Photopolymer compositions for thermostable photopolymers in the visible spectral range

A photopolymer composition comprising

• a) matrix polymers,
• b) writing monomers,
• c) at least one photoinitiator system,
• d) optionally, at least one non-photopolymerizable component,
• e) optionally, catalysts, radical stabilizers, solvents, additives and other auxiliaries and/or adjuvants,
• wherein the at least one photoinitiator system c) consists of at least one dye and at least one coinitiator, where at least one of the dyes has a structure according to formula (I)
• in which
• X1 stands for O, S, N—R211 or CR211aR211b,
• R211 stands for hydrogen, C1 to C16 alkyl, C4 to C7 cycloalkyl, C7 to C16 aralkyl, C6 to C10 aryl or a heterocyclic radical,
• R211a and R211b are identical and stand for methyl, ethyl or together stand for a —CH2—CH2—CH2— or —CH2—CH2—CH2—CH2— bridge,
• X2 stands for N or C—R212,
• R212 stands for hydrogen, cyano, C1 to C4 alkyl, C4 to C7 cycloalkyl, a C6 to C10 aryl which is optionally substituted by C1 to C4 alkoxycarbonyl or NR213R214, or a heterocyclic radical,
• R201 to R204, R213 and R214 stand independently of each other for hydrogen, C1 to C16 alkyl, C4 to C7 cycloalkyl, C7 to C16 aralkyl, C6 to C10 aryl or a heterocyclic radical or
• NR201R202, NR203R204 and NR213R214 stand independently of each other for a five- or six-membered saturated ring attached via N, which may additionally contain an N or O and/or may be substituted by nonionic radicals, or
• R201 to R204, R213 and R214 independently of each other and with a C atom of the benzene ring adjacent to the N atom form a two- or three-membered bridge, which may contain an O or N and/or may be substituted by nonionic radicals,
• R205, R206, R207, R208, R209 and R210 stand independently of each other for hydrogen, halogen or C1 to C4 alkyl,
• An− stands for an anion selected from halide, perchlorate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetraarylborate, triarylalkylborate, nitrate, cyanide, tosylate, trifluoromethylsulfonate, bis(trifluoromethyl)sulfonimide, azide, methylsulfonate, phosphate, hydrogen phosphate, dihydrogen phosphate, sulfate, hydrogensulfate, an arbitrarily substituted carboxylate, an arbitrarily substituted organic mono- or di-sulfonate, or an arbitrarily substituted organic mono- or di-carboxylate, and the at least one coinitiator has a calculated oxidation potential Eoxcalculated, determined according to the formula (1) below by the quantum mechanical calculation of the Gibbs energies at 298 K of the ground state and the oxidized state of the coinitiator consisting of conformer energy minimization by means of the AM1 force field followed by ab initio conformer energy calculation based on the previously determined molecular geometry coordinates, in the solvent acetonitrile under solvent field correction according to the PCM method, in the range from 1.16 V to 1.37 V against the saturated calomel electrode (SCE) in acetonitrile
• E
• ox
• calculated
• =
• -
• (
• G
• 2
• ⁢
• 9
• ⁢
• 8
• -
• G
• 2
• ⁢
• 9
• ⁢
• 8
• (
• oxidized
• )
• )
• 23.061
• kcal
• mol
• ·
• V
• +
• 4.14
• V
• .
• (
• 1
• )