case of imidazol-2-yl, imidazolin-2-yl and benzimidazol-2-yl both the nitrogen atoms are substituted by R21,
    B together with X22 and X24 and the atoms connecting them represents quinolin-2- or -4-ylene, 1,3-thiazol-2-ylene, 1,3-thiazolin-2-ylene, benzothiazol-2-ylene, imidazol-2-ylene, imidazolin-2-ylene, benzimidazol-2-ylene, pyrrolin-2-ylene or 3-H-indol-2-ylene, which may each be substituted by methyl, methoxy, chlorine, nitro or methoxycarbonyl, while in the case of imidazol-2-ylene, imidazolin-2-ylene and benzimidazol-2-ylene both the nitrogen atoms are substituted by R22,
    Y21 represents C—R27,
    w represents 0 or 1 and preferably represents 1,
    R21 and R22 independently of each other represent methyl, ethyl or benzyl,
    R27 represents hydrogen or cyano, and
    R28 and R29 represent hydrogen.


Likewise of outstanding preference are cationic dyes of formula (III)
where


    A together with X21 and X23 and the atoms connecting them represents 2- or 4-quinolyl, 1,3-thiazol-2-yl, 1,3-thiazolin-2-yl, benzothiazol-2-yl, imidazol-2-yl, imidazolin-2-yl, benzimidazol-2-yl, pyrrolin-2-yl or 3H-indol-2-yl, which may each be substituted by methyl, methoxy, chlorine, nitro or methoxycarbonyl, while in the case of imidazol-2-yl, imidazolin-2-yl and benzimidazol-2-yl both the nitrogen atoms are substituted by R21,
    B together with X22 and X24 and the atoms connecting them represents 1,3-thiazol-2-ylene, benzothiazol-2-ylene, imidazol-2-ylene, benzimidazol-2-ylene, which may each be substituted by methyl, ethyl, methoxy, chlorine, cyano, phenyl, methoxycarbonyl, represents 1,3,4-thiadiazol-2-ylene, which may be substituted by methyl, methoxy, methylthio, bromine, dimethylamino, diethylamino, dipropylamino, N-methyl-N-(2-cyanoethyl)amino, N-methylanilino, pyrrolidino, morpholino or piperidino, or represents 1,2,4-thiadiazol-3-ylene; which may be substituted by methyl, ethyl, methylthio or phenyl, while in the case of imidazol-2-ylene and benzimidazol-2-ylene both the nitrogen atoms are substituted by R22,
    Y21 represents N,
    w represents 1,
    R21 and R22 independently of each other represent methyl, ethyl or benzyl, and
    R28 and R29 represent hydrogen.


Very particular preference is likewise given to cationic dyes of formula (IV)




where

    C together with X31 and X32 and the atoms connecting them represents 2- or 4-pyridyl, 2- or 4-quinolyl, 1,3-thiazol-2-yl, 1,3-thiazolin-2-yl, benzothiazol-2-yl, 1,3-oxazolin-2-yl, benzoxazol-2-yl, imidazol-2-yl, imidazolin-2-yl, benzimidazol-2-yl, pyrrolin-2-yl, 3H-indol-2-yl or quinoxalin-2-yl, which may each be substituted by methyl, ethyl, benzyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl, while in the case of imidazol-2-yl, imidazolin-2-yl and benzimidazol-2-yl both the nitrogen atoms are substituted by R31, or
    C together with X31—R31 and X32 and the atoms connecting them represents pyrylium-2- or -4-yl, thiopyrylium-2- or -4-yl which are substituted by 2 moieties from the group phenyl, tolyl or anisyl,
    R31 represents methyl, ethyl, propyl, butyl, benzyl or phenethyl,
    R32 and R33 independently of each other represent methyl, ethyl, propyl, butyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, benzyl, phenyl, tolyl, anisyl, 4-ethoxyphenyl or chlorophenyl, and
    R32 may additionally represent hydrogen, or
    NR32R33 represents pyrrolidino, piperidino, morpholino or N-methylpiperazino,
    R34 represents hydrogen, chlorine, methyl or methoxy, or
    R34 combines with R32 to form a —CH2CH2—, —CH2CH2CH2— or —CH2CH2—O— bridge in which up to three hydrogen atoms may be replaced by methyl groups,
    R35 represents hydrogen, chlorine, methyl, methoxy, acetamino, propionylamino or methanesulphonylamino,
    R36 represents hydrogen or cyano,
    x represents 1, and
    x may additionally represent 0 when C represents 1,3-thiazol-2-yl, 1,3-thiazolin-2-yl, benzothiazol-2-yl, 1,3-oxazolin-2-yl, benzoxazol-2-yl, imidazol-2-yl, imidazolin-2-yl or benzimidazol-2-yl.


Of outstanding preference are cationic dyes of formula (IV)
where


    C together with X31 and X32 and the atoms connecting them represents 2- or 4-quinolyl, 1,3-thiazol-2-yl, 1,3-thiazolin-2-yl, benzothiazol-2-yl, imidazol-2-yl, imidazolin-2-yl, benzimidazol-2-yl, pyrrolin-2-yl or 3H-indol-2-yl which may each be substituted by methyl, methoxy, chlorine, nitro or methoxycarbonyl, while in the case of imidazol-2-yl, imidazolin-2-yl and benzimidazol-2-yl both the nitrogen atoms are substituted by R21, or
    C together with X31—R31 and X32 and the atoms connecting them represents pyrylium-2-yl, thiopyryliumyl which are substituted by 2 phenyl moieties,
    R31 represents methyl, ethyl or benzyl,
    R32 and R33 independently of each other represent methyl, ethyl, chloroethyl, cyanomethyl, cyanoethyl, benzyl, phenyl, anisyl or 4-ethoxyphenyl or
    NR32R33 represents pyrrolidino, piperidino or morpholino,
    R34 represents hydrogen,
    R35 represents hydrogen or methyl,
    R36 represents hydrogen or cyano, and
    x represents 1.


Very particular preference is likewise given to cationic dyes of formula (V)




where

    Y42 represents a radical of formulae (Va) or (Vb)






    R41, R41a and R41b independently of each other represent methyl, ethyl, propyl, butyl, benzyl or phenethyl and R41 and R41a may additionally represent hydrogen,
    R42 and R42a independently of each other represent hydrogen, methyl, ethyl, cyclohexyl, phenyl, tolyl, anisyl or chlorophenyl,
    R43 and R43a independently of each other represent hydrogen, methyl, methoxy or chlorine, or two adjacent R43 or R43a represent —CH═CH—CH═CH—,
    n and o independently of each other represent an integer from 0 to 2,
    Y41 represents CR44 or ═CR45aCR46═CR45b— when Y42 represents a moiety of formula (Va), or
    Y41 represents CR44 when Y42 represents a moiety of formula (Vb),
    Y43 represents CH, or
    Y41 and Y43 both represent N,
    R44, R45a, R45b and R46 represent hydrogen, and
    D together with X41 and X42 and the atoms connecting them represents pyridin-2- or -4-ylene, quinolin-2- or -4-ylene, 1,3-thiazol-2-ylene, 1,3-thiazolin-2-ylene, benzothiazol-2-ylene, 1,3,4-thiadizol-2-ylene, 1,3-oxazolin-2-ylene, benzoxazol-2-ylene, imidazol-2-ylene, imidazolin-2-ylene, benzimidazol-2-ylene, pyrrolin-2-ylene, 1,3,4-triazol-2-ylene, 3-H-indol-2-ylene or quinoxalin-2-ylene, which may each be substituted by methyl, ethyl, benzyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl, while in the case of imidazol-2-ylene, imidazolin-2-ylene and benzimidazol-2-ylene both the nitrogen atoms are substituted by R41b, and in the case of 1,3,4-thiadizol-2-ylene possible additional substituents are dimethylamino, diethylamino, dipropylamino, dibutylamino, N-methyl,N-cyanoethylamino, bis(cyanoethyl)amino, N-methyl-N-phenylamino, pyrrolidino, piperidino or morpholino, or
    D together with together with X41—R41b and X42 and the atoms connecting them represents 2H-pyran-2-ylene, 4H-pyran-4-ylene, 2H-thiopyran-2-ylene, 4H-thiopyran-4-ylene, which are substituted by 2 moieties from the group phenyl, tolyl or anisyl.


Of outstanding preference are cationic dyes of formula (V),
where


    Y42 represents a moiety of formulae (Va) or (Vb)






    R41, R41a and R41b independently of each other represent methyl, ethyl or benzyl,
    R42 and R42a independently of each other represent hydrogen, methyl or phenyl,
    R43 and R43a represent hydrogen,
    n and o independently of each other represent 1,
    Y41 represents CR44 or ═CR45aCR46═CR45b— when Y42 represents a moiety of formula (Va), or
    Y41 represents CR44 when Y42 represents a moiety of formula (Vb),
    Y43 represents CH,
    R44, R45a, R45b and R46 represent hydrogen, and
    D together with X41 and X42 and the atoms connecting them represents quinolin-2- or -4-ylene, 1,3-thiazol-2-ylene, benzothiazol-2-ylene, imidazol-2-ylene, imidazolin-2-ylene, benzimidazol-2-ylene, pyrrolin-2-ylene or 3-H-indol-2-ylene, which may each be substituted by methyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl, while in the case of imidazol-2-ylene, imidazolin-2-ylene and benzimidazol-2-ylene both the nitrogen atoms are substituted by R41b, or
    D together with together with X41—R41b and X42 and the atoms connecting them represents 2H-pyran-2-ylene, 4H-pyran-4-ylene, 2H-thiopyran-2-ylene, 4H-thiopyran-4-ylene, which are substituted by 2 phenyl moieties.
    Likewise of outstanding preference are cationic dyes of formula (V) where the pairs R41 and R41a, R42 and R42a, R43 and R43a and also n and o have the same meaning in each case.


Very particular preference is likewise given to cationic dyes of formula (VI)




where

    Y52 represents a moiety of formulae (VIa), (VIb) or (VIc)






    R51, R51a, R51b and R51c independently of each other represent methyl, ethyl, propyl, butyl, benzyl or phenethyl,
    R52 and R52a independently of each other represent cyclohexyl, phenyl, tolyl, anisyl or chlorophenyl,
    R53 and R53a independently of each other represent methyl, cyano, methoxycarbonyl or ethoxycarbonyl,
    R53d represents methyl, ethyl, cyclohexyl, phenyl, tolyl, anisyl or chlorophenyl,
    R53b represents hydrogen, methyl, methoxy or chlorine or two adjacent R53b represents —CH═CH—CH═CH—,
    m represents an integer from 0 to 2,
    Y51 represents CR54 or ═CR55a—CR56═CR55b— when Y52 represents a moiety of formulae (VIa) or (VIc), or
    Y51 represents CR54 when Y52 represents a moiety of formula (VIb),
    Y53 represents CH, or
    Y51 and Y53 both represent N,
    R54, R55a, R55b and R56 represent hydrogen,
    E together with X51 and X52 and the atoms connecting them represents pyridin-2- or -4-ylene, quinolin-2- or -4-ylene, 1,3-thiazol-2-ylene, 1,3-thiazolin-2-ylene, benzothiazol-2-ylene, 1,3,4-thiadizol-2-ylene, 1,3-oxazolin-2-ylene, benzoxazol-2-ylene, imidazol-2-ylene, imidazolin-2-ylene, benzimidazol-2-ylene, pyrrolin-2-ylene, 1,3,4-triazol-2-ylene, 3-H-indol-2-ylene or quinoxalin-2-ylene, which may each be substituted by methyl, ethyl, benzyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl, while in the case of imidazol-2-ylene, imidazolin-2-ylene and benzimidazol-2-ylene both the nitrogen atoms are substituted by R51c, and in the case of 1,3,4-thiadizol-2-ylene possible additional substituents are dimethylamino, diethylamino, dipropylamino, dibutylamino, N-methyl,N-cyanoethylamino, bis(cyanoethyl)amino, N-methyl-N-phenylamino, pyrrolidino, piperidino or morpholino, or
    E together with together with X51—R51c and X52 and the atoms connecting them represents 2H-pyran-2-ylene, 4H-pyran-4-ylene, 2H-thiopyran-2-ylene, 4H-thiopyran-4-ylene, which are substituted by 2 moieties from the group phenyl, tolyl or anisyl.


Of outstanding preference are cationic dyes of formula (VI),
where


    the pairs R51 and R51a, R52 and R52a and also R53 and R53a have the same meaning in each case.


Of outstanding preference are cationic dyes of formula (VI)
where


    Y52 represents a moiety of formulae (VIa), (VIb) or (VIc)






    R51, R51a, R51b and R51c independently of each other represent methyl, ethyl or benzyl,
    R52 and R52a independently of each other represent phenyl, tolyl, anisyl or chlorophenyl,
    R53 and R53a independently of each other represent methyl or methoxycarbonyl,
    R53d represents methyl or phenyl,
    R53b represents hydrogen,
    m represents 1,
    Y51 represents CR54 or ═CR55a—CR56═CR55b— when Y52 represents a moiety of formulae (VIa) or (VIc), or
    Y51 represents CR54 when Y52 represents a moiety of formula (VIb),
    Y53 represents CH,
    R54, R55a, R55b and R56 represent hydrogen,
    E together with X51 and X52 and the atoms connecting them represents quinolin-2- or -4-ylene, 1,3-thiazol-2-ylene, benzothiazol-2-ylene, imidazol-2-ylene, imidazolin-2-ylene, benzimidazol-2-ylene, pyrrolin-2-ylene or 3-H-indol-2-ylene, which may each be substituted by methyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl, while in the case of imidazol-2-ylene, imidazolin-2-ylene and benzimidazol-2-ylene both the nitrogen atoms are substituted by R41b, or
    E together with together with X51—R51c and X52 and the atoms connecting them represents 2H-pyran-2-ylene, 4H-pyran-4-ylene, 2H-thiopyran-2-ylene, 4H-thiopyran-4-ylene, which are substituted by 2 phenyl moieties.


Very particular preference is likewise given to cationic dyes of formula (VII)




where

    Y62 represents a moiety of formulae






    X61 and X61a independently of each other represent O or S,
    X62 and X62a independently of each other represent CR66 or N,
    R63 and R63a independently of each other represent hydrogen, methyl, 2-propyl, tert-butyl, chlorine, phenyl, tolyl, anisyl, chlorophenyl or NR64R65,
    R61, R61a, R62, R62a, R64 and R65 independently of each other represent methyl, ethyl, propyl, butyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, benzyl, phenyl, tolyl, anisyl or chlorophenyl, or
    NR61R62 and NR64R65 independently of each other represent pyrrolidino, piperidino, morpholino or N-methylpiperazino,
    Y61 represents ═CR67— or N,
    R67 represents hydrogen or a moiety of formula (VIIa),
    G together with X63 and X64 and the atoms connecting them represents pyridin-2- or -4-ylene, quinolin-2- or -4-ylene, 1,3-thiazol-2-ylene, 1,3-thiazolin-2-ylene, benzothiazol-2-ylene, 1,3-oxazolin-2-ylene, benzoxazol-2-ylene, imidazol-2-ylene, imidazolin-2-ylene, benzimidazol-2-ylene, pyrrolin-2-ylene, 3-H-indol-2-ylene or quinoxalin-2-ylene, which may each be substituted by methyl, ethyl, benzyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl, while in the case of imidazol-2-ylene, imidazolin-2-ylene and benzimidazol-2-ylene both the nitrogen atoms are substituted by R68,
    R68 represents methyl, ethyl, propyl, butyl, benzyl or phenethyl,
    X65 represents N or C—R67,
    R66 and R67 independently of each other represents hydrogen or cyano,
    R72 and R73 independently of each other represent methyl, ethyl, propyl, butyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, benzyl, phenyl, tolyl, anisyl or chlorophenyl, and
    R72 may additionally represent hydrogen, or
    NR72R73 represent pyrrolidino, piperidino, morpholino or N-methylpiperazino,
    R74a represents hydrogen,
    R74 represents hydrogen, methyl, methoxy or chlorine, or
    R74; R73 form a —CH2CH2—, —CH2CH2CH2— or —CH2CH2—O— bridge in which up to three hydrogen atoms may be replaced by methyl groups,
    R75 represents hydrogen, chlorine, methyl, methoxy, acetamino, propionylamino or methanesulphonylamino.


Of outstanding preference are cationic dyes of formula (VII),
where


    Y62 represents a moiety of formulae






    X61 and X61a independently of each other represent S,
    X62 and X62a independently of each other represent CR66 or N,
    R63 and R63a independently of each other represent hydrogen, methyl, phenyl or NR64R65,
    R61, R61a, R62, R62a, R64 and R65 independently of each other represent methyl, ethyl, propyl, butyl, cyanoethyl, benzyl or phenyl, or
    NR61R62 and NR64R65 independently of each other represent pyrrolidino, piperidino or morpholino,
    Y61 represents ═CR67—,
    R67 represents hydrogen or a moiety of formula (VIIa),
    G together with X63 and X64 and the atoms connecting them represents quinolin-2- or -4-ylene, 1,3-thiazol-2-ylene, benzothiazol-2-ylene, imidazol-2-ylene, imidazolin-2-ylene, benzimidazol-2-ylene, pyrrolin-2-ylene or 3-H-indol-2-ylene, which may each be substituted by methyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl, while in the case of imidazol-2-ylene, imidazolin-2-ylene and benzimidazol-2-ylene both the nitrogen atoms are substituted by R41b,
    R68 represents methyl, ethyl or benzyl,
    X65 represents C—R67,
    R66 and R67 represent hydrogen,
    R72 and R73 independently of each other represent methyl, ethyl, chloroethyl, cyanomethyl, cyanoethyl, benzyl or phenyl, or
    NR72R73 represent pyrrolidino, piperidino or morpholino,
    R74 and R74a represent hydrogen,
    R75 represents hydrogen or methyl.
    Likewise of outstanding preference are cationic dyes of formula (VII) where X61 and X61a, X62 and X62a, R61 and R61a, R62 and R62a, R63 and R63a are pairwise identical in each case.


Very particular preference is likewise given to cationic dyes of formula (VIII)




where

    R81 and R82 independently of each other represent methyl, ethyl, propyl, butyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, benzyl, phenyl, tolyl, anisyl or chlorophenyl,
    R83 and R84 independently of each other represents hydrogen, methyl, methoxy, chlorine, cyano, nitro, methoxycarbonyl or ethoxycarbonyl, or two adjacent R83 or R84 represent —CH═CH—CH═CH—, or
    R83; R81 and/or R84; R82 form a —CH2CH2—, —CH2CH2CH2— or —CH2CH2—O— bridge in which up to three hydrogen atoms may be replaced by methyl groups,
    q and r independently of each other represent an integer from 0 to 2.


Of outstanding preference are cationic dyes of formula (VIII)
where


    R81 and R82 independently of each other represent methyl or ethyl,
    R83 and R84 independently of each other represents hydrogen, methyl, methoxy, chlorine, cyano, nitro, methoxycarbonyl or ethoxycarbonyl, or two adjacent R83 or R84 represent —CH═CH—CH═CH—, or
    R83; R81 and/or R84; R82 form a —CH2CH2— or —CH2CH2CH2— bridge, and
    q and r represent 1.


Likewise of outstanding preference are cationic dyes of formula (VIII),
where


    the pairs R81 and R82, R83 and R84 and also q and r are identical.


Very particular preference is likewise given to cationic dyes of formula (IX)




where

    Y91 represents a moiety of formulae (IXa) or (IXb)






    R91 represents methyl, ethyl, propyl, butyl, cyanoethyl, benzyl or phenethyl,
    R92 and R93 independently of each other represent methyl, ethyl, propyl, butyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, benzyl, phenyl, tolyl, anisyl, 4-ethoxyphenyl or chlorophenyl, or
    NR92R93 represent pyrrolidino, piperidino, morpholino or N-methylpiperazino,
    R94a represents hydrogen,
    R94 represents hydrogen, methyl, methoxy or chlorine, or
    R94; R93 form a —CH2CH2— or —CH2CH2CH2— bridge in which up to three hydrogen atoms may be replaced by methyl groups,
    R95 represents hydrogen, chlorine, methyl, methoxy, acetamino, propionylamino, or methanesulphonylamino,
    R96 represents hydrogen or bromine,
    R97 represents methyl, ethyl, propyl, butyl, benzyl or phenethyl,
    R98 represents hydrogen, methyl, ethyl, cyclohexyl, phenyl, tolyl, anisyl or chlorophenyl,
    R99 represents hydrogen, methyl, methoxy or chlorine, or two adjacent R99 represents —CH═CH—CH═CH—,
    l represents an integer from 0 to 2, and
    j represents 0 or 1.


Of outstanding preference are cationic dyes of formula (IX)
where


    R91 represents methyl or ethyl,
    R92 and R93 independently of each other represent methyl, ethyl, chloroethyl, cyanoethyl, benzyl, phenyl, tolyl, anisyl or 4-ethoxyphenyl, or
    NR92R93 represents pyrrolidino, piperidino or morpholino,
    R94 and R94a represent hydrogen, or
    R94; R93 form a —CH2CH2— or —CH2CH2CH2— bridge in which up to three hydrogen atoms may be replaced by methyl groups,
    R95 represents hydrogen or methyl,
    R96 represents hydrogen or bromine,
    R97 represents methyl, ethyl or benzyl,
    R98 represents hydrogen, methyl or phenyl,
    R99 represents hydrogen,
    l represents 1, and
    j represents 0 or 1.


Very particular preference is likewise given to cationic dyes of formula (X)




where

    Y101 represents a moiety of formulae






    X101 represents O or S,
    X102 represents CR107 or N,
    R103 represents hydrogen, methyl, 2-propyl, tert-butyl, chlorine, phenyl, tolyl, anisyl, chlorophenyl or NR101aR102a,
    R101, R102, R101a, R102a, R105 and R106 independently of each other represent methyl, ethyl, propyl, butyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, benzyl, phenyl, tolyl, anisyl or chlorophenyl, or
    NR101R102 and/or NR101aR102a and/or NR105R106 represent pyrrolidino, morpholino, piperazino or piperidino,
    R107 represents hydrogen or cyano,
    H together with X103 and X104 and the atoms connecting them represents pyridin-2- or -4-ylene, quinolin-2- or -4-ylene, 1,3-thiazol-2-ylene, 1,3-thiazolin-2-ylene, benzothiazol-2-ylene, 1,3-oxazolin-2-ylene, benzoxazol-2-ylene, imidazol-2-ylene, imidazolin-2-ylene, benzimidazol-2-ylene, pyrrolin-2-ylene, 3-H-indol-2-ylene or quinoxalin-2-ylene, which may each be substituted by methyl, ethyl, benzyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl, while in the case of imidazol-2-ylene, imidazolin-2-ylene and benzimidazol-2-ylene both the nitrogen atoms are substituted by R104,
    R104 and R114 independently of each other represent methyl, ethyl, propyl, butyl, benzyl or phenethyl,
    Y102 represents CH,
    Y105 represents N or CH,
    Y103 represents CN,
    Y104 represents a cationic moiety of formulae






    CY103Y104 together represents a moiety of formulae






where the asterisk (*) indicates the ring atom from which the double bond emanates,

    R112 represents hydrogen, methyl, ethyl, cyanoethyl, benzyl or phenyl,
    R113 represents methyl, cyano, methoxycarbonyl or ethoxycarbonyl,
    J, K and L represents a moiety of formulae






and

    M represents a moiety of formulae






Of outstanding preference are cationic dyes of formula (X),
where


    Y101 represents a moiety of formulae






    X101 represents S,
    X102 represents CR107 or N,
    R103 represents hydrogen, methyl, phenyl or NR101aR102a,
    R101, R102, R101a, R102aR105 and R106 independently of each other represent methyl, ethyl, cyanoethyl, benzyl or phenyl, or
    NR101R102 and/or NR101aR102a and/or NR105R106 represent pyrrolidino, morpholino or piperazino,
    R107 represents hydrogen or cyano,
    H together with X103 and X104 and the atoms connecting them represents quinolin-2- or -4-ylene, 1,3-thiazol-2-ylene, benzothiazol-2-ylene, imidazol-2-ylene, imidazolin-2-ylene, benzimidazol-2-ylene, pyrrolin-2-ylene or 3-H-indol-2-ylene, which may each be substituted by methyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl, while in the case of imidazol-2-ylene, imidazolin-2-ylene and benzimidazol-2-ylene both the nitrogen atoms are substituted by R104,
    R104 and R114 independently of each other represent methyl, ethyl or benzyl,
    Y102 represents CH,
    Y105 represents CH,
    Y103 represents CN,
    Y104 represents a cationic moiety of formulae






    
    
        or
    
    
    CY103Y104 together represents a moiety of formulae






    
    
        where the asterisk (*) indicates the ring atom from which the double bond emanates,
    
    
    R112 represents methyl, ethyl, cyanoethyl or benzyl,
    R113 represents methyl, cyano or methoxycarbonyl,
    J, K and L represents a moiety of formulae






    
    
        and
    
    
    M represents a moiety of formulae






The invention further provides dyes of formula F+An−,
where


    F+ has the abovementioned general or preferred meaning, particularly the general to outstandingly preferred meaning indicated for formulae (I) to (X),
    An− represents a 4-(sec-alkyl)benzenesulphonate of formula (LI)






    a and b independently of each other represent an integer from 0 to 20 subject to the proviso that a+b is ≧3.
    a+b is preferably ≧5, more preferably ≧7 and even more preferably ≧9.


Formula (LI) also subsumes mixtures of anions with different values of a and b where a+b is identical. However, formula (LI) also subsumes mixtures of anions with different values of a and b.
Examples of anions of formula (LI) are:




and also as mixture of all five conceivable isomers.

The invention further provides dyes of formula F+An−,
where


    F+ has the abovementioned general or preferred meaning, particularly the general to outstandingly preferred meaning indicated for formulae (I) to (X),
    An− represents a sec-alkylsulphonate of formula (LII)






    c and d independently of each other represent an integer from 0 to 20 subject to the proviso that c+d is ≧5.
    c+d is preferably ≧7, more preferably ≧9 and even more preferably ≧11.


Formula (LII) also subsumes mixtures of anions with different values of c and d where c+d is identical. However, formula (LII) also subsumes mixtures of anions with different values of c and d.
Examples of anions of formula (LII) are:




and also as mixture of all conceivable isomers.

The invention further provides dyes of formula F+An−,
where


    F+ has the abovementioned general or preferred meaning, particularly the general to outstandingly preferred meaning indicated for formulae (I) to (X),
    An− represents a branched alkyl sulphate of formula (LIII)






    e represents an integer from 0 to 5,
    f and g independently of each other represent an integer from 0 to 15 subject to the proviso that e+f+g is ≧5 and
    
        the CH2 groups may additionally be substituted by further methyl or ethyl groups.
    
    
    e+f+g is preferably ≧7, more preferably ≧9 and even more preferably ≧11.
    e preferably represents 0 or 1.


Preferably two CH2 groups are methyl and/or ethyl substituted.
Formula (LIII) also subsumes mixtures of anions with different values of e, f and g, where e+f+g is identical. However, formula (LIII) also subsumes mixtures of anions with different values of e, f and g.
Examples of anions of formula (LIII) are:




The invention further provides dyes of formula F+An−,
where


    F+ has the abovementioned general or preferred meaning, particularly the general to outstandingly preferred meaning indicated for formulae (I) to (X),
    An− represents a cyclic phosphoric ester of formula (LIV)






    R200 represents hydrogen or halogen,
    h represents an integer from 1 to 4.


Preferably R200 represents chlorine or bromine and h represents 4.
Examples of anions of formula (LIV) are:




The invention further provides dyes of formula F+An−,
where


    F+ has the abovementioned general or preferred meaning, particularly the general to outstandingly preferred meaning indicated for formulae (III) to (X),
    An− represents an alkyl sulphate of formula (LV)






    i represents an integer from 8 to 25.


The invention further provides dyes of formula F+An−,
where


    F+ has the abovementioned general or preferred meaning, particularly the general to outstandingly preferred meaning indicated for formulae (I) and (II),
    An− represents an alkyl sulphate of formula (LV)






    i represents an integer from 12 to 25, or
    i represents an integer from 18 to 25 when
    F+ represents formula (I), X2 represents N, X1 represents O or S and R1 to R4 are the same and represent methyl or ethyl, or
    F+ represents formula (II) and NR11R12, NR13R14 and R18R19 are the same and represent dimethylamino, and

all other moieties have the indicated general to outstandingly preferred meaning.



Preferably i represents an integer from 18 to 25.
Examples of anions of formula (LV) are:




The invention further provides dyes of formula F+An−,
where


    F+ has the abovementioned general or preferred meaning, particularly the general to outstandingly preferred meaning indicated for formulae (I) to (X),
    An− represents a sulphosuccinate of formula (LVI)






    R201 and R202 independently of each other represent an unbranched C4- to C16-alkyl moiety.


Preferably R201 and R202 are the same.
The invention further provides dyes of formula F+An−,
where


    F+ has the abovementioned general or preferred meaning, particularly the general to outstandingly preferred meaning indicated for formulae (I) to (X),
    An− represents a sulphosuccinate of formula (LVI)






    R201 and R202 independently of each other represent a C2- to C12-alkyl moiety substituted by 4 or more fluorine atoms, a C5- to C7-cycloalkyl moiety or a C7- to C10-aralkyl moiety.


Preferably R201 and R202 are the same.
The invention further provides dyes of formula F+An−,
where


    F+ has the abovementioned general or preferred meaning, particularly the general to outstandingly preferred meaning indicated for formulae (I) where X2=C—R5 and (III), (VI) to (X),
    An− represents a sulphosuccinate of formula (LVI)






    R201 and R202 independently of each other represent a C4- to C16-alkyl moiety, which may be branched, a C2- to C12-alkyl moiety substituted by 4 or more fluorine atoms, a C5- to C7-cycloalkyl moiety or a C7- to C10-aralkyl moiety.


Preferably R201 and R202 are the same.
The invention further provides dyes of formula F+An−,
where


    F+ represents formula (I) where X2=N and (II), where
    X1 represents O, S, N—R6 or CR6aR6b,
    R6 represents hydrogen, methyl, ethyl, propyl, butyl, cyclohexyl, benzyl, phenyl, tolyl, anisyl or chlorophenyl,
    R6a and R6b are the same and represent methyl, ethyl or conjointly a —CH2—CH2—CH2— or —CH2—CH2—CH2—CH2— bridge,
    R1 to R4 independently of each other represent hydrogen, methyl, ethyl, propyl, butyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, benzyl, phenyl, tolyl, anisyl or chlorophenyl, although at least one of R1 to R4 does not represent methyl when X1 represents S, or NR1R2 does not represent diethylamino when X1 represents O,
    NR1R2 and NR3R4 independently of each other represent pyrrolidino, piperidino, morpholino or N-methylpiperazino,
    R9; R9a; R9b; R10, R10a and R10b represent hydrogen or in each case one of R9, R9a, R9b and/or one of R10, R10a and R10b represents methyl, or
    R1; R9; R2; R9a; R3; R10 and R4; R10a independently of each other form a —CH2CH2— or —CH2CH2CH2— bridge,
    R15 represents hydrogen, chlorine, methyl, methoxy or NR18R19,
    R11 to R14, R18 and R19 independently of each other represent hydrogen, ethyl, propyl, butyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, benzyl, phenyl, tolyl, anisyl or chlorophenyl, and
    R13, R14, R18 and R19 may additionally represent methyl, or
    NR11R12, NR13R14 and NR18R19 independently of each other represent pyrrolidino, piperidino, morpholino or N-methylpiperazino, or
    R12; R17b; R13; R17c and R18; R17a independently of each other form a —CH2CH2—, —CH2CH2CH2— or —CH2CH2—O— bridge in which up to three hydrogen atoms may be replaced by methyl groups,
    R16 represents hydrogen, chlorine, methoxycarbonyl or ethoxycarbonyl,
    R16a represents hydrogen, and
    R17a, R17b, and R17c independently of each other represent hydrogen or methyl,
    An− represents a sulphosuccinate of formula (LVI)






    R201 and R202 independently of each other represent a C4- to C16-alkyl moiety, which may be branched, a C2- to C12-alkyl moiety substituted by 4 or more fluorine atoms, a C5- to C7-cycloalkyl moiety or a C7- to C10-aralkyl moiety.


The invention further provides dyes of formula F+An−,
where


    F+ represents formula (II),
    R15 represents hydrogen, chlorine, methyl, methoxy or NR18R19,
    R11 to R14, R18, R19 and R20 independently of each other represent hydrogen, ethyl, propyl, butyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, benzyl, phenyl, tolyl, anisyl or chlorophenyl, or
    NR11R12, NR13R14 and NR18R19 independently of each other represent pyrrolidino, piperidino, morpholino or N-methylpiperazino, or
    R12; R17b, R13; R17c and R18; R17a independently of each other form a —CH2CH2—, —CH2CH2CH2— or —CH2CH2—O— bridge which may bear up to three methyl groups,
    R16 represents hydrogen, chlorine, methoxycarbonyl or ethoxycarbonyl,
    R16a represents hydrogen, and
    R17a, R17b, and R17c independently of each other represent hydrogen or methyl.
    An− represents a sulphosuccinate of formula (LVI)






    R201 and R202 independently of each other represent a C4- to C16-alkyl moiety, which may be branched, a C2- to C12-alkyl moiety substituted by 4 or more fluorine atoms, a C5- to C7-cycloalkyl moiety or a C7- to C10-aralkyl moiety.


The invention further provides dyes of formula F+An−,
where


    F+ represents formula (IV) and (V), where
    C together with X31 and X32 and the atoms connecting them represents 2- or 4-pyridyl, 2- or 4-quinolyl, 1,3-thiazol-2-yl, 1,3-thiazolin-2-yl, benzothiazol-2-yl, 1,3-oxazolin-2-yl, benzoxazol-2-yl, imidazol-2-yl, imidazolin-2-yl, benzimidazol-2-yl, pyrrolin-2-yl, 3H-indol-2-yl or quinoxalin-2-yl, which may each be substituted by methyl, ethyl, benzyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl, while in the case of imidazol-2-yl, imidazolin-2-yl and benzimidazol-2-yl both the nitrogen atoms are substituted by R31, or
    C together with X31—R31 and X32 and the atoms connecting them represents pyrylium-2- or -4-yl, thiopyrylium-2- or -4-yl which are substituted by 2 moieties from the group phenyl, tolyl or anisyl,
    R31 represents methyl, ethyl, propyl, butyl, benzyl or phenethyl,
    R32 and R33 independently of each other represent methyl, propyl, butyl, chloroethyl, cyanomethyl, methoxyethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, benzyl, phenyl, tolyl, anisyl or chlorophenyl, and
    R32 may additionally represent hydrogen or ethyl, or
    NR32R33 represents pyrrolidino, piperidino, morpholino or N-methylpiperazino,
    R34 represents hydrogen, chlorine, methyl or methoxy, or
    R34 combines with R32 to form a —CH2CH2—, —CH2CH2CH2— or —CH2CH2—O— bridge in which up to three hydrogen atoms may be replaced by methyl groups,
    R35 represents hydrogen, chlorine, methyl, methoxy, acetamino, propionylamino or methanesulphonylamino,
    R36 represents hydrogen or cyano,
    Y42 represents a moiety of formulae (Va) or (Vb)






    R41, R41a and R41b independently of each other represent methyl, ethyl, propyl, butyl, benzyl or phenethyl and R41 and R41a may additionally represent hydrogen,
    R42 and R42a independently of each other represent hydrogen, ethyl, cyclohexyl, phenyl, tolyl, anisyl or chlorophenyl,
    R43 and R43a independently of each other represents hydrogen, methyl, methoxy or chlorine, or two adjacent R43 or R43a represent —CH═CH—CH═CH—,
    n and o independently of each other represent an integer from 0 to 2,
    Y41 represents CR44 or ═CR45a—CR46═CR45b— when Y42 represents a moiety of formula (Va), or
    Y41 represents CR44 when Y42 represents a moiety of formula (Vb),
    Y43 represents CH, or
    Y41 and Y43 both represent N,
    R44, R45a, R45b and R46 represent hydrogen, and
    D together with X41 and X42 and the atoms connecting them represents pyridin-2- or -4-ylene, quinolin-2- or -4-ylene, 1,3-thiazol-2-ylene, 1,3-thiazolin-2-ylene, benzothiazol-2-ylene, 1,3,4-thiadiazol-2-ylene, 1,3-oxazolin-2-ylene, benzoxazol-2-ylene, imidazol-2-ylene, imidazolin-2-ylene, benzimidazol-2-ylene, pyrrolin-2-ylene, 1,3,4-triazol-2-ylene, 3-H-indol-2-ylene or quinoxalin-2-ylene, which may each be substituted by methyl, ethyl, benzyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl, while in the case of imidazol-2-ylene, imidazolin-2-ylene and benzimidazol-2-ylene both the nitrogen atoms are substituted by R41b, and in the case of 1,3,4-thiadizol-2-ylene possible additional substituents are dimethylamino, diethylamino, dipropylamino, dibutylamino, N-methyl,N-cyanoethylamino, bis(cyanoethyl)amino, N-methyl-N-phenylamino, pyrrolidino, piperidino or morpholino, or
    D together with together with X41—R41b and X42 and the atoms connecting them represents 2H-pyran-2-ylene, 4H-pyran-4-ylene, 2H-thiopyran-2-ylene, 4H-thiopyran-4-ylene, which are substituted by 2 moieties from the group phenyl, tolyl or anisyl,
    An− represents a sulphosuccinate of formula (LVI)






    R201 and R202 independently of each other represent a C4- to C16-alkyl moiety, which may be branched, a C2- to C12-alkyl moiety substituted by 4 or more fluorine atoms, a C5- to C7-cycloalkyl moiety or a C7- to C10-aralkyl moiety.


It is particularly preferable for R201 and R202 to represent a C6- to C12-alkyl moiety, which may be branched, or to represent cyclohexyl or benzyl. It is very particularly preferable for R201 and R202 to represent n-hexyl, n-octyl or 2-ethylhexyl. It is likewise very particularly preferable for R201 and R202 to represent 2,2,3,3-tetrafluoropropyl, 1H,1H-heptafluorobutyl, perfluorooctyl, 1H,1H,7H-dodecafluoroheptyl, 1H,1H,2H,2H-tridecafluorooctyl.
Examples of anions of formula (LVI) are:




The invention further provides dyes of formula F+An−,
where


    F+ has the abovementioned general or preferred meaning, particularly the general to outstandingly preferred meaning indicated for formulae (I) to (X),
    An− represents an ester sulphonate of formula (LVII)






    R203 represents a C2- to C22-alkyl or alkenyl moiety, which may be branched or substituted, and
    u represents an integer from 2 to 4.


Examples of anions of formula (LVII) are:




The invention further provides dyes of formula F+An−,
where


    F+ has the abovementioned general or preferred meaning, particularly the general to outstandingly preferred meaning indicated for formulae (I) to (X),
    An− represents an ester sulphonate or ester sulphates of formula (LVIII)






    v represents 0 or 1,
    R204 represents C1- to C18-alkyl, which may be branched and/or substituted,
    R205 represents hydrogen or C1- to C8-alkyl, and
    Y201 represents a direct bond, an aliphatic C1 to C22 bridge or an olefinic C2 to C22 bridge,
    where Y201 and R204 together have 7 or more carbon atoms.


The invention further provides dyes of formula F+An−,
where


    F+ has the abovementioned general or preferred meaning, particularly the general to outstandingly preferred meaning indicated for formulae (I) to (X),
    An− represents a fluorinated alkyl sulphate of formula (LX)






where

    R209 represents a C4- to C18-alkyl moiety bearing 4 or more fluorine atoms.


Examples of anions of formula (LX) are:




Examples of anions of formula (LVIII) are:




The invention further provides solutions of the dyes of formula F+An− which are according to the present invention.
Preference is given to such solutions in esters and ketones and also mixtures thereof. Suitable esters are the ethyl, propyl and butyl esters of formic acid, acetic acid and propionic acid. Propyl is to be understood as meaning 1-propyl and 2-propyl, butyl is to be understood as meaning 1-butyl, 2-butyl and also 2-methyl-1-propyl. Preferred esters are ethyl acetate and 1-butyl acetate. Suitable ketones are acetone, butanone and pentanone. Butanone is the preferred ketone. Preferred mixtures consist of ethyl acetate and/or 1-butyl acetate and/or butanone. The butanone fraction in such mixtures is preferably ≦50% and more preferably ≦20%.
The concentration in such solutions of dye according to the present invention is in the range from 1% to 50% by weight, preferably in the range from 5% to 40% by weight and more preferably in the range from 10% to 30% by weight.
Preference is given to such solutions which have a water content <0.3%, more preferably <0.2% and even more preferably <0.1%.
The invention further provides a process for producing the dyes of formula (I), characterized in that they are isolated from a suspension.
In this process, the dye of formula F+An′− where F+ is as defined above and An′− represents an anion which stems from the synthesis or isolation of the dye is dissolved or suspended in a suitable solvent or solvent mixture. A salt of the anion M+An− according to the present invention, where M+ represents a cation or one equivalent of a cation and An− has the abovementioned meaning of an anion, is likewise dissolved in a solvent or solvent mixture, while the solvents for the dye and the salt need not be the same but have to be miscible. This solution of the salt M+An− then, is added at room temperature or elevated temperature, to the solution or suspension of the dye F+An′−, and the dye of formula F+An− according to the present invention precipitates. It is filtered off, washed and, if necessary, can be triturated with a solvent in which it is only minimally soluble, if at all, or is recrystallized from this solvent. This provides the dye of formula F+An− where F+ and An− have the abovementioned meaning.
Examples of anions An′− are chloride, bromide, sulphate, hydrogensulphate, nitrate, methosulphate.
Examples of cations M+ are Na+, K+, NH4+.
The temperature can be between room temperature and the boiling point of the mixture. Particular preference is given to between room temperature and 50° C.
Suitable solvents are alcohols such as methanol, ethanol, 2-propanol, nitriles such as acetonitrile, acids such as glacial acetic acid, dipolar solvents such as N-ethylpyrrolidone, ethers such as tetrahydrofuran or water.
Examples of solvents suitable for trituration are diethyl ether and tert-butyl methyl ether. Examples of solvents suitable for recrystallization are glacial acetic acid and acetonitrile. It may be the case that the precipitation can be improved by addition of, for example, methanol or water.
Another version of this process is possible when a dye of formula F+An′− which is deprotonatable to an anhydrobase or forms a carbinol base of formula F-OH. Deprotonatable dyes of formula F+An′− are those of formula F′-H+An′−, where F′-H+ has the same meaning as F+. Such dyes can be converted with bases into the neutral anhydrobase F′ which are converted with an acid H+An− into the invention dye F′-H+An−=F+An−.
Examples are:




The invention further provides a process for producing the dyes of formula (I), characterized in that a two-phase mixture of water and a water-immiscible solvent is used.
In this process, the dye of formula F+An′−, where F+ is as defined above and An′− represents an anion stemming from the synthesis or isolation of the dye, is stirred together with a salt of the anion M+An− according to the present invention, where M+ represents a cation or one equivalent of a cation and An− has the abovementioned meaning of a sulphosuccinate, in a mixture of water and a water-immiscible solvent at room temperature or higher temperature. The aqueous phase is separated off. This can be done at room temperature or at higher temperature. Advantageously, the organic phase containing the dye of formula F+An− is stirred together with fresh water one or more times. The aqueous phase is separated off each time. The organic phase is suitably dried and finally evaporated. If necessary, the dry residue can additionally be triturated with a solvent in which it is only minimally soluble, if at all, or be recrystallized from this solvent. This provides the dye of formula F+An− where F+ and An− have the abovementioned meaning.
Examples of anions An′− are chloride, bromide, sulphate, hydrogensulphate, nitrate, methosulphate.
Examples of cations M+ are Na+, K+ and NH4+.
The temperature can be between room temperature and the boiling point of the mixture. Particular preference is given to between room temperature and 40 to 50° C.
Suitable water-immiscible solvents are halogenated alkanes such as dichloromethane, trichloromethane, tetrachloroethane and also aromatics such as toluene or chlorobenzene.
Examples of solvents suitable for trituration are diethyl ether and tert-butyl methyl ether. Examples of solvents suitable for recrystallization are glacial acetic acid and acetonitrile.
The invention further provides a process for producing the sulphosuccinates, characterized in that a two-phase mixture of water and an ester is used.
In this process, the dye of formula F+An′−, where F+ is as defined above and An′− represents an anion stemming from the synthesis or isolation of the dye, is stirred together with a salt of the anion M+An− according to the present invention, where M+ represents a cation or one equivalent of a cation and An− has the abovementioned meaning of a sulphosuccinate, in a mixture of water and an ester at room temperature or higher temperature. The aqueous phase is separated off. This can be done at room temperature or at higher temperature. Advantageously, the ester phase containing the dye of formula F+An− is stirred together with fresh water one or more times. The aqueous phase is separated off each time. The ester phase is suitably dried. This provides a solution of a dye of formula F+An− where F+ and An− have the abovementioned meaning.
Examples of anions An′− are chloride, bromide, sulphate, hydrogensulphate, nitrate, methosulphate.
Ester refers to esters of formic acid, acetic acid, propionic acid and butyric acid, preferably esters of acetic acid and propionic acid.
Examples of esters are propyl formate, butyl formate, ethyl acetate, butyl acetate, methoxypropyl acetate, ethoxypropyl acetate, methyl propionate, ethyl propionate, methyl butyrate. Ethyl acetate and butyl acetate are preferred.
Examples of cations M+ are Na+, K+ and NH4+.
The temperature can be between room temperature and the boiling point of the mixture. Particular preference is given to between room temperature and 50° C.
Drying the ester phase is to be understood as removing entrained and/or dissolved water. Entrained water can be removed for example by filtration through a suitable membrane or a hydrophobicized filter paper. Suitable drying methods are drying over anhydrous salts such as sodium sulphate or magnesium sulphate or over molecular sieve. A further drying method is the distillative removal of water as azeotrope. Advantageously, various of these methods are carried out in succession.
The invention further provides a process for producing the sulphosuccinates, characterized in that an ester is used in the absence of water.
In this process, the dye of formula F+An′−, where F+ is as defined above and An′− represents an anion stemming from the synthesis or isolation of the dye, is stirred together with a salt of the anion M+An− according to the present invention, where M+ represents a cation or one equivalent of a cation and An− has the abovementioned meaning of a sulphosuccinate, in an ester at room temperature or higher temperature and undissolved matter is filtered off. This provides a solution of a dye of formula F+An−, where F+ and An− have the abovementioned meaning, useful without further drying. However, in an individual case—when the starting materials used were not completely water-free for example—additional drying can also be necessary, and this is carried out as described above.
Examples of anions An′− are chloride, bromide, sulphate, hydrogensulphate, nitrate, methosulphate.
Ester refers to the above-recited esters.
Preferred esters are ethyl acetate and butyl acetate.
Examples of cations M+ are Na+, K+ and NH4+.
The temperature can be between room temperature and the boiling point of the acetic ester. Particular preference is given to between room temperature and 60° C.
The undissolved matter comprises mainly the salt of the composition M+An′−.
The invention further provides dyes of formulae (Vc) and (Vd)




where

    R49a and R49b represent hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, cyano or halogen and preferably are the same,
    R41 represents hydrogen, C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl or C6- to C10-aryl,
    R42 represents C1- to C16-alkyl, C3- to C6-alkenyl, C5- to C7-cycloalkyl or C7- to C16-aralkyl, C6- to C10-aryl or hetaryl,
    R43 represents hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, halogen, cyano, nitro or C1- to C4-alkoxycarbonyl or two adjacent R43 represent —CH═CH—CH═CH—,
    n represents an integer from 0 to 2,
    An− represents an anion, preferably an anion according to the present invention.


Preference is given to dyes of formulae (Vc) and (Vd),
where


    R49a and R49b represent hydrogen,
    R41 represents hydrogen, methyl, ethyl, cyanoethyl, allyl or benzyl,
    R42 represents methyl, ethyl, cyclohexyl, phenyl, tolyl, anisyl or chlorophenyl,
    R43 represents hydrogen, chlorine, cyano, methyl, methoxy, methoxycarbonyl or ethoxycarbonyl,
    n represents 1,
    An− represents an anion, preferably an anion according to the present invention.


As polyisocyanate component a) there can be used any compounds known per se to a person skilled in the art, or mixtures thereof, which on average contain two or more NCO functions per molecule. These can be aromatic, araliphatic, aliphatic or cycloaliphatic based. Monoisocyanates and/or unsaturation-containing polyisocyanates can also be used, in minor amounts.
Suitable examples are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,2,4- and/or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis(4,4′-isocyanatocyclohexyl)methane and mixtures thereof having any desired isomer content, isocyanatomethyl-1,8-octane diisocyanate, 1,4-cyclohexylene diisocyanate, the isomeric cyclohexanedimethylene diisocyanates, 1,4-phenylene diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate and/or triphenylmethane 4,4′,4′′-triisocyanate.
It is likewise possible to use derivatives of monomeric di- or triisocyanates having urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione and/or iminooxadiazinedione structures.
Preference is given to using polyisocyanates based on aliphatic and/or cycloaliphatic di- or triisocyanates.
It is particularly preferable for the polyisocyanates of component a) to comprise di- or oligomerized aliphatic and/or cycloaliphatic di- or triisocyanates.
Very particular preference is given to isocyanurates, uretdiones and/or iminooxadiazinediones based on HDI and also 1,8-diisocyanato-4-(isocyanatomethyl)octane or mixtures thereof.
Likewise useful as component a) are NCO-functional prepolymers having urethane, allophanate, biuret and/or amide groups. Prepolymers of component a) are obtained in a well-known conventional manner by reacting monomeric, oligomeric or polyisocyanates a1) with isocyanate-reactive compounds a2) in suitable stoichiometry in the presence or absence of catalysts and solvents.
Useful polyisocyanates a1) include all aliphatic, cycloaliphatic, aromatic or araliphatic di- and triisocyanates known per se to a person skilled in the art, it being immaterial whether they were obtained by phosgenation or by phosgene-free processes. In addition, it is also possible to use the well-known conventional higher molecular weight descendant products of monomeric di- and/or triisocyanates having a urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione or iminooxadiazinedione structure each individually or in any desired mixtures among each other.
Examples of suitable monomeric di- or triisocyanates useful as component a1) are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), 1,8-diisocyanato-4-(isocyanatomethyl)octane, isocyanatomethyl-1,8-octane diisocyanate (TIN), 2,4- and/or 2,6-toluene diisocyanate.
The isocyanate-reactive compounds a2) for constructing the prepolymers are preferably OH-functional compounds. These are analogous to the OH-functional compounds described hereinbelow for component b).
The use of amines for prepolymer preparation is also possible. For example, ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, diaminocyclohexane, diaminobenzene, diaminobisphenyl, difunctional polyamines, such as, for example, the Jeffamine® amine-terminated polymers having number average molar masses of up to 10 000 g/mol and any desired mixtures thereof with one another are suitable.
For the preparation of prepolymers containing biuret groups, isocyanate is reacted in excess with amine, a biuret group forming. All oligomeric or polymeric, primary or secondary, difunctional amines of the abovementioned type are suitable as amines in this case for the reaction with the di-, tri- and polyisocyanates mentioned.
Preferred prepolymers are urethanes, allophanates or biurets obtained from aliphatic isocyanate-functional compounds and oligomeric or polymeric isocyanate-reactive compounds having number average molar masses of 200 to 10 000 g/mol; particular preference is given to urethanes, allophanates or biurets obtained from aliphatic isocyanate-functional compounds and oligomeric or polymeric polyols or polyamines having number average molar masses of 500 to 8500 g/mol. Very particular preference is given to allophanates formed from HDI or TMDI and difunctional polyetherpolyols having number average molar masses of 1000 to 8200 g/mol.
The prepolymers described above preferably have residual contents of free monomeric isocyanate of less than 1% by weight, particularly preferably less than 0.5% by weight, very particularly preferably less than 0.2% by weight.
In addition to the prepolymers described, the polyisocyanate component can of course contain further isocyanate components proportionately. Aromatic, araliphatic, aliphatic and cycloaliphatic di-, tri- or polyisocyanates are suitable for this purpose. It is also possible to use mixtures of such di-, tri- or polyisocyanates. Examples of suitable di-, tri- or polyisocyanates are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,2,4- and/or 2,4,4-trimethylhexamethylene diisocyanate (TMDI), the isomeric bis(4,4′-isocyanatocyclohexyl)methanes and mixtures thereof having any desired isomer content, isocyanatomethyl-1,8-octane diisocyanate, 1,4-cyclohexylene diisocyanate, the isomeric cyclohexanedimethylene diisocyanates, 1,4-phenylene diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate, triphenylmethane 4,4′,4′′-triisocyanate or derivatives thereof having a urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione or iminooxadiazinedione structure and mixtures thereof. Polyisocyanates based on oligomerized and/or derivatized diisocyanates which were freed from excess diisocyanate by suitable processes are preferred. The oligomeric isocyanurates, uretdiones and iminooxadiazinediones of HDI and mixtures thereof are particularly preferred.
It is optionally also possible for the polyisocyanate component a) proportionately to contain isocyanates, which are partially reacted with isocyanate-reactive ethylenically unsaturated compounds. α,β-Unsaturated carboxylic acid derivatives, such as acrylates, methacrylates, maleates, fumarates, maleimides, acrylamides, and vinyl ethers, propenyl ethers, allyl ethers and compounds which contain dicyclopentadienyl units and have at least one group reactive towards isocyanates are preferably used here as isocyanate-reactive ethylenically unsaturated compounds; these are particularly preferably acrylates and methacrylates having at least one isocyanate-reactive group. Suitable hydroxy-functional acrylates or methacrylates are, for example, compounds such as 2-hydroxyethyl(meth)acrylate, polyethylene oxide mono(meth)acrylates, polypropylene oxide mono(meth)acrylates, polyalkylene oxide mono(meth)acrylates, poly(ε-caprolactone)mono(meth)acrylates, such as, for example, Tone® M100 (Dow, USA), 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 3-hydroxy-2,2-dimethylpropyl(meth)acrylate, the hydroxy-functional mono-, di- or tetra(meth)acrylates of polyhydric alcohols, such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and industrial mixtures thereof. In addition, isocyanate-reactive oligomeric or polymeric unsaturated compounds containing acrylate and/or methacrylate groups, alone or in combination with the abovementioned monomeric compounds, are suitable. The proportion of isocyanates which are partly reacted with isocyanate-reactive ethylenically unsaturated compounds, based on the isocyanate component a), is 0 to 99%, preferably 0 to 50%, particularly preferably 0 to 25% and very particularly preferably 0 to 15%.
It may also be possible for the abovementioned polyisocyanate component a) to contain, completely or proportionately, isocyanates which are reacted completely or partially with blocking agents known to the person skilled in the art from coating technology. The following may be mentioned as an example of blocking agents: alcohols, lactams, oximes, malonic esters, alkyl acetoacetates, triazoles, phenols, imidazoles, pyrazoles and amines, such as, for example, butanone oxime, diisopropylamine, 1,2,4-triazole, dimethyl-1,2,4-triazole, imidazole, diethyl malonate, ethyl acetoacetate, acetone oxime, 3,5-dimethylpyrazole, ε-caprolactam, N-tert-butylbenzylamine, cyclopentanone carboxyethyl ester or any desired mixtures of these blocking agents.
It is particularly preferable for the polyisocyanate component to be an aliphatic polyisocyanate or an aliphatic prepolymer and preferably an aliphatic polyisocyanate or a prepolymer with primary NCO groups.
All polyfunctional, isocyanate-reactive compounds which have on average at least 1.5 isocyanate-reactive groups per molecule can be used as polyol component b).
In the context of the present invention, isocyanate-reactive groups are preferably hydroxyl, amino or thio groups, and hydroxy compounds are particularly preferred.
Suitable polyfunctional, isocyanate-reactive compounds are, for example, polyester-, polyether-, polycarbonate-, poly(meth)acrylate- and/or polyurethanepolyols.
Suitable polyesterpolyols are, for example, linear polyesterdiols or branched polyesterpolyols, as are obtained in a known manner from aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or their anhydrides with polyhydric alcohols having an OH functionality of ≧2.
Examples of such di- or polycarboxylic acids or anhydrides are succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic, decanedicarboxylic, terephthalic, isophthalic, o-phthalic, tetrahydrophthalic, hexahydrophthalic or trimellitic acid and acid anhydrides, such as o-phthalic, trimellitic or succinic anhydride or any desired mixtures thereof with one another.
Examples of suitable alcohols are ethanediol, di-, tri- or tetraethylene glycol, 1,2-propanediol, di-, tri- or tetrapropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, trimethylolpropane, glycerol or any desired mixtures thereof with one another.
The polyesterpolyols may also be based on natural raw materials, such as castor oil. It is also possible for the polyesterpolyols to be based on homo- or copolymers of lactones, as can preferably be obtained by an addition reaction of lactones or lactone mixtures, such as butyrolactone, ε-caprolactone and/or methyl-ε-caprolactone, with hydroxy-functional compounds, such as polyhydric alcohols having an OH functionality of ≧2 for example of the aforementioned type.
Such polyesterpolyols preferably have number average molar masses of 400 to 4000 g/mol, particularly preferably of 500 to 2000 g/mol. Their OH functionality is preferably 1.5 to 3.5, particularly preferably 1.8 to 3.0.
Suitable polycarbonatepolyols are obtainable in a manner known per se by reacting organic carbonates or phosgene with diols or diol mixtures.
Suitable organic carbonates are dimethyl, diethyl and diphenyl carbonate.
Suitable diols or mixtures comprise the polyhydric alcohols mentioned in connection with the polyester segments and having an OH functionality of ≧2, preferably 1,4-butanediol, 1,6-hexanediol and/or 3-methylpentanediol, or polyesterpolyols can be converted into polycarbonatepolyols.
Such polycarbonatepolyols preferably have number average molar masses of 400 to 4000 g/mol, particularly preferably of 500 to 2000 g/mol. The OH functionality of these polyols is preferably 1.8 to 3.2, particularly preferably 1.9 to 3.0.
Suitable polyetherpolyols are polyadducts of cyclic ethers with OH- or NH-functional starter molecules, said polyadducts optionally having a block structure.
Suitable cyclic ethers are, for example, styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin and any desired mixtures thereof.
Starters which may be used are the polyhydric alcohols mentioned in connection with the polyesterpolyols and having an OH functionality of ≧2 and primary or secondary amines and amino alcohols.
Preferred polyetherpolyols are those of the abovementioned type, exclusively based on propylene oxide or random or block copolymers based on propylene oxide with further 1-alkylene oxides, the proportion of 1-alkylene oxides being not higher than 80% by weight. Propylene oxide homopolymers and random or block copolymers which have oxyethylene, oxypropylene and/or oxybutylene units are particularly preferred, the proportion of the oxypropylene units, based on the total amount of all oxyethylene, oxypropylene and oxybutylene units, accounting for at least 20% by weight, preferably at least 45% by weight. Here, oxypropylene and oxybutylene comprise all respective linear and branched C3- and C4-isomers.
Such polyetherpolyols preferably have number average molar masses of 250 to 10 000 g/mol, particularly preferably of 500 to 8500 g/mol and very particularly preferably of 600 to 4500 g/mol. The OH functionality is preferably 1.5 to 4.0, particularly preferably 1.8 to 3.1.
In addition, aliphatic, araliphatic or cycloaliphatic di-, tri- or polyfunctional alcohols having molecular weights below 500 g/mol and containing 2 to 20 carbon atoms are useful as polyfunctional, isocyanate-reactive compounds as constituents of polyol component b). These can be for example ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, positionally isomeric diethyloctanediols, 1,3-butylene glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), (2,2-dimethyl-3-hydroxypropyl) 2,2-dimethyl-3-hydroxypropionate. Examples of suitable triols are trimethylolethane, trimethylolpropane or glycerol. Suitable higher-functional alcohols are ditrimethylolpropane, pentaerythritol, dipentaerythritol or sorbitol.
It is particularly preferable for the polyol component to be a difunctional polyether, polyester or a polyether-polyester block copolyester or a polyether-polyester block copolymer with primary OH functions.
Particular preference is given to a combination of components a) and b) in the production of matrix polymers consisting of addition products of butyrolactone, e-caprolactone and/or methyl e-caprolactone onto polyetherpolyols having a functionality of 1.8 to 3.1 with number average molar masses of 200 to 4000 g/mol in conjunction with isocyanurates, uretdiones, iminooxadiazinediones and/or other oligomers based on HDI. Very particular preference is given to addition products of e-caprolactone onto poly(tetrahydrofuran)s having a functionality of 1.9 to 2.2 and number average molar masses of 500 to 2000 g/mol (especially 600 to 1400 g/mol), the number average overall molar mass of which is from 800 to 4500 g/mol and especially from 1000 to 3000 g/mol, in conjunction with oligomers, isocyanurates and/or iminooxadiazinediones based on HDI.
The photoinitiators used are typically initiators which are activatable by actinic radiation and which trigger a polymerization of the corresponding polymerizable groups. Photoinitiators are commercially available compounds known per se, which are classed as unimolecular (type I) and bimolecular (type II). Type II photoinitiators may more particularly comprise a cationic dye and a coinitiator. Useful coinitiators include ammonium arylborates as described for example in EP-A 0223587. Examples of suitable ammonium arylborates are tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinaphthylhexylborate, tetrabutylammonium tris(4-tert-butyl)phenylbutylborate, tetrabutylammonium tris(3-fluorophenyl)hexylborate, tetramethylammonium triphenylbenzylborate, tetra(n-hexyl)ammonium (sec-butyl)triphenylborate, 1-methyl-3-octylimidazolium dipentyldiphenylborate and tetrabutylammonium tris(3-chloro-4-methylphenyl)hexylborate (Cunningham et al., RadTech'98 North America UV/EB Conference Proceedings, Chicago, Apr. 19-22, 1998).
It can be advantageous to use mixtures of these compounds. Depending on the radiation source used for curing, type and concentration has to be adapted to photoinitiator in a manner known to a person skilled in the art. Further particulars are available for example from P. K. T. Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 3, 1991, SITA Technology, London, pp. 61-328.
Preferred photoinitiators are mixtures of tetrabutylammonium tetrahexylborate, tetrabutylammonium triphenylhexylborate, tetrabutylammonium tris(3-fluorophenyl)-hexylborate ([191726-69-9], CGI 7460, product from BASF SE, Basle) and tetrabutylammonium tris(3-chloro-4-methylphenyl)hexylborate ([1147315-11-4], CGI 909, product from BASF SE, Basle) with the dyes of formula F+An− according to the present invention.
In one further preferred embodiment, the photopolymer formulation additionally contains urethanes as plasticizers, which urethanes may be more particularly substituted with at least one fluorine atom.
The urethanes may preferably have the general formula (CI)




where s is ≧1 and ≦8 and R300, R301, R302 are independently of each other hydrogen, linear, branched, cyclic or heterocyclic unsubstituted or else optionally heteroatom-substituted organic moieties, wherein preferably at least one of R300, R301, R302 is substituted with at least a fluorine atom and more preferably R300 is an organic moiety with at least one fluorine atom. It is particularly preferable for R302 to be a linear, branched, cyclic or heterocyclic organic radical which is unsubstituted or else optionally substituted with heteroatoms such as fluorine for example.

In one further preferred embodiment, the writing monomer comprises at least a mono- and/or a multi-functional writing monomer, which may more particularly comprise mono- and multi-functional acrylate writing monomers. It is particularly preferable for the writing monomer to comprise at least a monofunctional and multifunctional urethane(meth)acrylate.
Acrylate writing monomers may be more particularly compounds of general formula (CII)




where in each case t is ≧1 and t≦4 and R303, R304 are independently of each other hydrogen, linear, branched, cyclic or heterocyclic unsubstituted or else optionally heteroatom-substituted organic radicals. It is particularly preferable for R304 to be hydrogen or methyl and/or R303 to be a linear, branched, cyclic or heterocyclic unsubstituted or else optionally heteroatom-substituted organic radical.

It is similarly possible to add further unsaturated compounds such as α,β-unsaturated carboxylic acid derivatives such as acrylates, methacrylates, maleates, fumarates, maleimides, acrylamides, also vinyl ether, propenyl ether, allyl ether and dicyclopentadienyl-containing compounds and also olefinically unsaturated compounds such as, for example, styrene, α-methylstyrene, vinyltoluene, olefins, for example 1-octene and/or 1-decene, vinyl esters, (meth)acrylonitrile, (meth)acrylamide, methacrylic acid, acrylic acid. Preference, however, is given to acrylates and methacrylates.
In general, esters of acrylic acid and methacrylic acid are designated as acrylates and methacrylates, respectively. Examples of acrylates and methacrylates which can be used are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, lauryl acrylate, lauryl methacrylate, isobornyl acrylate, isobornyl methacrylate, phenyl acrylate, phenyl methacrylate, p-chlorophenyl acrylate, p-chlorophenyl methacrylate, p-bromophenyl acrylate, p-bromophenyl methacrylate, 2,4,6-trichlorophenyl acrylate, 2,4,6-trichlorophenyl methacrylate, 2,4,6-tribromophenyl acrylate, 2,4,6-tribromophenyl methacrylate, pentachlorophenyl acrylate, pentachlorophenyl methacrylate, pentabromophenyl acrylate, pentabromophenyl methacrylate, pentabromobenzyl acrylate, pentabromobenzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxyethoxyethyl acrylate, phenoxyethoxyethyl methacrylate, phenylthioethyl acrylate, phenylthioethyl methacrylate, 2-naphthyl acrylate, 2-naphthyl methacrylate, 1,4-bis(2-thionaphthyl)-2-butyl acrylate, 1,4-bis(2-thionaphthyl)-2-butyl methacrylate, propane-2,2-diylbis[(2,6-dibromo-4,1-phenylene)oxy(2-{[3,3,3-tris(4-chlorophenyl)propanoyl]oxy}propane-3,1-diyl)oxyethane-2,1-diyl]diacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, tetrabromobisphenol A diacrylate, tetrabromobisphenol A dimethacrylate and the ethoxylated analogue compounds thereof, N-carbazolyl acrylates, to mention only a selection of acrylates and methacrylates which may be used.
Urethane acrylates may of course also be used. Urethane acrylates are understood as meaning compounds having at least one acrylic acid ester group which additionally have at least one urethane bond. It is known that such compounds can be obtained by reacting a hydroxy-functional acrylic acid ester with an isocyanate-functional compound.
Examples of isocyanate-functional compounds which can be used for this purpose are aromatic, araliphatic, aliphatic and cycloaliphatic di-, tri- or polyisocyanates. It is also possible to use mixtures of such di-, tri- or polyisocyanates. Examples of suitable di-, tri- or polyisocyanates are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,2,4- and/or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis(4,4′-isocyanatocyclohexyl)methanes and mixtures thereof having any desired isomer content, isocyanatomethyl-1,8-octane diisocyanate, 1,4-cyclohexylene diisocyanate, the isomeric cyclohexanedimethylene diisocyanates, 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluene diisocyanate, 1,5-naphthylene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, m-methylthiophenyl isocyanate, triphenylmethane 4,4′,4′′-triisocyanate and tris(p-isocyanatophenyl)thiophosphate or derivatives thereof having a urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione or iminooxadiazinedione structure and mixtures thereof. Aromatic or araliphatic di-, tri- or polyisocyanates are preferred.
Suitable hydroxy-functional acrylates or methacrylates for the preparation of urethane acrylates are compounds such as 2-hydroxyethyl(meth)acrylate, polyethylene oxide mono(meth)acrylates, polypropylene oxide mono(meth)acrylates, polyalkylene oxide mono(meth)acrylates, poly(ε-caprolactone)mono(meth)acrylates, such as, for example, Tone® M100 (Dow, Schwalbach, Germany), 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 3-hydroxy-2,2-dimethylpropyl(meth)acrylate, hydroxypropyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, the hydroxyfunctional mono-, di- or tetraacrylates of polyhydric alcohols, such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or industrial mixtures thereof. 2-Hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate and poly(ε-caprolactone)mono(meth)acrylates are preferred. In addition, isocyanate-reactive oligomeric or polymeric unsaturated compounds containing acrylate and/or methacrylate groups, alone or in combination with the abovementioned monomeric compounds, are suitable. The epoxy(meth)acrylates known per se containing hydroxyl groups and having OH contents of 20 to 300 mg KOH/g or polyurethane(meth)acrylates containing hydroxyl groups and having OH contents of 20 to 300 mg KOH/g or acrylated polyacrylates having OH contents of 20 to 300 mg KOH/g and mixtures thereof with one another and mixtures with unsaturated polyesters containing hydroxyl groups and mixtures with polyester(meth)acrylates or mixtures of unsaturated polyesters containing hydroxyl groups with polyester(meth)acrylates can likewise be used.
Preference is given particularly to urethane acrylates obtainable from the reaction of tris(p-isocyanatophenyl)thiophosphate and m-methylthiophenyl isocyanate with alcohol-functional acrylates such as hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate and hydroxybutyl(meth)acrylate.
The invention also provides a holographic medium containing a photopolymer formulation according to the invention, or obtainable using a photopolymer formulation according to the invention. The invention still further provides for the use of a photopolymer formulation according to the invention for producing holographic media.
The holographic media of the invention can be processible to holograms in the entire visible and near UV region (300-800 nm) by appropriate exposure processes for optical applications. Visual holograms comprise any hologram which is recordable by processes known to a person skilled in the art. This definition includes inter alia in-line (Gabor) holograms, off-axis holograms, full-aperture transfer holograms, white light transmission holograms (“rainbow holograms), Denisyuk holograms, off-axis reflection holograms, edge-lit holograms and also holographic stereograms. Preference is given to reflection holograms, Denisyuk holograms, transmission holograms.
Possible optical functions of the holograms obtainable using the photopolymer formulations of the present invention correspond to the optical functions of light elements such as lenses, mirrors, deflectors, filters, diffuser screens, diffraction elements, light conductors, waveguides, projection screens and/or masks. Frequently, these optical elements show a frequency selectivity, depending on how the holograms were exposed and on the dimensions of the hologram.
In addition, the photopolymer formulations of the invention can also be used to produce holographic pictures or images, for example for personal portraits, biometric representations in security documents or generally of images or image structures for advertising, security labels, brand protection, branding, labels, design elements, decorations, illustrations, multi-journey tickets, images and the like, and also images which can represent digital data, inter alia also in combination with the products described above. Holographic images can give the impression of a three-dimensional image, but they may also represent image sequences, short films or a number of different objects, depending on the angle from which they are illuminated, the light source (including moving light source) with which they are illuminated, etc. It is because of these diverse design possibilities that holograms, more particularly volume holograms, constitute an attractive technical solution for the abovementioned use.
The photopolymer formulations can be used more particularly for producing holographic media in the form of a film. A layer of a material or assembly of materials which is transparent to light in the visible spectrum (transmission greater than 85% in the wavelength range from 400 to 780 nm), as a support, is coated one- or both-sidedly and, optionally, a covering layer is applied on top of the photopolymer layer or layers.
Preferred materials or assemblies of materials for the support are based on polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene, polypropylene, cellulose acetate, cellulose hydrate, cellulose nitrate, cycloolefin polymers, polystyrene, polyepoxides, polysulphone, cellulose triacetate (CTA), polyamide, polymethyl methacrylate, polyvinyl chloride, polyvinyl butyral or polydicyclopentadiene or mixtures thereof. They are more preferably based on PC, PET and CTA. Assemblies of materials can be laminates of self-supporting polymeric sheets, or coextrudates. Preferred assemblies of materials are duplex and triplex films constructed according to one of the schemes A/B, A/B/A or A/B/C. Particular preference is given to PC/PET, PET/PC/PET and PC/TPU (TPU=thermoplastic polyurethane).
As an alternative to the abovementioned plastics supports, it is also possible to use planar glass plates, which are used particularly for large-area accurately imaging exposures, for example for holographic lithography. Holographic interference lithography for integrated optics. IEEE Transactions on Electron Devices (1978), ED-25(10), 1193-1200, ISSN:0018-9383).
The materials or assemblies of materials of the support may have an anti-stick, antistatic, hydrophobic or hydrophilic finish on one or both sides. On the side facing the photopolymer layer, the modifications mentioned serve the purpose of making it possible to remove the photopolymer layer from the support non-destructively. A modification of that side of the support which faces away from the photopolymer layer serves to ensure that the media of the present invention meet specific mechanical requirements, for example in relation to processing in roll laminators, more particularly in roll-to-roll processes.
The present invention further provides a dye of formula F+An− where F+ represents a cationic dye and An− represents an anion and wherein the anion An− is selected from the group sec-alkylbenzenesulphonates, branched alkyl sulphates, n-alkyl sulphates, sec-alkylsulphonates, sulphosuccinates, ester sulphates and ester sulphonates. It is particularly preferable here when the cationic dye F+ is selected from the group of acridine, xanthene, thioxanthene, phenazine, phenoxazine, phenothiazine, tri(het)arylmethane, particularly diamino- and triamino(het)arylmethane, mono-, di- and trimethinecyanine, hemicyanine, externally cationic merocyanine, externally cationic neutrocyanine, nullmethine, particularly naphtholactam and streptocyanine dyes.
EXAMPLES
The examples which follow illustrate the invention.
Methods of Measurement:
The reported OH numbers were determined according to DIN 53240-2.
The reported NCO values (isocyanate contents) were determined according to DIN EN ISO 11909.
The reported water contents (KF) from solution were determined to DIN 51777.
The 2-hydroxyethyl acrylate (HEA) content is determined on the lines of DIN/ISO 10283 (2007). 1.41 g of anthracene (calibrating substance) as internal standard substance are weighed into a 1 liter volumetric flask and made up with ethyl acetate to the mark. About 1 g of sample is weighed out and mixed with 10 mL of the above-described solution of the internal standard and 10 mL of ethyl acetate, of which 2.0 μL are separated by gas chromatography, and HEA content is computed in area-corrected % by weight.
Water imbibition of examples was determined by initially drying 5-10 g of the dyes in each case in an open glass dish at a pressure of 200 mbar and a temperature of 50° C. to constant mass. Samples were weighed after removal from the vacuum drying cabinet after they had a chance to cool down to room temperature during 60 min in the absence of moisture. To ensure absence of moisture prior to weighing, the glass dishes were sealed airtight with Parafilm M® (Pechiney Plastic Packaging, Chicago, Ill. 60631, USA, www.parafilm.com), and then weighed. This was followed by standing in air at room temperature (22° C.) and relative humidity of 90% for 7 days to constant mass and weighing. Water imbibition was then computed from formula (F-1)

W=(mf/mt−1)*100%  (F-1),

where mf is the mass of the dye after water saturation and mt is the mass of the dried dye.

Measurement of plateau modulus G0 of matrix network of photopolymers with oscillation rheometer in context of present invention
To produce the photopolymer formulation for determining the plateau modulus G0 of the matrix network, the writing monomers and also additives, the isocyanate-reactive component and the dye solution are added together and mixed in a Speedmixer for 5 minutes. The dye was dissolved in N-ethylpyrrolidone beforehand. Then, isocyanate is added followed by mixing in the Speedmixer for 1 minute. Thereafter, a solution of the catalyst in N-ethylpyrrolidone is added which is again followed by mixing in the Speedmixer for 1 minute. The concentration of catalyst in N-ethylpyrrolidone is 10 weight percent.
The still liquid formulation is then introduced into the plate-plate measuring system of a rheometer (from Anton Paar Physica model MCR 301 equipped with the oven model CTD 450 which was preheated to 80° C.). The curing of the matrix of the photopolymer formulation over time is then measured under the following conditions:

    
    
        Plate spacing 250 μm.
        Oscillation measuring mode at a constant angular frequency ω0 of 10 rad/s and a regulated deformation amplitude of 1%.
        Temperature 80° C., normal force regulation set to 0 newtons
        Recording the storage modulus G′ over the measuring time of at most 2 hours or until a constant value Gmax of G′ was reached. This value is then taken as the plateau modulus G0 of the matrix network of photopolymers.
    
    


FIG. 3 shows the course of curing the matrix network as a plot of storage modulus G′ against curing time.
According to M. Doi, S. F. Edwards, The Theory of Polymer Dynamics, Oxford Science Publications, 1986, the plateau modulus G0 can be related to the average molecular weight MC of segments bridging two polymer strands as follows.




  
    G
    0
  
  =
  
    
      ρ
      ·
      R
      ·
      T
    
    
      M
      C
    
  




R is Avogadro's constant, T is the absolute temperature in kelvin and ρ is the mass density. A low plateau modulus G0 or a high average molecular weight MC for segments bridging two polymer strands characterize a network of low crosslink density.
Therefore, given a solid composition for the photopolymer formulation, a reduced plateau modulus G0 is indicative of incomplete crosslinking of matrix polymer.
Measuring the holographic properties DE and Δn of holographic media via two-beam interference in reflection arrangement.
The experimental holographic set-up as depicted in FIG. 1 was used to measure the diffraction efficiency (DE) of media. The beam of an He—Ne laser (emission wavelength 633 nm) was transformed via the spatial filter (SF) and together with the collimation lens (CL) into a parallel homogeneous beam. The final cross sections of the signal and reference beams are fixed via the iris diaphragms (I). The diameter of the iris diaphragm opening is 0.4 cm. The polarization-dependent beam splitters (PBS) split the laser beam into two coherent identically polarized beams. Via the λ/2 plates, the power of the reference beam was adjusted to 0.5 mW and the power of the signal beam to 0.65 mW. The powers were determined using the semiconductor detectors (D) with sample removed. The angle of incidence (α0) of the reference beam is −21.8° and the angle of incidence (β0) of the signal beam is 41.8°. The angles are measured from the sample normal to the beam direction. According to FIG. 1, therefore, α0 has a negative sign and β0 has a positive sign. At the location of the sample (medium), the interference field of the two overlapping beams produced a grating of light and dark strips which are perpendicular to the angle bisector of the two beams incident on the samples (reflection hologram). The strip spacing Λ, also referred to as grating period, in the medium is  ̃225 nm (the refractive index of the medium is assumed to be  ̃1.504).
FIG. 1 shows the geometry of a holographic media tester (HMT) at λ=633 nm (He—Ne laser): M=mirror, S=shutter, SF=spatial filter, CL=collimator lens, λ/2=λ/2 plate, PBS=polarization-sensitive beam splitter, D=detector, I=iris diaphragm, α0=−21.8°, β0=41.8° are the angles of incidence of the coherent beams outside the sample (outside the medium). RD=reference direction of turntable.
Holograms were written into the medium in the following manner:

    
    
        Both shutters (S) are open for the exposure time t.
        Thereafter, with the shutters (S) closed, the medium was allowed 5 minutes for the diffusion of still unpolymerized writing monomers.
    
    


The written holograms were then read in the following manner. The shutter of the signal beam remained closed. The shutter of the reference beam was open. The iris diaphragm of the reference beam was closed to a diameter of <1 mm. This ensured that the beam was always completely in the previously written hologram for all angles (Ω) of rotation of the medium. The turntable, under computer control, then covered the angle range from Ωmin to Ωmax with an angle step width of 0.05°. Ω is measured from the sample normal to the reference direction of the turntable. The reference direction of the turntable occurs when, during writing of the hologram, the angle of incidence of the reference beam and of the signal beam are of equal magnitude, i.e. α0=−31.8° and β0=31.8°. Ωrecording is then =0°. For α0=−21.8° and β=41.8°, therefore, Ωrecording is 10°. The following is generally true for the interference field during recording (“writing”) of the hologram:

α0=θ0+Ωrecording.

θ0 is the semiangle in the laboratory system outside the medium and the following is true during recording of the hologram:




  
    θ
    0
  
  =
  
    
      
        
          α
          0
        
        -
        
          β
          0
        
      
      2
    
    .
  




In this case, θ0 is therefore −31.8°. At each angle Ω of rotation approached, the powers of the beam transmitted in the zeroth order were measured by means of the corresponding detector D and the powers of the beam transmitted in the first order were measured by means of detector D. The diffraction efficiency was obtained at each angle Ω approached as the quotient of:




  η
  =
  
    
      P
      D
    
    
      
        P
        D
      
      +
      
        P
        T
      
    
  




PD is the power in the detector of the diffracted beam and PT is the power in the detector of the transmitted beam.
By means of the method described above, the Bragg curve (it describes the diffraction efficiency η as a function of the angle Ω of rotation) of the recorded hologram was measured and stored in a computer. In addition, the intensity transmitted in the zeroth order was also recorded with respect to the angle Ω of rotation and stored in a computer.
The maximum diffraction efficiency (DE=ηmax) of the hologram, i.e. its peak value, was determined at Ωreconstruction. For this purpose, the position of the detector of the diffracted beam had to be changed, if necessary, in order to determine this maximum value.
The refractive index contrast Δn and the thickness d of the photopolymer layer were now determined by means of the Coupled Wave Theory (cf. H. Kogelnik, The Bell System Technical Journal, Volume 48, November 1969, Number 9, page 2909-page 2947) from the measured Bragg curve and the angle variation of the transmitted intensity. It should be noted that, owing to the thickness shrinkage occurring as a result of the photopolymerization, the strip spacing Λ′ of the hologram and the orientation of the strips (slant) may deviate from the strip spacing Λ of the interference pattern and the orientation thereof. Accordingly, the angle α0′ or the corresponding angle of the turntable Ωreconstruction at which maximum diffraction efficiency is achieved will also deviate from α0 or from the corresponding Ωrecording, respectively. As a result, the Bragg condition changes. This change is taken into account in the evaluation method. The evaluation method is described below:
all geometrical quantities which relate to the recorded hologram and not to the interference pattern are represented as quantities shown by dashed lines.
According to Kogelnik, the following is true for the Bragg curve η(Ω) of a reflection hologram:




  η
  =
  
    {
    
      
        
          
            
              
                
                  1
                  
                    1
                    -
                    
                      
                        1
                        -
                        
                          
                            (
                            
                              ξ
                              /
                              v
                            
                            )
                          
                          2
                        
                      
                      
                        
                          sin
                          2
                        
                        ⁡
                        
                          (
                          
                            
                              
                                ξ
                                2
                              
                              -
                              
                                v
                                2
                              
                            
                          
                          )
                        
                      
                    
                  
                
                ,
                
                  
                    
                      for
                      ⁢
                      
                        
                      
                      ⁢
                      
                        v
                        2
                      
                    
                    -
                    
                      ξ
                      2
                    
                  
                  <
                  0
                
              
            
          
          
            
              
                
                  1
                  
                    1
                    +
                    
                      
                        1
                        -
                        
                          
                            (
                            
                              ξ
                              /
                              v
                            
                            )
                          
                          2
                        
                      
                      
                        
                          sinh
                          2
                        
                        ⁡
                        
                          (
                          
                            
                              
                                v
                                2
                              
                              -
                              
                                ξ
                                2
                              
                            
                          
                          )
                        
                      
                    
                  
                
                ,
                
                  
                    
                      for
                      ⁢
                      
                        
                      
                      ⁢
                      
                        v
                        2
                      
                    
                    -
                    
                      ξ
                      2
                    
                  
                  ≥
                  0
                
              
            
          
        
        ⁢
        
          

        
        ⁢
        with
        ⁢
        
          :
        
        ⁢
        
          

        
        ⁢
        v
      
      =
      
        
          
            
              
                π
                ·
                Δ
              
              ⁢
              
                
              
              ⁢
              
                n
                ·
                
                  d
                  ′
                
              
            
            
              λ
              ·
              
                
                  
                  
                    
                      c
                      s
                    
                    ·
                    
                      c
                      r
                    
                  
                  
                
              
            
          
          ⁢
          
            

          
          ⁢
          ξ
        
        =
        
          
            
              
                -
                
                  
                    d
                    ′
                  
                  
                    2
                    ·
                    
                      c
                      s
                    
                  
                
              
              ·
              DP
            
            ⁢
            
              

            
            ⁢
            
              c
              s
            
          
          =
          
            
              
                
                  cos
                  ⁡
                  
                    (
                    
                      θ
                      ′
                    
                    )
                  
                
                -
                
                  
                    cos
                    ⁡
                    
                      (
                      
                        ψ
                        ′
                      
                      )
                    
                  
                  ·
                  
                    λ
                    
                      n
                      ·
                      
                        Λ
                        
                          ′
                          ⁢
                          
                            
                          
                        
                      
                    
                  
                
              
              ⁢
              
                

              
              ⁢
              
                
                  c
                  r
                
                =
                
                  cos
                  ⁡
                  
                    (
                    
                      θ
                      ′
                    
                    )
                  
                
              
              ⁢
              
                

              
              ⁢
              
                DP
                =
                
                  
                    π
                    
                      Λ
                      ′
                    
                  
                  ·
                  
                    (
                    
                      
                        2
                        ·
                        
                          cos
                          ⁡
                          
                            (
                            
                              
                                ψ
                                ′
                              
                              -
                              
                                θ
                                ′
                              
                            
                            )
                          
                        
                      
                      -
                      
                        λ
                        
                          n
                          ·
                          
                            Λ
                            ′
                          
                        
                      
                    
                    )
                  
                
              
              ⁢
              
                

              
              ⁢
              
                
                  ψ
                  ′
                
                =
                
                  
                    
                      β
                      ′
                    
                    +
                    
                      α
                      ′
                    
                  
                  2
                
              
              ⁢
              
                

              
              ⁢
              
                Λ
                ′
              
            
            =
            
              λ
              
                2
                ·
                n
                ·
                
                  cos
                  ⁡
                  
                    (
                    
                      
                        ψ
                        ′
                      
                      -
                      
                        α
                        ′
                      
                    
                    )
                  
                
              
            
          
        
      
    
  




When reading the hologram (“reconstruction”), the situation is analogous to that described above:

θ′0=θ0+Ω

sin(θ′0)=n·sin(θ′)

Under the Bragg condition, the “dephasing” DP is 0. Accordingly, the following is true:

α′0=θ0+Ωreconstruction 

sin(α′0)=n·sin(α′)

The still unknown angle β′ can be determined from the comparison of the Bragg condition of the interference field during recording of the hologram and the Bragg condition during reading of the hologram, assuming that only thickness shrinkage takes place. The following is then true:




  
    sin
    ⁡
    
      (
      
        β
        ′
      
      )
    
  
  =
  
    
      1
      n
    
    ·
    
      [
      
        
          sin
          ⁡
          
            (
            
              α
              0
            
            )
          
        
        +
        
          sin
          ⁡
          
            (
            
              β
              0
            
            )
          
        
        -
        
          sin
          ⁡
          
            (
            
              
                θ
                0
              
              +
              
                Ω
                reconstruction
              
            
            )
          
        
      
      ]
    
  




ν is the grating thickness, ξ is the detuning parameter and ψ′ is the orientation (slant) of the refractive index grating which was recorded. α′ and β′ correspond to the angles α0 and β0 of the interference field during recording of the hologram, but measured in the medium and applicable to the grating of the hologram (after thickness shrinkage). n is the mean refractive index of the photopolymer and was set at 1.504. λ is the wavelength of the laser light in vacuo.

The maximum diffraction efficiency (DE=ηmax) for ξ=0 is then:




  DE
  =
  
    
      
        tanh
        2
      
      ⁡
      
        (
        v
        )
      
    
    =
    
      
        tanh
        2
      
      ⁡
      
        (
        
          
            
              π
              ·
              Δ
            
            ⁢
            
              
            
            ⁢
            
              n
              ·
              
                d
                ′
              
            
          
          
            λ
            ·
            
              
                
                  cos
                  ⁡
                  
                    (
                    
                      α
                      ′
                    
                    )
                  
                
                ·
                
                  cos
                  ⁡
                  
                    (
                    
                      
                        α
                        ′
                      
                      -
                      
                        2
                        ⁢
                        ψ
                      
                    
                    )
                  
                
              
            
          
        
        )
      
    
  




FIG. 1 shows the measured transmitted power PT (right y axis) as a solid line plotted against the angle detuning ΔΩ, the measured diffraction efficiency η (left y axis) as solid circles plotted against the angle detuning ΔΩ (if permitted by the finite size of the detector) and the adaptation of the Kogelnik theory as a dashed line (left y axis).
The measured data of the diffraction efficiency, the theoretical Bragg curve and the transmitted intensity are plotted against the centred angle of rotation ΔΩ≡Ωreconstruction−Ω=α′0−θ′0, also referred to as angle detuning, as shown in FIG. 2.
Since DE is known, the shape of the theoretical Bragg curve according to Kogelnik is determined only by the thickness d′ of the photopolymer layer. Δn is corrected via DE for a given thickness d′ so that measurement and theory of DE always agree. d′ is now adjusted until the angular positions of the first secondary minima of the theoretical Bragg curve correspond to the angular positions of the first secondary maxima of the transmitted intensity and furthermore the full width at half maximum (FWHM) for the theoretical Bragg curve and for the transmitted intensity correspond.
Since the direction in which a reflection hologram rotates on reconstruction by means of an Ω scan, but the detector for diffracted light can detect only a finite angular range, the Bragg curve of broad holograms (small d′) is not completely registered with an Ω scan, but only the central region, with suitable detector positioning. The shape of the transmitted intensity which is complementary to the Bragg curve is therefore additionally used for adjusting the layer thickness d′.
FIG. 2 shows the plot of the Bragg curve η according to the Coupled Wave Theory (dashed line), the measured diffraction efficiency (solid circles) and the transmitted power (black solid line) against the angle detuning ΔΩ.
For one formulation, this procedure was possibly repeated several times for different exposure times t on different media in order to determine at which mean energy dose of the incident laser beam during recording of the hologram DE the saturation value is reached. The mean energy dose E is obtained as follows from the powers of the two partial beams coordinated with the angles α0 and β0 (reference beam with Pr=0.50 mW and signal beam with Ps=0.63 mW), the exposure time t and the diameter of the iris diaphragm (0.4 cm):




  
    E
    ⁡
    
      (
      
        mJ
        ⁢
        
          /
        
        ⁢
        
          cm
          2
        
      
      )
    
  
  =
  
    
      2
      ·
      
        [
        
          
            P
            r
          
          +
          
            P
            s
          
        
        ]
      
      ·
      
        t
        ⁡
        
          (
          s
          )
        
      
    
    
      
        π
        ·
        
          0.4
          2
        
      
      ⁢
      
        
      
      ⁢
      
        cm
        2
      
    
  




The powers of the partial beams were adjusted so that, at the angles α0 and β0 used, the same power density is reached in the medium.
As an alternative I, a test equivalent to the set-up depicted in illustration 1 was also performed with a green laser of emission wavelength λ in vacuo of 532 nm. For this, α0=−11.5° and β0=33.5° and Pr=1.84 mW and Ps=2.16 mW.
As an alternative II, a test equivalent to the set-up depicted in illustration 1 was also performed with a blue laser of emission wavelength λ in vacuo of 473 nm. For this, α0=−22.0° and β0=42.0° and Pr=1.78 mW and Ps=2.22 mW.
Substances:
The dyes and salts used as well as solvents and reagents were acquired commercially.

    CGI-909 Tetrabutylammonium tris(3-chloro-4-methylphenyl)(hexyl)borate, [1147315-11-4] is a product produced by BASF SE, Basle, Switzerland.
    Desmorapid Z Dibutyltin dilaurate[77-58-7], product from Bayer MaterialScience AG, Leverkusen, Germany.
    Desmodur® N 3900 Product from Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, iminooxadiazinedione proportion at least 30%, NCO content: 23.5%.
    Fomrez UL 28 Urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA.
    Safranin O/T It was found that commercial Safranin O/T consists of six coloured components. Three could be elucidated:






    
    
        The fourth is a further isomer with 2 methyl groups. For the other two, mass spectroscopy suggests the structures
    
    






    
    
        or isomers thereof to be plausible. For simplicity, only the formula of the main component is indicated below when Safranin O is used. But this is always to be understood as meaning the mixture of all six components—including in combination with the anions of the invention.
    
    


Example 1
3.00 g of Safranin O corresponding to a mixture with the dye of formula




as main component (obtained in 2010 from Chemos GmbH, Germany, Article No. 1308) were dissolved in a mixture of 20 ml of methanol and 30 ml of water. A solution of 2.98 g of sodium 4-(sec-dodecyl)benzenesulphonate (mixture with the five different sec-dodecyl moieties) was prepared from 3.10 g of 4-(sec-dodecyl)benzenesulphonic acid 90 percent pure (obtained in 2010 from Fluka, Article No. 44198) by neutralizing a solution in 50 ml of water with 1M aqueous sodium hydroxide solution. This solution was added dropwise to the dye solution at room temperature during 30 min under efficient agitation. During 30 min, 100 ml of water were added dropwise. The red suspension was stirred at room temperature for 5 h, filtered off with suction, washed with 200 ml of water in portions and dried at 50° C. under reduced pressure to obtain 5.99 g (91.2% of theory) of a mixture as a red powder which in one formula (dye: main component, anion: idealized) corresponds to





λmax in methanol: 528 nm.
Suitable laser wavelength: 532 nm.
Example 2
5.00 g of the dye of formula




(New Methylene Blue, obtained from in 2008 TCI Europe b.v.) were dissolved in a mixture of 60 ml of water and 10 ml of glacial acetic acid. This solution was diluted with 100 ml of water and 20 ml of methanol. 5.44 g of a 50 percent solution of sodium 2-ethylhexylsulphate (obtained from Aldrich in 2009) were diluted with 17 ml of water. This solution was added dropwise to the dye solution at room temperature during 60 min under efficient agitation to obtain a suspension which was subsequently stirred for 2 h. This was followed by filtration with suction and washing with 200 ml of water in portions. Drying at 50° C. under reduced pressure left 4.85 g (79.4% of theory) of a blue powder of formula





λmax in methanol: 625 nm.
Suitable laser wavelength: 633 nm.
Example 3
3.00 g of the dye of formula




(Fuchsin, obtained from Alfa-Aesar in 2009) were dissolved in 70 ml of methanol. 2.56 g of sodium dodecylsulphate (obtained from Applichem in 2009) were dissolved in 25 ml of water. This solution was added dropwise to the dye solution at room temperature during 30 min under efficient agitation to obtain a deeply red-violet solution which was precipitated by gradual addition of altogether 40 ml of water during 5 h. The precipitate was filtered off with suction, washed with 60 ml of 1:1 water/methanol and finally with 150 ml of water and dried at 50° C. under reduced pressure to obtain 3.38 g (67.0% of theory) of a violet powder of formula





λmax in methanol: 551 nm.
Suitable laser wavelength: 532 nm.
Example 4
2.00 g of Safranin O (supply source see example 1) which corresponds to a mixture with the dye of formula




as main component were dissolved in 60 ml of acetonitrile at 50° C. 4.96 g of triethylammonium salt of formula





prepared as per J. Org. Chem. 2004, 69, 8521-8524, were dissolved in 30 ml of acetonitrile at 50° C. This solution was added dropwise to the dye solution at 50° C. during 10 min under efficient agitation. The mixture was cooled down to room temperature and precipitated with 150 ml of water. The red suspension was filtered off with suction, washed with 150 ml of water portionwise and dried at 50° C. under reduced pressure to leave 5.34 g (86.3% of theory) of a red powder of formula





λmax in methanol: 528 nm.
Suitable laser wavelength: 532 nm.
Example 5
2.00 g of Safranin O (supply source see Example 1) which corresponds to a mixture with the dye of formula




as main component were partially dissolved in 20 ml of water. 1.74 g of sodium oleate (obtained from Riedel-de-Haen in 1982) were dissolved in 30 ml of water. This solution was added to the partial solution of the dye followed by stirring at room temperature for 24 h. A resinous red product has formed, and the aqueous phase was decanted from it. The resin was stirred with 30 ml of fresh water for 24 h. Another decanting was carried out. The red resin was dried at 50° C. under reduced pressure and finally stirred with 30 ml of tert-butyl methyl ether. The suspension formed was filtered off with suction, washed with 5 ml of tert-butyl methyl ether and dried at 50° C. under reduced pressure to leave 2.72 g (79.9% of theory) of a red powder of formula





λmax in methanol: 528 nm.
Suitable laser wavelength: 532 nm.
Example 6
2.00 g of the dye of formula




were dissolved in 45 ml of methanol by stirring at the heat of boiling. 1.78 g of sodium tetraphenylborate (obtained from ABCR in 2010) were added. The resulting suspension was boiled for 15 min, cooled down, filtered off with suction, washed with 20 ml of methanol and 100 ml of water and dried at 50° C. under reduced pressure. For purification, the crude dye was dissolved at room temperature in the least amount of N-ethylpyrrolidone needed, diluted with five times the amount of methanol and finally precipitated with water to the point of a pale coloured mother liquor. The precipitate was filtered off with suction, washed with 50 ml of methanol in portions and dried at 50° C. under reduced pressure to obtain 2.45 g (75.5% of theory) of a red, slightly greenishly iridescent powder of formula





λmax in methanol: 486 nm.
Suitable laser wavelength: 473 nm.
The starting dye was prepared similarly to existing methods as follows:
5.78 g of 2-methylpyridine and 8.20 g of α,α′-dibromo-o-xylene were stirred in 60 ml of γ-butyrolactone at 80° C. for 2 h. The mixture was cooled down and filtered with suction and the filter residue was dried. 12.0 g of this material were placed in a mixture of 27 ml of glacial acetic acid and 27 ml of morpholine and gradually mixed with 9.45 g of 4-diethylaminobenzaldehyde before stirring at 80° C. for 2 h. After cooling, the mixture was discharged onto water and the product was isolated and dried.
Example 7
2.00 g of dye of formula




(C. I. Basic Violet 7) were dissolved in 30 ml of ethanol. In the absence of light, 6.39 g of a 20 percent aqueous solution of lithium butyl triphenylborate (obtained from Hokko Chemical Ind., Japan, in 2009) were added dropwise at room temperature under agitation. The thick red suspension was stirred for 4 h, filtered off with suction, washed with 15 ml of ethanol and 100 ml of water in portions and dried at 50° C. under reduced pressure in the absence of light to obtain 2.78 g (97.7% of theory) of a purple-coloured powder of formula





λmax in methanol: 549 nm.
Suitable laser wavelength: 532 nm.
Example 8
3.00 g of dye of formula




prepared as described in German patent 1 158 646, were partially dissolved in 50 ml of methanol. 1.90 g of sodium tetraphenylborate (obtained from ABCR in 2010) were dissolved in 15 ml of methanol. This solution was added dropwise to the dye suspension at room temperature during 30 min under agitation. In the process, the red suspension turned into an orange suspension. After 2 h stirring it was filtered off with suction, washed with 10 ml of methanol and 100 ml of water in portions and dried at 50° C. under reduced pressure to obtain 2.00 g (28.2% of theory) of a reddish orange powder of formula





λmax in methanol: 467 nm.
Suitable laser wavelength: 473 nm.
Example 9
15.0 g of sodium bis(2-ethylhexyl)sulphosuccinate (obtained from Aldrich in 2010) were dissolved in 350 ml of water at 50° c. 24.5 g of dye of formula




(Basic Blue 3), as 53% by weight material and 220 ml of butyl acetate were added and stirred at 50° C. for 4 h. The aqueous phase was separated off and the organic phase was stirred three times with 50 ml of fresh water at 50° C. Finally the aqueous phase was separated off each time, the last time at room temperature. The deep blue organic phase was dried with anhydrous magnesium sulphate, filtered and freed of residual water by azeotropic distillation at 150 mbar. Anhydrous butyl acetate was added to finally obtain 250 g of deep blue solution which was 9.68% by weight in respect of the dye of formula





(96.4% of theory).
Water content (KF): 0.1%
λmax in methanol: 643 nm.
Suitable laser wavelength: 633 nm.
Evaporating the solution gave 24.2 g of a deep blue glass which crystallizes gradually in the form of goldingly lustrous prisms. They can in turn be used to prepare for example 20% by weight solutions in butanone or 7:3 ethyl acetate/butanone.
Example 10
3.71 g of anhydrous sodium bis(2-ethylhexyl)sulphosuccinate (obtained from Aldrich in 2010) were dissolved in 50 ml of anhydrous ethyl acetate. 4.00 g of the anhydrous dye of formula




(Basic Violet 7), were added. The deep red mixture was stirred at room temperature for 3 h and filtered through a fluted filter to obtain 49.3 g of a ruby-red solution which is 13.5% by weight in respect of the dye of formula





(99.2% of theory).
Water content (KF): 0.08%
λmax in methanol: 549 nm.
Suitable laser wavelength: 532 nm.
Example 11
2.78 g of sodium di-n-octylsulphosuccinate prepared as described in Phys. Chem. Chem. Phys. 1999, 1, 4395 were dissolved in 20 ml of ethyl acetate. 2.20 g of dye of formula




(Basic Orange 21), were added. The deep orange mixture was stirred at 45° C. for 8 h, cooled down to room temperature and filtered through a fluted filter to obtain a deep orange solution which was initially freed of entrained water by azeotropic distillation at atmospheric pressure and then adjusted to 23.0 g mass by addition of anhydrous ethyl acetate. The solution was 20.0% by weight in respect of the dye of formula





(99.5% of theory).
Water content (KF): 0.04%
λmax in methanol: 492 nm.
Suitable laser wavelength: 473 nm.
Example 12
3.33 g of dye of formula




(methylene blue, obtained from Applichem in 2010, 90% purity), were dissolved in a mixture of 72 ml of water and 9 ml of methanol and filtered to remove a small amount of insolubles. In the absence of light, 14.36 g of a 20% by weight aqueous solution of lithium n-butyltriphenylborate (obtained from Hokko Chemical Ind., Japan, in 2009) were added dropwise under agitation. Stirring for 1 h was followed in the absence of light by filtration with suction, washing with 50 ml of water and drying at 50° C. under reduced pressure to obtain 4.73 g (86.4% of theory) of a blue powder of formula





λmax in methanol: 653 nm, 612 (sh) nm.
Suitable laser wavelength: 633 nm.
The dyes in Table 2 hereinbelow are obtainable in a similar manner.







TABLE 2







Inventive dyes













Suit-





able





laser


Ex-


wave-


am-


length


ple
F+
An−
(nm)













13








473 532


 


14








473 532


 


15








532


 


16








532


 


17








532


 


18








532


 


19








633


 


20








633


 


21








532


 


22








532


 


23








532


 


25








633


 


27








633


 


29








532


 


32








532


 


34








532


 


35








532


 


37








532


 


38








532


 


39








473


 


40








473


 


41








473


 


42








473


 


43








473


 


44








473


 


45








633


 


46








633


 


47








473


 


48








473


 


49








473


 


50








473


 


51








473


 


52








473


 


54








532


 


55








532


 


56








532


 


57








532


 


58








633


 


59








532


 


60








532


 


61








633


 


62








532


 


63








532


 


64








532


 


65








532


 


67








633


 


68








633


 


69








633


 


71








633


 


72








633


 


73








473


 


74








473


 


76








532


 


78








532


 


79








532


 


81








633


 


82








633


 


83








633


 


85








633


 


86








633


 


87








633


 


88








473


 


89








633


 


90








532


 


91








532


 


94








532


 


96








532


 


97








633


 


98








532


 


99








473


 


100








473


 


101








473


 


102








473


 


103








473


 


104








523


 


106








473


 


107








532


 


108








473


 


109








473


 


110








473


 


111








473


 


112








532


 


113








532









Table 3 summarizes the observed water imbibitions W for selected examples.







TABLE 3







Water imbibition of selected examples










Example
F+
An−
W [%]













1








2.7


 


14








0.03


 


25








0.1


 


30








1.9


 


39








1.6


 


41








0.49


 


46








2.3









Comparative Examples V 1-2 are the commercial dyes Safranin O/T and methylene blue. Comparative Example V 3 is Basic Orange 21, prepared by a method from H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Methine Dyes and Pigments, Wiley-VCH Verlag, 2008. V-4 was obtained from methylene blue and lithium perchlorate as described hereinbelow. Table 4 summarizes the observed water imbibitions W of Comparative Examples V 1-4.







TABLE 4







Water imbibition of selected comparative examples










Com-





parative





Ex-


W


ample
F+
An−
[%]













V-1




Cl-
14.8


 


V-2




Cl-
20.9


 


V-3




Cl-
9.5


 


V-4




ClO4−
6.2









Preparation of Comparative Example V4
5.55 g of methylene blue hydrate (90 percent pure, obtained from Fluka in 2010) were partially dissolved in 90 ml of water. To this partial solution, a solution of 1.66 g of lithium perchlorate (obtained from Acros in 2009) in 15 ml of water was added dropwise at room temperature during 1 h under efficient agitation. This was followed by stirring for 3 h, filtration with suction and washing with 2×25 ml of water. Drying at 50° C. under reduced pressure left 5.97 g (99.5%) of a blue powder of formula




Preparing the Components

Preparation of Polyol 1

In a 1 L flask, 0.18 g of tin octoate, 374.8 g of ε-caprolactone and 374.8 g of a difunctional polytetrahydrofuran polyetherpolyol (equivalent weight 500 g/mol of OH) were initially charged and heated up to 120° C. and maintained at that temperature until the solids content (proportion of nonvolatile constituents) was 99.5% by weight or higher. This was followed by cooling to obtain the product as a waxy solid.
Preparation of acrylate 1 (phosphorus thioyltris(oxy-4,1-phenyleneiminocarbonyl-oxyethane-2,1-diyl)triacrylate)
In a 500 mL round-bottom flask, 0.1 g of 2,6-di-tert-butyl-4-methylphenol, 0.05 g of dibutyltin dilaurate (Desmorapid® Z, Bayer MaterialScience AG, Leverkusen, Germany) and also and 213.07 g of a 27% solution of tris(p-isocyanatophenyl)thiophosphate in ethyl acetate (Desmodur® RFE, product from Bayer MaterialScience AG, Leverkusen, Germany) were initially charged and heated to 60° C. Thereafter, 42.37 g of 2-hydroxyethyl acrylate were added dropwise and the mixture was further maintained at 60° C. until the isocyanate content had dropped below 0.1%. This was followed by cooling and complete removal of the ethyl acetate under reduced pressure to obtain the product as a partly crystalline solid.
Preparation of acrylate 2 2-({[3-(methylsulphanyl)phenyl]carbamoyl}oxy)ethyl prop-2-enoate)
In a 100 mL round-bottom flask, 0.02 g of 2,6-di-tert-butyl-4-methylphenol, 0.01 g of Desmorapid® Z, 11.7 g of 3-(methylthio)phenyl isocyanate were initially charged and heated to 60° C. Thereafter, 8.2 g of 2-hydroxyethyl acrylate were added dropwise and the mixture was further maintained at 60° C. until the isocyanate content had dropped below 0.1%. This was followed by cooling to obtain the product as a pale yellow liquid.
Preparation of additive 1: (Bis(2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl) 2,2,4-trimethylhexane-1,6-diyl biscarbamate)
In a round-bottom flask, 0.02 g of Desmorapid Z and 3.6 g of 2,4,4-trimethylhexanes 1,6-diisocyanate were initially charged and heated to 70° C. This was followed by the dropwise addition of 11.39 g of 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptan-1-ol and the mixture was further maintained at 70° C. until the isocyanate content had dropped below 0.1%. This was followed by cooling to obtain the product as a colourless oil.
Preparation of Formulations to Determine Modulus Build-Up and Plateau Modulus G0.
Example Formulation 1
2.00 g of acrylate 1, 2.00 g of acrylate 2, 1.50 g of additive 1 were mixed with 3.465 g of polyol 1 and a solution of 0.026 g of dye from Example 25 in 0.512 g of N-ethylpyrrolidone in a Speedmixer for 5 minutes to obtain a homogeneous solution. The polyol solution described above was then admixed with 0.667 g of Desmodur® N 3900 (product from Bayer MaterialScience AG, Leverkusen, Germany) by mixing in a Speedmixer for a further minute. This is followed by the addition of 0.01 gram of a 10% by weight solution of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) in N-ethylpyrrolidone, again followed by mixing in a Speedmixer for one minute. The liquid mass obtained was introduced into the plate-plate measuring system of the oscillation rheometer.
Comparative Formulation 1
2.00 g of acrylate 1, 2.00 g of acrylate 2, 1.50 g of additive 1 were mixed with 3.471 g of polyol 1 and a solution of 0.015 g of dye from Comparative Example V-2 in 0.512 g of N-ethylpyrrolidone in a Speedmixer for 5 minutes to obtain a homogeneous solution. The polyol solution described above was then admixed with 0.668 g of Desmodur® N 3900 (product from Bayer MaterialScience AG, Leverkusen, Germany) by mixing in a Speedmixer for a further minute. This is followed by the addition of 0.01 gram of a 10% by weight solution of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) in N-ethylpyrrolidone, again followed by mixing in a Speedmixer for one minute. The liquid mass obtained was introduced into the plate-plate measuring system of the oscillation rheometer.
Example Formulation 2
2.00 g of acrylate 1, 2.00 g of acrylate 2, 1.50 g of additive 1 were mixed with 3.465 g of polyol 1 and a solution of 0.026 g of dye from Example 41 in 0.512 g of N-ethylpyrrolidone in a Speedmixer for 5 minutes to obtain a homogeneous solution. The polyol solution described above was then admixed with 0.667 g of Desmodur® N 3900 (product from Bayer MaterialScience AG, Leverkusen, Germany) by mixing in a Speedmixer for a further minute. This is followed by the addition of 0.01 gram of a 10% by weight solution of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) in N-ethylpyrrolidone, again followed by mixing in a Speedmixer for one minute. The liquid mass obtained was introduced into the plate-plate measuring system of the oscillation rheometer.
Comparative Formulation 2
2.00 g of acrylate 1, 2.00 g of acrylate 2, 1.50 g of additive 1 were mixed with 3.471 g of polyol 1 and a solution of 0.015 g of dye from Comparative Example V-3 in 0.512 g of N-ethylpyrrolidone in a Speedmixer for 5 minutes to obtain a homogeneous solution. The polyol solution described above was then admixed with 0.668 g of Desmodur® N 3900 (product from Bayer MaterialScience AG, Leverkusen, Germany) by mixing in a Speedmixer for a further minute. This is followed by the addition of 0.01 gram of a 10% by weight solution of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) in N-ethylpyrrolidone, again followed by mixing in a Speedmixer for one minute. The liquid mass obtained was introduced into the plate-plate measuring system of the oscillation rheometer.
Example Formulation 3
2.00 g of acrylate 1, 2.00 g of acrylate 2, 1.50 g of additive 1 were mixed with 3.465 g of polyol 1, 0.512 g of N-ethylpyrrolidone and 0.125 g of a 20.7 (% by weight) solution of dye from Example 30 in butyl acetate and 2-butanone (80% by weight of butyle acetate, 20% by weight of 2-butanone) in a Speedmixer for 5 minutes to obtain a homogeneous solution. The polyol solution described above was then admixed with 0.667 g of Desmodur® N 3900 (product from Bayer MaterialScience AG, Leverkusen, Germany) by mixing in a Speedmixer for a further minute. This is followed by the addition of 0.01 gram of a 10% by weight solution of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) in N-ethylpyrrolidone, again followed by mixing in a Speedmixer for one minute. The liquid mass obtained was introduced into the plate-plate measuring system of the oscillation rheometer.
Comparative Formulation 3
2.00 g of acrylate 1, 2.00 g of acrylate 2, 1.50 g of additive 1 were mixed with 3.471 g of polyol 1 and a solution of 0.015 g of dye from Comparative Example V-1 in 0.512 g of N-ethylpyrrolidone in a Speedmixer for 5 minutes to obtain a homogeneous solution. The polyol solution described above was then admixed with 0.668 g of Desmodur® N 3900 (product from Bayer MaterialScience AG, Leverkusen, Germany) by mixing in a Speedmixer for a further minute. This is followed by the addition of 0.01 gram of a 10% by weight solution of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) in N-ethylpyrrolidone, again followed by mixing in a Speedmixer for one minute. The liquid mass obtained was introduced into the plate-plate measuring system of the oscillation rheometer.
Example Formulation 4
2.00 g of acrylate 1, 2.00 g of acrylate 2, 1.50 g of additive 1 were mixed with 3.465 g of polyol 1 and 0.125 g of a 20.7 (% by weight) solution of dye from Example 30 in butyl acetate and 2-butanone (80% by weight of butyl acetate, 20% by weight of 2-butanone) in a Speedmixer for 5 minutes to obtain a homogeneous solution. The polyol solution described above was then admixed with 0.667 g of Desmodur® N 3900 (product from Bayer MaterialScience AG, Leverkusen, Germany) by mixing in a Speedmixer for a further minute. This is followed by the addition of 0.01 gram of a 10% by weight solution of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) in N-ethylpyrrolidone, again followed by mixing in a Speedmixer for one minute. The liquid mass obtained was introduced into the plate-plate measuring system of the oscillation rheometer.
Plateau Modulus G0 and Modulus Build-Up:
The formulations obtained as described were subsequently tested for their rheological properties in the manner described above. The following measurements were obtained for the plateau modulus G0:







TABLE 5







Plateau modulus G0 of selected examples










Plateau modulus G0
Temperature


Formulation
(Pa)
(° C.)





Example formulation 1
430 000
80


Comparative formulation 1
400 000
80


Example formulation 2
357 000
80


Comparative formulation 2
336 000
80


Example formulation 3
372 000
80


Comparative formulation 3
303 000
80


Example formulation 4
480 000
80









The example formulations recited in Table 5 prove that their plateau modulus is always greater than that of the corresponding comparative formulation. Therefore, the dyes which are selected according to the present invention provide better polymer matrix crosslinking than the dyes with high water imbibition. Incomplete crosslinking of matrix polymer has an adverse effect on the stability of holograms recorded therein.
FIG. 4 shows the comparison of modulus build-up over the curing time between Example Formulation 1 and Comparative Formulation 1. FIG. 5 shows the comparison of modulus build-up over the curing time between Example Formulation 2 and Comparative Formulation 2. FIG. 6 shows the comparison of modulus build-up over the curing time between Example Formulation 3 and Comparative Formulation 3 and Example Formulation 4. It is evident that the example formulations generally exhibit a faster modulus build-up than the corresponding comparative formulations, i.e. reach a higher storage modulus G′ after a fixed curing time. This is for example advantageous for more efficient coating of substrate foils with the photopolymer formulations for producing holographic films, since the photopolymer formulations of the present invention make it possible to realize shorter curing times to reach block resistance (i.e. the photopolymer formulation is mechanically so stable on reaching block resistance that the coated media can be further processed, generally wound up in a continuous roll-to-roll process). The photopolymer formulations of the present invention also make it possible to dispense with N-ethylpyrrolidone, thereby providing a further increase in the plateau modulus and its rise over the curing time, as evidenced by Example Formulation 4.
Producing the Media to Determine the Holographic Properties
Example Medium 1
3.38 g of polyol component 1 were mixed with 2.00 g of acrylate 1, 2.00 g of acrylate 1, 1.50 g of additive 1, 0.10 g of CGI 909 (product from BASF SE, Basle, Switzerland), 0.017 g of dye from Example 25 and 0.35 g of N-ethylpyrrolidone at 60° C. to obtain a clear solution. The solution was then cooled down to 30° C., 0.65 g of Desmodur® N3900 (commercial product from Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, portion on iminooxadiazinedione at least 30%, NCO content: 23.5%) was added before renewed mixing. Finally, 0.01 g of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) was added and again briefly mixed in. The liquid mass obtained was then applied to a glass plate and covered thereon with a second glass plate. This sample specimen was left to lie at room temperature for 12 hours for curing.
Example Medium 2
3.38 g of polyol component 1 were mixed with 2.00 g of acrylate 1, 2.00 g of acrylate 1, 1.50 g of additive 1, a mixture of a 30% by weight solution of 0.10 g of CGI 909 (product from BASF SE, Basle, Switzerland) in ethyl acetate and 0.103 g of the 9.68% by weight dye solution from Example 9 were mixed at 60° C. to obtain a clear solution. The solution was then cooled down to 30° C., 0.65 g of Desmodur® N3900 (commercial product from Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, portion on iminooxadiazinedione at least 30%, NCO content: 23.5%) was added before renewed mixing. Finally, 0.01 g of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) was added and again briefly mixed in. The liquid mass obtained was then applied to a glass plate and covered thereon with a second glass plate. This sample specimen was left to lie at room temperature for 12 hours for curing.
Example Medium 3
Example Medium 1 was repeated except that 0.01 g of the dye from Example 13 instead of 0.017 g of dye from Example 25 was used.
Example Medium 4
Example Medium 1 was repeated except that 0.01 g of the dye from Example 31 instead of 0.017 g of dye from Example 25 was used.
Comparative Medium 1
3.38 g of polyol component 1 were mixed with 2.00 g of acrylate 1, 2.00 g of acrylate 1, 1.50 g of additive 1, 0.10 g of CGI 909 (product from BASF SE, Basle, Switzerland), 0.010 g of dye from Comparative Example V-2 and 0.35 g of N-ethylpyrrolidone at 60° C. to obtain a clear solution. The solution was then cooled down to 30° C., 0.65 g of Desmodur® N3900 (commercial product from Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, portion on iminooxadiazinedione at least 30%, NCO content: 23.5%) was added before renewed mixing. Finally, 0.01 g of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) was added and again briefly mixed in. The liquid mass obtained was then applied to a glass plate and covered thereon with a second glass plate. This sample specimen was left to lie at room temperature for 12 hours for curing.
Holographic Testing:
The media obtained as described were subsequently tested for their holographic properties in the manner described above using a measuring arrangement as per FIG. 1. The following measurements were obtained for Δnsat at dose E [mJ/cm2]:







TABLE 6







Holographic assessment of selected examples












Dye

Wavelength


Dose E


Example
Medium
[nm]
DE
Δnsat
[mJ/cm2]















25
1
633
0.98
0.033
9


9
2
633
0.98
0.035
36


13
3
473
0.99
0.036
48


31
4
532
0.98
0.033
8









The values found show that the inventive dyes used in photopolymer formulations are very useful in holographic media owing to the high value of Δnsat, provide a more rapid modulus build-up in curing the matrix network and using them a higher plateau modulus G0 and hence more complete crosslinking of matrix polymer is achieved.
Moreover, the photopolymer formulations of the present invention also show higher photosensitivity in the holographic medium. As shown by FIG. 7, which plots the Δn achieved versus the exposure dose E, holographic writing ensues in Example Medium 1 at lower doses E than in Comparative Medium 1.
In a manner similar to Example Media 1-4, the inventive dyes of Examples 1-8, 10-12, 14-24, 26-30 and 32-106 make it possible to obtain holographic media having comparable holographic data.

## Claims

1. A photopolymer formulation comprising a polyol component, a polyisocyanate component, a writing monomer and a photoinitiator containing a coinitiator and a dye of formula


F+An−,

where
F+ represents a cationic dye selected from the group consisting of acridine, xanthene, thioxanthene, phenazine, phenoxazine, tri(het)arylmethane, diamino(het)arylmethane, triamino(het)arylmethane, monomethinecyanine, dimethinecyanine, trimethinecyanine, hemicyanine, nullmethine, naphtholactam and streptocyanine dyes, and
An− is sec-C11- to C18-alkanesulphonate, C13- to C25-alkyl sulphate, branched C8- to C25-alkyl sulphate, optionally branched bis-C6- to C25-alkyl sulphosuccinate, sec- or tert-C4- to C25-alkylbenzenesulphonate, sulphonated or sulphated, optionally mono- or polyunsaturated C8- to C25-fatty acid esters of aliphatic C1- to C8-alcohols of glycerol, bis(sulpho-C2- to C6-alkyl) C3- to C12-alkanedicarboxylic esters, or (sulpho-C2- to C6-alkyl) C6- to C18-alkanecarboxylic esters,
wherein the dye of formula F+An− has a water imbibition of ≦5%, and wherein the anion An− has an AClogP in the range of 1-6.5.

2. The photopolymer formulation according to claim 1, wherein the dye has a water imbibition of ≦3%.

3. The photopolymer formulation according to claim 1, wherein the dye has a water imbibition of ≦2%.

4. The photopolymer formulation according to claim 1, wherein the anion An− has a molar mass >150 g/mol.

5. The photopolymer formulation according to claim 1, wherein the anion An− has an AClogP in the range of 1-4 and the anion An− has a molar mass >250 g/mol.

6. The photopolymer formulation according to claim 1, wherein the anion An− has one or more than one linear or branched aliphatic moiety or when it has more than one linear or branched aliphatic moiety, these together have 8 to 36 carbon atoms.

7. The photopolymer formulation according to claim 1, wherein the polyisocyanate component is an aliphatic polyisocyanate or a prepolymer with primary NCO groups.

8. The photopolymer formulation according to claim 1, wherein the polyol component is a difunctional polyether, polyester or a polyether-polyester block copolyester with primary OH functions.

9. The photopolymer formulation according to claim 1, wherein the writing monomer comprises at least a monofunctional and a multifunctional urethane (meth)acrylate.

10. The photopolymer formulation according to claim 1, wherein it additionally comprises a plasticizer which conforms to general formula (CI)



where s is ≧1 and ≦8 and R300, R301, R302 are independently of each other hydrogen, linear, branched, cyclic or heterocyclic unsubstituted or else optionally heteroatom-substituted organic moieties, wherein optionally at least one of R300, R301, R302 is substituted with at least a fluorine atom and optionally R30° is an organic moiety with at least one fluorine atom.

11. A holographic medium containing the photopolymer formulation according to claim 1 coated upon a substrate.

12. A process for recording of in-line, off-axis, full-aperture transfer, white light transmission, Denisyuk, off-axis reflection or edge-lit holograms or holographic stereograms, which comprises interferometrically exposing the holographic medium according to claim 11.