Selection method for additives in photopolymers

Abstract

The invention relates to a method for selecting compounds which can be used as additives in photopolymer formulations for producing light holographic media, and to photopolymer formulations which contain at least one softener which are selected according to the claimed method. The invention also relates to the use of photopolymer formulations for producing holographic media.

Claims

1. A method for preparing a photopolymer formulation comprising providing at least one plasticizer, wherein the at least one plasticizer has a volatility TGA95 of >100 C. and a refractive index n.sub.D.sup.20 of 1.4600, and wherein the at least one plasticizer comprises urethanes of formula (II) ##STR00006## wherein n is from 1 to 8 and R.sup.1, R.sup.2, R.sup.3 represent, independently of one another, hydrogen or linear, branched, cyclic or heterocyclic organic radicals, wherein at least one of the radicals R.sup.1, R.sup.2, R.sup.3 is substituted by at least one fluorine atom, providing a matrix polymer, a writing monomers and a photoinitiator, and preparing the photopolymer formulation by incorporating the at least one plasticizer into the photopolymer formulation.

2. The method according to claim 1, wherein the plasticizer has a volatility TGA95 of >120 C. and the refractive index thereof nD is 1.4300.

3. A photopolymer formulation comprising matrix polymers, writing monomers and photoinitiators, wherein the photopolymer formulation is prepared by the method according to claim 1 and wherein the matrix polymers comprise polyurethanes and wherein the at least one plasticizer comprises urethanes of formula (II) ##STR00007## wherein n is from 1 to 8 and R.sup.1, R.sup.2, R.sup.3 represent, independently of one another, hydrogen or linear, branched, cyclic or heterocyclic organic radicals, wherein at least one of the radicals R.sup.1, R.sup.2, R.sup.3 is substituted by at least one fluorine atom, urethanes, and wherein the urethane is optionally substituted by at least one fluorine atom.

4. The photopolymer formulation according to claim 3, wherein the photoinitiators comprise an anionic, cationic or neutral dye and a coinitiator.

5. The photopolymer formulation according to claim 3, wherein R1 represents an organic radical having at least one fluorine atom.

6. The photopolymer formulation according to claim 3, wherein the writing monomers comprise a monofunctional acrylate of the formula (IV) ##STR00008## wherein R.sup.7, R.sup.8, independently of one another, represent hydrogen or linear, branched, cyclic or heterocyclic organic radicals which are unsubstituted or optionally also substituted by heteroatoms.

7. The photopolymer formulation according to claim 3, wherein the writing monomers comprise a polyfunctional writing monomer.

8. The photopolymer formulation according to claim 3, wherein, the writing monomers comprise a polyfunctional acrylate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The foregoing brief description, as well as the following detailed description, may be better understood when read in conjunction with the appended drawings. For the purpose of assisting in the explanation of the invention, there are shown in the drawings representative embodiments which are considered illustrative. It should be understood, however, that the invention is not limited in any manner to the precise arrangements and instrumentalities shown.

(2) In the drawings:

(3) FIG. 1 illustrates a holographic experimental setup with which the diffraction efficiency (DE) of the media was measured

(4) FIG. 2 illustrates a graph showing the measured data of the diffraction efficiency, the theoretical Bragg curve and the transmitted intensity plotted against the angle detuning.

(5) FIG. 3 illustrates a comparison between the experimental refractive indices and TGA95 values of Examples 1-39 and those estimated by the selection method according to an embodiment of the present invention.

(6) FIG. 4 illustrates a comparison between the experimental refractive indices and TGA95 values of Examples 1-39 and those estimated by the selection method according to an embodiment of the present invention.

(7) FIG. 5 illustrates a graph showing the vapor pressure curves of Examples 2 and 7.

DETAILED DESCRIPTION OF EMBODIMENTS

Preferred Embodiments

(8) According to a first embodiment, the conformer with the lowest energy which is found in the conformer analysis, preferably all conformers which are up to 4 kJ/mol and particularly preferably all conformers which are up to 8 kJ/mol above the lowest conformer, are taken into account for the method.

(9) In a particularly preferred embodiment of the method according to the invention, a check is carried out in step k) to determine whether the volatility of the compound to be tested is >120 C. and the refractive index n.sup.20;.sub.D thereof is 1.4500, preferably 1.4400, particularly preferably 1.4300.

(10) A further aspect of the invention relates to a photopolymer formulation comprising matrix polymers, writing monomers and photoinitiators, said photopolymer formulation containing at least one plasticizer which is selected by the method according to the invention.

(11) The matrix polymers may be in particular polyurethanes. Preferably, the polyurethanes are obtained by reacting an isocyanate component a) with an isocyanate-reactive component b).

(12) The isocyanate component a) preferably comprises polyisocyanates. Polyisocyanates which may be used are all compounds well known to the person skilled in the art or mixtures thereof, which on average have two or more NCO functions per molecule. These may have an aromatic, araliphatic, aliphatic or cycloaliphatic basis. In minor amounts, it is also possible concomitantly to use monoisocyanates and/or polyisocyanates containing unsaturated groups.

(13) For example, butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,2,4- and/or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis(4,4-isocyanatocyclohexyl)methanes and mixtures thereof having any desired isomer content, isocyanatomethyl-1,8-octane diisocyanate, 1,4-cyclohexylene diisocyanate, the isomeric cyclohexanedimethylene diisocyanates, 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4- or 4,4-diphenylmethane diisocyanate and/or triphenylmethane 4,4,4-triisocyanate.

(14) The use of derivatives and monomeric di- or triisocyanates having urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione and/or iminooxadiazinedione structures is likewise possible.

(15) The use of polyisocyanates based on aliphatic and/or cycloaliphatic di- or triisocyanates is preferred.

(16) The polyisocyanates of component a) are particularly preferably dimerized or oligomerized aliphatic and/or cycloaliphatic di- or triisocyanates.

(17) Isocyanurates, uretdiones and/or iminooxadiazinediones based on HDI, 1,8-diisocyanato-4-(isocyanatomethyl)octane or mixtures thereof are very particularly preferred.

(18) NCO-functional prepolymers having urethane, allophanate, biuret and/or amide groups can likewise be used as component a). Prepolymers of component a) are obtained in a manner well known per se to the person skilled in the art by reacting monomeric, oligomeric or polyisocyanates a1) with isocyanate-reactive compounds a2) in suitable stoichiometry with optional use of catalysts and solvents.

(19) Suitable polyisocyanates a1) are all aliphatic, cycloaliphatic, aromatic or araliphatic di- and triisocyanates know per se to the person skilled in the art, it being unimportant whether these were obtained by means of phosgenation or by phosgene-free processes. In addition, the higher molecular weight secondary products of monomeric di- and/or triisocyanates having a urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione or iminooxadiazinedione structure, which are known per se to the person skilled in the art, can also be used, in each case individually or as any desired mixtures with one another.

(20) Examples of suitable monomeric di- or triisocyanates which can be used as component a1) are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), 1,8-di isocyanato-4-(isocyanatomethyl)octane, isocyanatomethyl-1,8-octane diisocyanate (TMDI), 2,4- and/or 2,6-toluene diisocyanate.

(21) OH-functional compounds are preferably used as isocyanate-reactive compounds a2) for the synthesis of the prepolymers. These are analogous to the OH-functional compounds as described below for the component b).

(22) The use of amines for the prepolymer preparation is also possible. For example, ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, diaminocyclohexane, diaminobenzene, diaminobisphenyl, difunctional polyamines, such as, for example, Jeffamine, amine-terminated polymers having number average molar masses of up to 10 000 g/mol or any desired mixtures thereof with one another are suitable.

(23) For the preparation of prepolymers containing biuret groups, isocyanate is reacted in excess with amine, a biuret group forming. Suitable amines in this case for the reaction with the di-, tri- and polyisocyanates mentioned are all oligomeric or polymeric, primary or secondary, difunctional amines of the abovementioned type.

(24) Preferred prepolymers are urethanes, allophanates or biurets of aliphatic isocyanate-functional compounds and oligomeric or polymeric isocyanate-reactive compounds having number average molar masses of 200 to 10 000 g/mol; urethanes, allophanates or biurets of aliphatic isocyanate-functional compounds and oligomeric or polymeric polyols or polyamines having number average molar masses of 500 to 8500 g/mol are particularly preferred and allophanates of HDI or TMDI and difunctional polyetherpolyols having number average molar masses of 1000 to 8200 g/mol are very particularly preferred.

(25) The prepolymers described above preferably have residual contents of free monomeric isocyanate of less than 1% by weight, particularly preferably less than 0.5% by weight, very particularly preferably less than 0.2% by weight.

(26) Of course, the isocyanate component may contain further isocyanate components proportionately in addition to the prepolymers described. Aromatic, araliphatic, aliphatic and cycloaliphatic di-, tri- or polyisocyanates are suitable for this purpose. It is also possible to use mixtures of said di-, tri- or polyisocyanates. Examples of suitable di-, tri- or polyisocyanates are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,2,4- and/or 2,4,4-trimethylhexamethylene diisocyanate (TMDI), the isomeric bis(4,4-isocyanatocyclo-hexyl)methanes and mixtures thereof having any desired isomer content, isocyanatomethyl 1,8-octane diisocyanate, 1,4-cyclohexylene diisocyanate, the isomeric cyclohexanedimethylene diisocyanates, 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4- or 4,4-diphenylmethane diisocyanate, triphenylmethane 4,4,4-triisocyanate or derivatives thereof having a urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione, iminooxadiazinedione structure and mixtures thereof. Polyisocyanates based on oligomerized and/or derivatized diisocyanates which were freed from excess diisocyanate by suitable methods, in particular those of hexamethylene diisocyanate, are preferred. The oligomeric isocyanurates, uretdiones and iminooxadiazinediones of HDI and mixtures thereof are particularly preferred.

(27) It is optionally also possible for the isocyanate component a) proportionately to contain isocyanates which are partly reacted with isocyanate-reactive ethylenically unsaturated compounds. ,-Unsaturated carboxylic acid derivatives, such as acrylates, methacrylates, maleates, fumarates, maleimides, acrylamides, and vinyl ethers, propenyl ethers, allyl ethers and compounds which contain dicyclopentadienyl units and have at least one group reactive towards isocyanates are preferably used here as isocyanate-reactive ethylenically unsaturated compounds; these are particularly preferably acrylates and methacrylates having at least one isocyanate-reactive group. Suitable hydroxy-functional acrylates or methacrylates are, for example, compounds such as 2-hydroxyethyl (meth)acrylate, polyethylene oxide mono(meth)acrylates, polypropylene oxide mono(meth)acrylates, polyalkylene oxide mono(meth)acrylates, poly(-caprolactone) mono(meth)acrylates, such as, for example, Tone M100 (Dow, USA), 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxy-2,2-dimethylpropyl (meth)acrylate, the hydroxy-functional mono-, di- or tetra(meth)acrylates of polyhydric alcohols, such as trimethylolpropane, glycerol, pentaerythritol, di pentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or the industrial mixtures thereof. In addition, isocyanate-reactive oligomeric or polymeric unsaturated compounds containing acrylate and/or methacrylate groups are suitable alone or in combination with the abovementioned monomeric compounds. The proportion of isocyanates which are partly reacted with isocyanate-reactive ethylenically unsaturated compounds, based on the isocyanate component a) is 0 to 99%, preferably 0 to 50%, particularly preferably 0 to 25% and very particularly preferably 0 to 15%.

(28) It is optionally also possible for the abovementioned isocyanate component a) completely or proportionately to contain isocyanates, which are completely or partly reacted with blocking agents known to the person skilled in the art from coating technology. The following may be mentioned as an example of blocking agents: alcohols, lactams, oximes, malonic esters, alkyl acetoacetates, triazoles, phenols, imidazoles, pyrazoles and amines, such as, for example, butanone oxime, di isopropylamine, 1,2,4-triazole, dimethyl-1,2,4-triazole, imidazole, diethyl malonate, ethyl acetoacetate, acetone oxime, 3,5-dimethylpyrazole, -caprolactam, N-tert-butylbenzylamine, cyclopentanone carboxyethyl ester or any desired mixtures of these blocking agents.

(29) All polyfunctional, isocyanate-reactive compounds which have on average at least 1.5 isocyanate-reactive groups per molecule can in principle be used as component b).

(30) Isocyanate-reactive groups in the context of the present invention are preferably hydroxy, amino or thio groups; hydroxy compounds are particularly preferred.

(31) Suitable polyfunctional, isocyanate-reactive compounds are, for example, polyester-, polyether-, polycarbonate-, poly(meth)acrylate- and/or polyurethanepolyols.

(32) Suitable polyesterpolyols are, for example, linear polyesterdiols or branched polyester polyols, as are obtained in a known manner from aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or their anhydrides with polyhydric alcohols having an OH functionality of 2.

(33) Examples of such di- or polycarboxylic acids or anhydrides are succinic, glutaric, adipic, pimelic, suberic, azelaic, sebaccic, nonanedicarboxylic, decanedicarboxylic, terephthalic, isophthalic, o-phthalic, tetrahydrophthalic, hexahydrophthalic or trimellitic acid and acid anhydrides such as o-phthalic, trimellitic or succinic anhydride, or any desired mixtures thereof with one another.

(34) Examples of such suitable alcohols are ethanediol, di-, tri- and tetraethylene glycol, 1,2-propanediol, di-, tri- and tetrapropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-di hydroxycyclohexane, 1,4-dimethylolcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, trimethylolpropane, glycerol or any desired mixtures thereof with one another.

(35) The polyesterpolyols may also be based on natural or raw materials, such as castor oil. It is also possible for the polyesterpolyols to be based on homo- or copolymers of lactones, as can preferably be obtained by an addition reaction of lactones or lactone mixtures, such as butyrolactone, -caprolactone and/or methyl--caprolactone, with hydroxy-functional compounds, such as polyhydric alcohols having an OH functionality of 2, for example of the abovementioned type.

(36) Such polyesterpolyols preferably have number average molar masses of 400 to 4000 g/mol, particularly preferably of 500 to 2000 g/mol. Their OH functionality is preferably 1.5 to 3.5, particularly preferably 1.8 to 3.0.

(37) Suitable polycarbonatepolyols are obtainable in a manner known per se by reacting organic carbonates or phosgene with diols or diol mixtures.

(38) Suitable organic carbonates are dimethyl, diethyl and diphenyl carbonate.

(39) Suitable diols or mixtures comprise the polyhydric alcohols mentioned per se in connection with the polyester segments and having an OH functionality of 2, preferably 1,4-butanediol, 1,6-hexanediol and/or 3-methylpentanediol, or polyesterpolyols can be converted into polycarbonatepolyols.

(40) Such polycarbonatepolyols preferably have number average molar masses of 400 to 4000 g/mol, particularly preferably of 500 to 2000 g/mol. The OH functionality of these polyols is preferably 1.8 to 3.2, particularly preferably 1.9 to 3.0.

(41) Suitable polyetherpolyols are polyadducts of cyclic ethers with OH- or NH-functional starter molecules, said polyadducts optionally having a block structure.

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

(43) Starters which may be used are the polyhydric alcohols mentioned per se in connection with the polyesterpolyols and having an OH functionality of 2 and primary or secondary amines and amino alcohols.

(44) Preferred polyetherpolyols are those of the abovementioned type, exclusively based on propylene oxide, or random or block copolymers based on propylene oxide with further 1-alkylene oxides, the proportion of the 1-alkylene oxide not being higher than 80% by weight. In addition, poly(trimethylene oxides) and mixtures of the polyols mentioned as being preferred are preferred. Propylene oxide homopolymers and random or block copolymers which have oxyethylene, oxypropylene and/or oxybutylene units are particularly preferred, the proportion of oxypropylene units, based on the total amount of all oxyethylene, oxypropylene and oxybutylene units, accounting for at least 20% by weight, preferably at least 45% by weight. Here, oxypropylene and oxybutylene comprise all respective linear and branched C3- and C4-isomers.

(45) Such polyetherpolyols preferably have number average molar masses of 250 to 10 000 g/mol, particularly preferably of 500 to 8500 g/mol and very particularly preferably of 600 to 4500 g/mol. The OH functionality is preferably 1.5 to 4.0, particularly preferably 1.8 to 3.1.

(46) In addition, aliphatic, araliphatic or cycloaliphatic di-, tri- or polyfunctional alcohols which have a low molecular weight, i.e. having molecular weights of less than 500 g/mol, and a short chain, i.e. containing 2 to 20 carbon atoms, are also suitable as polyfunctional, isocyanate-reactive compounds as constituents of component c).

(47) These may be, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentylglycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, positional isomers of diethyloctanediol, 1,3-butylene glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2- and 1,4-cyclohexanediol, hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), 2,2-dimethyl-3-hydroxy-propionic acid (2,2-dimethyl-3-hydroxypropyl ester). Examples of suitable triols are trimethylolethane, trimethylolpropane or glycerol. Suitable higher-functional alcohols are ditrimethylolpropane, pentaerythritol, dipentaerythritol or sorbitol.

(48) One or more photoinitiators are used as component c). These are usually initiators which can be activated by actinic radiation and initiate a polymerization of the corresponding polymerizable groups. Photoinitiators are commercially distributed compounds known per se, a distinction being made between monomolecular (type I) and bimolecular (type II) initiators. Furthermore, these initiators are used for free radical, anionic (or), cationic (or mixed) forms of the abovementioned polymerizations, depending on the chemical nature.

(49) (Type I) systems for the free radical photopolymerization are, for example, aromatic ketone compounds, e.g. benzophenones, in combination with tertiary amines, alkylbenzophenones, 4,4-bis(dimethylamino)benzophenone (Michlers ketone), anthrone and halogenated benzophenones or mixtures of said types. (Type II) initiators, such as, benzoin and its derivatives, benzil ketals, acylphosphine oxides, e.g. 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bisacylophosphine oxides, phenylglyoxylic esters, campherquinone, alpha-aminoalkylphenones, alpha-,alpha-dialkoxyacetophenones, 1-[4-(phenylthio)phenyl]octane-1,2-dione 2-(O-benzoyloxime), differently substituted hexarylbisimidazoles (HABI) with suitable coinitiators, such as, for example, mercaptobenzoxazole and alpha-hydroxyalkylphenones are furthermore suitable. The photoinitiator systems described in EP-A 0223587 and consisting of a mixture of an ammonium aryl borate and one or more dyes can also be used as a photoinitiator. For example, tetrabutylammonium triphenylhexyl borate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinaphthylbutylborate, tetramethylammonium triphenylbenzylborate, tetra(n-hexyl)ammonium (sec-butyl)triphenylborate, 1-methyl-3-octylimidazolium dipentyldiphenylborate, tetrabutylammonium tris(4-tert-butyl)phenyl-butylborate, tetrabutylammonium tris(3-fluorophenyl)hexylborate and tetrabutylammonium tris(3-chloro-4-methylphenyl)hexylborate are suitable as the ammonium aryl borate. Suitable dyes are, for example, new methylene blue, thionine, basic yellow, pinacynol chloride, rhodamine 6G, gallocyanine, ethylviolet, Victoria blue R, celestine blue, quinaldine red, crystal violet, brilliant green, astrazone orange G, darrow red, pyronine Y, basic red 29, pyrillium I, safranine O, cyanine and methylene blue, azure A (Cunningham et al., RadTech'98 North America UV/EB Conference Proceedings, Chicago, Apr. 19-22, 1998).

(50) The photoinitiators used for the anionic polymerization are as a rule (type 1) systems and are derived from transition metal complexes of the first series. Here are chromium salts, such as, for example, trans-Cr(NH.sub.3).sub.2(NCS).sub.4 (Kutal et al, Macromolecules 1991, 24, 6872) or ferrocenyl compounds (Yamaguchi et al., Macromolecules 2000, 33, 1152). A further possibility of anionic polymerization consists in the use of dyes, such as crystal violet leuconitrile or malchite green leuconitrile, which can polymerize cyanoacrylates by photolytic decomposition (Neckers et al., Macromolecules 2000, 33, 7761). However, the chromophore is incorporated thereby into the polymer so that the resulting polymers are coloured throughout.

(51) The photoinitiators used for the cationic polymerization substantially comprise three classes: aryldiazonium salts, onium salts (here specifically: iodonium, sulphonium and selenonium salts) and organometallic compounds. On irradiation both in the presence and in the absence of a hydrogen donor, phenyldiazonium salts can produced a cation that initiates the polymerization. The efficiency of the overall system is determined by the nature of the counterion used for the diazonium compound. The not very reactive but very expensive SbF.sub.6.sup., AsF.sub.6.sup. or PF.sub.6.sup. are preferred here. These compounds are as a rule not very suitable for use in coating of the thin films since the nitrogen liberated after the exposure reduces the surface quality (pinholes) (Li et al., Polymeric Materials Science and Engineering, 2001, 84, 139). Very widely used and commercially available in many forms are onium salts, especially sulphonium and iodonium salts. The photochemistry of these compounds has been investigated for a long time. After excitation, the iodonium salts initially decompose homolytically and thus produce a free radical and a radical anion which is stabilized by H abstraction and releases a proton and then initiates the cationic polymerization (Dektar et al. J. Org. Chem. 1990, 55, 639; J. Org. Chem., 1991, 56, 1838). This mechanism permits the use of iodonium salts also for free radical photopolymerization. The choice of the counterion is once again of considerable importance here; SbF.sub.6.sup., AsF.sub.6.sup. or PF.sub.6.sup. are likewise preferred. Otherwise, this choice of the substitution of the aromatic is completely free in this structure class and is determined substantially by the availability of suitable starting building blocks for the synthesis. The sulphonium salts are compounds which decompose in according to Norrish(II) (Crivello et al., Macromolecules, 2000, 33, 825). In the case of the sulphonium salts, too, the choice of the counterion is of critical importance and manifests itself substantially in the curing rate of the polymers. The best results are as a rule obtained with SbF.sub.6.sup. salts. Since the self-absorption of iodonium and sulphonium salts is at <300 nm, these compounds must be appropriately sensitized for the photopolymerization with near UV or short-wave visible light. This is effected by the use of more highly absorbing aromatics such as, for example, anthracene and derivatives (Gu et al., Am. Chem. Soc. Polymer Preprints, 2000, 41 (2), 1266) or phenothiazine or derivatives thereof (Hua et al, Macromolecules 2001, 34, 2488-2494).

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

(53) Preferred photoinitiators c) are mixtures of tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinaphthylbutylborate, tetrabutylammonium tris-(4-tert-butyl)phenylbutylborate, tetrabutylammonium tris-(3-fluorophenyl)hexylborate and tetrabutylammonium tris-(3-chloro-4-methylphenyl)hexylborate with dyes, such as, for example, astrazone orange G, methylene blue, new methylene blue, azure A, pyrillium I, safranine O, cyanine, gallocyanine, brilliant green, crystal violet, ethyl violet and thionine.

(54) The photopolymer formulation may additionally contain urethanes as plasticizers, it being possible for the urethanes preferably to be substituted by at least one fluorine atom.

(55) The urethanes are preferably compounds which have a structural element of the general formula I.

(56) ##STR00001##

(57) They can be obtained from monofunctional alcohols and monofunctional isocyanates. These are preferably substituted by at least one fluorine atom.

(58) It is more preferable if the fluorourethanes have the general formula II

(59) ##STR00002##
in which n is 1 and n is 8 and R.sup.1, R.sup.2, R.sup.3 are hydrogen and/or, independently of one another, linear, branched, cyclic or heterocyclic organic radicals which are unsubstituted or optionally also substituted by heteroatoms, at least one of the radicals R.sup.1, R.sup.2, R.sup.3 being substituted by at least one fluorine atom. Here, R.sup.1 is particularly preferably an organic radical having at least one fluorine atom.

(60) According to a further embodiment. R.sup.1 may comprise 1-20 CF.sub.2 groups and/or one or more CF.sub.3 groups, particularly preferably 1-15 CF.sub.2 groups and/or one or more CF.sub.3 groups, particularly preferably 1-10 CF.sub.2 groups and/or one or more CF.sub.3 groups, very particularly preferably 1-8 CF.sub.2 groups and/or one or more CF.sub.3 groups, R.sup.2 may comprise a C1-C20 alkyl radical, preferably a C1-C15 alkyl radical, particularly preferably a C1-C10 alkyl radical or hydrogen, and/or R.sup.3 may comprise a C1-C20 alkyl radical, preferably a C1-C15 alkyl radical, particularly preferably a C1-C10 alkyl radical or hydrogen.

(61) The fluorourethanes may have a fluorine content of 10-80% by weight of fluorine, preferably of 13-70% by weight of fluorine and particularly preferably 17.5-65% by weight of fluorine.

(62) According to a further preferred embodiment of the invention, it is envisaged that the photopolymer formulation contains 10 to 89.999% by weight, preferably 25 to 70% by weight, of matrix polymers, 10 to 60% by weight, preferably 25 to 50% by weight, of writing monomers, 0.001 to 5% by weight of photoinitiators and optionally 0 to 4% by weight, preferably 0 to 2% by weight, of catalyst, 0 to 5% by weight, preferably 0.001 to 1% by weight, of free radical stabilizers, 0 to 30% by weight, preferably 0 to 25% by weight, of plasticizers and 0 to 5% by weight, preferably 0.1 to 5% by weight, of further additives, the sum of all constituents being 100% by weight.

(63) Photopolymer formulations having 25 to 70% by weight of matrix polymers consisting of compounds of component a) and of component b), 25 to 50% by weight of writing monomers, 0.001 to 5% by weight of photoinitiators, 0 to 2% by weight of catalyst, 0.001 to 1% by weight of free radical stabilizers, optionally 0 to 25% by weight of the urethanes described above and optionally 0.1 to 5% by weight of further additives are particularly preferably used.

(64) A further preferred embodiment of the invention envisages that the photopolymer formulation contains urethanes having a number average molecular weight of 250 g/mol, preferably of 200 g/mol and particularly preferably of 190 g/mol.

(65) The photopolymer formulation therefore advantageously contains aliphatic urethanes. In this case, the aliphatic urethanes may have in particular the general formula (III)

(66) ##STR00003##
in which R.sup.4, R.sup.5, R.sup.6, independently of one another, are linear or branched (C1-C20)-alkyl radicals optionally substituted by heteroatoms. It is particularly preferable if R.sup.4 is a linear or branched (C1-C8)-alkyl radical, R.sup.5 is a linear or branched (C1-C8)-alkyl radical and/or R.sup.6 is a linear or branched (C1-C8)-alkyl radical, it being particularly preferable if R.sup.4 is a linear or branched (C1-C4)-alkyl radical and R.sup.5 is a linear or branched (C1-C6)-alkyl radical and R.sup.6 is hydrogen. In this case, it was in fact found that the urethanes thus obtained are very compatible with the polyurethane matrix and show the effect described here.

(67) According to a further preferred embodiment, it is envisaged that the urethanes have substantially no free NCO groups.

(68) The writing monomers can preferably comprise a monofunctional acrylate of the general formula (IV)

(69) ##STR00004##
in which R.sup.7, R.sup.8 are hydrogen and/or, independently of one another, linear, branched, cyclic or heterocyclic unsubstituted organic radicals.

(70) It is also possible for the writing monomers to comprise a polyfunctional writing monomer, it being possible for this to be in particular a polyfunctional acrylate.

(71) The polyfunctional acrylate can preferably have the general formula (V)

(72) ##STR00005##
in which n is 2 and n is 4 and R.sup.9, R.sup.10 are hydrogen and/or, independently of one another, linear, branched, cyclic or heterocyclic organic radicals which are unsubstituted or optionally also substituted by heteroatoms.

(73) The present invention furthermore relates to the use of a photopolymer formulation according to the invention for the production of holographic media, in particular for the production of in-line holograms, off-axis holograms, full-aperture transfer holograms, white light transmission holograms, Denisyuk holograms, off-axis reflection holograms, edge-lit holograms and holographic stereograms.

EXAMPLES

(74) The invention is explained in more detail below with reference to examples. First, the synthesis and characterization of the example molecules are described and thereafter the handling thereof in the method according to the invention.

(75) Unless noted otherwise, all stated percentages relate to percent by weight.

(76) Determination of the Refractive Index

(77) Measurement of the refractive index n.sup.20;.sub.D at a wavelength of 589 nm: a sample of the example compound was introduced into an Abbe refractometer and n.sup.20;.sub.D was measured.

(78) Determination of the Vapour Pressure

(79) For Examples 2 and 7, the synthesis of which is described further below, the vapour pressures were determined under a nitrogen atmosphere in a circulation apparatus (isobar in an Ebulliometer) by the Rck method according to the OECD guideline for the testing of chemicals, No. 104. The resulting vapour pressure curves are shown in FIG. 5 in the temperature range from 90 to 180 C. The resulting parameters of the Antoine equation

(80) $\lg \frac{P^{\mathrm{Sat}}}{\mathrm{hPa}}=A-\frac{B}{C+T\left(C.\right)}$
are accordingly:

(81) TABLE-US-00001 TABLE 1 Physical data of Examples 2 and 7 Vapour Vapour Parameters of the pressure pressure TGA Antoine equation at 80 C. at 100 C. 95 Example A B C [hPa] [hPa] [ C.] 2 15.6189 2616.075 90.3596 1.30 7.30 72.5 7 6.5466 1053.404 42.458 0.13 0.42 111.8

(82) It is evident from this that the equilibrium vapour pressure, for example for a temperature of 100 C. in both Examples 2 and 7, is <10 hPa, so that it would be expected that the two components have sufficient stability in the formulation. The TGA95 values of the two two Examples 2 and 7 on the other hand correlate substantially better with the observed behaviour during the film coating.

(83) FIG. 1 shows the measured vapour pressure curves of Examples 2 and 7.

(84) Determination of the TGA95 Value

(85) The TGA95 values of the individual components are determined by weighing an amount of about 10 mg of the respective component into an aluminium pan having a volume of 70 l, introducing the aluminium pan into an oven of a thermobalance, preferably a TG50 thermobalance from Mettler-Toledo, and measuring the loss of mass (of the sample) in the open aluminium pan at a constant oven heating rate of 20 K/min, the starting temperature being 30 C. and the end temperature of the oven being 600 C., the oven being flushed with a 200 ml/min nitrogen stream during the determination and the temperature at which a loss of mass of the sample of 5% by weight, based on the originally weighed in amount of the sample, has occurred being determined as the TGA95 value of the respective component.

(86) Measurement of the Holographic Properties DE and n of the Holographic Media by Means of Two-Beam Interference in Reflection Arrangement

(87) For the measurement of the holographic performance, the protective foil of the holographic film is peeled off and the holographic film is laminated on the photopolymer side with a 1 mm thick glass plate of suitable length and width using a rubber roller with gentle pressure. This sandwich of glass and photopolymer film can now be used for determining the holographic performance parameters DE and n.

(88) The holographic media produced as described below were then tested with regard to the holographic properties by means of a measurement arrangement according to FIG. 3, as follows:

(89) The beam of an HeNe laser (emission wavelength 633 nm) was converted with the aid of the spatial filter (SF) and together with the collimation lens (CL) into a parallel homogeneous beam. The final cross sections of the signal and reference beam are established by the iris diaphragm (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 equally polarized beams. Via the /2 plates, the power of the reference beam was adjusted to 0.5 mW and the power of the signal beam to 0.65 mW. The powers were determined using the semiconductor detectors (D) with sample removed. The angle of incidence (.sub.0) of the reference beam is 21.8 and the angle of incidence (.sub.0) of the signal beam is 41.8. The angles are measured starting from the sample normal to the beam direction. According to FIG. 3, .sub.0 therefore 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 grating of lighter and darker strips which are perpendicular to the angle dissectors of the two beams incident on the sample (reflection hologram). The strip spacing , also referred to as grating period, in the medium is 225 nm (the refractive index of the medium is seen to be 1.504).

(90) FIG. 3 shows the holographic experimental setup with which the diffraction efficiency (DE) of the media was measured.

(91) Holograms were recorded in the medium in the following manner: both shutters (S) are opened for the exposure time t. thereafter, with closed shutters (S), the medium was allowed a time of 5 minutes for diffusion of the still unpolymerized writing monomers.

(92) The holograms recorded were now read 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 in the previously recorded hologram for all angles of rotation () of the medium. The turntable, now computer controlled, covered 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 angle of incidence of the reference beam and that of the signal beam have the same absolute value during recording of the hologram, i.e. .sub.0=31.8 and .sub.0=31.8. .sub.recording is then 0. For .sub.0=21.8 and .sub.0=41.8. .sub.recording is therefore 10. In general, the following is true for the interference field during recording of the hologram:
.sub.0=.sub.0+.sub.recording.
.sub.0 is the semiangle on the laboratory system outside the medium and the following is true during recording of the hologram:

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

(94) In this case, .sub.0 is therefore 31.8. At each angle of rotation approached, the powers of the beam transmitted in the zeroth order were measured by means of the corresponding detector D and the powers of the beam diffracted in the first order were measured by means of the detector D. The diffraction efficiency was obtained at each angle approached as a quotient of:

(95) $=\frac{P_D}{P_D+P_T}$
P.sub.D is the power in the detector of the diffracted beam and P.sub.T is the power in the detector of the transmitted beam.

(96) By means of the method described above, the Bragg curve (it describes the diffraction efficiency as a function of the angle of rotation of the recorded hologram) was measured and was stored in a computer. In addition, the intensity transmitted in the zeroth order was plotted against the angle of rotation and stored in a computer.

(97) The maximum diffraction efficiency (DE=.sub.max) of the hologram, i.e. its peak value, was determined at .sub.reconstruction. It may have been necessary for this purpose to change the position of the detector of the diffracted beam in order to determine this maximum value.

(98) The refractive index n and the thickness d of the photopolymer layer was now determined by means of the coupled wave theory (cf. H. Kogelnik, The Bell System Technical Journal, Volume 48, November 1969, Number 9, page 2909-page 2947) from the measured Bragg curve and variation of the transmitted intensity as a function of angle. It should be noted that, owing to the thickness shrinkage occurring as result of the photopolymerization, the strip spacing of the hologram and the orientation of the strips (slant) may 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 reached will also differ from .sub.0 and from the corresponding .sub.recording, respectively. The Bragg condition changes as a result. This change is taken into account in the evaluation method. The evaluation method is described below:

(99) All geometrical quantities which relate to the recorded hologram and not to the interference pattern are shown as quantities represented by a dashed line.

(100) According to Kogelnik, the following is true for the Bragg curve () of reflection hologram:

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

(102) On reading the hologram (reconstruction), the following is true, as shown analogously above:
.sub.0=.sub.0+
sin(.sub.0)=n.Math.sin()

(103) Under the Bragg condition, the dephasing DP is 0. Accordingly, the following is true:
.sub.0=.sub.0+.sub.reconstruction
sin(.sub.0)=n.Math.sin()

(104) The still unknown angle can be determined from the comparison of the Bragg condition of the interference field on recording of the hologram and the Bragg, condition on reading the hologram, assuming that only thickness shrinkage takes place. Then follows:

(105) $\sin \left(\text{'}\right)=\frac{1}{n}.Math.\left[\sin \left({}_0\right)+\sin \left({}_0\right)-\sin \left({}_0+{}_{\mathrm{recontruction}}\right)\right]$
v is the grating thickness, is the detuning parameter and is the orientation (slant) of the refractive index grating which was recorded. and correspond to the angles .sub.0 and .sub.0 of the interference field on recording of the hologram, but measured in the medium and applicable to the grating of the hologram (after thickness shrinkage). n is the mean refractive index of the photopolymer and was set at 1.504. is the wavelength of the laser light in vacuo.

(106) The maximum diffraction efficiency (DE=.sub.max) is then obtained for =0 as:

(107) 0$\mathrm{DE}={\tanh }^2\left(v\right)={\tanh }^2\left(\frac{.Math.n.Math.d\text{'}}{.Math.\sqrt{\cos \left(\text{'}\right).Math.\cos \left(\text{'}-2\right)}}\right)$

(108) The measured data of the diffraction efficiency, the theoretical Bragg curve and the transmitted intensity are, as shown in FIG. 4, plotted against the centred angle of rotation =.sub.reconstruction=.sub.0.sub.0, also referred to as angle detuning.

(109) 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 subsequently corrected via DE for a given thickness d so that measurement and theory of DE always agree. d is now adapted until the angle positions of the first secondary minima of the theoretical Bragg curve agree with the angle positions of the first secondary maxima of the transmitted intensity and additionally the full width at half maximum (FWHM) for the theoretical Bragg curve and the transmitted intensity agree.

(110) Since the direction in which a reflection hologram concomitantly rotates on reconstruction by means of an scan, but the detector for the diffracted light can detect only a finite angle range, the Bragg curve of broad holograms (small d) is not completely detected in an scan, but only the central region, with suitable detector positioning. That shape of the transmitted intensity which is complementary to the Bragg curve is therefore additionally used for adapting the layer thickness d.

(111) FIG. 4 shows the plot of the Bragg curve according to the coupled wave theory (dashed line), of the measured diffraction efficiency (solid circles) and of the transmitted power (black solid line) against the angle detuning .

(112) For a formulation, this procedure was possibly repeated several times for different exposure times t on different media in order to determine the average energy dose of the incident laser beam at which DE reaches the saturation value during recording of the hologram. The average energy dose E is obtained from the powers of the two part-beams coordinated with the angles .sub.0 and .sub.0 (reference beam with P.sub.r=0.50 mW and signal beam with P.sub.s=0.63 mW), the exposure time t and the diameter of the iris diaphragm (0.4 cm), as follows:

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

(114) The powers of the part-beams were adapted so that the same power density is achieved in the medium at the angles .sub.0 and .sub.0 used.

(115) In examples, respectively the maximum value in n is reported, and the doses used are between 4 and 64 mJ/cm.sup.2 per arm.

(116) Substances Used

(117) CGI-909 (tetrabutylammonium tris(3-chloro-4-methyl phenyl)(hexyl)borate, [1147315-11-4]) is an experimental product produced by CIBA Inc., Basle, Switzerland.

(118) The (fluorinated) alcohols and monofunctional isocyanates used were obtained in the chemicals trade.

(119) 1,8-Diisocyanato-4-(isocyanatomethyl)octane (TIN) was prepared as described in EP 749958.

(120) 2,4,4-Trimethylhexane 1,6-diisocyanate, Vestanat TMDI, is a product of Evonik Degussa GmbH, Marl, Germany.

(121) Preparation of the Polyol Component:

(122) In a 1 l flask, 0.18 g of tin octoate, 374.8 g of -caprolactone and 374.8 g of a difunctional polytetrahydrofuranpolyetherpolyol (equivalent weight 500 g/mol OH) were initially introduced and heated to 120 C. and kept at this temperature until the solids content (proportion of nonvolatile constituents) was 99.5% by weight or more. Thereafter, cooling was effected and the product was obtained as a waxy solid.

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

(123) In a 500 ml round-bottomed flask, 0.1 g of 2,6-di-tert-butyl-4-methylphenol, 0.05 g of dibutyltin dilaurate (Desmorapid Z, Bayer MaterialScience AG, Leverkusen, Germany) and and 213.07 g of a 27% strength solution of tris(p-isocyanatophenyl) thiophosphate in ethyl acetate (Desmodur RFE, product of Bayer MaterialScience AG, Leverkusen, Germany) were initially introduced and heated to 60 C. Thereafter, 42.37 g of 2-hydroxyethyl acrylate were added dropwise and the mixture was further kept at 60 C. until the isocyanate content had fallen below 0.1%. Thereafter, cooling was effected and the ethyl acetate was completely removed in vacuo. The product was obtained as a semicrystalline solid.

Preparation of urethane acrylate 2: 2-({[3-(methylsulphanyl)phenyl]carbamoyl}oxy)-ethyl prop-2-enoate)

(124) In a 100 ml round-bottomed flask, 0.02 g of 2,6-di-tert-butyl-4-methylphenol, 0.01 g of Desmorapid Z, 11.7 g of 3-(methylthio)phenyl isocyanate were initially introduced and heated to 60 C. Thereafter, 8.2 g of 2-hydroxyethyl acrylate were added dropwise and the mixture was further kept at 60 C. until the isocyanate content had fallen below 0.1%. Thereafter, cooling was effected. The product was obtained as a light yellow liquid.

Example 1: Trifluoroethyl butylcarbamate

(125) In a 2 l round-bottomed flask, 0.50 g of Desmorapid Z and 498 g of n-butyl isocyanate were initially introduced and heated to 60 C. Thereafter, 502 g of trifluoroethanol were added dropwise and the mixture was further kept at 60 C. until the isocyanate content had fallen below 0.1%. Thereafter, cooling was effected. The product was obtained as a colourless solid. The refractive index n.sup.20;.sub.D determined by method B is 1.3900 and the measured TGA95 value is 63.7 C.

Further Examples

(126) Examples 2-25 were prepared in the manner described for Example 1, in the compositions stated in Table 2. The associated n.sup.20;.sub.D and TGA95 values for all examples were measured as described in the above correspondingly named sections.

(127) TABLE-US-00002 TABLE 2 Preparation and characterization of Examples 2-35 Isocyanate and Catalyst and Temp Example Name amount Alcohol and amount amount [ C.] Description 2 2,2,2-Trifluoroethyl hexylcarbamate n-Hexyl isocyanate Trifluoroethanol Desmorapid Z 60 C. colourless 55.9 g 44.0 g 0.05 g liquid 3 2,2,3,3-Tetrafluoropropyl butylcarbamate n-Butyl isocyanate 2,2,3,3-Tetra-fluoropropan- Desmorapid Z 60 C. colourless 10.7 g 1-ol 14.3 g 0.01 g liquid 4 Bis(2,2,2-trifluoroethyl)-(2,2,4- 2,4,4-Trimethylhexane 1,6- Trifluoroethanol Desmorapid Z 60 C. colourless trimethylhexane-1,6-diyl) biscarbamate diisocyanate (TMDI) 496 g 463 g 0.48 G liquid 5 Bis(2,2,2-trifluoroethyl)-[4- 1,8-Diisocyanato-4-(iso- Trifluoroethanol Desmorapid Z 60 C. colourless ({[(2,2,2-trifluoroethoxy)- cyanatomethyl)octane 272 g 0.48 g liquid carbonyl]amino}methyl)octane- (TIN) 228 g 1,8-diyl] biscarbamate 6 2,2,3,3,4,4,4-Heptafluorobutyl n-Butyl isocyanate 2,2,3,3,4,4,4-Hepta- Desmorapid Z 60 C. colourless butylcarbamate 24.8 g fluorobutanol 50.1 g 0.04 g solid 7 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- n-Butyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- Desmorapid Z 60 C. colourless Hexadecafluorononyl butylcarbamate 186 g Hexadecafluoro-nonanol 813 g 0.50 g liquid 8 Bis(2,2,3,3,4,4,4-heptafluorobutyl)- 2,4,4-Trimethylhexane 2,2,3,3,4,4,4-Hepta- Desmorapid Z 60 C. colourless (2,2,4-trimethylhexane-1,6-diyl) 1,6-diisocyanate fluorobutanol 0.01 g liquid biscarbamate (TMDI) 6.88 g 13.1 g 9 Bis(2,2,3,3,4,4,4-heptafluorobutyl)-[4- 1,8-Diisocyanato-4-(iso- 2,2,3,3,4,4,4-Hepta- Desmorapid Z 60 C. colourless ({[(2,2,3,3,4,4,4-heptafluoro- cyanatomethyl)octane fluorobutanol 14.1 g 0.01 g oil butoxy)carbonyl]amino}methyl)octane-1,8- (TIN) 5.91 g diyl] biscarbamate 10 2,2,3,3,4,4,5,5,5-Nonafluoropentyl n-Butyl isocyanate 2,2,3,3,4,4,5,5,5-Nona- Desmorapid Z 70 C. colourless butylcarbamate 4.25 g fluoropentan-1-ol 10.7 g 0.02 g liquid 11 Bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl)- 2,4,4-Trimethylhexane 1,6- 2,2,3,3,4,4,5,5,5-Nona- Desmorapid Z 70 C. colourless (2,2,4-trimethylhexane-1,6-diyl) diisocyanate (TMDI) 4.43 g fluoropentan-1-ol 10.6 g 0.02 g liquid biscarbamate 12 2,2,3,3,4,4,5,5,5-Nonafluoropentyl n-Hexyl isocyanate 2,2,3,3,4,4,5,5,5-Nona- Desmorapid Z 70 C. colourless hexylcarbamate 5.05 g fluoropentan-1-ol 9.94 g 0.02 g liquid 13 2,2,3,3,4,4,5,5,5-Nonafluoropentyl i-Propyl isocyanate 2,2,3,3,4,4,5,5,5-Nona- Desmorapid Z 70 C. colourless propan-2-yl carbamate 3.81 g fluoropentan-1-ol 11.2 g 0.02 g liquid 14 2,2,3,3,4,4,5,5,6,6,6-Undecafluorohexyl n-Butyl isocyanate 2,2,3,3,4,4,5,5,6,6,6- Desmorapid Z 70 C. colourless butylcarbamate 3.72 g Undecafluorohexan-1-ol 11.3 g 0.02 g liquid 15 Bis(2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl)- 2,4,4-Trimethylhexane 1,6- 2,2,3,3,4,4,5,5,6,6,6- Desmorapid Z 70 C. colourless (2,2,4-trimethylhexane-1,6-diyl) biscarbamate diisocyanate (TMDI) 3.88 g Undecafluorohexan-1-ol 11.1 g 0.02 g oil 16 2,2,3,3,4,4,5,5,6,6,6-Undecafluorohexyl n-Hexyl isocyanate 2,2,3,3,4,4,5,5,6,6,6- Desmorapid Z 70 C. colourless hexylcarbamate 4.46 g Undecafluorohexan-1-ol 10.5 g 0.02 g liquid 17 Bis(2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl)- 2,4,4-Trimethylhexane 1,6- 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70 C. colourless (2,2,4-trimethylhexane-1,6-diyl) biscarbamate diisocyanate (TMDI) 3.60 g Dodecafluoroheptan-1-ol 11.4 g 0.02 g oil 18 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl n-Hexyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70 C. colourless hexylcarbamate 4.15 g Dodecafluoroheptan-1-ol 10.8 g 0.02 g liquid 19 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl i-Propyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70 C. colourless propan-2-ylcarbamate 3.06 g Dodecafluoroheptan-1-ol 11.93 g 0.02 g liquid 20 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl Cyclohexyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70 C. colourless cyclohexylcarbamate 4.10 g Dodecafluoroheptan-1-ol 10.9 g 0.02 g liquid 21 2,2,3,4,4,4-Hexafluorobutyl butylcarbamate n-Butyl isocyanate 2,2,3,4,4,4- Desmorapid Z 70 C. colourless 5.28 g Hexafluorobutan-1-ol 9.71 g 0.02 g liquid 22 2,2,3,4,4,4-Hexafluorobutyl hexylcarbamate n-Hexyl isocyanate 2,2,3,4,4,4-Hexafluoro- Desmorapid Z 70 C. colourless 6.16 g butan-1-ol 8.83 g 0.02 g liquid 23 2,2,3,4,4,4-Hexafluorobutyl propan-2- i-Propyl isocyanate 2,2,3,4,4,4-Hexafluoro- Desmorapid Z 70 C. colourless ylcarbamate 4.77 g butan-1-ol 10.2 g 0.02 g oil 24 2,2,3,3,4,4,5,5-Octafluoropentyl n-Butyl isocyanate 2,2,3,3,4,4,5,5-Octa- Desmorapid Z 70 C. colourless butylcarbamate 4.48 g fluoropentan-1-ol 10.5 g 0.02 g liquid 25 Bis(2,2,3,3,4,4,5,5-octafluoropentyl)-{4- 1,8-Diisocyanato-4- 2,2,3,3,4,4,5,5-Octa- Desmorapid Z 70 C. colourless [({[(2,2,3,3,4,4,5,5-octafluoropentyl)- (isocyanatomethyl)octane fluoropentan-1-ol 11.0 g 0.02 g oil oxy]carbonyl}amino)methyl]octane 1,8- (TIN) 3.98 g diyl}biscarbamate 26 Bis(2,2,3,3,4,4,5,5-octafluoropentyl)-(2,2,4- 2,4,4-Trimethylhexane 1,6- 2,2,3,3,4,4,5,5-Octa- Desmorapid Z 70 C. colourless trimethylhexane-1,6-diyl) biscarbamate diisocyanate (TMDI) 4.67 g fluoropentan-1-ol 10.3 g 0.02 g oil 27 2,2,3,3,4,4,5,5-Octafluoropentyl propan- i-Propyl isocyanate 2,2,3,3,4,4,5,5-Octa- Desmorapid Z 70 C. colourless 2-ylcarbamate 4.02 g fluoropentan-1-ol 10.9 g 0.02 g liquid 28 2,2,3,3,4,4,5,5-Octafluoropentyl Cyclohexyl isocyanate 2,2,3,3,4,4,5,5-Octa- Desmorapid Z 70 C. colourless cyclohexylcarbamate 5.25 g fluoropentan-1-ol 9.73 g 0.02 g liquid 29 Bis(2,2,3,3-tetrafluoropropyl)-[4- 1,8-Diisocyanato-4- 2,2,3,3-Tetrafluoro-1- Desmorapid Z 70 C. colourless ({[(2,2,3,3-tetrafluoro- (isocyanatomethyl)octane propanol 9.16 g 0.02 g oil propoxy)carbonyl]amino}methyl)octan-1,8- (TIN) 5.83 g diyl] biscarbamate 30 Bis(2,2,3,3-tetrafluoropropyl)-(2,2,4- 2,4,4-Trimethylhexane 1,6- 2,2,3,3-Tetrafluoro-1- Desmorapid Z 70 C. colourless trimethylhexane-1,6-diyl) biscarbamate diisocyanate (TMDI) 6.64 g propanol 8.35 g 0.02 g liquid 31 2,2,3,3-Tetrafluoropropyl propan- i-Propyl isocyanate 2,2,3,3-Tetrafluoro- Desmorapid Z 70 C. colourless 2-ylcarbamate 5.87 g propan-1-ol 9.11 g 0.02 g liquid 32 Ethyl hexylcarbamate n-Hexyl isocyanate Ethanol 13.3 g Desmorapid Z 60 C. colourless 36.7 g 0.02 g liquid 33 iso-Propyl hexylcarbamate n-Hexyl isocyanate iso-Propanol 16.0 g Desmorapid Z 60 C. colourless 34.0 g 0.02 g liquid 34 3-Ethyl butylcarbamate n-Butyl isocyanate Ethanol 15.9 g Desmorapid Z 60 C. colourless 34.1 g 0.02 g liquid 35 iso-Propyl butylcarbamate n-Butyl isocyanate iso-Propanol 18.9 g Desmorapid Z 60 C. colourless 31.1 g 0.02 g liquid

Estimation of the Refractive Index (nD20) and of the Volatility (TGA95) of 2,2,2-Trifluoroethyl Butylcarbamate(Example 1)

(128) The three-dimensional structure of the abovementioned compound (Example 1) was generated and preoptimized with the aid of the graphic user interface of the molecular modelling package Materials Studio of Accelrys. This preoptimized structure was then used as input for the conformer analysis, for which a Monte Carlo algorithm was used, which, in each case starting from the conformer generated just beforehand, changes all dihedral angles within the molecule according to the random principle. In this way, 1000 random conformers were generated and directly preoptimized. In the procedure, all conformers which have a relative energy of >8.37 kJ/mol were directly discarded.

(129) After this procedure, all 90 conformers obtained was subsequently optimized using a more stringent convergence criterion and then subjected to a similarity analysis, very similar conformers being discarded. The remaining 34 conformers were then optimized geometrically using the quantum chemistry package TURBOMOLE with the aid of the density functional theory. The B-P86 density functional and the triple valence basis set TZVP, which was taken from the TURBOMOLE basis set library, were used and the COSMO option, using the optimized COSMO radii, was switched on.

(130) For the 22 conformers whose relative DFT/COSMO Energy was <8 kJ/mol, the individual descriptors V.sub.i, A.sub.i and M.sup.2.sub.i were subsequently calculated according to steps e and f of the method according to the invention. For this purpose, the COSMOtherm of COSMOlogic was used. The results are listed in Table 3.

(131) TABLE-US-00003 TABLE 3 Rel. energy Boltzmann Conformer in kJ/mol Weight in % V (.sup.3) A (.sup.2) M.sup.2 1 0.00 15.92 224.534 224.129 69.717 2 0.14 15.02 224.692 224.472 69.698 3 0.46 13.21 223.745 228.546 74.656 4 0.95 10.86 222.437 228.836 74.314 5 1.80 7.70 224.267 226.684 73.407 6 1.90 7.39 224.614 226.738 73.401 7 3.86 3.35 222.143 224.595 74.151 8 3.96 3.22 223.430 227.027 74.845 9 4.09 3.06 224.181 220.790 73.732 10 4.24 2.88 226.841 218.562 73.464 11 5.07 2.06 222.067 227.356 72.800 12 5.08 2.05 224.635 224.359 72.785 13 5.35 1.84 225.926 217.658 76.949 14 5.58 1.68 227.028 216.153 72.131 15 6.32 1.24 222.207 226.866 74.032 16 6.39 1.21 224.162 220.368 71.597 17 6.97 0.95 224.831 226.248 75.008 18 7.55 0.76 224.889 222.006 71.440 19 7.60 0.74 225.386 223.325 75.264 20 7.72 0.71 225.336 225.147 74.730 21 7.88 0.66 221.676 224.815 72.557 22 7.88 0.66 226.532 216.022 73.523

(132) This gives the following as Boltzmann-weighted mean values:

(133) A=225.308 .sup.2, V=224.137 .sup.3, M.sup.2=72.609

(134) It results in the values 85.0 C. and 1.197 g/mol for the volatility (TGA95) and the density.

(135) The molar polarizability was estimated as 40.310 m.sup.3/mol with the aid of the QSPR approach published in 1986 by Crippen and implemented in the Materials Studio QSAR module, which, in combination with the density, results in a refractive index of (n.sub.D.sup.20)=1.3999. The substance, with a TGA95 value of 85.0 C. and a refractive index of 1.3999, is therefore not suitable overall in the context of the selection method according to the invention as an additive for photopolymer formulations since its estimated volatility is clearly too high. As shown by the comparison with experimental values, this evaluation is correct.

(136) The volatilities and refractive indices of Examples 2-39 were calculated in a manner analogous to that of Example 1 and the results were summarized in Table 4. A further 30 fluorinated urethanes (Examples 2-31), 4 unfluorinated urethanes (Examples 32-35) and four commercial plasticizers (Examples 36-39) are contained therein.

(137) TABLE-US-00004 TABLE 4 Comparison of estimated and experimental refractive indices and TGA95 values. Exam- M/ MP/ (n.sub.D.sup.20) TGA95 (n.sub.D.sup.20) TGA95 ple Name V/.sup.3 A/.sup.2 M.sup.2 (g/mol) (m.sup.3/mol) (QSPR) (QSPR) (QSPR) (Exp.) (Exp.) 2 2,2,2-Trifluoroethyl hexylcarbamate 266.609 268.162 76.273 227.23 49.51 1.146 1.4136 72.2 1.3984 72.5 3 2,2,3,3-Tetrafluoropropyl butylcarbamate 254.440 253.494 94.734 231.19 44.09 1.241 1.3893 86.5 1.3879 71.6 4 Bis(2,2,2-trifluoroethyl)-(2,2,4- 449.384 412.813 142.624 410.35 83.03 1.285 1.4333 135.5 1.4202 167.1 trimethylhexane-1,6-diyl) biscarbamate 5 Bis(2,2,2-trifluoroethyl)-[4-({[(2,2,2- 571.236 540.825 214.491 551.40 103.39 1.384 1.4322 172.5 1.4213 174.9 trifluoroethoxy)carbonyl]amino}methyl)- octane-1,8-diyl] biscarbamate 6 2,2,3,3,4,4,4-Heptafluorobutyl 299.099 285.161 71.344 299.19 49.65 1.372 1.3727 75.5 1.3625 69.8 butylcarbamate 7 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- 476.888 415.268 92.904 531.23 72.10 1.569 1.3459 116.6 1.3555 111.8 Hexadecafluorononyl butylcarbamate 8 Bis(2,2,3,3,4,4,4-heptafluorobutyl)- 606.335 522.310 136.852 610.38 101.71 1.432 1.3930 151.5 1.3887 139.1 (2,2,4-trimethylhexane-1,6-diyl) biscarbamate 9 Bis(2,2,3,3,4,4,4-heptafluorobutyl)-[4- 813.142 689.703 193.478 851.44 131.40 1.517 1.3846 191.3 1.3876 159.7 ({[(2,2,3,3,4,4,4-heptafluorobutoxy)- carbonyl]amino}methyl)octane- 1,8-diyl] biscarbamate 10 2,2,3,3,4,4,5,5,5-Nonafluoropentyl 336.687 311.927 73.341 349.19 54.31 1.433 1.3640 83.5 1.3580 72.8 butylcarbamate 11 Bis(2,2,3,3,4,4,5,5,5-nonafluoropentyl)- 683.549 574.484 135.816 710.40 111.04 1.484 1.3807 160.5 1.3820 157 (2,2,4-trimethylhexane-1,6-diyl) biscarbamate 12 2,2,3,3,4,4,5,5,5-Nonafluoropentyl 379.492 352.267 73.741 377.25 63.52 1.369 1.3780 89.9 1.3690 83.5 hexylcarbamate 13 2,2,3,3,4,4,5,5,5-Nonafluoropentyl 315.705 289.954 70.340 335.17 49.61 1.469 1.3541 79.0 1.3497 58.5 propan-2-ylcarbamate 14 2,2,3,3,4,4,5,5,6,6,6-Undecafluorohexyl 374.581 335.864 68.869 399.20 58.98 1.479 1.3560 87.7 1.3538 82.6 butylcarbamate 15 Bis(2,2,3,3,4,4,5,5,6,6,6- 757.048 613.121 134.098 810.41 120.38 1.536 1.3736 169.4 1.3750 152.7 undecafluorohexyl)-(2,2,4-trimethyl- hexane-1,6-diyl) biscarbamate 16 2,2,3,3,4,4,5,5,6,6,6-Undecafluorohexyl 416.853 379.371 73.759 427.25 68.18 1.419 1.3704 96.4 1.3640 90 hexylcarbamate 17 Bis(2,2,3,3,4,4,5,5,6,6,7,7- 811.336 671.039 176.795 874.44 127.93 1.560 1.3739 187.5 1.3839 158.6 dodecafluoroheptyl)-(2,2,4- trimethylhexane-1,6-diyl) biscarbamate 18 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl 445.778 401.101 94.859 459.27 71.96 1.440 1.3690 112.1 1.3716 117.6 hexylcarbamate 19 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro- 381.492 338.779 91.463 417.19 58.05 1.534 1.3470 103.0 1.3563 93.3 heptylpropan-2-yl carbamate 20 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl 430.049 369.790 83.268 457.25 69.90 1.491 1.3731 105.9 1.3830 123.7 cyclohexylcarbamate 21 2,2,3,4,4,4-Hexafluorobutyl 291.826 273.825 90.643 281.20 49.25 1.332 1.3829 90.0 1.3775 73.8 butylcarbamate 22 2,2,3,4,4,4-Hexafluorobutyl 335.639 313.390 92.270 309.25 58.45 1.271 1.3959 95.5 1.3876 89.5 hexylcarbamate 23 2,2,3,4,4,4-Hexafluorobutyl propan-2- 269.738 259.029 91.749 267.17 44.54 1.368 1.3733 87.7 1.3682 71.5 ylcarbamate 24 2,2,3,3,4,4,5,5-Octafluoropentyl 330.134 303.188 88.913 331.20 53.42 1.393 1.3674 93.7 1.3731 80.5 butylcarbamate 25 Bis(2,2,3,3,4,4,5,5-octafluoropentyl)-{4- 895.878 763.826 254.799 947.50 142.73 1.552 1.3840 215.0 1.3955 172.5 [({[(2,2,3,3,4,4,5,5-octafluoropentyl)- oxy]carbonyl}amino)methyl]octane-1,8- diyl} biscarbamate 26 Bis(2,2,3,3,4,4,5,5-octafluoropentyl)- 667.015 566.787 174.890 674.42 109.26 1.457 1.3880 172.4 1.3971 163.9 (2,2,4-trimethylhexane-1,6-diyl) biscarbamate 27 2,2,3,3,4,4,5,5-Octafluoropentyl propan-2- 308.600 286.261 90.842 317.18 48.72 1.429 1.3577 92.3 1.3654 74.4 ylcarbamate 28 2,2,3,3,4,4,5,5-Octafluoropentyl- 355.202 319.977 87.653 357.24 60.56 1.400 1.3905 96.7 1.3977 110.5 cyclohexylcarbamate 29 Bis(2,2,3,3-tetrafluoropropyl)-[4- 668.003 606.741 275.686 647.45 114.73 1.417 1.4162 202.8 1.4240 197.9 ({[(2,2,3,3-tetrafluoropropoxy)- carbonyl]amino}methyl)octane-1,8- diyl]biscarbamate 30 Bis(2,2,3,3-tetrafluoropropyl)-(2,2,4- 517.127 461.959 184.103 474.39 90.59 1.313 1.4155 161.6 1.4229 185.3 trimethylhexane-1,6-diyl) biscarbamate 31 2,2,3,3-Tetrafluoropropyl propan-2- 234.335 231.845 93.129 217.16 39.38 1.268 1.3770 85.2 1.3831 78.1 ylcarbamate 32 Ethyl hexylcarbamate 241.340 247.593 72.851 173.26 48.81 0.941 1.4431 65.5 1.4376 83.9 33 iso-Propyl hexylcarbamate 264.827 264.082 70.384 187.28 53.23 0.930 1.4413 67.9 1.4336 84.9 34 3 Ethyl butylcarbamate 197.717 207.505 71.325 145.20 39.61 0.960 1.4367 59.2 1.4313 66.1 35 iso-Propyl butylcarbamate 220.538 224.943 68.619 159.23 44.03 0.946 1.4361 60.1 1.4284 63.9 36 Propylene carbonate 115.733 128.139 71.612 102.09 21.49 1.167 1.4059 64.3 1.4210 87 37 Dimethyl adipate 221.881 226.334 97.343 174.20 42.28 1.055 1.4256 86.5 1.4280 80.4 38 Diethylene glycol diacetate 231.636 242.845 113.550 190.19 43.90 1.110 1.4261 97.9 1.4300 99.1 39 Triethyl citrate 328.385 305.298 134.859 276.28 64.18 1.174 1.4575 123.9 1.4420 131
Comparison Between Experimental and Estimated TGA95 and Refractive Index Values

(138) The comparison between the experimental refractive indices and TGA95 values of Examples 1-39 and those estimated by the selection method according to the invention (Table 4), which is illustrated in the correlation diagrams in FIG. 3 and FIG. 4, clearly show the suitability of the method. The refractive indices could be determined with a standard deviation of 0.0082, the maximum error over the total set, with an absolute value of 0.0155 for Example 39, likewise being very small. The standard deviation for the TGA95 values is 15.8 C., with an absolute maximum error of 42.5 C. for the fluorinated urethane of Example 25. However, this comparatively large error is not significant since both the experimental value of 172.5 C. and the estimated value of 215.0 C. are substantially above the suitability limit of 100 C. Thus, in spite of the error, the compound is correctly classed by the method according to the invention as being suitable as an additive for photopolymer formulations. In general, it may be stated that very large differences between predicted and experimental TGA95 typically occur in the case of comparatively high absolute values (typically >150 C.), which is attributable to incipient decomposition of the substances. This fact does not imply any limitation of the informative power of the selection method according to the invention since the threshold value for the suitability of the substance at 100 C. is typically well below the decomposition temperature of customary additive molecules.

(139) Selection of the Example Molecules on the Basis of the Method According to the Invention

(140) The refractive indices of Examples 1-39 are all below 1.4600. In this case, the TGA95 estimated by the method according to the invention are therefore decisive regarding the suitability as additives in photopolymer formulations. All examples whose estimated volatility, according to TGA95, is greater than 100 C. are summarized in Table 5.

(141) TABLE-US-00005 TABLE 5 Additives selected according to the invention. (n.sub.D.sup.20) (n.sub.D.sup.20) TGA95 Example (QSPR) TGA95(QSPR) (Exp.) (Exp.) 4 1.4333 135.5 1.4202 167.1 5 1.4322 172.5 1.4213 174.9 7 1.3459 116.6 1.3555 111.8 8 1.3930 151.5 1.3887 139.1 9 1.3846 191.3 1.3876 159.7 11 1.3807 160.5 1.3820 157.0 15 1.3736 169.4 1.3750 152.7 17 1.3739 187.5 1.3839 158.6 18 1.3690 112.1 1.3716 117.6 19 1.3470 103.0 1.3563 93.3 20 1.3731 105.9 1.3830 123.7 25 1.3840 215.0 1.3955 172.5 26 1.3880 172.4 1.3971 163.9 29 1.4162 202.8 1.4240 197.9 30 1.4155 161.6 1.4229 185.3 39 1.4575 123.9 1.4420 131.0

(142) Examples 7 and 17 which, owing to their low refractive indices and the sufficiently high volatility, should be very efficient are selected for an experimental investigation of the holographic activity. The compound 2 which, with an estimated volatility of 72.2 C., is substantially outside the limits of the method according to the invention is selected as a comparative example.

Preparation of the Photopolymer Formulation for the Production of Holographic Films

Film Example 1

(143) 6.77 g of the polyol component prepared as described above were mixed with 4.00 g of phosphorothioyltris(oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate (urethane acrylate 1), 4.00 g of 2-({[3-(methylsulphanyl)phenyl]carbamoyl}oxy)propylprop-2-enoate (urethane acrylate 2) 3.00 g of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl butylcarbamate (Example 7), 0.02 g of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA), 0.30 g of CGI 909 (experimental product of Ciba Inc, Basle, Switzerland), 0.03 g of new methylene blue, 0.06 g of BYK 310 and 1.02 g of N-ethylpyrrolidone at 60 C. so that a clear solution was obtained. Thereafter, cooling to 30 C. was effected, 1.25 g of Desmodur N3900 (commercial product of Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%) were added and mixing was effected again. The liquid material obtained is then applied by means of a knife coater to a 36 m thick polyethylene terephthalate film and dried for 4.5 minutes at 80 C. in an air circulation dryer. Thereafter, the photopolymer layer is covered with a 40 m thick polyethylene film and rolled up.

Film Example 2

(144) 6.77 g of the polyol component prepared as described above were mixed with 4.00 g of phosphorothioyltris(oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate (urethane acrylate 1), 4.00 g of 2-({[3-(methylsulphanyl)phenyl]carbamoyl}oxy)propylprop-2-enoate (urethane acrylate 2) 3.00 g of bis(2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl)-(2,2,4-trimethylhexane-1,6-diyl) biscarbamate (Example 17), 0.02 g of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA), 0.30 g of CGI 909 (experimental product of Ciba Inc, Basle, Switzerland), 0.03 g of new methylene blue, 0.06 g of BYK 310 and 1.02 g of N-ethylpyrrolidone at 60 C. so that a clear solution was obtained. Thereafter, cooling to 30 C. was effected, 1.25 g of Desmodur N3900 (commercial product of Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%) were added and mixing was effected again. The liquid material obtained is then applied by means of a knife coater to a 36 m thick polyethylene terephthalate film and dried for 4.5 minutes at 80 C. in an air circulation dryer. Thereafter, the photopolymer layer is covered with a 40 m thick polyethylene film and rolled up.

Comparative Film Example 1

(145) 6.77 g of the polyol component prepared as described above were mixed with 4.00 g of phosphorothioyltris(oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate (urethane acrylate 1), 4.00 g of 2-({[3-(methylsulphanyl)phenyl]carbamoyl}oxy)propylprop-2-enoate (urethane acrylate 2) 3.00 g of 2,2,2-trifluoroethyl butylcarbamate (Example 1), 0.02 g of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA), 0.30 g of CGI 909 (experimental product of Ciba Inc, Basle, Switzerland), 0.03 g of new methylene blue, 0.06 g of BYK 310 and 1.02 g of N-ethylpyrrolidone at 60 C. so that a clear solution was obtained. Thereafter, cooling to 30 C. was effected, 1.25 g of Desmodur N3900 (commercial product of Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%) were added and mixing was effected again. The liquid material obtained is then applied by means of a knife coater to a 36 m thick polyethylene terephthalate film and dried for 4.5 minutes at 80 C. in an air circulation dryer. Thereafter, the photopolymer layer is covered with a 40 m thick polyethylene film and rolled up.

(146) TABLE-US-00006 TABLE 6 Holographic evaluation of film examples Example, [% by weight] n Film Example 1 7, 15 0.038 2 17, 15 0.032 Comparative film example 1 2, 15 0.012

(147) The values described by n were obtained at doses of 4-32 mJ/cm.sup.2.

(148) The values found for the holographic property n of the holographic media show that the additives selected by the method according to the invention are better suited for use in holographic photopolymer films.