HOLOGRAPHIC MEDIA CONTAINING CHAIN-SUBSTITUTED CYANINE DYES

Abstract

The present invention relates to a photopolymer composition comprising a photopolymerizable component and a photoinitiator system comprising a chain-substituted cyanine dye. The invention further provides a photopolymer comprising a photopolymer composition according to the invention, a holographic medium comprising a photopolymer according to the invention, the use of a holographic medium according to the invention, and a process for producing a holographic medium by using the photopolymer according to the invention and the exposure of the corresponding holographic medium with the aid of pulsed laser radiation.

Claims

1.-16. (canceled)

17. A photopolymer composition comprising a photopolymerizable component and a photoinitiator system, wherein the composition contains a chain-substituted cyanine dye of the formula (I) ##STR00063## in which K is a radical of the formula (II) ##STR00064## (III) ##STR00065## or (IV) ##STR00066## ring A together with N and X.sup.1 and the atoms that connect them and ring B together with N and X.sup.2 and the atoms that connect them are independently a five- or six-membered aromatic or quasiaromatic or partly hydrogenated heterocyclic ring which may contain 1 to 4 heteroatoms and/or may be benzo- or naphthofused and/or may be substituted by C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, aryl, fluorine, chlorine, bromine, methoxy, ethoxy, where the unsaturated unit (*(C=K)-Q.sup.1) in the formula (I) joins onto the ring A or B in position 2 or 4 relative to X.sup.1 or X.sup.2, X.sup.1 is O, S, NR.sup.7, CR.sup.9 or CR.sup.11R.sup.12, X.sup.2 is O, S, NR.sup.8, CR.sup.10 or CR.sup.13R.sup.14, Q.sup.1 is hydrogen, cyano or methyl, Q.sup.2 is hydrogen or cyano, Q.sup.3 is hydrogen or a radical of the formula (V) ##STR00067## where at least one of the Q.sup.1, Q.sup.2 and Q.sup.3 radicals is not hydrogen, X.sup.3 is O or S, X.sup.4 is N or CR.sup.6, X.sup.5 is N, O or CR.sup.20R.sup.20, R.sup.1, R.sup.2, R.sup.7, R.sup.8, R.sup.15 and R.sup.19 are independently C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl and R.sup.15 may additionally be hydrogen, R.sup.9 and R.sup.0 are independently hydrogen or C.sub.1- to C.sub.2-alkyl, R.sup.11, R.sup.12, R.sup.13, R.sup.14 and R.sup.20 are independently C.sub.1- to C.sub.4-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl or R.sup.11 and R.sup.12 together and/or R.sup.13 and R.sup.14 together form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 bridge and, in addition, R.sup.7, R.sup.9 or R.sup.12 together with Q.sup.1 can form a CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2CH.sub.2 bridge, R.sup.3 and R.sup.4 are independently C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl, C.sub.7- to C.sub.10-aralkyl or C.sub.6- to C.sub.10-aryl or R.sup.3, R.sup.4 form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CHOCH.sub.2CH.sub.2, CH.sub.2CH.sub.2NHCH.sub.2CH.sub.2 or CH.sub.2CH.sub.2N(alkyl)-CH.sub.2CH.sub.2 bridge, R.sup.5 and R.sup.16 are independently hydrogen, C.sub.1- to C.sub.8-alkyl, C.sub.4- to C.sub.7-cycloalkyl of C.sub.6- to C.sub.10-aryl, R.sup.6 is hydrogen, alkyl or cyano, R.sup.17 and R.sup.18 are independently hydrogen, chlorine, methyl, ethyl, methoxy or ethoxy, n and m are independently 0 or 1, where m is only 1 when n is also 1, and An.sup. represents the equivalent of one anion.

18. The photopolymer composition according to claim 17, wherein Q.sup.1 is cyano or, together with R.sup.12, forms a CH.sub.2CH.sub.2CH.sub.2 bridge, Q.sup.2 is hydrogen Q.sup.3 is hydrogen, the ring A together with R.sup.1, N and X.sup.1 and the atoms that connect them are a radical of the formulae ##STR00068## R.sup.1 is C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, R.sup.11 and R.sup.12 are independently C.sub.1- to C.sub.4-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, or together form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CHCH.sub.2CH.sub.2CH.sub.2 bridge, R.sup.21 and R.sup.22 are independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, R.sup.23 and R.sup.24 are independently hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, the ring B together with R.sup.2, N and X.sup.2 and the atoms that connect them are a radical of the formulae ##STR00069## R.sup.2 is C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, R.sup.13 and R.sup.14 are independently C.sub.1- to C.sub.4-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, or together form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 bridge, R.sup.25 and R.sup.26 are independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, R.sup.27 and R.sup.28 are independently hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, X.sup.3 is S, X.sup.4 is N or CR.sup.6, R.sup.3 and R.sup.4 are independently C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl, C.sub.7- to C.sub.10-aralkyl or C.sub.6- to C.sub.10-aryl or R.sup.3; R.sup.4 form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2(H.sub.2OCH.sub.2CH.sub.2 bridge, R.sup.5 is C.sub.1- to C.sub.8-alkyl or C.sub.6- to C.sub.10-aryl, R.sup.6 is hydrogen or cyano, R.sup.15 is hydrogen, C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, R.sup.16 is hydrogen, C.sub.1- to C.sub.4-alkyl, C.sub.5- to C.sub.6-cycloalkyl or C.sub.6-aryl, R.sup.17 and R.sup.18 are independently hydrogen, chlorine, methyl or methoxy, n and m are independently 0 or 1, where m is only 1 when n is also 1, and An.sup. represents the equivalent of one anion.

19. The photopolymer composition according to claim 17, wherein Q.sup.1 is cyano or, together with R.sup.12, forms a CH.sub.2CH.sub.2CH.sub.2 bridge, Q.sup.2 is hydrogen Q.sup.3 is hydrogen, the ring A together with R.sup.1, N and X.sup.1 and the atoms that connect them are a radical of the formulae ##STR00070## R.sup.1 is C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, R.sup.11 and R.sup.12 are independently C.sub.1- to C.sub.4-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, or together form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 bridge, R.sup.21 and R.sup.22 are independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, where just one f the two is not hydrogen, R.sup.23 and R.sup.24 are independently hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, where just one of the two is not hydrogen, the ring B together with R.sup.2, N and X.sup.2 and the atoms that connect them are a radical of the formulae ##STR00071## R.sup.2 is C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, R.sup.13 and R.sup.14 are independently C.sub.1- to C.sub.4-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, or together form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 bridge, R.sup.25 and R.sup.26 are independently hydrogen, chlorine, nitro, cyano, n ethoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, where just one of the two is not hydrogen, R.sup.27 and R.sup.28 are independently hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, where just one of the two is not hydrogen, X.sup.3 is S, X.sup.4 is N, R.sup.3 and R.sup.4 are independently C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl, C.sub.7- to C.sub.10-aralkyl or C.sub.6- to C.sub.10-aryl or R.sup.3; R.sup.4 form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2 bridge, R.sup.5 is C.sub.1- to C.sub.8-alkyl or C.sub.6- to C.sub.10-aryl, R.sup.6 is hydrogen or cyano, R.sup.15 is hydrogen, C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, R.sup.16 is hydrogen, C.sub.1- to C.sub.4-alkyl, C.sub.8- to C.sub.6-cycloalkyl or C.sub.6-aryl, R.sup.17 and R.sup.18 are independently hydrogen, chlorine, methyl or methoxy, where just one of the two is not hydrogen, n and m are independently 0 or 1, where m is only 1 when n is also 1, and An.sup. represents the equivalent of one anion.

20. The photopolymer composition according to claim 17, wherein Q.sup.1 and Q.sup.2 are hydrogen, Q.sup.3 is a radical of the formula (V), the ring A together with R.sup.1, N and X.sup.1 and the atoms that connect them are a radical of the formulae ##STR00072## R.sup.1 and R.sup.19 are independently C.sub.1- to Ca-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to CT-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, R.sup.11 and R.sup.12 are independently C.sub.1- to C.sub.4-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, or together form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 bridge, R.sup.21 and R.sup.22 are independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, R.sup.23 and R.sup.24 are independently hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, the ring B together with R.sup.2, N and X.sup.2 and the atoms that connect them are a radical of the formulae ##STR00073## R.sup.2 is C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, R.sup.13 and R.sup.14 are independently C.sub.1- to C.sub.4-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, or together form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 bridge, R.sup.25 and R.sup.26 are independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, R.sup.27 and R.sup.28 are independently hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, X.sup.5 is S or C(CH.sub.3).sub.2, X.sup.3 is S, X.sup.4 is N or CR.sup.6, R.sup.3 and R.sup.4 are independently C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl, C.sub.7- to C.sub.10-aralkyl or C.sub.6- to C.sub.10-aryl or R.sup.3, R.sup.4 form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2 bridge, R.sup.5 is C.sub.1- to C.sub.8-alkyl or C.sub.6- to C.sub.10-aryl, R.sup.6 is hydrogen or cyano, R.sup.15 is hydrogen, C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, R.sup.16 is hydrogen, C1- to C4-alkyl, C5- to C6-cycloalkyl or C6-aryl, R.sup.17 and R.sup.18 are independently hydrogen, chlorine, methyl or methoxy, n and m are both 1 and An.sup. represents the equivalent of one anion.

21. The photopolymer composition according to claim 17, wherein Q.sup.1 and Q.sup.2 are hydrogen, Q.sup.3 is a radical of the formula (V), the ring A together with R.sup.1, N and X.sup.1 and the atoms that connect them are a radical of the formulae ##STR00074## R.sup.1 and R.sup.19 are independently C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, R.sup.11 and R.sup.12 are independently C.sub.1- to C.sub.4-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, or together form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2C.sub.2CH.sub.2CH.sub.2CH.sub.2 bridge, R.sup.21 and R.sup.22 are independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, where just one of the two is not hydrogen, R.sup.23 and R.sup.24 are independently hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, where just one of the two is not hydrogen, the ring B together with R.sup.2, N and X.sup.2 and the atoms that connect them are a radical of the formulae ##STR00075## R.sup.2 is C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, R.sup.13 and R.sup.14 are independently C.sub.1- to C.sub.4-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, or together form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 bridge, R.sup.25 and R.sup.26 are independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, where just one f the two is not hydrogen, R.sup.27 and R.sup.28 are independently hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, where just one of the two is not hydrogen, X.sup.5 is S or C(CH.sub.3).sub.2, X.sup.3 is S, X.sup.4 is N, R.sup.3 and R.sup.4 are independently C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to CT-cycloalkyl, C.sub.7- to C.sub.10-aralkyl or C.sub.6- to C.sub.10-aryl or R.sup.3, R.sup.4 form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2H.sub.2OCH.sub.2CH.sub.2 bridge, R.sup.5 is C.sub.1- to C.sub.8-alkyl or C.sub.6- to C.sub.10-aryl, R.sup.6 is hydrogen or cyano, R.sup.15 is hydrogen, C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, R.sup.16 is hydrogen, C1- to C4-alkyl, C5- to C6-cycloalkyl or C6-aryl, R.sup.17 and R.sup.18 are independently hydrogen, chlorine, methyl or methoxy, where just one of the two is not hydrogen, n and m are both 1 and An.sup. represents the equivalent of one anion.

22. The photopolymer composition according to claim 17, wherein Q.sup.1 is cyano or, together with R.sup.12, forms a CH.sub.2CH.sub.2CH.sub.2 bridge, Q.sup.2 and Q.sup.3 are hydrogen, the ring A together with R.sup.1, N and X.sup.1 and the atoms that connect them are a radical of the formulae ##STR00076## R.sup.1 is methyl, ethyl, 1-propyl, 1-butyl, benzyl or cyanoethyl, R.sup.11 and R.sup.12 are each independently methyl, ethyl or benzyl or together form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 bridge, R.sup.21 is hydrogen, chlorine, cyano, methoxycarbonyl, ethoxycarbonyl, methyl or methoxy, R.sup.23 and R.sup.24 are hydrogen, R.sup.23 is hydrogen, chlorine, cyano, methyl or methoxy, the ring B together with R.sup.2, N and X.sup.2 and the atoms that connect them are a radical of the formula ##STR00077## R.sup.2 is methyl, ethyl, 1-propyl, 1-butyl, benzyl or cyanoethyl, R.sup.13 and R.sup.14 are each independently methyl, ethyl or benzyl or together form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 bridge, R.sup.25 is hydrogen, chlorine, cyano, methoxycarbonyl, ethoxycarbonyl, methyl or methoxy, R.sup.26 is hydrogen, X.sup.3 is S, X.sup.4 is N, R.sup.3 and R.sup.4 are each independently methyl, ethyl, 1-propyl, 1-butyl, 1-octyl, cyclohexyl or benzyl or R.sup.3, R.sup.4 form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2 bridge, R.sup.5 is methyl, ethyl, tert-butyl, phenyl, 4-methylphenyl or 4-methoxyphenyl, R.sup.15 is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-octyl or benzyl, R.sup.16 is hydrogen, methyl or phenyl, R.sup.17 is hydrogen, chlorine or methyl, R.sup.18 is hydrogen and An.sup. represents the equivalent of one anion.

23. The photopolymer composition according to claim 17, wherein the composition comprises matrix polymers and at least one writing monomer.

24. The photopolymer composition according to claim 17, wherein the photoinitiator system additionally comprises a coinitiator.

25. The photopolymer composition according to claim 24, wherein the coinitiator comprises at least one triazine.

26. The photopolymer comprising a photopolymer composition according to claim 23, wherein the matrix polymers are in a crosslinked state.

27. The photopolymer comprising a photopolymer composition according to claim 23, wherein the matrix polymers are in a three-dimensionally crosslinked state.

28. The photopolymer according to claim 23, wherein the matrix polymers are polyurethanes.

29. A holographic medium, especially in the form of a film, comprising a photopolymer according to claim 24.

30. A hologram comprising the holographic medium according to claim 29, wherein at holographic information has been exposed into same.

31. A process for recording of in-line, off-axis, full-aperture transfer, white light transmission, reflection, Denisyuk, off-axis reflection or edge-lit holograms and also of holographic stereograms, which comprises utilizing the hologram comprising the holographic medium according to claim 29.

32. A process for producing a holographic medium which comprises utilizing the photopolymer according to claim 24.

33. The process for according to claim 32, wherein the medium is exposed using pulsed laser radiation.

34. The process according to claim 33, wherein pulse durations of 200 ns are used.

35. A dye of the formula (I) ##STR00078## in which K is a radical of the formula I ##STR00079## n and m are 0 and ring A together with N and X.sup.1 and the atoms that connect them are independently a five- or six-membered aromatic or quasiaromatic or partly hydrogenated heterocyclic ring which may contain 1 to 4 heteroatoms and/or may be benzo- or naphthofused and/or may be substituted by C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl, aryl, fluorine, chlorine, bromine, methoxy, ethoxy, where the unsaturated unit (*(C=K)-Q.sup.1) in the formula (I) joins onto the ring A or B in position 2 or 4 relative to X.sup.1, X.sup.1 is O, S, NR.sup.7, CR.sup.9 or CR.sup.11R.sup.12, Q.sup.1 is hydrogen, cyano or methyl, X.sup.3 is O or S, X.sup.4 is N or CR.sup.6, R.sup.2, and R.sup.7, and are independently C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl and R.sup.9 is independently hydrogen or C.sub.1- to C.sub.2-alkyl, R.sup.11 and R.sup.12, are independently C.sub.1- to C.sub.4-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.7- to C.sub.10-aralkyl or R.sup.11 and R.sup.12 together form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 bridge and, in addition, R.sup.7, R.sup.9 or R.sup.12 together with Q.sup.1 can form a CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2CH.sub.2 bridge, R.sup.3 and R.sup.4 are independently C.sub.1- to C.sub.8-alkyl, C.sub.3- to C.sub.6-alkenyl, C.sub.4- to C.sub.7-cycloalkyl, C.sub.7- to C.sub.10-aralkyl or C.sub.6- to C.sub.10-aryl or R.sup.3, R.sup.4 form a CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2OCH.sub.2CH.sub.2, CH.sub.2CH.sub.2NHCH.sub.2CH.sub.2 or CH.sub.2CH.sub.2N(alkyl)-CH.sub.2CH.sub.2 bridge, R.sup.5 are independently hydrogen, C.sub.1- to C.sub.8-alkyl, C.sub.4- to C.sub.7-cycloalkyl or C.sub.6- to C.sub.10-aryl, R.sup.6 is hydrogen, alkyl or cyano, and An.sup. represents the equivalent of one anion.

Description

[0266] The examples which follow serve to illustrate the invention, but without restricting it thereto.

[0267] FIG. 1 describes a film coating system for production of holographic media on films.

[0268] FIG. 2 describes a holographic test setup for determining the diffraction efficiency after exposure, especially laser pulse exposure.

EXAMPLES

[0269] Test Methods:

[0270] OH number:

[0271] Reported OH numbers were determined to DIN 53240-2.

[0272] NCO value:

[0273] Reported NCO values (isocyanate contents) were quantified to DIN EN ISO 11909.

[0274] Determination of Diffraction Efficiency in Laser Pulse Exposure:

[0275] To determine the diffraction efficiency in pulsed exposure, the Denisyuk hologram of a mirror was recorded in a sample consisting of a glass plate laminated with a photopolymer film. The substrate of a photopolymer film and the glass substrate faced the laser source and the mirror, respectively. The sample was exposed with its planar face perpendicular to the laser beam. The distance between the sample and the mirror was 3 cm.

[0276] The laser used was a Brilliant b pulsed laser from Quantel of France. The laser in question was a Q-switched Nd-YAG laser equipped with a module for frequency doubling to 532 nm. The single frequency mode was guaranteed by a seed laser. Coherence length was arithmetically about 1 m. Pulse duration was 4 ns and average power output was 3 watts at a pulse repetition rate of 10 Hz.

[0277] The electronically controlled shutter was used to ensure a single pulse exposure. The waveplate made it possible to rotate the polarization plane of the laser light and the subsequent polarizer was used to reflect the S-polarized portion of the laser light in the direction of the sample. The exposed area was adjusted by beam expansion. The waveplate and the beam expansion were adjusted such that the sample was given an exposure dose of 100 mJ/cm.sup.2/pulse.

[0278] To determine the diffraction efficiency, the samples were each exposed with exactly one pulse. After exposure, the sample was bleached on a light table.

[0279] A transmission spectrum was measured through the hologram of the bleached sample. An HR4000 spectrometer from Ocean Optics was used. The sample was placed perpendicularly to the light beam. The transmission spectrum showed a transmission collapse at a wavelength at which the Bragg condition was satisfied. The depth of the transmission collapse to the base line was evaluated as the diffraction efficiency DE of the Denisyuk hologram of the mirror.

[0280] Substances:

[0281] The solvents used were obtained commercially. [0282] Desmorapid Z dibutyltin dilaurate [77-58-7], product from Bayer MaterialScience AG, Leverkusen, Germany. [0283] Desmodur N 3900, product from Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5% [0284] Fomrez UL 28 Urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA.

Example 1

[0285] 1.00 g of the aldehyde

##STR00027##

[0286] (prepared according to J. Amer. Chem. Soc. 2009, 131, 12960) and 1.08 g of the thiazole of the formula

##STR00028##

[0287] (prepared according to R. Flaig, Thesis, University of Halle-Wittenberg, 1996) were dissolved in 15 ml of glacial acetic acid. 3 ml of acetic anhydride and 0.425 g of methanesulphonic acid were added while stirring and the mixture was stirred at 70 C. for 4 h. After cooling, the cherry-red solution was discharged into 60 ml of water and clarified with a little activated carbon. 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 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 filtercake was stirred with 50 ml of methanol for 1 h. The mixture was filtered with suction again and washed with 210 ml of methanol and 30 ml of water. Drying at 50 C. under reduced pressure gave 2.16 g (63.2% of theory) of a pink powder of the formula

##STR00029##

[0288] .sub.max (in CH.sub.3CN)=538, 510 (sh) nm, =735101 mol.sup.1 cm.sup.1.

Example 2

[0289] 2.00 g of the methylene base of the formula

##STR00030##

[0290] (prepared from 3,4-dimethylhydrazine and 2-methylcyclohexanone analogously to US2013/175509, followed by a methylation with dimethyl sulphate analogously to Chemistry of Heterocyclic Compounds (New York), 1982, 18, 923) and 1.77 g of the aldehyde of the formula

##STR00031##

[0291] were dissolved in 14 ml of acetic anhydride while heating. 0.85 g of methanesulphonic acid was added dropwise while stirring over the course of 5 min. The mixture was stirred at 60 C. for 6 h. After cooling, the violet solution was discharged into 50 ml of water and clarified with a little activated carbon. 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 with suction and washed with 225 ml of water. After drying at 50 C. under reduced pressure, the violet powder was boiled three times with 20 ml of methanol and filtered off with suction after each cooling operation. Drying at 50 C. under reduced pressure gave 3.00 g (46.8% of theory) of a violet powder of the formula

##STR00032##

[0292] .sub.max (in CH.sub.3CN)=543, 521 (sh) nm, =36810 l mol.sup.1 cm.sup.1.

Example 3

[0293] 4.03 g of the aldehyde of the formula

##STR00033##

[0294] and 3.59 g of 2-cyanomethylbenzothiazole were stirred in 25 ml of acetic anhydride at 90 C. for 1.5 h. After cooling, the thick crystal slurry was discharged into 100 ml of water and diluted with 15 ml of methanol. The mixture was filtered with suction and washed with 200 ml of water until the water running off was colourless. Drying at 50 C. under reduced pressure gave 7.03 g (98.3% of theory) of an orange crystal powder of the formula

##STR00034##

[0295] To 2.50 g of this dye in 20 ml of anhydrous toluene was added 0.91 g of dimethyl sulphate, and the mixture was stirred at 90 C. for 16 h, with two further additions each of 0.91 g of dimethyl sulphate during this period. The thick suspension was filtered with suction and the filtercake was washed three times with 25 ml of toluene. While still moist, the product was twice stirred with 50 ml of toluene at 70 C. for 3 h, filtered off with suction each time and washed with 100 ml of toluene. Drying at 50 C. under reduced pressure gave 2.46 g (72.7% of theory) of a red crystal powder of the formula

##STR00035##

[0296] 2.00 g of this dye were dissolved in 15 ml of methanol and filtered through a fluted filter. A solution of 1.43 g of sodium tetraphenylborate in 5 ml of methanol was added dropwise to the filtrate while stirring. The latter was filtered with suction and washed with 810 ml of methanol. The moist filtercake was then stirred in 25 ml of methanol at 45 C. for 3 h, filtered with suction again and washed with 610 ml of methanol. Drying at 50 C. under reduced pressure gave 1.94 g (67.8% of theory) of a red powder of the formula

##STR00036##

[0297] .sub.max (in CH.sub.3CN)=519, 500 (sh) nm, =91130 l mol.sup.1 cm.sup.1.

Example 4

[0298] 3.00 g of the cyanomethylene base of the formula

##STR00037##

[0299] and 1.29 g of diphenylformamidine were stirred in 15 ml of acetic anhydride with addition of 0.62 g of methanesulphonic acid at 90 C. for 6 h. After cooling, the red solution was discharged onto 75 ml of water. 3 ml of methanol were added. After adding activated carbon, a little precipitated resin was filtered off. A solution of 2.25 g of sodium tetraphenylborate in 15 ml of water was added dropwise to the filtrate with good stirring. The thick suspension was filtered with suction and washed with 200 ml of water. After drying at 50 C. under reduced pressure, 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 were slowly added dropwise. The mixture was filtered with suction and washed with a mixture of 10 ml of methanol and 3 ml of water and then with 100 ml of water. Drying at 50 C. under reduced pressure gave 2.36 g (46.1% of theory) of a vermilion-red powder of the formula

##STR00038##

[0300] .sub.max (in CH.sub.3CN)=515 nm, =54870 l mol.sup.1 cm.sup.1.

Example 5

[0301] Analogously to Example 6 of DE 1 073 662, 6.98 g of the cyanomethylene base of the formula

##STR00039##

[0302] and 6.16 g of the aldehyde of the formula

##STR00040##

[0303] in 30 ml of anhydrous toluene were admixed gradually with 3.57 g of thionyl chloride while stirring. 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 each time of toluene and filtered off with suction again each time. After drying at 50 C. under reduced pressure, the red dye was substantially dissolved in 100 ml of water. A solution of 12.38 g of sodium bis(2-ethylhexyl)sulphosuccinate in 100 ml of butyl acetate was added. The biphasic mixture was stirred for 1 h and then transferred into a separating funnel. The aqueous phase was discharged and the organic phase was washed four times with 40 ml of water. After the last water wash had been removed, the organic phase was diluted with 250 ml of butyl acetate and distilled on a rotary evaporator under reduced pressure until free of water. This also distilled off about 200 ml of butyl acetate, such that what was ultimately obtained was 150.1 g of a red solution of the dye of the formula

##STR00041##

[0304] in butyl acetate, which was storage-stable.

[0305] A sample was taken and the rest of the solvent was drawn off under reduced pressure. Drying at 50 C. under reduced pressure gave the dye as a red resinous substance.

[0306] .sub.max (in CH.sub.3CN)=498 nm and 523 nm, =89580 (at 498 nm) and 99423 l mol.sup.1 cm.sup.1 (at 523 nm) 1 mol.sup.1 cm.sup.1.

[0307] With these spectroscopic data, it was possible to determine the concentration of the above solution to be 10.0%.

Example 6

[0308] 3.35 g of the compound of the formula

##STR00042##

[0309] known from DE 2 617 345, were heated to reflux in 40 ml of chlorobenzene while stirring, and 2.52 g of dimethyl sulphate were added. After 16 h at reflux, the mixture was cooled, filtered with suction and washed with 320 ml of chlorobenzene. Drying at 50 C. under reduced pressure gave 4.41 g (95% of theory) of the dye of the formula

##STR00043##

[0310] .sub.max (in CH.sub.3OH)=426 nm

[0311] 2.31 g of this dye were dissolved in 15 ml of methanol. A solution of 1.72 g of sodium tetraphenylborate in 5 ml of methanol was added dropwise while stirring. The mixture was filtered with suction and washed with 20 ml of methanol. Drying at 50 C. under reduced pressure gave 2.71 g (80% of theory) of a yellow powder of the formula

##STR00044##

Example 7

[0312] 3.00 g of the cyanomethylene base of the formula

##STR00045##

[0313] 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 onto 75 ml of water. 3 ml of methanol were added. The mixture was filtered with suction and washed with water until the water running off was almost colourless. Drying at 50 C. under reduced pressure gave 3.16 g (91.1% of theory) of a green crystal powder of the formula

##STR00046##

[0314] .sub.max (in CH.sub.3CN)=616, 580 (sh) nm, =116965 l mol.sup.1 cm.sup.1.

[0315] 2.00 g of this dye and 1.59 g of sodium bis(2-ethylhexyl)sulphosuccinate were stirred in a mixture of 30 ml of water and 30 ml of butyl acetate for 5 h. After transfer to a separating funnel, the aqueous phase was discharged. The organic phase was washed five times with 15 ml of water until, finally, no chloride ions were detectable with silver nitrate any longer in the water. The organic phase was dried with anhydrous magnesium sulphate. This gave 39.5 g of a solution which, via spectroscopic content determination, had a content of 8.0 percent of the dye of the formula

##STR00047##

Example 8

[0316] 0.80 g of the malonaldehyde of the formula

##STR00048##

[0317] (prepared according to Coll. Czech. Chem. Commun. 1972, 37, 2273) and 1.80 g of 1,3,3-trimethyl-2-methyleneindoline were mixed. 3.16 g of phosphorus oxychloride were slowly added dropwise to the slurry with a syringe while stirring. The mixture turned blue immediately. The mixture was heated to 80 C. and kept at this temperature for 2 h. After cooling, the blue resin was dissolved by cautiously adding 10 ml of methanol in a water bath. A solution of 2.39 g of sodium tetraphenylborate in 10 ml of methanol was added dropwise to this solution while stirring. The mixture was filtered. 20 ml of water were slowly added dropwise to the filtrate while stirring, in the course of which the dye partly separated out as a resin. After dropwise addition of a solution of 4.5 g of sodium tetraphenylborate in 30 ml of water, the precipitation is complete and the product has solidified. The product 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. under reduced pressure, the crude product was dissolved in 100 ml of acetone and precipitated by dropwise addition of 50 ml of water and filtered off with suction. This operation was repeated. The product was filtered off with suction and washed with 15 ml of acetone/water 2:1 and 10 ml of water. Drying at 50 C. under reduced pressure gave 1.68 g (41.4% of theory) of a copper oxide-coloured crystal powder of the formula

##STR00049##

[0318] .sub.max (in CH.sub.3CN)=605, 566 (sh) nm, =178480 l mol.sup.1 cm.sup.1.

[0319] Further dyes according to the invention can be found in the following table:

TABLE-US-00001 Ex- .sub.max in ample Dye cation An.sup. CH.sub.3CN 9 [00050] (C.sub.6H.sub.5).sub.4B.sup. 424 nm 10 [00051] C, 6; H, 5; N, 4 wt %. 523, 498 (sh) nm 11 [00052] (C.sub.6H.sub.5).sub.4B.sup. 521, 497 nm 12 [00053] Bis(2- ethylhexyl)- sulpho- succinate 520, 497 nm 13 [00054] (C.sub.6H.sub.5).sub.3 BCN.sup. 521, 497 nm 14 [00055] Bis(2- ethylhexyl)- sulpho- succinate 529, 503 (sh) nm 15 [00056] (C.sub.6H.sub.5).sub.4B.sup. 527, 500 nm 16 [00057] (C.sub.6H.sub.5).sub.4B.sup. 501 nm 17 [00058] (C.sub.6H.sub.5).sub.4B.sup. 488 nm

[0320] Comparative Dyes (Known from EP 2 633 544 A2):

[0321] Comparative Dye 1:

##STR00059##

[0322] Comparative Dye 2:

##STR00060##

[0323] Comparative Dye 3:

##STR00061##

[0324] Comparative Dye 4:

##STR00062##

[0325] Preparation of Farther Components for the Photopolymer Composition:

[0326] Preparation of Polyol 1:

[0327] A 1 l flask was initially charged with 0.18 g of tin octoate, 374.8 g of -caprolactone and 374.8 g of a difunctional polytetrahydrofuran polyether polyol (equivalent weight 500 g/mol OH), which were heated to 120 C. and kept at this temperature until the solids content (proportion of nonvolatile constituents) was 99.5% by weight or higher. Subsequently, the mixture was cooled and the product was obtained as a waxy solid.

[0328] Preparation of Urethane Acrylate 1 (Writing Monomer): Phosphorothloyltros(Oxybenzene-4,1-Diylcarbamoyloxyethane-2,1-Diyl) Trisacrylate

[0329] A 500 ml round-bottom flask was initially charged with 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 from Bayer MaterialScience AG, Leverkusen, Germany), which were heated to 60 C. Subsequently, 42.37 g of 2-hydroxyethyl acrylate were added dropwise and the mixture was still kept at 60 C. until the isocyanate content had fallen below 0.1%. This was followed by cooling and complete removal of the ethyl acetate in vacuo. The product was obtained as a partly crystalline solid.

[0330] Preparation of Urethane Acrylate 2 (Writing Monomer): 2-({[3-(Methylsulphanyl)Phenyl]Carbamoyl}Oxy)Ethyl Prop-2-Enoate

[0331] A 100 ml round-bottom flask was initially charged with 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 the mixture was heated to 60 C. Subsequently, 8.2 g of 2-hydroxyethyl acrylate were added dropwise and the mixture was still kept at 60 C. until the isocyanate content had fallen below 0.1%. This was followed by cooling. The product was obtained as a colourless liquid.

[0332] 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

[0333] A 50 ml round-bottom flask was initially charged with 0.02 g of Desmorapid Z and 3.6 g of 2,4,4-trimethylhexane 1,6-diisocyanate (TMDI), and the mixture was heated to 60 C. Subsequently, 11.9 g of 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptan-1-ol were added dropwise and the mixture was still kept at 60 C. until the isocyanate content had fallen below 0.1%. This was followed by cooling. The product was obtained as a colourless oil.

[0334] Preparation of the Borate (Photoinitiator): Benzylhexadecyklimethylammonium Tris-(3-Chloro-4-Methylphenyl)Hexylborate

[0335] Prepared according to WO 2015/055576 A1.

[0336] Triazine 1

[0337] 2-(3-Methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine

[0338] Prepared analogously to U.S. Pat. No. 3,987,037.

[0339] Triazine 2

[0340] 2-(4-(2-Ethylhexyl)carbonylphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine

[0341] Prepared analogously to EP 0 332 042.

[0342] Production of Media to Determine the Holographic Properties

[0343] Production of Holographic Media on a Film Coating System

[0344] There follows a description of the continuous production of holographic media in the form of films of inventive and noninventive photopolymer compositions.

[0345] For the production, the film coating system shown in FIG. 1 was used, and the individual components are assigned the reference numerals which follow. FIG. 1 shows the schematic structure of the coating system used. In the figure, the individual components have the following reference numerals: [0346] 1, 1 reservoir vessel [0347] 2, 2 metering unit [0348] 3, 3 vacuum devolatilization unit [0349] 4, 4 filter [0350] 5 static mixer [0351] 6 coating unit [0352] 7 air circulation dryer [0353] 8 carrier substrate [0354] 9 covering layer

[0355] To produce the photopolymer composition, a mixture of 30.0 g of urethane acrylate 1 and 30.0 g of urethane acrylate 2, 22.5 g of additive 1, 0.15 g of triazine 1 or 2, 1.5 g of the borate, 0.075 g of Fomrez UL 28 and 1.35 g of the surface-active additive BYK 310 and 50 g of ethyl acetate was added stepwise to 53.7 g of polyol 1 (OH number 59.7), and mixed. Subsequently, 0.3 g of a dye according to the invention was added to the mixture in the dark and mixed, so as to obtain a clear solution. If necessary, the composition was heated at 60 C. for a short period in order to bring the starting materials into solution more quickly. This mixture was introduced into one of the two reservoir vessels 1 of the coating rig. The second reservoir vessel 1 was charged with the polyisocyanate component (Desmodur N 3900, commercial product from Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%). The two components were then each conveyed by means of the metering units 2 in a ratio of 18.2 (component mixture) to 1.0 (isocyanate) to the vacuum devolatilization unit 3 and devolatilized. From here, they were then each passed through the filters 4 into the static mixer 5, in which the components were mixed to give the photopolymer composition. The liquid material obtained was then sent in the dark to the coating unit 6.

[0356] The coating unit 6 in the present case was a doctor blade system known to those skilled in the art. Alternatively, however, it is also possible to use a slot die. With the aid of the coating unit 6, the photopolymer composition was applied at a processing temperature of 20 C. to a carrier substrate 8 in the form of a 36 m-thick polyethylene terephthalate film, and dried in an air circulation dryer 7 at a crosslinking temperature of 80 C. for 5.8 minutes. This gave a medium in the form of a film, which was then provided with a 40 m-thick polyethylene film as covering layer 9 and wound up. All these steps were effected in the dark.

[0357] The desired layer thickness of the film was preferably 1 to 60 m, preferably 5 to 25 m, more preferably 10 to 15 m.

[0358] The production speed was preferably in the range from 0.2 m/min to 300 m/min and more preferably in the range from 1.0 m/min to 50 m/min.

[0359] The layer thickness achieved in the film was 12 m1 m.

[0360] Comparative Medium V

[0361] The above procedure was followed, except that 0.3 g of one of the comparative dyes was used.

[0362] Holographic Testing:

[0363] The media obtained as described were tested for their holographic properties by using a measuring arrangement as per FIG. 2 in the manner described above (see test methods, Determination of diffraction efficiency in pulsed exposure). The following measurements were obtained for DE at a fixed dose of 100 mJ/cm.sup.2:

TABLE-US-00002 TABLE 2 Holographic assessment of selected media and comparative media 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 Compara- Compara- Triazine Triazine tive tive dye 1 2 DE medium Comparative dye [%] [%] [%] [%] C-1 Comparative dye 1 0.2 0.1 8 C-2 Comparative dye 2 0.2 0.1 3 C-3 Comparative dye 2 0.2 0.1 2 C-4 Comparative dye 3 0.2 0.1 2 C-5 Comparative dye 4 0.2 0.1 0

[0364] The values found for Example media B-1 to B-5 show that the inventive chain-substituted cyanine dyes of the formula (I) used in the photopolymer compositions are very useful in holographic media to be exposed with pulsed laser. Comparative media C-1 and C-5 using analogous cationic dyes lacking inventive chain substituents are unsuitable for use in holographic media to be exposed with pulsed laser.