EP3314607A1

EP3314607A1 - Holographic media containing chain-substituted cyanine dyes

Info

Publication number: EP3314607A1
Application number: EP16733368.1A
Authority: EP
Inventors: Horst Berneth; Thomas Fäcke; Thomas RÖLLE; Serguei Kostromine; Friedrich-Karl Bruder; Dennis Hönel
Original assignee: Covestro Deutschland AG
Current assignee: Covestro Deutschland AG
Priority date: 2015-06-23
Filing date: 2016-06-21
Publication date: 2018-05-02
Also published as: TW201710405A; WO2016207155A1; KR20180020162A; CN107743595A; JP2018526475A; US20180223100A1

Abstract

The invention relates to a photopolymer composition comprising a photopolymerisable component and a photoinitiator system containing a chain-substituted cyanine dye. The invention also relates to a photopolymer comprising a claimed photopolymer composition, a holographic medium containing a claimed photopolymer, the use of a claimed holographic medium, and a method for producing a holographic medium using the claimed photopolymer as well as the exposure of the corresponding holographic medium with the aid of pulsed laser radiation.

Description

Holographic media containing chain-substituted cyanine dyes

The present invention relates to a photopolymer composition comprising a photopolymerizable component and a photoinitiator system containing a chain-substituted cyanine colorant. Further objects of the invention are a photopolymer comprising a photopolymer composition according to the invention, a holographic medium containing a photopolymer according to the invention, the use of a holographic medium according to the invention and a method for producing a holographic medium using the photopolymer according to the invention and the exposure of the corresponding holographic medium with the help of pulsed laser radiation.

Photopolymer compositions of the type mentioned above are known in the art. For example, WO 2008/125229 A1 describes a photopolymer composition and a photopolymer obtainable therefrom which comprise polyurethane matrix polymers, an acrylate-based writing monomer and photoinitiators comprising a coinitiator and a dye. In the case of the use of photopolymers, the refractive index modulation Δη produced by the holographic exposure plays the decisive role. In holographic exposure, the interference field of signal and reference light beam (in the simplest case, that of two plane waves) is converted by the local photopolymerization of random monomers, e.g. high refractive acrylates are imaged into a refractive index grating at high intensity locations in the interference field. The refractive index grating in the photopolymer (the hologram) contains all the information of the signal light beam. By illuminating the hologram only with the reference light beam, the signal can then be reconstructed. The strength of the thus reconstructed signal in relation to the intensity of the incident reference light is called diffraction efficiency, hereinafter referred to as diffraction efficiency.

In the simplest case of a hologram, which results from the superposition of two plane waves, the DE results from the quotient of the intensity of the light diffracted during the reconstruction and the sum of the intensities of non-diffracted and diffracted light. The higher the DE, the more efficient a hologram is in terms of the amount of light of the reference light needed to make the signal visible with a given brightness.

In order to be able to realize the highest possible Δη and the highest possible DE in holograms, the matrix polymers and the writing monomers of a photopolymer composition should in principle be chosen such that they differ as much as possible in their refractive indices. A possibility To realize is to use matrix polymers with the lowest possible and writing monomers with the highest possible refractive index. Suitable low refractive index matrix polymers are, for example, polyurethanes obtainable by reaction of a polyol with a polyisocyanate component. In addition to high DE and Δη values, it is also of great importance for holographic media of photopolymer compositions that the matrix polymers are highly crosslinked in the finished medium. If the degree of crosslinking is too low, the medium does not have sufficient stability. This can lead to a significant reduction in the quality of holograms written in the media. In the worst case, the holograms can even be destroyed later.

Furthermore, it is of great importance, in particular for the large-scale use of holographic media from photopolymer compositions, that the photosensitivity is sufficient to be able to expose a large area and without loss of index modulation for a given laser light source. Here, in particular, the choice of a suitable photoinitiator is of crucial importance for the properties of the photopolymer.

However, holographic exposure with a continuous laser source encounters technical limitations in the case of large-area exposure, since it is always necessary to irradiate a certain light dose per unit area in order to ensure efficient formation of the hologram and limit the technically available laser power. In addition, large-area exposures at relatively low dose require long exposure times, which in turn make very high demands on the mechanical vibration damping of the exposure setup.

Another possibility for the large-area exposure of holograms is the use of very short light pulses, such as those produced by pulsed lasers or continuous wave lasers in conjunction with very fast shutters. Typical pulse durations for pulsed lasers are 500 ns or shorter. Typical pulse durations for continuous wave lasers with very fast shutters are 100 μ8 or shorter. The same absorbed dose can be irradiated as with continuous lasers in seconds. In this way, holograms can be written point by point. Since pulsed lasers or fast optical shutters are technically available and such an exposure structure has very low requirements with respect to the mechanical vibration damping, it is a good technical alternative to the above-described constructions with continuous lasers for large-area exposure of holograms. The photopolymers known from WO 2008/125229 Al have, because of the photoinitiators used there, too low photosensitivity in order to be able to use them when writing holograms with pulsed lasers.

Therefore, the object of the present invention was to provide a photopolymer composition with the aid of which it is possible to produce photopolymers into which holograms can be written with pulsed lasers because of their higher photosensitivity.

This object is achieved by a photopolymer composition comprising a photopolymerizable component and a photoinitiator system comprising a chain-substituted cyanine dye of the formula (I)

contains, in which

K is a radical of the formula (II)

(HI)

or (IV)

(IV) stands,

Ring A together with N and X ¹ and the atoms connecting them and ring B together with N and X ² and the atoms connecting them independently represent a five- or six-membered aromatic or quasi-aromatic or partially hydrogenated heterocyclic ring containing 1 to 4 heteroatoms may contain and / or benzo or naphthoanneliert and / or with Ci to Cs alkyl, C3 to C6 alkenyl, C4 to C7 cycloalkyl or C7 to Cio-aralkyl, aryl, fluorine, chlorine, bromine Methoxy, ethoxy, where the unsaturated building block (* (C = K) -Q ¹ ) of formula (I) on ring A or B in position 2 or 4 relative to X ¹ or X ² attacks,

X ^{1 is} O, S, NR ⁷ , CR ⁹ or CR ^U R ¹² ,

X ^{2 is} O, S, NR ⁸ , CR ¹⁰ or CR ¹³ R ¹⁴ ,

Q ^{1 is} hydrogen, cyano or methyl,

Q ^{2 is} hydrogen or cyano,

Q ^{3 is} hydrogen or a radical of the formula (V) Air

(V)

where at least one of Q ¹ , Q ² and Q ³ does not stand for hydrogen, O or S,

X ^{4 is} N or CR ⁶ ,

X ^{5 is} N, O or CR ²⁰ R ²⁰ , R ¹ , R ² , R ⁷ , R ⁸ , R ¹⁵ and R ¹⁹ independently of one another are C ₁ - to C ₆ -alkyl, C ₃ - to C ₆ -alkenyl, C ₄ - to C ₇ -cycloalk I or C ₇ - to Ci- Aralkyl stand and

R ^{15 can} additionally be hydrogen,

R ⁹ and R ¹⁰ independently of one another represent hydrogen or C 1 - to C 2 -alkyl,

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ²⁰ independently of one another are C ₁ - to C ₄ -alkyl, C ₃ - to C ₆ -alkenyl, C ₄ - to C ₇ -cycloalkyl or C ₇ - to Cio-aralkyl or R ¹¹ and R ¹² together and / or R ¹³ and R ¹⁴ together are a -CH2-CH2-CH2-CH2- or -CH ₂ form -CH2-CH2-CH2-CH ₂ bridge, and in addition

R ⁷ , R ⁹ or R ¹² together with Q ^{1 can form} a -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 -bridge,

R ³ and R ⁴ independently of one another are C 1 - to C 6 -alkyl, C ₃ - to C ₆ -alkenyl, C ₄ - to C 7 -cycloalkyl, C 7 - to C 10 -aralkyl or C - to C 10 -aryl or

R ³ , R ^{4 is} a -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ --NH-CH ₂ Form -CH 2 - or -CH ₂ -CH ₂ -N (alkyl) -CH ₂ -CH ₂ - bridge, R ⁵ and R ¹⁶ independently of one another represent hydrogen, C 1 - to C 8 -alkyl, C ₄ - to C 7 -cycloalkyl or

C 3 -C 10 aryl,

R ^{6 is} hydrogen, alkyl or cyano, R ¹⁷ and R ¹⁸ independently of one another represent hydrogen, chlorine, methyl, ethyl, methoxy or ethoxy, n and m independently of one another denote 0 or 1, where m is only 1, even if n stands for 1, and

An ^"stands for the equivalent of an anion. Another embodiment of the invention orders that

Q ^{1 is} cyano or together with R ^{12 forms} a -Cfb-Cfb-CI-b bridge, Q ^{2 is} hydrogen or cyano, preferably hydrogen, Q ^{3 is} hydrogen, the ring A together with R ¹ , N and X ¹ and the atoms connecting them for a remainder of the

stands,

R ^{1 is} C ¹ -C ₈ -alk, C ₃ -C -alkenyl, C ₄ -C ₇ -cycloalk 1 or C ₇ -C 10 -arylalkyl,

R ¹¹ and R ^{12 are} independently C 1 to C 4 alkyl, C 3 to C 6 alkenyl, C 4 to C 7 cycloalk I or C 7 to C 10 aralkyl, or together represent a -CH 2 -CH 2 -CH 2 -CH 2 - or -CH2-CH2- CH ₂ -CH ₂ -CH ₂ bridge form,

R ²¹ and R ^{22 are} independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen,

R ²³ and R ^{24 are} independently hydrogen, chloro, cyano, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen, ring B together with R ² , N and X ² and the atoms connecting them for a rest of the formulas

stands,

R ^{2 is} C 1 -C ₈ -alk, C ₃ -C ₆ -alkenyl, C ₄ -C ₇ -cycloalkyl or C ₇ -C 10 -arylalkyl,

R ¹³ and R ¹⁴ independently of one another are C 1 - to C 4 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalk I or C 7 - to C 10 -aralkyl, or together form a -CH 2 -CH 2 -CH 2 -CH 2 - or -CH2-CH2- CH ₂ -CH ₂ -CH ₂ bridge form,

R ²⁵ and R ²⁶ are each independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen,

R ²⁷ and R ²⁸ independently represent hydrogen, chlorine, cyano, methyl, ethyl, methoxy or

Ethoxy, preferably only one of which is not hydrogen,

X ³ stands for S,

X ^{4 is} N or CR ⁶ , preferably N,

R ³ and R ⁴ independently of one another are C 1 - to C 6 -alkyl, C ³ - to C 6 -alkenyl, C ⁴ - to C 7 -cycloalkyl, C 7 - to C 10 -aralkyl or C 1 - to C 10 -aryl, or

R ³ , R ^{4 form} a -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -bridge,

R ^{5 is} Ci- to Cs-alkyl or Ce- to Cio-aryl,

R ^{6 is} hydrogen or cyano, R ^{15 is} hydrogen, C ₁ - to C ₈ -alkyl, C ₃ - to C ₆ -alkenyl, C ₄ - to C ₇ -cycloalkyl or C ₇ - to Cio- aralkyl,

R ^{16 is} hydrogen, C 1 -C ₄ -alkyl, C ₅ -C ₆ -cycloalkyl or C ₆ -aryl,

R ¹⁷ and R ¹⁸ are each independently hydrogen, chloro, methyl or methoxy, preferably only one of which is not hydrogen, n and m are independently 0 or 1, where m is 1 only, albeit n stands for 1, and

An ^"stands for the equivalent of an anion.

A further embodiment of the invention is characterized in that Q ¹ and Q ^{2 are} hydrogen,

Q ^{3 is} a radical of the formula (V), the ring A together with R ¹ , N and X ¹ and the atoms connecting them is a radical of

stands,

R ¹ and R ¹⁹ independently of one another represent C ¹ - to C 6 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalkyl or C 7 - to C 10 -aralkyl, R ¹¹ and R ¹² independently of one another are C 1 - to C 4 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalk I or C 7 - to C 1 -alkenyl or together form a -CH 2 -CH 2 -CH 2 -CH 2 - or -CH2-CH2- CH ₂ -CH ₂ -CH ₂ bridge form,

stands,

R ^{2 is} Ci- to Cs-alkyl, C3- to Ce-alkenyl, C4- to C7-cycloalk I or C7- to Cio-aralkyl,

R ¹³ and R ¹⁴ independently of one another are C 1 - to C 4 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalkyl or C 7 - to C 10 -aralkyl or together form a -CH 2 -CH 2 -CH 2 -CH 2 - or - Form CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -bridge,

R ²⁷ and R ²⁸ independently of one another are hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, preferably only one of which does not represent hydrogen,

X ^{5 is} S or C (CH ₃ ) ₂ , X ³ stands for S,

X ^{4 is} N or CR ⁶ , preferably N,

R ^{5 is} C ₁ -C -alkyl or C ₆ -C 10 -aryl,

R ^{6 is} hydrogen or cyano,

R ^{15 represents} hydrogen, C ₁ - to C ₆ -alkyl, C ₃ - to C ₆ -alkenyl, C ₄ - to C ₇ -cycloalkyl or C ₇ - to C 10 -aralkyl,

R ^{16 is} hydrogen, C 1 - to C ₄ -alkyl, C ₅ - to Ce-cycloalkyl or Ce-aryl,

R ¹⁷ and R ^{18 are} independently hydrogen, chloro, methyl or methoxy, preferably only one of which is not hydrogen, n and m are both 1 and

An ^"stands for the equivalent of an anion.

Another embodiment of the invention is that

Q ^{1 is} cyano or together with R ^{12 forms} a -Ctb-Ctb-CI-b bridge,

Q ² and Q ^{3 are} hydrogen, the ring A together with R ¹ , N and X ¹ and the atoms connecting them for a remainder of

stands,

R ^{1 is} methyl, ethyl, 1-propyl, 1-butyl, benzyl or cyanoethyl,

R ¹¹ and R ¹² are, independently of one another represent methyl, ethyl or benzyl together a - CH2-CH2-CH2-CH2- or -CH ₂ -CH2-CH2-CH2-CH ₂ bridge form,

R ^{21 represents} hydrogen, chlorine, cyano, methoxycarbonyl, ethoxycarbonyl, methyl or methoxy,

R ²² and R ^{24 are} hydrogen,

R ^{23 is} hydrogen, chlorine, cyano, methyl or methoxy, with R ² , N and X ² and the atoms connecting them, a radical of the formula

stands,

R ^{2 is} methyl, ethyl, 1-propyl, 1-butyl, benzyl or cyanoethyl,

R ¹³ and R ¹⁴ are, independently of one another represent methyl, ethyl or benzyl together a - CH2-CH2-CH2-CH2- or -CH ₂ -CH2-CH2-CH2-CH ₂ bridge form,

R ^{25 is} hydrogen, chlorine, cyano, methoxycarbonyl, ethoxycarbonyl, methyl or methoxy,

R ^{26 is} hydrogen, X ³ stands for S,

X ⁴ stands for N,

R ³ and R ⁴ independently of one another are methyl, ethyl, 1-propyl, 1-butyl, 1-octyl, cyclohexyl or benzyl or

R ^{5 is} methyl, ethyl, tert-butyl, phenyl, 4-methylphenyl or 4-methoxyphenyl,

R ^{15 is} hydrogen, methyl, ethyl, 1-propyl-1-butyl, 1-octyl or benzyl,

R ^{16 is} hydrogen, methyl or phenyl,

R ^{17 is} hydrogen, chlorine or methyl,

R ¹⁸ stands for hydrogen and stands on ^"the equivalent of an anion.

Alkyl and alkoxy radicals can be unbranched or branched. They may also carry further radicals such as fluorine, chlorine, alkoxy, cyano or alkoxycarbonyl. Examples are methyl, ethyl, 1- or 2-propyl, 1- or 2-butyl, tert-butyl, 1-octyl, chloroethyl, cyanoethyl, methoxyethyl or trifluoromethyl.

Cycloalkyl radicals are preferably cyclopentyl or cyclohexyl.

Aralkyl radicals can be unbranched or branched in the alkyl moiety and carry further radicals in the aryl moiety. Examples are benzyl, phenethyl, 2- or 3-phenylpropyl, 4-chlorobenzyl, 4-methoxybenzyl.

Aryl radicals are phenyl or naphthyl, preferably phenyl, and may carry further radicals such as fluorine, chlorine, alkoxy, nitro, cyano or alkoxycarbonyl. Examples of such substituted phenyl radicals are 2-, 3- or 4-fluorophenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4- Methoxyphenyl, 2-, 3- or 4-cyanophenyl, biphenylyl, 3,4-dichlorophenyl, 3,4-dimethylphenyl, 3,4-dimethoxyphenyl.

In one embodiment of the invention, the photopolymer composition according to the invention contains matrix polymers and at least one writing monomer.

In a further embodiment of the invention, the photopolymer composition additionally contains a coinitiator. Suitable coinitiators are ammonium alkylarylborates which together with the dyes of the invention form a type II photoinitiator (Norrish type II) are described in principle in EP 0 223 587.

Such suitable ammonium alkylaryl borates are, for example, (Cunningham et al., RadTech'98 North America UV / EB Conference Proceedings, Chicago, Apr. 19-22, 1998): tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinapthylhexylborate, tetrabutylammonium tris (4-tert-butyl ) -phenylbutylborate, tetrabutylammonium tris (3-fluorophenyl) -hexyrborate hexylborate ([191726-69-9], CGI 7460, product of BASF SE, Basel, Switzerland), 1-methyl-3-octylimidazolium dipentyldiphenylborate and tetrabutylammonium tris ( 3-chloro-4-methylphenyl) hexyl borate ([1147315-11-4], CGI 909, product of BASF SE, Basel, Switzerland). Other suitable borates are known from WO 2015/055576 A1 and can be used as coinitiators for the purposes of the invention.

Other suitable coinitiators are electron acceptors such. B. tris (trihalogenomethyl) triazine and / or its derivatives, in particular substituted bis (trihalogenomethyl) triazines, as z. In JP 2008201912, EP 1 457 190 A1, EP 0 332 042, US Pat. No. 3,987,037 or US Pat. No. 5,489,499. For the purposes of the invention, the photoinitiator system can thus be prepared from at least one ammonium alkylaryl borate as described above and / or at least one electron acceptor such as, for. Example, a tris (trihalogenomethyl) triazine and / or its derivatives, in particular a substituted bis (trihalogenomethyl) triazine exist. Further, from the prior art (US000005500453A1, WO2006138637A1) known electron acceptors such as iodonium or sulfonium salts could be part of the photoinitiator system. It is also possible to use any mixtures of said coinitiators. The invention likewise relates to photopolymers which contain a photopolymer composition according to the invention.

The matrix polymers of the photopolymer according to the invention may in particular be crosslinked and particularly preferably be crosslinked three-dimensionally. It is also advantageous if the matrix polymers are polyurethanes, where the polyurethanes may be obtainable in particular by reacting at least one polyisocyanate component a) with at least one isocyanate-reactive component b).

The polyisocyanate component a) preferably comprises at least one organic compound having at least two NCO groups. These organic compounds may in particular be monomeric di- and triisocyanates, polyisocyanates and / or NCO-functional prepolymers. The polyisocyanate component a) may also contain or consist of mixtures of monomeric di- and triisocyanates, polyisocyanates and / or NCO-functional prepolymers.

As monomeric di- and triisocyanates, it is possible to use all the compounds or mixtures thereof which are well known to the person skilled in the art. These compounds may have aromatic, araliphatic, aliphatic or cycloaliphatic structures. In minor amounts, the monomeric di- and tri-isocyanates may also be monoisocyanates, i. include organic compounds having an NCO group.

Examples of suitable monomeric di- and triisocyanates are 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 2,2,4-trimethylhexamethylene diisocyanate and / or 2,4,4-trimethylhexamethylene diisocyanate ( TMDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, bis (4,4'-isocyanatocyclohexyl) methane and / or bis (2 ', 4-isocyanatocyclohexyl) methane and / or their mixtures any isomer content, 1, 4-cyclohexane diisocyanate, the isomeric bis (isocyanatomethyl) cyclohexanes, 2,4- and / or 2,6-diisocyanato-l-methylcyclohexane (hexahydro-2,4- and / or 2,6- toluene diisocyanate, H _Ö -DI), 1, 4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate (TDI), 1, 5-naphthylene diisocyanate (NDI), 2,4'- and / or 4,4 '- Diphenylmethane diisocyanate (MDI), l, 3-bis (isocyanatomethyl) benzene (XDI) and / or the analogous 1,4-isomers or any mixtures of the aforementioned compounds. Suitable polyisocyanates are compounds having urethane, urea, carbodiimide, acylurea, amide, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione and / or iminooxadiazinedione structures which are obtainable from the abovementioned di- or triisocyanates.

The polyisocyanates are particularly preferably oligomerized aliphatic and / or cycloaliphatic di- or triisocyanates, it being possible in particular to use the abovementioned aliphatic and / or cycloaliphatic di- or triisocyanates.

Very particular preference is given to polyisocyanates containing isocyanurate, uretdione and / or iminooxadiazinedione structures and biurets based on HDI or mixtures thereof.

Suitable prepolymers contain urethane and / or urea groups and optionally further structures formed by modification of NCO groups as mentioned above. Such prepolymers are obtainable, for example, by reacting the abovementioned monomeric diisocyanates and triisocyanates and / or polyisocyanates a1) with isocyanate-reactive compounds b1).

As isocyanate-reactive compounds bl) it is possible to use alcohols, amino or mercapto compounds, preferably alcohols. These may in particular be polyols. Very particular preference is given to using as the isocyanate-reactive compound bl) polyester, polyether, polycarbonate, poly (meth) acrylate and / or polyurethane polyols.

Suitable polyester polyols are, for example, linear polyester diols or branched polyester polyols which can be obtained in a known manner by reacting aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or their anhydrides with polyhydric alcohols having an OH functionality> 2. Examples of suitable di- or polycarboxylic acids are polybasic carboxylic acids such as succinic, adipic, cork, sebacic, decanedicarboxylic, phthalic, terephthalic, isophthalic-tetrahydr-ophthalic or trimellitic acid, and also acid anhydrides such as phthalic, trimellitic or succinic anhydride or their mixtures with each other. The polyester polyols can also be based on natural raw materials such as castor oil. It is likewise possible that the polyesterpolyols are based on homopolymers or copolymers of lactones, which preferably by addition of lactones or lactone mixtures such as butyrolactone, ε-caprolactone and / or methyl-s-caprolactone to hydroxy-functional compounds such as polyhydric alcohols of an OH functionality > 2, for example of the type mentioned below can be obtained.

Examples of suitable alcohols are all polyhydric alcohols such as the C2 - Cn-diols, the isomeric cyclohexanediols, glycerol or any mixtures thereof. Suitable polycarbonate polyols 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 include the polyhydric alcohols of an OH functionality> 2, preferably 1,4-butanediol, 1,6-hexanediol and / or 3-methylpentanediol, which are per se in the context of the polyester segments. Polyester polyols can also be converted to polycarbonate polyols.

Suitable polyether polyols are optionally block-formed polyaddition of cyclic ethers to OH or NH-functional starter molecules.

Suitable cyclic ethers are, for example, styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin and any desired mixtures thereof.

The starter used may be the polyhydric alcohols of OH functionality> 2 mentioned in the context of the polyesterpolyols and also primary or secondary amines and amino alcohols.

Preferred polyether polyols are those of the aforementioned type based solely on propylene oxide or random or block copolymers based on propylene oxide with further 1-alkylene oxides. Particular preference is given to propylene oxide homopolymers and also random or block copolymers which contain oxyethylene, oxypropylene and / or oxybutylene units, the proportion of oxypropylene units, based on the total amount of all oxyethylene, oxypropylene and oxybutylene units, being at least 20% by weight at least 45% by weight. Oxypropylene and oxybutylene here include all respective linear and branched C3 and C4 isomers. In addition, as constituents of the polyol component bl) as polyfunctional, isocyanate-reactive compounds are also low molecular weight, i. with molecular weights <500 g / mol, short chain, i. 2 to 20 carbon atoms containing aliphatic, araliphatic or cycloaliphatic di-, tri- or polyfunctional alcohols suitable.

These may include, for example, in addition to the above-mentioned compounds, neopentyl glycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, positional isomeric diethyloctanediols, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2- and 1, 4 Cyclohexanediol, hydrogenated bisphenol A, 2,2-bis (4-hydroxy-cyclohexyl) -propane or 2,2-dimethyl-3-hydroxypropionic acid, 2,2-dimethyl-3-hydroxypropyl ester. Examples of suitable triols are trimethylolethane, trimethylolpropane or Glycerol. Suitable higher functional alcohols are di (trimethylolpropane), pentaerythritol, dipentaerythritol or sorbitol.

It is particularly preferred if the polyol component is a difunctional polyether, polyester or a polyether-polyester block copolyester or a polyether-polyester block copolymer having primary OH functions.

It is also possible to use as isocyanate-reactive compounds bl) amines. Examples of suitable amines are ethylene diamine, propylene diamine, diaminocyclohexane, 4,4'-Dicylohexylmethandiamin, isophoronediamine (IPDA), difunctional polyamines such as Jeffamine ^®, amine-terminated polymers, in particular having number average molecular weights of <10000 g / mol. Mixtures of the aforementioned amines can also be used.

It is also possible to use as isocyanate-reactive compounds bl) amino alcohols. Examples of suitable amino alcohols are the isomeric aminoethanols, the isomeric aminopropanols the isomeric aminobutanols and the isomeric aminohexanols or any mixtures thereof.

All of the aforementioned isocyanate-reactive compounds B1) can be mixed with one another as desired.

It is also preferred if the isocyanate-reactive compounds bl) have a number average molecular weight of> 200 and <10000 g / mol, more preferably> 500 and <8000 g / mol and very particularly preferably> 800 and <5000 g / mol. The OH functionality of the polyols is preferably 1.5 to 6.0, particularly preferably 1.8 to 4.0. The prepolymers of the polyisocyanate component a) may in particular have a residual content of free monomeric di- and triisocyanates <1% by weight, more preferably <0.5% by weight and most preferably <0.3% by weight.

If appropriate, it is also possible for the polyisocyanate component a) to comprise completely or proportionally organic compound whose NCO groups have been completely or partially reacted with blocking agents known from coating technology. Examples of blocking agents are alcohols, lactams, oximes, malonates, pyrazoles and amines, such as butanone oxime, diisopropylamine, diethyl malonate, acetoacetic ester, 3,5-dimethylpyrazole, ε-caprolactam, or mixtures thereof. It is particularly preferred if the polyisocyanate component a) comprises compounds having aliphatically bonded NCO groups, aliphatic NCO groups being understood to mean those groups which are bonded to a primary carbon atom. The isocyanate-reactive component b) preferably comprises at least one organic compound which has on average at least 1.5 and preferably from 2 to 3 isocyanate-reactive groups. In the context of the present invention, hydroxy, amino or mercapto groups are preferably considered as isocyanate-reactive groups.

The isocyanate-reactive component may in particular comprise compounds which have a number average of at least 1.5 and preferably 2 to 3 isocyanate-reactive groups.

Suitable polyfunctional, isocyanate-reactive compounds of component b) are, for example, the compounds bl) described above.

In a further preferred embodiment, it is provided that the writing monomer c) comprises or consists of at least one mono- and / or one multifunctional writing monomer. More preferably, the writing monomer may comprise or consist of at least one mono- and / or a multifunctional (meth) acrylate random monomer. Most preferably, the writing monomer may comprise or consist of at least one mono- and / or a multifunctional urethane (meth) acrylate.

Suitable acrylate Schreibmonomere are in particular compounds of the general formula (VI)

in which o> l and n <4 and R ^{100 is} a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radical and / or R ^{101 is} hydrogen, a linear, branched, cyclic or heterocyclic unsubstituted or optionally also with Heteroatoms substituted organic radical is. R ¹⁰¹ is preferably hydrogen or methyl and / or R ^{100 is} a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radical. As acrylates or methacrylates herein esters of acrylic acid or methacrylic acid are referred to. Examples of preferably usable acrylates and methacrylates are phenyl acrylate, phenyl 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, bisphenol A diacrylate, Bisphenol A dimethacrylate, and their ethoxylated analogues, N-carbazolyl acrylates.

Urethane acrylates in the present context are understood as meaning compounds having at least one acrylic acid ester group and at least one urethane bond. Such compounds can be obtained, for example, by reacting a hydroxy-functional acrylate or methacrylate with an isocyanate-functional compound.

Examples of suitable isocyanate-functional compounds are monoisocyanates and the monomeric diisocyanates, triisocyanates and / or polyisocyanates mentioned under a). Examples of suitable monoisocyanates are phenyl isocyanate, the isomeric Methylthiophenylisocyanate, the isomeric Phenylthiophenylisocyanate. Di-, tri- or polyisocyanates are mentioned above as well as triphenylmethane-4,4 ', 4 "-triisocyanate and tris (p-isocyanatophenyl) thiophosphate or their derivatives with urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate Aromatic di-, tri- or polyisocyanates are preferred as hydroxy-functional acrylates or methacrylates for the preparation of urethane acrylates, for example compounds such as 2-hydroxyethyl (meth) acrylate , polyethylene oxide mono (meth) acrylates, Polypropylenoxidmono (meth) acrylates, Polyalkylenoxidmono (meth) acrylates, poly (s- caprolactone) mono (meth) acrylates, such as Tone ^® Ml 00 (Dow, Schwalbach, Germany), 2- Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, hydroxypropyl (meth) acrylate, acrylic acid (2-hydroxy-3-phenoxypropyl ester), the hydroxy-functional mono , Di- or tetraacrylates of polyhydric alcohols such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or technical mixtures thereof. Preference is given to 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate and poly (s-caprolactone) mono (meth) acrylate. It is also possible to use the hydroxyl-containing epoxy (meth) acrylates known per se with OH contents of 20 to 300 mg KOH / g or hydroxyl-containing polyurethane (meth) acrylates with OH contents of 20 to 300 mg KOH / g or acrylated polyacrylates with OH Contents of 20 to 300 mg KOH / g and mixtures thereof and mixtures with hydroxyl-containing unsaturated polyesters and mixtures with polyester (meth) acrylates or mixtures of hydroxyl-containing unsaturated polyester with polyester (meth) acrylates.

In particular, urethane acrylates are obtainable from the reaction of tris (p-isocyanatophenyl) thiophosphate and / or m-methylthiophenyl isocyanate and / or m- or o-phenylthiophenyl isocyanates with alcohol-functional acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and / or hydroxybutyl (meth) acrylate.

It is also possible that the writing monomer further unsaturated compounds such as α, β-unsaturated carboxylic acid derivatives such as maleinates, fumarates, maleimides, acrylamides, vinyl ethers, propenyl ethers, allyl ether and dicyclopentadienyl units containing compounds and olefinically unsaturated compounds such. Styrene, α-methylstyrene, vinyltoluene and / or olefins, or consists thereof.

Photoinitiators of component d) are usually activatable by actinic radiation compounds which can initiate a polymerization of the writing monomers. In the photoinitiators, a distinction can be made between unimolecular (type I) and bimolecular (type II) initiators. Furthermore, depending on their chemical nature, they are distinguished in photoinitiators for radical, anionic, cationic or mixed type of polymerization.

For the purposes of this invention type II photoinitiators are used.

Radical polymerization type Π photoinitiators (Norrish type II) consist of a dye as a sensitizer and a coinitiator and undergo a bimolecular reaction upon irradiation with dye-adapted light. First, the dye absorbs a photon and transfers energy to the coinitiator from an excited state. This releases the polymerization-initiating radicals by electron or proton transfer or direct hydrogen abstraction.

Preferred anions On ^"in the inventive chain substituted cyanine dyes are particularly Cs to C25 alkane, preferably C - to C25-alkane, C3 to Cis perfluoroalkanesulfonate, C4 to Cis-perfluoroalkanesulfonate, which in the alkyl chain, at least 3 Hydrogen, C9 to C25 alkanoate, C9 to C25 alkenoate, C5 to C25 alkyl sulphate, preferably C13 to C25 alkyl sulphate, C5 to C25 alkenyl sulphate, preferably C6 to C25 alkenyl sulphate, C3 bis Cis perfluoroalkyl sulfate, C4 to C18 perfluoroalkyl sulfate bearing at least 3 hydrogen atoms in the alkyl chain, polyether sulfates based on at least 4 equivalents of ethylene oxide and / or equivalents 4 propylene oxide, B1S-C4 to C25 alkyl, C5 to C7 cycloalkyl -, C3 to Cs alkenyl or C7 to Cn aralkyl sulfosuccinate, substituted by at least 8 fluorine atoms B1S-C2 to Cio-alkyl sulfosuccinate, Cs to C25 alkyl sulfoacetate, by at least one radical of the group Halogen, C4- to C25-alkyl, perfluoro-Ci- to Cs-alkyl and / or Ci- to Ci2-alkoxycarbonyl-substituted benzenesulfonate, optionally substituted by nitro, cyano, hydroxy, Ci- to C25-alkyl, Ci to Ci2- Alkoxy, amino, Ci to Ci2-alkoxycarbonyl or chlorine-substituted naphthalene or biphenyl sulfonate, if necessary durc h is nitro, cyano, hydroxy, Ci to C25 alkyl, Ci to Cn alkoxy, Ci to Ci2 alkoxycarbonyl or chlorine substituted benzene, naphthalene or biphenyl disulphonate, by dinitro, Ce to C25 alkyl, C4 to Cn Alkoxycarbonyl, benzoyl, chlorobenzoyl or toluoyl substituted benzoate, the anion of naphthalenedicarboxylic acid, diphenyl ether, sulfonated or sulfated, optionally at least monounsaturated Cs to C25 fatty acid esters of aliphatic Ci- to Cs-alcohols or glycerol, bis (sulfo-C2 - to C6-alkyl) -C3- to C 12 -alkanedicarboxylic acid esters, bis (sulfo-C 2 - to C 6 -alkyl) -itaconic acid esters, (sulfo-C 2 - to C 6 -alkyl) C 6 - to cis-alkanecarboxylic acid esters, (sulfonated C 2 - to C 6 -alkyl) -acrylic or methacrylic acid esters, optionally substituted by up to 12 halogen radicals substituted triscatechol phosphate, an anion of the group tetraphenylborate, cyanotriphenylborate, tetraphenoxyborate, C 4 - to C 12 -alkyl-triphenylborate, their phenyl or phenoxy radicals Halogen, C 1 to C 4 alkyl and / or cis bis C4 to C12 alkoxy can be substituted, C4 to C12 alkyl trinaphthylborate, tetra-Ci- to C2o-alkoxyborate, 7,8- or 7,9-dicarba-nido undecaborate (l -) or (2-), the optionally substituted on the B and / or C atoms by one or two C 1 - to C 12 -alkyl or phenyl groups, dodecahydro-dicarbadodecaborate (2-) or B-C 1 - to C 1 -alkyl-C-phenyl- dodecahydro-dicarbadodecaborate (l -), where in multivalent anions such as naphthalene disulfonate A ^"is one equivalent of this anion, and wherein the alkane and alkyl groups may be branched and / or substituted by halogen, cyano, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl could be.

It is also preferred if the anion An ^"of the dye has an AClogP in the range of 1 to 30, more preferably in the range of 1 to 12 and particularly preferably in the range of 1 to 6.5 ., 2005, 19, 453; Virtual Computational Chemistry Laboratory, http://www.vcclab.org. When the cationic chain-substituted cyanine dye has the formula (VII), the counter anions may be arbitrary, excluding dibenzylsulfosuccinate as the anion.

It may be advantageous to use mixtures of these photoinitiators. Depending on the radiation source used, the type and concentration of photoinitiator must be adapted in a manner known to the person skilled in the art. Further details are described, for example, in P.K.T. Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 3, 1991, SITA Technology, London, pp. 61-328.

It is very particularly preferred if the photoinitiator comprises a combination of dyes whose absorption spectra at least partially cover the spectral range from 400 to 800 nm with at least one co-initiator adapted to the dyes.

It is also preferred if at least one suitable for a laser light color selected from blue, green, yellow and red photoinitiator is included in the photopolymer composition.

It is also preferred if the photopolymer composition contains at least two laser light colors selected from blue, green, yellow and red, each containing a suitable photoinitiator.

Finally, it is very particularly preferred if the photopolymer composition in each case contains a suitable photoinitiator for each of the laser light colors blue, green and red.

According to a further preferred embodiment, it is provided that the photopolymer composition additionally contains urethanes as additives, wherein the urethanes may be substituted in particular with at least one fluorine atom.

The urethanes may preferably have the general formula (VIII) have in which p> l and m <8 and R ²⁰⁰ , R ²⁰¹ and R ^{202 are} linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radicals and / or R ²⁰¹ , R ^{202 are} independently hydrogen, wherein preferably at least one of the radicals R ²⁰⁰ , R ²⁰¹ , R ²⁰² is substituted by at least one fluorine atom and more preferably R ^{200 is} an organic radical having at least one fluorine atom. R ²⁰¹ is particularly preferably a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by heteroatoms such as fluorine organic radical.

A further subject of the present invention is a photopolymer comprising matrix polymers, a writing monomer and a photoinitiator, wherein the photoinitiator contains a coinitiator and a cationic dye and the cationic dye contains a chain-substituted cyanine dye of the formula (I)

is and the radicals have the meaning described above.

Dyes of the formula (I) in which K is a radical of the formulas (II) where n = 0 and m = 1, or (IV) are known, for example, from DE 1 073 662. Dyes of the formula (I) in which K is a radical of the formula (II) and n = m = 0, are known, for example, from DE 2 617 345.

Dyes of the formula (I) in which K is a radical of the formula (III) can be prepared, for example, by reacting aldehydes of the formula the formula

or by reacting methylene bases of the formula

Aldehydes of the formula

The reaction can be carried out, for example, under acidic conditions in the presence of protic acids or inorganic acid chlorides. Examples of suitable protic acids are sulfuric acid and sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, inorganic acid chlorides are, for example, phosgene, thionyl chloride or phosphoroxychloride. Solvents in the case of the use of protic acids are polar solvents, for example alcohols such as ethanol, carboxylic acids such as glacial acetic acid, aprotic solvents such as dimethyl sulfoxide, N-ethylpyrrolidone, dimethylformamide. In the case of the use of inorganic acid chlorides, solvents are aromatics such as toluene, xylene, chlorinated solvents such as trichloromethane, chlorobenzene.

The reaction takes place at room temperature to the boiling point of the medium, preferably at 30 to 90 ° C. formula

are known from DD 294 246 or can be prepared analogously. el

are known from J. Amer. Chem. Soc. 2009, 131, 12960 or can be prepared analogously. formula

are known from Z. Chem. 1968, 8, 182 or Tetrahedron 2005, 61, 903 or can be prepared analogously. ehyde of the formula

are known from US 3 573 289 or J. Chem. Soc. Perkin Trans. 1990, 329 or can be prepared analogously. The matrix polymers of the photopolymer according to the invention may in particular be crosslinked and particularly preferably be crosslinked three-dimensionally.

It is also advantageous if the matrix polymers are polyurethanes, where the polyurethanes may be obtainable in particular by reacting at least one polyisocyanate component with at least one isocyanate-reactive component. The statements made above with regard to the photopolymer composition according to the invention with regard to further preferred embodiments apply analogously to the photopolymer according to the invention.

The invention also provides a holographic medium, in particular in the form of a film, comprising a photopolymer according to the invention or obtainable using a photopolymer composition according to the invention. Yet another object of the invention the use of a photopolymer composition according to the invention for the production of holographic media.

In a preferred embodiment of the holographic medium according to the invention, holographic information is imprinted therein. The holographic media according to the invention can be processed into holograms by appropriate exposure processes for optical applications in the entire visible and near UV range (300-800 nm). The invention likewise relates to holograms comprising a holographic medium according to the invention. Visual holograms include all holograms that can be recorded by methods known to those skilled in the art. These include 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 holographic stereograms, particularly for the production of optical elements, images or image representations. Preference is given to reflection holograms, denisy-holograms, transmission holograms.

Possible optical functions of the holograms which can be produced with the photopolymer compositions according to the invention correspond to the optical functions of light elements such as lenses, mirrors, deflection mirrors, filters, diffusers, diffractive elements, diffusers, light guides, waveguides, projection screens and / or masks. Also, combinations of these optical functions may be unified independently in a hologram. Frequently, these optical elements exhibit frequency selectivity depending on how the holograms were exposed and the dimensions of the hologram.

In addition, holographic images or representations can also be produced by means of the media according to the invention, for example for personal portraits, biometric representations in security documents, or generally for images or image structures for advertising, security labels, trademark protection, branding, labels, design elements, decorations, illustrations, trading cards , Images and the like, as well as images that can represent digital data, including in combination with the previously presented products. Holographic images can have the impression of a three-dimensional image, but they can also represent image sequences, short films or a number of different objects, depending on which angle, with which (even moving) light source, etc., this is illuminated. Because of these diverse design possibilities Holograms, in particular volume holograms, an attractive technical solution for the above application is.

The present invention furthermore relates to the use of a holographic medium according to the invention for recording in-line, off-axis, full-aperture transfer, white-light transmissions, denisyuk, off-axis reflection or edge-lit holograms and holographic stereograms, in particular for Production of optical elements, images or image representations.

A further subject of the present invention is also a process for producing a holographic medium using the photopolymer composition or the photopolymer composition according to the invention. In a preferred embodiment of the method, the holographic medium is exposed using laser light, wherein the exposure is effected by pulsed laser radiation.

Likewise provided by the invention is a method for producing a hologram, in which pulsed laser radiation is used for the exposure of the medium.

In one embodiment of the method according to the invention, the pulse duration is <200 ns, preferably <100 ns, particularly preferably <60 ns. The pulse duration must not be less than 0.5 ns. Particularly preferred is a pulse duration of 4 ns.

The photopolymer compositions can be used in particular for producing holographic media in the form of a film. In this case, a layer of a material or composite material transparent to light in the visible spectral range (transmission greater than 85% in the wavelength range from 400 to 780 nm) is coated on one or both sides and optionally a cover layer applied to the photopolymer layer (s).

Preferred materials or composite materials of the carrier are based on polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene, polypropylene, cellulose acetate, cellulose hydrate, cellulose nitrate, cycloolefin polymers, polystyrene, polyepoxides, polysulfone, cellulose triacetate (CTA), polyamide, polymethyl methacrylate, polyvinyl chloride, polyvinyl butyral or polydicyclopentadiene or mixtures thereof. Most preferably, they are based on PC, PET and CTA. Composite materials may be film laminates or co-extrudates. Preferred composite materials are duplex and triplex films constructed according to one of the schemes A / B, A / B / A or A / B / C. Especially preferred are PC / PET, PET / PC / PET and PC / TPU (TPU = Thermoplastic Polyurethane). The materials or composite materials of the carrier may be unilaterally or bilaterally anti-adhesive, antistatic, hydrophobed or hydrophilated. The modifications mentioned serve on the photopolymer layer side facing the purpose that the photopolymer layer can be detached from the carrier nondestructive. A modification of the side of the carrier facing away from the photopolymer layer serves to ensure that the media according to the invention satisfy specific mechanical requirements which are required, for example, in processing in roll laminators, in particular in roll-to-roll processes.

Another object of the invention are dyes of the formula (I) wherein

K is a radical of the formula (III), and the further radicals have the abovementioned meaning.

Preference is given to dyes of the formula (I) in which

K is a radical of formula (III), n and m are 0, cyano or together with R ^{12 forms} a CEb-CEb-CEb bridge, the ring A together with R ¹ , N and X ¹ and the atoms connecting them for a remainder of the formulas

stands,

R ^{1 is} C ¹ -C ₈ -alk, C ₃ -C ₆ -alkenyl, C ₄ -C ₇ -cycloalkyl or C ₇ -C 10 -arylalkyl,

R ¹¹ and R ^{12 are} independently C 1 to C 4 alkyl, C 3 to C 6 alkenyl, C 4 to C 7 cycloalk I or C 7 to C 10 aralkyl, or together represent a -CH 2 -CH 2 -CH 2 -CH 2 - or -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ - bridge, R ²¹ and R ^{22 are} independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl,

Methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen,

R ²³ and R ^{24 are} independently hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen,

X ³ stands for S,

X ^{4 is} N or CR ⁶ , preferably N,

R ^{5 is} C ₁ -C -alkyl or C ₆ -C 10 -aryl,

R ^{6 is} hydrogen or cyano and An ^"represents the equivalent of an anion. Particular preference is given to dyes of the formula (I) in which

K is a radical of the formula (III), n and m are 0,

Q ^{1 is} cyano, the ring A together with R ¹ , N and X ¹ and the atoms connecting them for a remainder of the

stands,

R ^{1 is} methyl, ethyl, 1-propyl, 1-butyl, benzyl or cyanoethyl,

R ¹¹ and R ¹² independently represent methyl, ethyl or benzyl or together form a - CH ₂ -CH ₂ -CH ₂ -CH 2 or -CH 2 CH ₂ -CH 2 -CH 2 CH ₂ bridge form,

R ²² and R ^{24 are} hydrogen,

R ^{23 is} hydrogen, chlorine, cyano, methyl or methoxy,

X ³ stands for S, X ^{4 is} N or C-CN, preferably N,

R ^3, R ⁴ is a -CH ₂ -CH ₂ -CH ₂ -CH2-, -CH2-CH2-CH2-CH2-CH2- or -CH ₂ -CH ₂ form -0-CH ₂ -CH 2 Bmcke, R ⁵ is methyl, ethyl, tert-butyl, phenyl, 4-methylphenyl or 4-methoxyphenyl, preferably tert-butyl or phenyl and

An ^"represents the equivalent of an anion. Very particular preference is given to dyes of the formula (I) which represent a radical of the formula (III) where n and m are 0,

Q ^{1 is} cyano, with R ¹ , N and X ¹ and the atoms connecting them to a radical of the formula

stands,

R ^{1 is} methyl or benzyl, R ¹¹ and R ^{12 are} methyl,

R ^{21 is} hydrogen, methoxycarbonyl or ethoxycarbonyl,

R ^{22 is} hydrogen, X ^{3 is} S, X ^{4 is} N,

R ³ and R ^{4 are the} same and are methyl or ethyl or

R ^{5 is} phenyl and

An ^"stands for the equivalent of an anion.

The following examples serve to exemplify the invention without, however, limiting it to these.

FIG. 1 describes a film coating installation for producing holographic media on films.

FIG. 2 describes a holographic measuring arrangement for determining the diffraction efficiency after exposure, in particular laser pulse exposure.

Examples of measurement methods:

OH number:

The indicated OH numbers were determined according to DIN 53240-2. NCO value:

The indicated NCO values (isocyanate contents) were determined in accordance with DIN EN ISO 11909. Determination of the diffraction efficiency with laser pulse exposure:

To determine the diffraction efficiency at pulse exposure, the Denisyuk hologram of a mirror was recorded in a sample consisting of a glass plate with laminated photopolymer film. The substrate of a photopolymer film pointed to the laser source and the glass substrate to the mirror. The sample was aligned with the plane of its exposure perpendicular to the laser beam. The distance sample to the mirror was 3 cm.

The laser used was a pulse laser from Quantel, France, model Brilliant b. It was a Q-switched Nd-YAG laser with a module for frequency doubling to 532 nm. The single frequency mode was guaranteed by a seed laser. The calculated coherence length was about 1 m. The pulse duration 4 ns and the average output power 3 watts at a pulse repetition rate of 10 Hz.

The electronically controlled shutter ensured single pulse exposure. The wave plate allowed the rotation of the polarization plane of the laser light and with the following polarizer, the S-polarized portion of the laser light was reflected towards the sample. The beam expansion allowed adjustment of the exposed area. The wave plate and the beam spread were adjusted so that the sample reached an exposure dose of 100 mJ / cm ² / pulse.

To determine the diffraction efficiency, the samples were each exposed exactly with one pulse. After exposure, the sample was bleached on a light table. The hologram of the bleached sample was used to measure a transmission spectrum. A spectrometer from Ocean Optics, Model HR4000 was used. The sample was placed perpendicular to the light beam. The transmission spectrum showed a breakdown in transmission at the wavelength at which the Bragg condition was met. The depth of the transmission dip to the baseline was evaluated as the diffraction efficiency DE of the Denisyuk hologram of the mirror.

substances:

The solvents used were purchased in the chemicals trade.

Desmorapid Z dibutyltin dilaurate [77-58-7], product of Bayer MaterialScience

AG, Leverkusen, Germany.

Desmodur ^® N 3900 product of Bayer MaterialScience AG, Leverkusen, Germany

Hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%.

Fomrez UL 28 urethanization catalyst, commercial product

Performance Chemicals, Wilton, CT, USA.

example 1

1.00 of the aldehyde of the formula

(prepared according to J. Amer. Chem. Soc., 2009, 131, 12960) and 1.08 g of the thiazole of the formula

(prepared according to R. Flaig, Dissertation University of Halle-Wittenberg, 1996) were dissolved in 15 mL glacial acetic acid. 3 ml of acetic anhydride and 0.425 g of methanesulfonic acid were added with stirring and it was stirred at 70 ° C for 4 h. After cooling, the cherry-red solution was discharged to 60 mL of water and clarified with a little A-coal. A solution of 1.53 g of sodium tetraphenylborate in 10 mL of methanol was slowly added dropwise with good stirring. The very thick suspension was filtered off with suction. After washing with 20 ml of methanol / water 1: 1, 20 ml of methanol / water 1: 3 and 50 ml of water, the still moist filter cake was stirred with 50 ml of methanol for 1 h. It was again filtered off with suction and washed with 2 × 10 ml of methanol and 30 ml of water. After drying at 50 ° C. under reduced pressure, 2.16 g (63.2% of theory) of a pink powder of the formula ## STR16 ## were obtained

(in CH ₃ CN) = 538, 510 (sh) nm, ε = 73510 L mol ¹ cm ¹ . Example 2

2.00 of the methylene base of the formula

(prepared from 3,4-dimethylhydrazine and 2-ethylcyclohexanone analogously to US2013 / 175509, followed by methylation with dimethyl sulfate analogously to Chemistry of Heterocyclic Compounds (New York), 1982, 18 923) and 1.77 g of the aldehyde of the formula

were dissolved in 14 mL acetic anhydride with warming. 0.85 g of methanesulfonic acid were added dropwise while stirring for 5 min. 6 h was stirred at 60 ° C. After cooling, the violet solution was discharged to 50 mL of water and clarified with a little charcoal. A filtered solution of 3.02 g of sodium tetraphenylborate in 100 mL of water was added dropwise with good stirring. The fine violet suspension was filtered off with suction and washed with 2 × 25 ml of water. After drying at 50 ° C in vacuo, the violet powder was boiled three times with 20 mL of methanol and filtered off with suction after each cooling. After drying at 50 ° C. in vacuo, 3.00 g (46.8% of theory) of a violet powder of the formula ## STR16 ## were obtained

(in CH ₃ CN) = 543, 521 (sh) nm, ε = 36810 L mol ¹ cm ¹ . Example 3

4.03 of the aldehyde of the formula

and 3.59 g of 2-cyanomethylbenzothiazole were stirred in 25 mL of acetic anhydride at 90 ° C for 1.5 h. The thick crystal slurry was discharged after cooling to 100 mL of water and diluted with 15 mL of methanol. It was filtered off with suction and washed with 200 ml of water until colorless. After drying at 50 ° C. in vacuo, 7.03 g (98.3% of theory) of an orange crystal powder were obtained

2.50 g of this dye were mixed in 20 ml of anhydrous toluene with 0.91 g of dimethyl sulfate and stirred at 90 ° C for 16 h, during which time twice each 0.91 g of dimethyl sulfate were added. The thick suspension was filtered off with suction and the filter cake was washed three times with 25 ml of toluene. While still moist, the product was stirred twice with 50 ml of toluene at 70 ° C. for 3 h, in each case filtered off with suction and washed with 100 ml of toluene. After drying at 50 ° C. in vacuo, 2.46 g (72.7% of theory) of a red crystalline powder of the formula ## STR16 ## were obtained

2.00 g of this dye were dissolved in 15 mL of methanol and filtered through a pleated filter. A solution of 1.43 g of sodium tetraphenylborate in 5 ml of methanol was added dropwise with stirring to the filtrate. It was filtered off with suction and washed with eight times 10 ml of methanol. The moist filter cake was then stirred in 25 mL of methanol for 3 h at 45 ° C, filtered off with suction again and washed with six times 10 mL of methanol. After drying at 50 ° C. in vacuo, 1.94 g (67.8% of theory) of a red powder of the formula ## STR16 ## were obtained

(in CH ₃ CN) = 519, 500 (sh) nm, ε = 91130 L mol ¹ cm ^"1 Example 4

3.00 of Cyanmethylenbase the formula

and 1.29 g of diphenylformamidine were stirred in 15 mL of acetic anhydride with the addition of 0.62 g of methanesulfonic acid at 90 ° C for 6 h. After cooling, the red solution was discharged to 75 mL of water. 3 mL of methanol was added. Few precipitated resin was filtered off after addition of A carbon. With vigorous stirring, a solution of 2.25 g of sodium tetraphenylborate in 15 ml of water was added dropwise to the filtrate. The thick suspension was filtered off with suction and washed with 200 ml of water. After drying at 50 ° C in vacuo, the dye was stirred in a mixture of 1 mL of methanol and 2 mL of glacial acetic acid for 3 h. Finally, 5 mL of water was slowly added dropwise. It was filtered off with suction, washed with a mixture of 10 ml of methanol and 3 ml of water and then with 100 ml of water. After drying at 50 ° C. under reduced pressure, 2.36 g (46.1% of theory) of a vermilion powder of the formula ## STR16 ## were obtained (in CH ₃ CN) = 515 nm, ε = 54870 L mol ¹ cm ^"

Example 5

Analogously to Example 6 of DE 1 073 662 were 6.98 g of Cyanmethylenbase the formula

and 6.16 of the aldehyde of the formula

in 30 mL of anhydrous toluene slowly added while stirring with 3.57 g of thionyl chloride. The mixture was then stirred at 100 ° C. for 1 h and cooled. 50 ml of toluene were added and the dye was filtered off with suction. It was stirred three times with 30 ml of toluene each time and each time sucked off again. After drying at 50 ° C in vacuo, the red dye was largely dissolved in 100 mL of water. A solution of 12.38 g of sodium bis (2-ethylhexyl) sulfosuccinate in 100 mL of butyl acetate was added. The two-phase mixture was stirred for 1 h and then transferred to a separatory funnel. The aqueous phase was drained off and the organic phase was washed four times with 40 ml of water. After separation of the last water wash, the organic phase was diluted with 250 mL of butyl acetate and distilled on a rotary evaporator in vacuo anhydrous. In this case, about 200 mL of butyl acetate were distilled off, so that finally 150.1 g of a red solution of the dye of the formula

in butyl acetate which was storage stable.

A sample was taken and the residual solvent removed in vacuo. After drying at 50 ° C in vacuo, the dye was obtained as a red resinous substance.

(in CH ₃ CN) = 498 nm and 523 nm, ε = 89580 (at 498 nm) and 99423 L mol ¹ cm ¹ (at 523 nm) L mol ^"1 cm ^{" 1} .

With these spectroscopic data, the concentration of the above solution could be determined to be 10.0%.

Example 6

3.35 g of the compound of the formula

known from DE 2 617 345 were heated in 40 mL of chlorobenzene with stirring to reflux and treated with 2.52 g of dimethyl sulfate. After 16 h at reflux, it was cooled, filtered off with suction and washed with 3 × 20 ml of chlorobenzene. After drying at 50 ° C. under reduced pressure, 4.41 g (95% of theory) of the dyestuff of the formula ## STR16 ## were obtained

2.31 g of this dye was dissolved in 15 mL of methanol. While stirring, a solution of 1.72 g of sodium tetraphenylborate in 5 ml of methanol was added dropwise. It was filtered off with suction and washed with 20 ml of methanol. After drying at 50 ° C. in vacuo, 2.71 g (80% of theory) of a yellow powder of the formula were obtained

Example 7

3.00 of Cyanmethylenbase the formula

and 1.70 g of malonaldehyde dianil hydrochloride were stirred in 15 mL of acetic anhydride at 90 ° C for 20 min. After cooling, the blue suspension was discharged to 75 mL of water. 3 mL of methanol was added. It was filtered off with suction and washed with water until almost colorless. After drying at 50 ° C. under reduced pressure, 3.16 g (91.1% of theory) of a green crystal powder were obtained

(in CH ₃ CN) = 616, 580 (sh) nm, ε = 116965 L mol ¹ cm ¹ .

2.00 g of this dye and 1.59 g of sodium bis (2-ethylhexyl) sulfosuccinate were stirred in a mixture of 30 ml of water and 30 ml of butyl acetate for 5 h. After transfer to a separatory funnel, the aqueous phase was drained off. The organic phase was washed five times with 15 mL of water until finally no more chloride ions could be detected in the water with silver nitrate. The organic phase was dried with anhydrous magnesium sulfate. This gave 39.5 g of a solution over

was. Example 8

ehyds of the formula

(prepared according to Coli. Czech. Chem. Commun. 1972, 37, 2273) and 1.80 g of 1,3,3-trimethyl-2-methylene-indoline were mixed. 3.16 g of phosphorus oxychloride were slowly added dropwise to the slurry with the syringe while stirring. The mixture turned blue immediately. It was heated to 80 ° C and held for 2 h at this temperature. After cooling, the blue resin was dissolved by careful addition of 10 mL of methanol in a water bath. With stirring, a solution of 2.39 g of sodium tetraphenylborate in 10 ml of methanol was added dropwise to this solution. It was filtered. 20 ml of water were slowly added dropwise to the filtrate, with stirring, whereby the dye parted off partially as a resin. After dropwise addition of a solution of 4.5 g of sodium tetraphenylborate in 30 ml of water, the precipitation has been completed and the product has solidified. It was filtered off with suction and washed with 100 ml of methanol / water 1: 2 and 100 ml of water. After drying at 50 ° C in vacuo, the crude product was dissolved in 100 mL of acetone and precipitated by dropwise addition of 50 mL of water and filtered with suction. This process was repeated. It was filtered off with suction and washed with 15 ml of acetone / water 2: 1 and 10 ml of water. After drying at 50 ° C. in vacuo, 1.68 g (41.4% of theory) of a copper-oxide-colored crystal of the formula ## STR16 ## were obtained

(in CH ₃ CN) = 605, 566 (sh) nm, ε = 178480 L mol ¹ cm ¹ .

Further dyes according to the invention can be found in the following table:

Example Dye cation An ^" in CH ₃ CN

9 CN (C _O H _S ^ B ^" 424 nm

Comparative Dyes (Known from EP 2 638 544 A2): Comparative Dye 1:

Coloring Dye 2:

Comparative Dye 3:

Light Dye 4:

Preparation of the other components for the photopolymer composition: Preparation of Polyol 1:

0.18 g of tin octoate, 374.8 g of ε-caprolactone and 374.8 g of a difunctional polytetrahydrofuranpolyether polyol (equivalent weight 500 g / mol OH) were placed in a 1 l flask and heated to 120 ° C. and kept at this temperature until the solids content (proportion of non-volatile ingredients) was 99.5% by weight or above. It was then cooled and the product obtained as a waxy solid.

Preparation of urethane acrylate 1 (writing monomer): phosphorothioyltris (oxybenzene-4, 1-diylcarbamoyloxyethane-2, 1-diyl) trisacrylate

In a 500 mL round bottom flask, 0.1 g of 2,6-di-tert-butyl-4-methylphenol, 0.05 g of dibutyltin dilaurate and 213.07 g of a 27% solution of tris (p-isocyanatophenyl) thiophosphate in ethyl acetate (Desmodur® RFE , Product of Bayer MaterialScience AG, Leverkusen, Germany) and heated to 60 ° C. Subsequently, 42.37 g of 2-hydroxyethyl acrylate were added dropwise and the mixture on maintained at 60 ° C until the isocyanate content had dropped below 0.1%. It was then cooled and the ethyl acetate was completely removed in vacuo. The product was obtained as a partially crystalline solid.

Preparation of urethane acrylate 2 (writing monomer): 2 - ({[3-

(Methylsulfanyl) phenyl] carbamoyl} oxy) ethylprop-2-enoate In a 100 mL round bottomed 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 [28479-1 -8] and heated to 60 ° C. Subsequently, 8.2 g of 2-hydroxyethyl acrylate were added dropwise and the mixture was kept at 60 ° C until the isocyanate content had dropped below 0.1%. It was then cooled. The product was obtained as a colorless liquid. Preparation of Additive 1 Bis (2,2,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl) - (2,2,4-trimethylhexane-1,6-diyl) biscarbamate

0.02 g of Desmorapid Z and 3.6 g of 2,4,4-trimethylhexane 1,6-diisocyanate (TMDI) were introduced into a 50 mL round-bottomed flask and heated to 60.degree. Subsequently, 11.9 g of 2,2,3,3,4,5,5,6,6,7,7-dodecafluoroheptan-1-ol were added dropwise and the mixture was kept at 60 ° C. until the isocyanate content was below 0.1%. had sunk. It was then cooled. The product was obtained as a colorless oil.

Preparation of the borate (photoinitiator): benzyl-hexadecyldimethylammonium tris (3-chloro-4-methylphenyl) hexylborate

Manufactured according to WO 2015/055576 AI. Triazine 1

2- (3-Methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine Prepared analogously to US 3,987,037. Triazine 2

2- (4- (2-ethylhexyl) carbonylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine Prepared analogously to EP 0 332 042. Preparation of media for determining holographic properties

Production of holographic media on a film coater

The following describes the continuous production of holographic media in the form of films of photopolymer compositions according to the invention and not of the invention.

For the production, the film coating machine shown in Fig. 1 was used, wherein the individual components are assigned the following reference numerals. Figure 1 shows the schematic structure of the coating system used. In the figure, the individual components have the following reference numerals:

1, 1 'reservoir

2, 2 'metering device

3, 3 'vacuum degassing device;

4, 4 'filters

5 Static mixer

6 coating device

7 circulating air dryer

8 carrier substrate

9 covering layer

To prepare the photopolymer composition, 53.7 g of the polyol 1 (OH number 59.7) was added stepwise with a mixture of 30.0 g of the urethane acrylate 1 and 30.0 g of the urethane acrylate 2, 22.5 g of the additive 1, 0.15 g of the triazine 1 or 2, 1.5 g borate, 0.075 g of Fomrez UL 28, and 1.35g of the surface-active additive BYK ^® 310 and 50 g of ethyl acetate and mixed. Subsequently, 0.3 g of a dye of the invention was added to the mixture in the dark and mixed to obtain a clear solution. When necessary, the composition was heated at 60 ° C for a short time to more quickly dissolve the feeds. This mixture was introduced into one of the two reservoirs 1 of the coating system. In the second reservoir Γ, the polyisocyanate component (Desmodur ^® N 3900, commercial product of Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of hninooxadiazindion at least 30%, NCO content: 23.5%) was filled. Both components were then each by the metering devices 2 in the ratio of 18.2 (component mixture) to 1.0 (isocyanate) to Vacuum degassing 3 funded and degassed. From here, they were then each passed through the filters 4 in the static mixer 5, in which the mixing of the components for photopolymer composition took place. The resulting liquid mass was then fed to the coating device 6 in the dark.

The coating device 6 in the present case was a doctor blade known to the person skilled in the art. Alternatively, however, a slot nozzle can also be used. With the help of the coating device 6, the photopolymer composition was applied at a processing temperature of 20 ° C to a carrier substrate 8 in the form of a 36 μηι thick polyethylene terephthalate and dried for 5.8 minutes at a crosslinking temperature of 80 ° C in a circulating air dryer 7. In this case, a medium in the form of a film was obtained, which was then provided with a 40 μηι thick polyethylene film as a cover layer 9 and wound up. All these steps were in the dark.

The desired target layer thickness of the film was preferably 1 to 60 μηι, preferably 5 to 25 μηι, more preferably 10 to 15 μηι.

The production rate was preferably in the range of 0.2 m / min to 300 m / min and more preferably in the range of 1.0 m / min to 50 m / min.

The achieved layer thickness of the film was 12 μηι ± 1 μηι. Comparison medium V

The procedure was as above, but 0.3 g of one of the comparative dyes were used.

Holographic test:

The media produced as described were tested for their holographic properties by means of a measuring arrangement according to FIG. 2 in the manner described above (see Methods of Measuring Determination of the Diffraction Efficiency with Pulse Exposure). The following measured values for DE resulted at a fixed dose of 100 mJ / cm ² : Dye triazine 1 triazine 2 DE

Medium dye

[%] [%] [%] [%]

B-1 example 5 0.2 0.1 49

B-2 Example 11 0.2 0.1 41

B-3 Example 14 0.2 0.1 21

B-4 Example 3 0.2 0.1 16

B-5 Example 5 0.2 0.1 34

comparison

Comparative triazine 1 triazine 2 DE

Comparative dye dye

Medium [%] [%] [%]

[%]

V-1 comparative dye 1 0.2 0.1 8

V-2 comparative dye 2 0.2 0.1 3

V-3 Comparative Dye 2 0.2 0.1 2

V-4 comparative dye 3 0.2 0.1 2

V-5 comparative dye 4 0.2 0.1 0

Tab. 2: Holographic evaluation of selected media and comparative media

The values found for the example media B-1 to B-5 show that the chain-substituted cyanine dyes of the formula (I) used in the photopolymer compositions of the invention are very well suited for use in holographic media when exposed to pulsed laser exposure. Comparative media V-1 to V-5 using analogous cationic dyes without chain substituents according to the invention are unsuitable for use in holographic media when exposed to pulsed laser exposure.

Claims

claims

Photopolymer composition comprising a photopolymerisable component and a photoinitiator system characterized in that it comprises a chain-substituted cyanine dye of the formula (I) At-

(I)

contains, in which

K is a radical of the formula (II)

(III)

stands, Ring A together with N and X ¹ and the atoms connecting them and ring B together with N and X ² and the atoms connecting them independently represent a five- or six-membered aromatic or quasi-aromatic or partially hydrogenated heterocyclic ring containing 1 to 4 heteroatoms may contain and / or benzo or naphthoanneliert and / or with C to C alkyl, C3 to C6 alkenyl, C4 to C7 cycloalkyl or C7 to Cio-aralkyl, aryl, fluorine, chlorine, bromine Methoxy, ethoxy, where the unsaturated building block (* (C = K) -Q ¹ ) of formula (I) on ring A or B in position 2 or 4 relative to X ¹ or X ² attacks,

X ^{1 is} O, S, NR ⁷ , CR ⁹ or CR ^U R ¹² ,

X ^{2 is} O, S, NR ⁸ , CR ¹⁰ or CR ¹³ R ¹⁴ ,

Q ^{1 is} hydrogen, cyano or methyl,

Q ^{2 is} hydrogen or cyano,

Q ³ for hydrogen or a (V) Air

(V)

wherein at least one of the radicals Q ¹ , Q ² and Q ³ does not stand for hydrogen,

X ^{3 is} O or S,

X ^{4 is} N or CR ⁶ ,

X ^{5 is} N, O or CR ²⁰ R ²⁰ ,

R ¹ , R ² , R ⁷ , R ⁸ , R ¹⁵ and R ^{19 are} independently C ₁ to C 8 alkyl, C ₃ to C ₆ alkenyl, C ₄ to C ₇ cycloalkyl or C 7 to C 10 aralkyl stand and R ^{15 can} additionally be hydrogen,

R ⁹ and R ¹⁰ independently of one another represent hydrogen or C ₁ - to C ₂ -alkyl,

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ²⁰ independently of one another are ci- to C ₄ -alkyl, C ₃ - to C ₆ -alkenyl, C ₄ - to C ₇ -cycloalkyl or C ₇ - to Cio-aralkyl or R ¹¹ and R ¹² together and / or R ¹³ and R ¹⁴ together are a -CH2-CH2-CH2-CH2- or -CH ₂ form -CH2-CH2-CH2-CH ₂ bridge, and in addition

R ⁷ , R ⁹ or R ¹² together with Q ^{1 can form} a --CH 2 --CH 2 - or --CH 2 --CH 2 --CH 2 --B radical,

R ³ and R ⁴ independently of one another represent C 1 - to C 6 -alkyl, C ³ - to C 6 -alkenyl, C ⁴ - to C 7 -cycloalkyl, C 7 - to C 10 -aralkyl or Ce- to Cio-aryl or

R ³ , R ^{4 is} a -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ --NH-CH ₂ Form -CH 2 - or -CH ₂ -CH ₂ -N (alkyl) -CH ₂ -CH ₂ -bridge,

R ⁵ and R ¹⁶ independently of one another represent hydrogen, C 1 -C 5 -alkyl, C 4 -C 7 -cycloalkyl or C 1 -C 10 -aryl,

R ^{6 is} hydrogen, alkyl or cyano,

R ¹⁷ and R ¹⁸ independently of one another represent hydrogen, chlorine, methyl, ethyl, methoxy or ethoxy,

n and m are independently 0 or 1, where m stands for 1 only if n stands for 1, and

stands for the equivalent of an anion.

A photopolymer composition according to claim 1, characterized in that Q ^{1 is} cyano or together with R ^{12 forms} a -Ctb-CI-b-Cl-b bridge, Q ^{2 is} hydrogen or cyano, preferably hydrogen, Q ³ represents hydrogen, ring A together with R ¹ , N and X ¹ and the atoms connecting them represent a residue of

stands,

R ^{1 is} ci- to C ₈ -alkyl, C ₃ - to C ₆ -alkenyl, C ₄ - to C ₇ -cycloalkyl or C ₇ - to Cio-aralkyl,

R ¹¹ and R ¹² independently of one another are C 1 - to C 4 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalkyl or C 7 - to C 10 -aralkyl or together form a -CH 2 -CH 2 -CH 2 -CH 2 - or - _CH2 -CH2-CH2-CH2-CH ₂ bridge form,

R ²¹ and R ^{22 are} independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen, R ²³ and R ^{24 are} independently hydrogen, chloro, cyano, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen, ring B together with R ² , N and X ² and the atoms connecting them for a rest of

stands,

R ^{2 is} C ₁ -C ₄ -alkyl, C ₃ -C ₆ -alkenyl, C ₄ -C ₇ -cycloalkyl or C ₇ -C 10 -arylalkyl,

R ¹³ and R ¹⁴ independently of one another are C 1 - to C 4 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalkyl or C 7 - to C 10 -aralkyl or together form a -CH 2 -CH 2 -CH 2 -CH 2 - or - CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ bridge,

X ³ stands for S,

X ^{4 is} N or CR ⁶ , preferably N,

R ³ and R ⁴ independently of one another represent C 1 - to C 6 -alkyl, C ³ - to C 6 -alkenyl, C ⁴ - to C 7 -cycloalkyl, C 7 - to C 10 -aralkyl or Ce- to Cio-aryl or R ³ , R ^{4 form} a -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -bridge,

R ^{5 is} C 1 -C ₈ -alkyl or C ₆ -C 10 -aryl,

R ^{6 is} hydrogen or cyano,

R ^{15 represents} hydrogen, C ₁ - to Cg-alkyl, C ₃ - to C ₆ -alkenyl, C ₄ - to C ₇ -cycloalkyl or C ₇ - to C 10 -aralkyl,

An ^"stands for the equivalent of an anion.

Photopolymer composition according to at least one of claims 1 or 2, characterized in that

Q ¹ and Q ^{2 are} hydrogen,

Q ^{3 is} a radical of the formula (V), the ring A together with R ¹ , N and X ¹ and the atoms connecting them for a remainder of

stands,

R ¹ and R ¹⁹ independently of one another are C ¹ -C 5 -alkyl, C 3 -C 6 -alkenyl, C 4 -C 7 -cycloalk I or C 7 -C 10 -arylalkyl,

R ¹¹ and R ¹² independently of one another are C 1 -C 4 -alk1, C 3 -C 10 -alkenyl, C 4 -C 7 -cycloalkyl or C 7 -C 10 -arylalkyl or together form a -CH 2 -CH 2 -CH 2 -CH 2 - or Form -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -bridge,

R ²³ and R ^{24 are} independently hydrogen, chloro, cyano, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen, ring B together with R ² , N and X ² and the atoms connecting them for a remainder of the F

R ^{2 is} C ₁ -C ₄ -alkyl, C ₃ -C ₆ -alkenyl, C ₄ -C ₇ -cycloalkyl or C ₇ -C 10 -arylalkyl, R ¹³ and R ¹⁴ independently of one another are C 1 -C 4 -alkyl, C 3 -C 6 -alkenyl, C 4 -C 7 -cycloalk I or C 7 -C 10 -arylalkyl or together form a -CH 2 -CH 2 -CH 2 -CH 2 - or - CH ₂ form -CH2-CH2-CH2-CH ₂ bridge,

R ²⁵ and R ²⁶ independently of one another represent hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, where preferably only one of the two does not represent hydrogen, R ²⁷ and R ²⁸ independently of one another represent hydrogen, Chlorine, cyano, methyl, ethyl, methoxy or

Ethoxy, preferably only one of which is not hydrogen,

X ^{5 is} S or C (CH ₃ ) ₂ , X ^{3 is} S,

X ^{4 is} N or CR ⁶ , preferably N,

R ^{5 is} C ₁ -C -alkyl or C ₆ -C 10 -aryl,

R ^{6 is} hydrogen or cyano, R ^{15 represents} hydrogen, C ₁ -C ₄ -alkyl, C ₃ -C ₆ -alkenyl, C ₄ -C ₇ -cycloalkyl or C ₇ -C -aralkyl,

An ^"stands for the equivalent of an anion.

Photopolymer composition according to at least one of claims 1 to 3, characterized in that

Q ^{1 is} cyano or together with R ^{12 forms} a -Ctb-Ctb-Ctb bridge, Q ² and Q ^{3 are} hydrogen, the ring A together with R ¹ , N and X ¹ and the atoms connecting them to a radical the formulas

stands,

R ^{1 is} methyl, ethyl, 1-propyl, 1-butyl, benzyl or cyanoethyl,

R ¹¹ and R ¹² are, independently of one another represent methyl, ethyl or benzyl together a - CH2-CH2-CH2-CH2- or -CH ₂ -CH2-CH2-CH2-CH ₂ bridge form, R ^{21 represents} hydrogen, chlorine, cyano, methoxycarbonyl, ethoxycarbonyl, methyl or methoxy,

R ²² and R ^{24 are} hydrogen,

R ^{23 is} hydrogen, chlorine, cyano, methyl or methoxy, ring B together with R ² , N and X ² and the atoms connecting them is a radical of

formula

stands,

R ^{2 is} methyl, ethyl, 1-propyl, 1-butyl, benzyl or cyanoethyl,

R ¹³ and R ¹⁴ independently represent methyl, ethyl or benzyl, or together a - CH2-CH2-CH2-CH2- or _-CH2-CH2 -CH2-CH2-CH ₂ bridge form,

R ^{26 is} hydrogen,

X ³ stands for S,

X ⁴ stands for N,

R ³ and R ⁴ independently of one another are methyl, ethyl, 1-propyl, 1-butyl, 1-octyl, cyclohexyl or benzyl or R ³ , R ^{4 form} a -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -bridge,

R ^{5 is} methyl, ethyl, tert-butyl, phenyl, 4-methylphenyl or 4-methoxyphenyl,

R ^{15 is} hydrogen, methyl, ethyl, 1-propyl-1-butyl, 1-octyl or benzyl,

R ^{16 is} hydrogen, methyl or phenyl,

R ^{17 is} hydrogen, chlorine or methyl,

R ^{18 is} hydrogen and

An ^"stands for the equivalent of an anion.

Photopolymer composition according to at least one of claims 1 to 4, characterized in that it contains matrix polymers and at least one writing monomer.

Photopolymer composition according to at least one of claims 1 to 5, characterized in that the photoinitiator system additionally contains a coinitiator.

Photopolymer composition according to claim 6, characterized in that the coinitiator contains at least one triazine.

Photopolymer containing a photopolymer composition according to at least one of claims 5 to 7, characterized in that the matrix polymers are crosslinked and preferably three-dimensionally crosslinked.

Photopolymer according to one of claims 5 to 8, characterized in that the matrix polymers are polyurethanes.

10. Holographic medium, in particular in the form of a film, containing a photopolymer according to at least one of claims 8 to 9. 11. Hologram containing a holographic medium according to claim 10, characterized in that holographic information is imprinted.

12. Use of a holographic medium according to claim 10 for recording in-line, off-axis, full-aperture transfer, white light transmissions, reflection, denisyuk, off-axis reflection or edge-lit holograms and holographic stereograms, in particular for

Production of optical elements, images or image representations.

13. A process for producing a holographic medium according to claim 10 using a photopolymer according to any one of claims 8 to 9.

14. A method for producing a hologram according to claim 11, characterized in that for the exposure of the medium pulsed laser radiation is used.

15. A method for producing a hologram according to claim 14, characterized in that

Pulse durations of <200 ns are used.

16. Dyes of the formula (I) in which

K is a radical of the formula (III), n and m are 0 and the other radicals have the meaning of claim 1.