Naphthyl acrylates as writing monomers for photopolymers

Abstract

The invention relates to naphthyl urethane acrylates particularly useful as writing monomers in photopolymer formulations for holographic media. The invention further relates to a photopolymer formulation comprising matrix polymers, writing monomers and photoinitiators, wherein the writing monomers comprise a naphthyl urethane acrylate according to the invention, to a holographic medium comprising matrix polymers, writing monomers and photoinitiators, wherein the writing monomers comprise a naphthyl urethane acrylate according to the invention, and also to a display comprising a holographic medium according to the invention.

Claims

1. A photopolymer formulation comprising matrix polymers, writing monomers and photoinitiators, wherein the writing monomers comprise a compound according of formula (I) ##STR00007## a) which is substituted at least one of the carbon atoms 1, 2, 3, 4, 5, 6, 7, 8 with a moiety R.sub.arcyl of formula (II) ##STR00008## where in said formula (II) R.sup.1 is hydrogen or a (C.sub.1-C.sub.6)-alkyl group, X is a carboxamide (C(O)N) or a carboxylic ester (C(O)O) or a sulphonamide (SO.sub.2N) group, Y is a saturated or unsaturated or linear or branched optionally substituted moiety having 2-10 carbon atoms or a polyether having from one up to five (CH.sub.2CH.sub.2O) or (C(CH.sub.3)HCH.sub.2O) groups or a polyamine having from one to five nitrogen atoms, and Z is oxygen or sulphur, b) and the compound of formula (I) is substituted at not less than one of carbon atoms 1, 2, 3, 4, 5, 6, 7, or 8 with a naphthalene moiety of formula (III) ##STR00009## where in said formula (III) the carbon atoms of the compound of formula (III) are each independently substituted with hydrogen, halogen, a cyano group, a nitro group or an optionally substituted alkyl, alkenyl, alkynl, aralkyl, aryl or heteroaryl group or an optionally substituted alkoxy or alkylthio group or any substituted carbamoyl group, which also may be linked bridgingly to a moiety of formula (I), or a trifluoromethyl group or a trifluoromethoxy group or a moiety R.sub.arcyl of formula (IV), ##STR00010## where in said formula (IV) R.sup.1 is hydrogen or a (C1-C6)-alkyl group, X is a carboxamide (C(O)N) or a carboxylic ester (C(O)O) or a sulphonamide (SO.sub.2N) group, Y is a saturated or unsaturated or linear or branched optionally substituted moiety having 2-10 carbon atoms or a polyether having from one to five (CH.sub.2CH.sub.2O) or (C(CH.sub.3)HCH.sub.2O) groups or a polyamine having from one to five nitrogen atoms, and Z is oxygen or sulphur, the remaining carbon atoms of the compound of formula (I) are each independently substituted with hydrogen, halogen, a cyano group, a nitro group or an optionally substituted alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl group or an optionally substituted alkoxy or alkylthio group or a trifluoromethyl group or a trifluoromethoxy group.

2. The photopolymer formulation according to claim 1, wherein it is substituted with the moiety of formula (III) on the carbon atom in position 5 of formula (I), wherein the moiety of formula (III) is preferably bonded to the carbon atom in position 5 via the carbon atom in position 8.

3. The photopolymer formulation according to claim 1, wherein it is substituted with the moiety R.sub.arcyl of formula (II) on the carbon atom in position 6 of formula (I).

4. The photopolymer formulation according to claim 1, wherein the moiety of formula (III) is substituted with the moiety R of formula (IV) on the carbon atom in position 7.

5. The photopolymer formulation according to claim 1, wherein X is carboxamide in moiety R.sub.arcyl and/or X is carboxamide in moiety R.

6. The photopolymer formulation according to claim 1, wherein R.sub.1 is hydrogen or a CH.sub.3 moiety in moiety R.sub.arcyl and/or R.sub.1 is hydrogen or a CH.sub.3 moiety in moiety R.

7. The photopolymer formulation according to claim 1, wherein Y is a CH.sub.2CH.sub.2 moiety in moiety R.sub.arcyl and/or Y is a CH.sub.2CH.sub.2 moiety in moiety R.

8. The photopolymer formulation according to claim 1, wherein Z and/or Z are oxygen.

9. A holographic medium comprising the photopolymer formulation according to claim 1.

10. The holographic medium according to claim 9, wherein the matrix polymers are crosslinked matrix polymers.

11. The holographic medium according to claim 9, wherein the holographic medium comprises at least a fluorourethane as additive.

12. The holographic medium according to claim 9, wherein the holographic medium is a film.

13. The holographic medium according to claim 9, wherein the holographic medium contains at least one exposed hologram.

14. A display comprising a holographic medium according to claim 9.

15. The holographic medium according to claim 9, having a refractive index modulation n in the range from 0.037 to 0.060.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows the geometry of a holographic media tester.

(2) FIG. 2 shows the plot of the Bragg curve

(3) FIG. 3 shows the schematic set-up for the coating system.

(4) The invention will now be more particularly described by means of examples.

(5) Methods of Measurement:

(6) OH number: Reported OH numbers were determined to DIN 53240-2.

(7) NCO value: Reported NCO values (is canate contents) were quantified to DIN EN ISO 11909.

(8) Solids content: Reported solids content were determined to DIN EN ISO 3251.

(9) Measurement of the Holographic Properties DE and n of the Holographic Media By Means of Twin Beam Interface in Reflection Arrangement

(10) The media obtained as described in Preparation of media for determination of holographic properties were tested for their holographic properties as follows using a measuring arrangement according to FIG. 1: The beam of a HeNe laser (emission wavelength 633 nm) was converted to a parallel homogeneous beam with the aid of the spatial filter (SF) and together with the collimation lens (CL). The final cross sections of the signal and reference beam are fixed by the iris diaphragms (I). The diameter of the iris diaphragm opening is 0.4 cm. The polarization-dependent beam splitters (PBS) split the laser beam into two coherent beams of identical polarization. By means of the /2 plates, the power of the reference beam was set to 0.5 mW and the power of the signal beam to 0.65 mW. The powers were determined using the semiconductor detectors (D) with the sample removed. The angle of incidence (.sub.0) of the reference beam is 21.8; the angle of incidence (.sub.0) of the signal beam is 41.8. The angles are measured proceeding from the sample normal to the beam direction. According to FIG. 1, therefore, .sub.0 has a negative sign and .sub.0 a positive sign. At the location of the sample (medium), the interference field of the two overlapping beams produced a pattern of light and dark strips perpendicular to the angle bisectors of the two beams incident on the sample (reflection hologram). The strip spacing , also called grating period, in the medium is 225 nm (the refractive index of the medium assumed to be 1.504).

(11) FIG. 1 shows the geometry of a holographic media tester (HMT) at =633 nm (HeNe laser): M=mirror, S=shutter, SF=spatial filter, CL=collimator lens, /2=/2 plate, PBS=polarization-sensitive beam splitter, D=detector, I=iris diaphragm, .sub.0=21.8, .sub.0=41.8 are the angles of incidence of the coherent beams measured outside the sample (outside the medium). RD=reference direction of turntable. A holographic test setup as shown in FIG. 1 was used to measure the diffraction efficiency (DE) of the media.

(12) Holograms were recorded in the medium in the following manner: Both shutters (S) are opened for the exposure time t. Thereafter, with the shutters (S) closed, the medium is allowed 5 minutes for the diffusion of the as yet unpolymerized writing monomers.

(13) The written holograms were then read out in the following manner: The shutter of the signal beam remained closed. The shutter of the reference beam was opened. The iris diaphragm of the reference beam was closed to a diameter of 1 mm. This ensured that the beam was always completely within the previously recorded hologram for all angles of rotation () of the medium. The turntable, under computer control, swept over the angle range from .sub.min to .sub.max with an angle step width of 0.05. is measured from the sample normal to the reference direction of the turntable. The reference direction of the turntable is obtained when the angles of incidence of the reference beam and of the signal beam have the same absolute value on recording of the hologram, i.e. .sub.0=31.8 and .sub.0=31.8. In that case, .sub.recording=0. When .sub.0=21.8 and .sub.0=41.8, .sub.recording is therefore 10. In general, for the interference field in the course of recording of the hologram:
.sub.0=.sub.0+.sub.recording.

(14) .sub.0 is the semiangle in the laboratory system outside the medium and, in the course of recording of the hologram:

(15) ${}_0=\frac{{}_0-{}_0}{2}.$

(16) Thus, in this case, .sub.0=31.8. At each setting for the angle of rotation , the powers of the beam transmitted in the zeroth order were measured by means of the corresponding detector D, and the powers of the beam diffracted in the first order by means of the detector D. The diffraction efficiency was calculated at each setting of angle as the quotient of:

(17) $=\frac{P_D}{P_D+P_T}$

(18) P.sub.D is the power in the detector for the diffracted beam and P.sub.T is the power in the detector for the transmitted beam.

(19) By means of the process described above, the Bragg curve, which describes the diffraction efficiency as a function of the angle of rotation , for the recorded hologram, was measured and saved on a computer. In addition, the intensity transmitted into the zeroth order was also recorded against the angle of rotation and saved on a computer.

(20) The maximum diffraction efficiency (DE=.sub.max) of the hologram, i.e. the peak value thereof, was determined at .sub.reconstruction. In some cases, it was necessary for this purpose to change the position of the detector for the diffracted beam in order to determine this maximum value.

(21) The refractive index contrast n and the thickness d of the photopolymer layer were now determined by means of coupled wave theory (see: H. Kogelnik, The Bell System Technical Journal, Volume 48, November 1969, Number 9 page 2909-page 2947) from the measured Bragg curve and the angle profile of the transmitted intensity. In this context, it should be noted that, because of the shrinkage in thickness which occurs as a result of the photopolymerization, the strip spacing of the hologram and the orientation of the strips (slant) can differ from the strip spacing of the interference pattern and the orientation thereof. Accordingly, the angle .sub.0 and the corresponding angle of the turntable .sub.reconstruction at which maximum diffraction efficiency is achieved will also differ from .sub.0 and from the corresponding .sub.recording. This alters the Bragg condition. This alteration is taken into account in the evaluation process. The evaluation process is described hereinafter:

(22) All geometric parameters which relate to the recorded hologram and not to the interference pattern are shown as parameters with primes.

(23) For the Bragg curve () of a reflection hologram, according to Kogelnik:

(24) $=\{\begin{array}{cc}\frac{1}{1-\frac{1{\left(/v\right)}^2}{{\sin }^2\left(\sqrt{{}^2-v^2}\right)}},& \mathrm{for}{v}^2-{}^2<0\\ 1+\frac{\begin{array}{c}1\\ 1-{\left(/v\right)}^2\end{array}}{{\sinh }^2\left(\sqrt{v^2-{}^2}\right)},& \mathrm{for}{v}^2-{}^{2}0\end{array}\mathrm{with}\text{:}v=\frac{.Math.n.Math.d^{}}{.Math.\sqrt{.Math.c_x.Math.c_r.Math.}}=-\frac{d^{}}{2.Math.c_s}.Math.\mathrm{DP}{c}_s=\cos \left({}^{}\right)-\cos \left({}^{}\right).Math.\frac{}{n.Math.{}^{}}{c}_r=\cos \left({}^{}\right)\mathrm{DP}=\frac{}{{}^{}}.Math.\left(2.Math.\cos \left({}^{}-{}^{}\right)-\frac{}{n.Math.{}^{}}\right){}^{}=\frac{{}^{}+{}^{}}{2}{}^{}=\frac{}{2.Math.n.Math.\cos \left({}^{}-{}^{}\right)}$

(25) The following holds for the reading out (reconstruction) of the hologram similarly to the above explanation:
.sub.0=.sub.0+
sin(.sub.0)=n.Math.sin()

(26) Under the Bragg condition, the dephasing DP=0. And it follows correspondingly that:
.sub.0=.sub.0+.sub.reconstruction
sin(.sub.0)=n.Math.sin()

(27) The as yet unknown angle can be determined from the comparison of the Bragg condition of the interference field in the course of recording of the hologram and the Bragg condition in the course of reconstruction of the hologram, assuming that only shrinkage in thickness takes place. It then follows that:

(28) $\sin \left({}^{}\right)=\frac{1}{n}.Math.\left[\sin \left({}_0\right)+\sin \left({}_0\right)-\sin \left({}_0+{}_{\mathrm{reconstruction}}\right)\right]$

(29) v is the grating intensity, is the detuning parameter and is the orientation (slant) of the refractive index grating written. and correspond to the angles .sub.0 and .sub.0 of the interference field during the recording of the hologram, but measured in the medium and valid for the grating of the hologram (shrinkage in thickness). n is the average refractive index of the photopolymer and was set equal to 1.504. is the wavelength of the laser light in a vacuum.

(30) The maximum diffraction efficiency (DE=.sub.max), when =0, is then calculated to be:

(31) $DE={\tanh }^2\left(v\right)={\tanh }^2\left(\frac{.Math.n.Math.d^{}}{.Math.\sqrt{\cos \left({}^{}\right).Math.\cos \left({}^{}-2\right)}}\right)$

(32) FIG. 2 shows the measured transmitted power P.sub.T (right-hand y-axis) plotted as a solid line against the angle detuning ; the measured diffraction efficiency (left-hand y-axis) is plotted as filled circles against the angle detuning (to the extent allowed by the finite size of the detector), and the fitting to the Kogelnik theory as a broken line (left-hand y-axis).

(33) The measured data for the diffraction efficiency, the theoretical Bragg curve and the transmitted intensity are, as shown in FIG. 2, plotted against the centred angle of rotation =.sub.reconstruction=.sub.0.sub.0, also called angle detuning.

(34) Since DE is known, the shape of the theoretical Bragg curve, according to Kogelnik, is determined only by the thickness d of the photopolymer layer. n is corrected via DE for a given thickness d such that measurement and theory for DE are always in agreement. d is adjusted until the angle positions of the first secondary minima of the theoretical Bragg curve correspond to the angle positions of the first secondary maxima of the transmitted intensity, and there is additionally agreement in the full width at half maximum (FWHM) for the theoretical Bragg curve and for the transmitted intensity.

(35) Since the direction in which a reflection hologram also rotates when reconstructed by means of an scan, but the detector for the diffracted light can cover only a finite angle range, the Bragg curve of broad holograms (small d) is not fully covered in an scan, but rather only the central region, given suitable detector positioning. Therefore, the shape of the transmitted intensity, which is complementary to the Bragg curve, is additionally employed for adjustment of the layer thickness d.

(36) FIG. 2 shows the plot of the Bragg curve according to the coupled wave theory (broken line), the measured diffraction efficiency (filled circles) and the transmitted power (black solid line) against the angle detuning .

(37) For a formulation, this procedure was repeated, possibly several times, for different exposure times t on different media, in order to find the mean energy dose of the incident laser beam in the course of recording of the hologram at which DE reaches the saturation value. The mean energy dose E is calculated as follows from the powers of the two component beams assigned to the angles .sub.0 and .sub.0 (reference beam where P.sub.r=0.50 mW and signal beam where P.sub.s=0.63 mW), the exposure time t and the diameter of the iris diaphragm (0.4 cm):

(38) $E\left(\mathrm{mJ}\text{/}{\mathrm{cm}}^2\right)=\frac{2.Math.\left[P_r+P_s\right].Math.t\left(s\right)}{.Math.{0.4}^2{\mathrm{cm}}^2}$

(39) The powers of the component beams were adjusted such that the same power density is attained in the medium at the angles .sub.0 and .sub.0 used.

(40) Substances:

(41) The solvents and reagents used were obtained commercially.

(42) BINOL (+/+)-1,1-bi(2-napthol) [602-09-5] is available from ABCR GmbH & Co. KG, Karlsruhe, Germany.

(43) 6,6-Dibromo-1,1-bi naphthalene-2,2-diol [80655-81-8] is available from ABCR GmbH & Co. KG, Germany.

(44) 7-Methoxy-2-naphthol [5060-82-2] is available from Aldrich Chemie, Steinheim, Germany.

(45) Methyl 3-hydroxy-2-naphthoate [883-99-8] is available from ABCR GmbH & Co. KG, Karlsruhe, Germany.

(46) 6-Bromo-2-naphthol [15231-91-1] is available from ABCR GmbH & Co. KG, Karlsruhe, Germany.

(47) 6-Cyano2-naphthol [52927-22-7] is available from ABCR GmbH & Co. KG, Karlsruhe, Germany.

(48) 2-(Phenylthio)-phenyl isocyanate [13739-55-4], is available from ABCR GmbH & Co. KG, Karlsruhe, Germany.

(49) CGI-909 tetrabutylammonium tris(3-chloro-4-methylphenyl)(hexyl)borate [1147315-11-4] is a product manufactured by CIBA Inc., Basle, Switzerland.

(50) Desmodur N 3900 product from Bayer MaterialScience AG, Leverkusen, Del., hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%. 23.5%.

(51) Desmodur H product from Bayer MaterialScience AG, Leverkusen, Del., monomeric aliphatic diisocyanate, hexamethylene 1,6-diisocyanate (HDI) or 1,6-diisocyanatohexane, NCO content: 49.7%.

(52) Vestanat TMDI product from Evonik Industries AG, Essen, Del., monomeric substituted aliphatic diisocyanate, an approximately 1:1 mixture of 2,2,4- and 2,4,4-trimethythexamethylene diisocyanate, This mixture is for reasons of clarity not reflected in the designation of the examples made in that only the particular 2,2,4-isomer was described. The 2,4,4-isomer, which is likewise formed, is likewise intended and encompassed.

(53) Desmorapid Z dibutyltin dilaurate [77.58-7], product from. Bayer MaterialScience AG, Leverkusen, Germany.

(54) Fomrez UL 28 urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA.

(55) Borchi Kat 22 urethanization catalyst, product from OMG Borchers GmbH, Langenfeld, Germany.

(56) KarenzAOI 2-isocyanatoethyl acrylate, [13641-96-8], product from SHOWA DENKO K.K., Fine Chemicals Group, Specialty Chemicals Department, Chemicals Division.

(57) KarenzMOI2-isocyanatoethyl methacrylate, [30674-80-7], product from SHOWA DENKO K.K., Fine Chemicals Group, Specialty Chemicals Department, Chemicals Division.

(58) Dye 1 C. I. Basic Blue 3 (as bis(2-ethylhexyl) sulphosuccinate) was prepared by the method known from WO2012062655, Example 9.

(59) Unless otherwise indicated, percentages are all by weight.

Example 1: 2-[({[2-({[2-(Acryloyloxy)ethyl]carbamoyl}oxy)-1,1-binaphthyl-2-yl]oxy}carbonyl)amino]ethyl methacrylate

(60) A 100 mL round-bottom flask was initially charged with 18.4 g of BINOL, 0.08 g of Desmorapid Z and 0.03 g of 2,6-ditert-butyl-4-methylphenol in 25 mL of dichloromethane. Then, a 1:1 mixture of 10.0 g of KarenzMOI and 9.1 g of KarenzAOI was added dropwise and the mixture was stirred at room temperature until the isocyanate content had fallen to below 0.1%. The product was then freed of dichloromethane on a rotary evaporator. The product was obtained as a colourless solid.

Example 2: Dimethyl 2,2-bis({[2-(methacryloyloxy)ethyl]carbamoyl}oxy)-1,1-binaphthyl-3,3-dicarboxylate

(61) A 25 mL round-bottom flask was initially charged with 3.0 g of dimethyl 2,2-dihydroxy-1,1-binaphthyl-3,3-dicarboxylate ([47644-69-9], prepared as described in Tetrahedron Letters (1994), 35(43), 7983-4), 0.01 g of Borchi Kat 22 and 0.01 g of 2,6-ditert-butyl-4-methylphenol in 10 mL of ethyl acetate. Then, 2.3 g of KarenzMOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 3: 1,1-Binaphthyl-2,2-diylbis(oxycarbonyliminoethane-2,1-diyl) bisacrylate

(62) A 250 mL round-bottom flask was initially charged with 40.0 g of BINOL, 0.18 g of Desmorapid Z and 0.06 g of 2,6-ditert-butyl-4-methylphenol in 80 mL of dichloromethane. Then, 39.4 g of KarenzAOI were added dropwise and the mixture was stirred at room temperature until the isocyanate content had fallen to below 0.1%. The product was then freed of dichloromethane on a rotary evaporator. The product was obtained as a colourless solid.

Example 4: 1,1-Binaphthyl-2,2-diylbis(oxycarbonyliminoethane-2,1-diyl) bis(2-methylacrylate)

(63) A 100 mL round-bottom flask was initially charged with 12.0 g of BINOL, 0.05 g of Desmorapid Z and 0.02 g of 2,6-ditert-butyl-4-methylphenol in 25 mL of dichloromethane. Then, 13.0 g of KarenzMOI was added dropwise and the mixture was stirred at room temperature until the isocyanate content had fallen to below 0.1%. The product was then freed of dichloromethane on a rotary evaporator The product was obtained as a colourless solid.

Example 5: (6,6-Dicyano-1,1-binaphthyl-2,2-diyl)bis(oxycarbonyliminoethane-2,1-diyl) bisacrylate

(64) A 25 mL round-bottom flask was initially charged with 3.0 g of 2,2-dihydroxy-1,1-binaphthyl-6,6-dicarbonitrile ([164171-19-1], prepared from 6-cyano-2-naphthol as described in Tetrahedron Letters (1994), 35(43), 7983-4), 0.01 g of Borchi Kat 22 and 0.01 g of 2,6-ditert-butyl-4-methylphenol in 10 mL of ethyl acetate. Then, 2.5 g of KarenzAOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 6: (6,6-Dibroma-1,1-binaphthyl-2,2-diyl)bis(oxycarbonyliminoethane-2,1-diyl) bisacrylate

(65) A 25 mL round-bottom flask was initially charged with 2.5 g of 6,6-dibromo-1,1-binaphthyl-2,2-diol ([80655-81-8], available from ABCR GmbH & Co. KG, Karlsruhe, Germany), 0.01 g of Borchi Kat 22 and 0.01 g of 2,6-ditert-butyl-4-methylphenol in 10 mL of ethyl acetate. Then, 1.6 g of KarenzAOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 7: (6,6-Dibromo-1,1-binaphthyl-2,2-diyl)bis(oxycarbonyliminoetbane-2,1-diyl) bis(2-methylacrylate)

(66) A 25 mL round-bottom flask was initially charged with 2.5 g of 6,6-dibromo-1,1-binaphthyl-2,2-diol ([80655-81-8], available from ABCR GmbH & Co. KG, Karlsruhe, Germany), 0.01 g of Borchi Kat 22 and 0.01 g of 2,6-ditert-butyl-4-methylphenol in 10 mL of ethyl acetate. Then, 1.7 g of KarenzMOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1% The product was then freed of ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 8: (7,7-Dimethoxy-1,1-binaphthyl-2,2-diyl)bis(oxycarbonyliminoethane-2,1-diyl) bisacrylate

(67) A 25 mL round-bottom flask was initially charged with 3.0 g of 7,7-dimethoxy-1,1-binaphthyl-2,2-diol ([128702-28-3], prepared from 7-methoxy-2-naphthol as described in Tetrahedron Letters (1994), 35(43). 7983-4), 0.01 g of Borchi Kat 22 and 0.01 g of 2,6-ditert-butyl-4-methylphenol in 10 mL of ethyl acetate. Then, 2.5 g of KarenzAOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 9: 2-{[({2-[(Hexylcarbamoyl)oxy]-1,1-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl acrylate

(68) A 250 mL round-bottom flask was initially charged with 34.6 g of BINOL and 0.09 g of Borchi Kat 22 in 50 mL of ethyl acetate. Then, 15.4 g of hexyl isocyanate were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. This gave 49.3 g of 2-hydroxy-1,1-binaphthyl-2-yl hexylcarbamate as a colourless solid.

(69) A 100 mL round-bottom flask was initially charged with 18.6 g of 2-hydroxy-1,1-binaphthyl-2-yl hexylcarbamate, 0.03 g of Borchi Kat 22 and 0.01 g of 2,6-ditert-butyl-4-methylphenol in 25 mL of ethyl acetate. Then, 6.35 g of KarenzAOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 10: 2-{[({2-[(Hexylcarbamayl)oxy]-1,1-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl methacrylate

(70) A 100 mL round-bottom flask was initially charged with 18.1 g of 2-hydroxy-1,1-binaphthyl-2-yl hexylcarbamate (see Example 9), 0.03 g of Borchi Kat 22 and 0.01 g of 2,6-ditert-butyl-4-methylphenol in 25 mL of ethyl acetate. Then, 6.81 g of KarenzMOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 11: 2-{[({2-[(Hexylcarbamoyl)oxy]-1,1-bhiaphthyl-2-yl}oxy)carbonyl]amino}ethyl acrylate

(71) A 250 mL round-bottom flask was initially charged with 35.3 g of BINOL and 0.09 g of Borchi Kat 22 in 50 mL of ethyl acetate. Then, 14.7 g of phenyl isocyanate were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. This gave 49.2 g of 2-hydroxy-1,1-binaphthyl-2-yl phenylcarbamate as a colourless solid.

(72) A 100 mL round-bottom flask was initially charged with 18.5 g of 2-hydroxy-1,1-binaphthyl-2-yl phenylcarbamate, 0.03 g of Borchi Kat 22 and 0.01 g of 2,6-ditert-butyl-4-methylphenol in 25 mL of ethyl acetate. Then, 6.44 g of KarenzAOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 12: 2-{[({2-[(Hexylcarbamoyl)oxy]-1,1-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl acrylate

(73) A 100 mL round-bottom flask was initially charged with 18.0 g of 2-hydroxy-1,1-binaphthyl-2-ylphenylcarbamate (see Example 11), 0.03 g of Borchi Kat 22 and 0.01 g of 2,6-ditert-butyl-4-methylphenol in 25 mL of ethyl acetate. Then, 6.90 g of KarenzMOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 13: 2-[({[2-({[3-(Methylsulphanyl)phenyl]carbamayl}oxy)-1,1-binaphthyl-2-yl]oxy}carbonyl)amino]ethyl acrylate

(74) A 250 mL round-bottom flask was initially charged with 31.7 g of BINOL and 0.08 g of Borchi Kat 22 in 50 mL of ethyl acetate. Then, 18.3 g of 3-methylthiophenyl isocyanate were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. This gave 49.5 g of T-hydroxy-1,1-binaphthyl-2-yl [3-(methylsulphanyl)phenyl]carbamate as a colourless solid.

(75) A 100 mL round-bottom flask was initially charged with 19.0 g of 2-hydroxy-1,1-binaphthyl-2-yl [3-(methylsulphanyl)phenyl]carbamate, 0.03 g of Borchi Kat 22 and 0.02 g of 2,6-ditert-butyl-4-methylphenol in 25 mL, of ethyl acetate. Then, 5.94 g of KarenzAOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 14: 2-{[({2-[(Hexylcarbamayl)oxy]-1,1-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl methacrylate

(76) A 100 mL round-bottom flask was initially charged with 18.6 g of 2-hydroxy-1,1-binaphthyl-2-yl [3-(methylsulphanyl)phenyl]carbamate (see Example 13), 0.03 g of Borchi Kat 22 and 0.01 g of 2,6-ditert-butyl-4-methylphenol in 25 mL of ethyl acetate. Then, 6.38 g of KarenzMOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 15: 2-[({[2-({[3-(Methylsulphanyl)phenyl]carbamoyl}oxy)-1,1-binaphthyl-2-yl]oxy}carbonyl)amino]ethyl acrylate

(77) A 250 mL round-bottom flask was initially charged with 27.8 g of BINOL and 0.07 g of Borchi Kat 22 in 50 mL of ethyl acetate. Then, 22.1 g of 2-isocyanatophenyl phenyl sulphide ([13739-55-4] were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. This gave 48.9 g of 2-hydroxy-1,1-binaphthyl-2-yl [2-(phenylsulphanyl)phenyl]carbamate as a colourless solid.

(78) A 100 mL round-bottom flask was initially charged with 19.6 g of 2-hydroxy-1,1-binaphthyl-2-yl [2-(phenylsulphanyl)phenyl]carbamate, 0.03 g of Borchi Kat 22 and 0.02 g of 2,6-ditert-butyl-4-methylphenol in 25 mL of ethyl acetate. Then, 5.38 g of KarenzAOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 16: 2-{[({2-[(Hexylcarbamoyl)oxy]-1,1-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl methacrylate

(79) A 100 mL round-bottom flask was initially charged with 19.2 g of 2-hydroxy-1,1-binaphthyl-2-yl [2-(phenylsulphanyl)phenyl]carbamate (see Example 15), 0.03 g of Borchi Kat 22 and 0.01 g of 2,6-ditert-butyl-4-methylphenol in 25 mL of ethyl acetate. Then, 5.79 g of KarenzMOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 17: 2-{[({2-[(1-Naphthylcarbamoyl)oxy]-1,1-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl acrylate

(80) A 250 mL round-bottom flask was initially charged with 31.4 g of BINOL and 0.08 g of Borchi Kat 22 in 50 mL of ethyl acetate. Then, 18.5 g of 1-naphthyl isocyanate were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. This gave 49.1 g of 2-hydroxy-1,1-binaphthyl-2-yl 1-naphthylcarbamate as a colourless solid.

(81) A 100 mL round-bottom flask was initially charged with 19.0 g of 2-hydroxy-1,1-binaphthyl-2-yl [2-(phenylsulphanyl)phenyl]carbamate, 0.03 g of Borchi Kat 22 and 0.02 g of 2,6-ditert-butyl-4-methylphenol in 25 of ethyl acetate. Then, 5.90 g of KarenzAOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 18: 2-{[({2-[(1-Naphthylcarbamoyl)oxy]-1,1-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl methacrylate

(82) A 100 mL round-bottom flask was initially charged with 18.6 g of 2-hydroxy-1,1-binaphthyl-2-yl 1-naphthylcarbamate (see Example 17), 0.03 g of Borchi Kat 22 and 0.01 g of 2,6-ditert-butyl-4-methylphenol in 25 mL of ethyl acetate. Then, 6.34 g of KarenzMOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had fallen to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 19: Hexane-1,6-diylbis(carbamoyloxy-1,1-binaphthyle-2,2-diyloxycarbonyliminoethane-2,1-diyl) bisacrylate

(83) A 250 mL round-bottom flask was charged initially with 37.2 g of BINOL in 150 g of ethyl acetate at 80 C. and then with 0.005 g of Desmorapid Z. A 10.7 g quantity of hexamethylene diisocyanate (Desmodur H, product from Bayer MaterialScience AG, NCO content >49.7%) was admixed under intensive stirring, the stirring being continued at this temperature until the isocyanate content had dropped to below 0.1%. The bis(2-hydroxy-1,1-binaphthyl-2-yl) hexane-1,6-diylbiscarbamate thus obtained had a solids content of 24.2% in ethyl acetate.

(84) A 61.2 g quantity of the above solution of bis(2.sup.1-hydroxy-1,1-binaphthyl-2-yl) hexane-1,6-diylbiscarbamate in ethyl acetate was admixed with 5.6 g of KarenzAOI added dropwise at 80 C. under an air stream, and stirred at this temperature until the isocyanate content had dropped to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless oil.

Example 20: Hexane-1,6-diylbis(carbamoylaxy-1,1-binaphthyle-2,2-diyloxycarbonyliminoethane-2,1-diyl) bis(2-methylacrylate)

(85) A 61.2 g quantity of the solution of bis(2)-hydroxy-1,1-binaphthyl-2-yl) hexane-1,6-diylbiscarbamate (see Example 19) in ethyl acetate was admixed with 6.2 g of KarenzMOI added dropwise at 80 C. under an air stream, and stirred at this temperature until the isocyanate content had dropped to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless oil.

Example 21.1: (2,2,4-Trimethylhexane-1,6-diyl)bis(carbamoyloxy-1,1-binaphthyl-2,2-diyloxycarbonyliminoethane-2,1-diyl) bisacrylate

(86) A 250 mL round-bottom flask was charged initially with 40.1 g of BINOL in 150 g of ethyl acetate at 80 C. and then with 0.005 g of Desmorapid Z. A 14.5 g quantity of trimethylhexamethylene diisocyanate (Vestanat TMDI, product from Evonik Industries, NCO content=40.0%) was admixed under intensive stirring, the stirring being continued at this temperature until the isocyanate content had dropped to below 0.1%. The bis(2-hydroxy-1,1-binaphthyl-2-yl) (2,2,4-trimethylhexane-1,6-diyl)biscarbamate thus obtained had a solids content of 26.7% in ethyl acetate.

(87) A 58.7 g quantity of the above solution of bis(2-hydroxy-1,1-binaphthyl-2-yl) (2,2,4-trimethylhexane-1,6-diyl)biscarbamate in ethyl acetate was admixed with 5.6 g of Karen-zAOI added dropwise at 80 C. under an air stream, and stirred at this temperature until the isocyanate content had dropped to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless oil.

Example 22: (2,2,4-Trimethylhexane-1,6-diyl)bis(carbamoyloxy-1,1-binaphthyl-2,2-diyloxycarbonyliminoethane-2,1-diyl) bis(2-methylacrylate)

(88) A 58.7 g quantity of the solution of bis(2-hydroxy-1,1-binaphthyl-2-yl) (2,2,4-trimethylhexane-1,6-diyl)biscarbamate in ethyl acetate (see Example 21) was admixed with 6.2 g of KarenzMOI added dropwise at 80 C. under an air stream, and stirred at this temperature until the isocyanate content had dropped to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless oil.

Example 23: 2-({[(2-{[(3-{[({[2-({[2-(Acryloyloxy)ethyl]carbamoyl}oxy)-1,1-binaphthyl-2-yl]oxy}carbonyl)amino]methyl}-3,5,5-trimethyleyclahexyl)carbamoyl]-oxy}-1,1-binaphthyl-2-yl)oxy]carbonyl}amino)ethyl acrylate

(89) A 250 mL round-bottom flask was charged initially with 40.1 g of BINOL in 150 g of ethyl acetate at 80 C. and then with 0.005 g of Desmorapid Z. A 15.2 g quantity of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanat (Desmodur I, isophorone diisocyanat (IPDI), product from Bayer MaterialScience AG, NCO content >37.5%) was admixed under intensive stirring, the stirring being continued at this temperature until the isocyanate content had dropped to below 0.1%. The T-hydroxy-1,1-binaphthyl-2-yl{3-[({[(2-hydroxy-1,1-binaphthyl-2-yl)oxy]carbonyl}amino)methyl]3,5,5-trimethylcyclohexyl}carbamate thus obtained had a solids content of 26.9% in ethyl acetate.

(90) A 59.1 g quantity of the above solution of 2-hydroxy-1,1-binaphthyl-2-yl{3-[({[(2-hydroxy-1,1-binaphthyl-2-yl)oxy]carbonyl}amino)methyl]3,5,5-trimethylcyclohexyl}carbamate in ethyl acetate was admixed with 5.6 g of KarenzAOI added dropwise at 80 C. under an air stream, and stirred at this temperature until the isocyanate content had dropped to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless oil.

Example 24: 2-({[(2-{[(3-{[({[2-({[2-(Methacryloyloxy)ethyl]carbamoyl}oxy)-1,1-binaphthyl-2-yl]oxy}carbonyl)amino]methyl}-3,5,5-trimethylcyclohexyl)carbamoyl]oxy}-1,1-binaphthyl-2-yl)oxy]carbonyl}amino)ethyl methacrylate)

(91) A 59.1 g quantity of the solution of 2-hydroxy-1,1-binaphthyl-2-yl {3-[({[(2-hydroxy-1,1-binaphthyl-2-yl)oxy]carbonyl}amino)methyl]3,5,5-trimethylcyclohexyl) carbamate in ethyl acetate (see Example 23) was admixed with 6.2 g of KarenzMOI added dropwise at 80 C. under an air stream, and stirred at this temperature until the isocyanate content had dropped to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless oil.

Example 25: (6-Bromo-1,1-binaphthyl-2,2-diyl)bis(oxycarbonyliminoethane-2,1-diyl) bisacrylate

(92) In a glass beaker, 16.0 g of 2-naphtol, 22.5 g of 6-bromo-2-naphthol and 1.5 g of CuCl(OH)*TMEDA (prepared as described in Tetrahedron Letters 1994 (35), 7983-7984) were intensively mixed and then heated to 100 C. for 120 min. The mixture obtained was washed with 200 mL of 10% ammonia solution and twice with 200 mL of water, dried and purified by chromatography. This gave 21.2 g of 6-bromo-1,1-binaphthyl-2,2-diol.

(93) 4.41 g of 6-bromo-1,1-binaphthyl-2,2-diol were added together with 0.015 g of Desmorapid Z and 0.01 g of 2,6-ditert-butyl-4-methylphenol to the initial charge of 25 mL ethyl acetate. Then, 3.41 g of KarenzAOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had dropped to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 26: (6-Bromo-1,1-binaphthyl-2,2-diyl)bis(oxycarbonyliminoethane-2,1-diyl) bis(2-methylacrylate)

(94) 4.23 g of 6-bromo-1,1-binaphthyl-2,2-diol (prepared as described in Example 25) were added together with 0.015 g of Desmorapid Z and 0.01 g of 2,6-ditert-butyl-4-methylphenol to the initial charge of 25 mL ethyl acetate. Then, 3.59 g of KarenzMOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had dropped to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 27: (6-Cyano-1,1-binaphthyl-2,2-diyl)bis(oxycarbonyliminoethane-2,1-diyl) bisacrylate

(95) In a glass beaker, 20.8 g of 2-naphtol, 22.2 g of 6-cyano-2-naphthol and 1.5 g of CuCl(OH)*TMEDA (prepared as described in Tetrahedron Letters 1994 (35), 7983-7984) were intensively mixed and then heated to 100 C. for 120 min. The mixture obtained was washed with 200 mL of 10% ammonia solution and twice with 200 mL of water, dried and purified by chromatography. This gave 4.80 g of 6-cyano-1,1-binaphthyl-2,2-diol.

(96) 4.10 g of 6-cyano-1,1-binaphthyl-2,2-diol were added together with 0.015 g of Desmorapid Z and 0.01 g of 2,6-ditert-butyl-4-methylphenol to the initial charge of 25 mL ethyl acetate. Then, 3.72 g of KarenzAOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had dropped to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 28: (6-Cyano-1,1-binaphthyl-2,2-diyl)bis(oxycarbonyliminoethane-2,1-diyl) bis(2-methylacrylate)

(97) 3.92 g of 6-cyano-1,1-binaphthyl-2,2-diol (prepared as described in Example 27) were added together with 0.015 g of Desmorapid Z and 0.01 g of 2,6-ditert-butyl-4-methylphenol to the initial charge of 25 mL ethyl acetate. Then, 3.90 g of KarenzMOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had dropped to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 29: (6-Bromo-6-cyano-1,1-binaphthyl-2,2-diyl)bis(oxycarbonyliminoethane-2,1-diyl) bisacrylate

(98) In a glass beaker, 22.8 g of 6-bromo-2-naphtol, 15.8 g of 6-cyano-2-naphthol and 1.4 g of CuCl(OH)*TMEDA (prepared as described in Tetrahedron Letters 1994 (35), 7983-7984) were intensively mixed and then heated to 100 C. for 120 min. The mixture obtained was washed with 200 mL of 10% ammonia solution and twice with 200 mL of water, dried and purified by chromatography. This gave 4.70 g of 6-bromo-2,2-dihydroxy-1,1-binaphthyl-6-carbonitrile.

(99) 4.54 g of 6-bromo-2,2-dihydroxy-1,1-binaphthyl-6-carbonitrile were added together with 0.015 g of Desmorapid Z and 0.01 g of 2,6-ditert-butyl-4-methylphenol to the initial charge of 25 mL ethyl acetate. Then, 3.28 g of KarenzAOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had dropped to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

Example 30: (6-Bromo-6-cyano-1,1-binaphthyl-2,2-diyl)bis(oxycarbonyliminoethane-2,1-diyl) bis(2-methylacrylate)

(100) 4.36 g of 6-bromo-2,2-dihydroxy-1,1-binaphthyl-6-carbonitrile (prepared as described in Example 29) were added together with 0.015 g of Desmorapid Z and 0.01 g of 2,6-ditert-butyl-4-methylphenol to the initial charge of 25 mL ethyl acetate. Then, 3.46 g of KarenzMOI were added dropwise and the mixture was stirred at 80 C. until the isocyanate content had dropped to below 0.1%. The product was then freed of the ethyl acetate on a rotary evaporator. The product was obtained as a colourless solid.

(101) Preparation of Further Components for the Photopolymer Formulation:

(102) Preparation of Polyol 1:

(103) 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.

(104) Preparation of Urethane Acrylate (Writing Monomer) 1: 2-({[3-(Methylsulphanyl)phenyl]carbamoyl}oxy)ethyl prop-2-enoate

(105) 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.

Preparation of additive 1 bis(2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl)(2,2,4-trimethythexane-1,6-diyl) biscarbamate

(106) A 50 ml round-bottom flask was initially charged with 0.02 g of Desmorapid Z and 3.6 g of Vestanat 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.

Preparation of Comparative Example 1 (Writing Monomer)

Phosphorothioyltris(oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate

(107) 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 crystal-line solid.

Preparation of Comparative Example 2 (Writing Monomer)

(Mixture of (4-methylbenzene-1,3-diyl)bis[carbamoyloxy-3-(biphenyl-2-yloxy)propane-2,1-diyl]bisacrylate and (4-methylbenzene-1,3-diyl)bis[carbamoyloxy3-(biphenyl-2-yloxy)propane-1,2-diyl]bisacrylate and analogous isomers)

(108) A three-neck flask fitted with reflux condenser and stirrer was initially charged with 430.2 g of Denacol EX 142 (Nagase-Chemtex, Japan), 129.7 g of acrylic acid, 1.18 g of tri-phenylphosphine and 0.006 g of 2,6-ditert-butyl-4-methylphenol. In addition, the system was temperature-regulated to 60 C. and a slow stream of air was passed through it. The reaction mixture is then stirred at 90 C. for 24 hours. This gave a clear liquid of OH number=157.8 mg KOH/g. 21.3 g of this intermediate and 5.2 g of a mixture of 2,4- and 2,6-toluidene diisocyanate (Desmodur T80, Bayer MaterialScience AG, Leverkusen, Germany) were initially charged to a three-neck flask fitted with reflux condenser and stirrer. In addition, the system was temperature-regulated to 60 C. and a slow stream of air was passed through it. Following initial exothermism, the product was stirred at 60 C. for 24 hours. This gave a clear, colourless, glassy product with NCO=0%.

(109) Production of Media to Determine the Holographic Properties

(110) Example Medium I

(111) 338 g of polyol component 1 were mixed with 2.00 g of Example 1 as per formula (I), 2.00 g of urethane acrylate 2, 1.50 g of additive 1, 0.10 g of CGI 909, 0.026 g of dye 1 and 0.35 g of N-ethylpyrrolidone at 60 C. to obtain a clear solution. This was followed by cooling to 30 C., admixture of 0.65 g of Desmodur N3900 and renewed mixing. This was finally followed by admixture of 0.01 g of Fomrez UL 28 and renewed brief mixing. The liquid mass obtained was then poured onto a glass plate and covered thereon with a second glass plate. This test specimen was left at room temperature for 12 hours for curing.

(112) Example media II-IX were prepared as described under Example medium I. As listed in table 1, Example 1 was replaced by the same weight fraction of the example adduced in the particular row.

(113) Comparative Medium V-I

(114) 3.38 g of polyol component 1 were mixed with 2.00 g of Comparative Example 1, 2.00 g of urethane acrylate 1, 1.50 g of additive 1, 0.10 g of CGI 909, 0.010 g of dye 1 and 0.35 g of N-ethylpyrrolidone at 60 C. to obtain a clear solution. This was followed by cooling to 30 C., admixture of 0.65 g of Desmodur N3900 and renewed mixing. This was finally followed by admixture of 0.01 g of Fomrez UL 28 and renewed brief mixing. The liquid mass obtained was then poured onto a glass plate and covered thereon with a second glass plate. This test specimen was left at room temperature for 12 hours for curing.

(115) Comparative Medium V-II

(116) 3.38 g of polyol component 1 were mixed with 2.00 g of Comparative Example 2, 2.00 g of urethane acrylate 1, 1.50 g of additive 1, 0.10 g of CGI 909, 0.010 g of dye 1 and 0.35 g of N-ethylpyrrolidone at 60 C. to obtain a clear solution. This was followed by cooling to 30 C., admixture of 0.65 g of Desmodur N3900 and renewed mixing. This was finally followed by admixture of 0.01 g of Fomrez UL 28 and renewed brief mixing. The liquid mass obtained was then poured onto a glass plate and covered thereon with a second glass plate. This test specimen was left at room temperature for 12 hours for curing.

(117) Production of Holographic Media on a Film Coating System

(118) To achieve the most accurate determination of the refractive index modulation n in a holographically exposed photopolymer by the method described above, the diffraction efficiency is not fully saturated but close to 100%. The diffraction efficiency DE depends on the product of n and the layer thickness d of the photopolymer. The very bright holograms obtained here, which have a very high refractive index contrast n, therefore require the preparation of test specimens having a very thin layer thickness d. To this end, a selected example (Example 3) was processed into a photopolymer in a continuous coating system.

(119) FIG. 3 shows the schematic set-up for the coating system used, featuring the following component parts: 1a, b stock reservoir vessel 2a, b metering unit 3a, b vacuum degassing unit 4a, b filter 5 static mixer 6 coating unit 7 circulating air dryer 8 carrier substrate 9 covering layer

(120) To prepare the photopolymer formulation, 45.7 g of polyol 1 in a stirred vessel was incrementally admixed with 290.0 g of ethyl acetate, 20.0 g of Example 1, 60.0 g of urethane-acrylate 1, 60.0 g of additive 1, 0.10 g of Fomrez UL 28, 1.80 g of BYK 310 and 0.52 g of dye 1 to obtain a clear solution. This mixture was imported into stock reservoir vessel 1a of the coating system. The second stock reservoir vessel 1b was filled with a separately prepared clear mixture of 3.0 g of CGI 909, 8.87 of Desmodur N 3900 and 2.22 g of butyl acetate. The two components were then each fed by the metering units 2a and 2b in a ratio of 16.3:1 (stock reservoir vessel 1a:1b) to the vacuum degassing units 3a and 3b for degassing. From here, they were then each passed through the filters 4a and 4b into the static mixer 5, in which the components were mixed to give the photopolymer formulation. The liquid material obtained was then sent in the dark to the coating unit 6.

(121) The coating unit 6 in the present case was a slot die known to a person skilled in the art. Alternatively, however, a doctor blade system or a roller application system can also be employed. With the aid of the coating unit 6, the photopolymer formulation 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.

(122) The layer thickness achieved in the film was 6-8 m.

(123) Holographic Testing:

(124) The media obtained as described were tested for their holographic properties by using a measuring arrangement as per FIG. 1 in the manner described above. The following measurements were obtained for n at a fixed dose of 36 mJ/cm.sup.2:

(125) TABLE-US-00001 TABLE 1 Holographic assessment of selective examples Example Example as per medium formula (I) n I 1 0.043 II 3 0.050 III 4 0.051 IV 6 0.050 V 7 0.040 VI 8 0.040 VII 19 0.038 VIII 20 0.037 IX 22 0.038 X 3 0.060

(126) TABLE-US-00002 TABLE 2 Holographic assessment of selected comparative media Comparative medium n V-I 0.035 V-II 0.035

(127) The values found for Example media I to IX show that the inventive formula (I) compounds used in the photopolymer formulations are very useful in holographic media having a very high refractive index modulation n. Comparative media V-1 and V-2 are free from any compound of formula (I) according to the invention and have lower n values in holographic media. Example medium X shows that the employed compounds of formula (I) according to the invention have a very high refractive index modulation n.