EP2766902A1 - Réactifs de transfert de chaîne soufrés dans des formulations photopolymères à base de polyuréthane - Google Patents

Réactifs de transfert de chaîne soufrés dans des formulations photopolymères à base de polyuréthane

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Publication number
EP2766902A1
EP2766902A1 EP12770130.8A EP12770130A EP2766902A1 EP 2766902 A1 EP2766902 A1 EP 2766902A1 EP 12770130 A EP12770130 A EP 12770130A EP 2766902 A1 EP2766902 A1 EP 2766902A1
Authority
EP
European Patent Office
Prior art keywords
photopolymer formulation
formulation according
photopolymer
substituted
chain transfer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12770130.8A
Other languages
German (de)
English (en)
Inventor
Marc-Stephan Weiser
Friedrich Bruder
Thomas RÖLLE
Thomas Fäcke
Dennis Hönel
Horst Berneth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Intellectual Property GmbH
Original Assignee
Bayer Intellectual Property GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Intellectual Property GmbH filed Critical Bayer Intellectual Property GmbH
Priority to EP12770130.8A priority Critical patent/EP2766902A1/fr
Publication of EP2766902A1 publication Critical patent/EP2766902A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/2403—Layers; Shape, structure or physical properties thereof
    • G11B7/24035—Recording layers
    • G11B7/24044—Recording layers for storing optical interference patterns, e.g. holograms; for storing data in three dimensions, e.g. volume storage
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/245—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing a polymeric component

Definitions

  • the present invention relates to a photopolymer formulation comprising matrix polymers A) obtainable by reacting at least one polyisocyanate component a) and one isocyanate-reactive component b), a writing monomer B), a photoinitiator C) and a catalyst D).
  • a holographic medium containing or obtainable by use of a photopolymer formulation according to the invention, the use of a photopolymer formulation according to the invention for the preparation of holographic media and a process for the production of a holographic medium using a photopolymer formulation according to the invention.
  • Photopolymer formulation of the type mentioned are known from WO 201 1/054797 and WO 201 1/067057 known. They can be used to make holographic media. Visually visible holograms can be imprinted in the holographic media. It is also possible to use them for the production of holographic-optical elements. Visual holograms include all holograms that can be recorded by methods known to those skilled in the art.
  • holograms include in-line (Gabor) holograms, off-axis holograms, full-aperture transfer holograms, white-light transmission holograms ("rainbow holograms"), denisy-hologram, off-axis reflection holograms, edge-lit holograms, and flolographic stereograms
  • optical elements are lenses, mirrors, deflection mirrors, filters, diffusers, diffractive elements, optical fibers, waveguides, projection screens and masks.
  • transmission holograms and optical elements it is important that the holgraphic medium has a high transparency after the exposure and fixation of the hologram.
  • polyurethane-based photopolymer formulations can be used to prepare the holographic media.
  • the necessary high transparency is achieved, for example, when using formulations for holographic data storage as described in WO 2003/102959 and in WO 2008/125229.
  • multiplexing the writing of many weak follicles in the same volume or in overlapping volumes
  • only a small conversion of the radical photochemistry is achieved in each exposure step.
  • holographic media which are used both for the production of visually visible holograms and holographic-optical elements (HOEs)
  • the complete photochemistry is reacted in a single exposure step.
  • a sulfur-containing chain transfer agent E is understood as meaning a compound which has at least one covalent bond capable of homolytic radical formation and at least one sulfur atom.
  • Chain transfer agent E one or more compounds selected from the group of monofunctional thiols, multifunctional thiols, preferably primary thiols or at least difunctional secondary thiols, disulfides and thiophenols.
  • the sulfur-containing chain transfer agent E) comprises one or more compounds selected from the group consisting of , di- and multifunctional primary thiols or at least difunctional secondary thiols, preferably mono-, di- and multifunctional aliphatic thiols having primary thio groups and very particularly preferably n-alkylthiols having 8 to 18 carbon atoms and mercaptoesters of mono- and polyfunctional aliphatic alcohols with 1 to 18 carbon atoms.
  • the chain transfer agent E comprises one or more compounds selected from the group consisting of w-octylthiol, w-hexylthiol, n-decylthiol, -dodecylthiol, 11,1 1 -dimethyldodecane-1-thiol, 2-phenylethylmercaptan, 1, 8-dithionaphthalene, octane-1, 8-dithiol.
  • polyisocyanate component a it is possible to use all compounds which are 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 be aromatic, araliphatic, aliphatic or cycloaliphatic. In minor amounts, it is also possible to use monoisocyanates and / or polyisocyanates containing unsaturated groups.
  • the polyisocyanates of component a) are particularly preferably di- or oligomerized aliphatic and / or cycloaliphatic di- or tnisocyanates.
  • NCO-functional prepolymers with urethane, allophanate, biuret and / or amide groups are obtained in a manner well-known to the person skilled in the art by reacting monomeric, oligomeric or polyisocyanates a1) with isocyanate-reactive compounds a2) in suitable stoichiometry with the optional use of catalysts and solvents.
  • Suitable polyisocyanates a1) are all aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates and tnisocyanates known to those skilled in the art, it being immaterial whether these were obtained by phosgenation or by phosgene-free processes.
  • the higher molecular weight secondary products of monomeric di- and / or triisocyanates with urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione, iminooxadiazinedione structure, which are well known per se, can also be used each be used individually or in any mixtures with each other.
  • Suitable monomeric di- or triisocyanates which can be used as component al) are butylene diisocyanate, hexamethylene diisocyanate (H Dl), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TM DI). l, 8-diisocyanato-4- (isocyanatomethyl) octane, isocyanatomethyl-1, 8-octane diisocyanate (TIN), 2,4- and / or 2,6-toluene diisocyanate.
  • H Dl hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • TM DI trimethylhexamethylene diisocyanate
  • l 8-diisocyanato-4- (isocyanatomethyl) octane, isocyanatomethyl-1, 8-octane diisocyanate (TIN), 2,4- and / or 2,6
  • Ol l-lun ashamedel le compounds are preferably used. These are analogous to the OH-functional compounds as described below for component b).
  • amines for prepolymer production. Suitable examples are ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, diamino nocyclohexan, diaminobenzene, Diaminobisphenyl, difunctional polyamines such as Jeffamine ®, amine-terminated polymers having number average molecular weights up to 10,000 g / mol or any desired mixtures thereof with one another.
  • isocyanate is reacted in excess with amine to form a biuret group.
  • amines are suitable in this
  • Preferred prepolymers are urethanes, allophanates or biurets of aliphatic isocyanate-functional compounds and oligomeric or polymeric isocyanate-reactive compounds having number average molecular weights of 200 to 10,000 g / mol, particularly preferred are urethanes, allophanates or biurets of aliphatic isocyanate-functional compounds and oligomeric or polymeric polyols or polyamines having number average molecular weights of 500 to 8500 g / mol and very particularly preferred are allophanates of H Dl or TM DI and difunctional polyether polyols having number average molecular weights of 1000 to 8200 g / mol.
  • the prepolymers described above have residual contents of free monomeric isocyanate of less than 1 wt .-%, more preferably less than 0.5 wt .-% and most preferably less than 0.2 wt .-% to.
  • the polyisocyanate component may contain proportionally in addition to the prepolymers described further isocyanate components. Suitable for this purpose are aromatic, araliphatic, aliphatic and cycloaliphatic di-, tri- or polyisocyanates. It is also possible to use mixtures of such di-, tri- or polyisocyanates.
  • Suitable di-, tri- or polyisocyanates are butylene diisocyanate, hexamethylene diisocyanate (I IDI), isophorone diisocyanate (I PDI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, 2,2,4- and / or 2,4, 4-trimethylhexamethylene diisocyanate (TMDI), the isomeric bis (4,4'-isocyanatocyclohexyl) methanes and mixtures thereof of any 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-toluene diisocyanate, 1,5-naphthylene diisocyanate, 2,4'- or 4,
  • the polyisocyanate component a) contains proportionate isocyanates which are partially reacted with isocyanate-reactive ethylenically unsaturated compounds.
  • isocyanate-reactive ethylenically unsaturated compounds ⁇ , ⁇ -unsaturated carboxylic acid derivatives such as acrylates, methacrylates, maleate, fumarates, maleimides, acrylamides, and vinyl ether, Propenyiether, AUylether and dicyclopentadienyl units containing compounds having at least one isocyanate-reactive group used.
  • 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 2-1-hydroxyethyl (meth) acrylate, polyethylene oxide mono (meth) acrylates, polypropylene oxide mono (methacrylates, polyalkylene oxide mono (meth) acrylates, poly (e-caprolactone) mono (meth) acrylates, such as Tone ® Ml 00 (Dow, USA), 2-hydroxypropyl (meth) acrylate, 4-i lydroxy- butyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, the hydroxyfunctional mono- , Di- or tetra (meth) acrylates of polyhydric alcohols, such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, gly
  • the abovementioned polyisocyanate component a) contains completely or proportionally isocyanates which are completely or partially reacted with blocking agents known to the person skilled in the art from coating technology.
  • blocking agents which may be mentioned are: alcohols, lactams, oximes, malonic esters, alkyl acetoacetates, triazoles, phenols, imidazoles, pyrazoles and amines, such as e.g.
  • Butanone oxime diisopropylamine, 1, 2,4-triazole, ethyl-1, 2,4-triazole, imidazole, diethyl malonate, acetoacetic ester, acetone oxime, 3,5-dimethylpyrazole, ⁇ -caprolactam, N-tert-butylbenzylamine, cyclopentanonecarboxyethyl ester or any mixtures of these blocking agents.
  • the polyisocyanate component is an aliphatic polyisocyanate or an aliphatic prepolymer and preferably an aliphatic polyisocyanate or prepolymer with primary NCO groups.
  • isocyanate-reactive component b) it is possible to use all polyfunctional, isocyanate-reactive compounds per se, which on average are at least 1 .5 isocyanate-reactive
  • Isocyanate-reactive groups in the context of the present invention are preferably hydroxy, amino or thio groups, especially preferred are hydroxy compounds.
  • Suitable polyfunctional, isocyanate-reactive compounds are, for example, polyester, polyether, polycarbonate, poly (meth) acrylate and / or polyurethane polyols.
  • Suitable polyester polyols are, for example, linear polyester diols 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> 2.
  • di- or polycarboxylic acids or anhydrides examples include succinic, glutaric, adipic, pimelic, cork, azelaic, sebacic, nonanedicarboxylic, decanedicarboxylic, terephthalic, isophthalic, o-phthalic, Tetrahydrophthalic, hexahydrophthalic or trimellitic acid and acid anhydrides such as o-phthalic, trimellitic or succinic anhydride or any mixtures thereof with one another.
  • suitable alcohols are ethanediol, di-, tri-, tetraethylene glycol, 1,2-propanediol, di-, tri-, tetrapropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, butanediol -2,3, pentanediol-1,5, hexanediol-1, 6, 2,2-dimethyl-l, 3-propanediol, 1, 4-dihydroxycyclohexane, 1, 4-dimethylolcyclohexane, octanediol-1,8, decanediol - 1, 10, üodecandiol- 1.12, trimethylolpropane, glycerol or any mixtures thereof.
  • the polyester polyols can also be based on natural raw materials such as castor oil. It is likewise possible that the polyesterpolyols are based on homo- or copolymers of lactones, as they are preferably by addition of lactones or lactone mixtures such as butyrolactone, ⁇ -caprolactone and / or methyl-e-caprolactone to hydroxy-functional compounds such as polyhydric alcohols of an OH -Functionality> 2, for example, the type mentioned above can be obtained.
  • polyester polyols preferably have number-average molar masses of from 400 to 4000 g / mol, particularly preferably from 500 to 2000 g / mol.
  • Their OH functionality is preferably 1.5 to 3.5, more preferably 1.8 to 3.0.
  • Suitable polycarbonate polyols are obtainable in a manner known per se by reacting organic carbonates or phosgene with diols or diol mixtures.
  • Suitable organic carbonates are dimethyl, diethyl and diphenyl carbonate.
  • Suitable diols or mixtures include the polyhydric alcohols of an OH functionality> 2, preferably 1,4-butanediol, 1,6-hexanediol and / or 3-methylpentanediol, which are per se in the context of the polyester segments, or also polyester polyols can be added to polycarboxylic be re-processed.
  • Such polycarbonate polyols preferably have number-average molar masses of from 400 to 4000 g / mol, particularly preferably from 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.
  • Suitable polyether polyols are optionally block-formed polyaddition products of cyclic ethers on Ol I or NH-functional starter molecules.
  • Suitable cyclic ethers are, for example, styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, and any desired mixtures thereof.
  • the starter used may be the polyhydric alcohols of an OH functionality> 2 mentioned in the context of the polyesterpolyols and also primary or secondary amines and aminoalcohols.
  • Preferred polyether polyols are those of the aforementioned type exclusively based on propylene oxide or random or block copolymers based on propylene oxide with further 1-alkylene oxides, wherein the 1 - Alykenoxidanteil is not higher than 80 wt .-%.
  • Particular preference is given to propylene oxide homopolymers and also random or block copolymers which contain oxyethylene, oxypropylene and / or oxybutylene units, the proportion of oxypropylene units, based on the total amount of all oxyethylene, oxypropylene and oxybutylene units, being at least 20% by weight at least 45% by weight.
  • Oxypropylene and oxybutylene here include all respective linear and branched C3 and C4 isomers.
  • Such polyether polyols preferably have number-average molar masses of from 250 to 10,000 g / mol, more preferably from 500 to 8500 g / mol and very particularly preferably from 600 to 4500 g mol.
  • the OH functionality is preferably from 1.5 to 4.0, particularly preferably
  • R is a hydrogen, alkyl, or aryl radical which may also be substituted or interrupted by heteroatoms (such as ether oxygens)
  • Y is the underlying starter and the Proportion of the segments X. based on the total amount of the segments X. and Y is at least 50 wt .-%.
  • the outer blocks X. make up at least 50% by weight, preferably 66% by weight, of the total molar mass of Y (Xi-H) n and consist of monomer units which conform to the formula I.
  • n in Y (X; -H) is a number from 2 to 6, more preferably 2 or 3, and most preferably equal to 2.
  • Y (Xi-H) n a number from 1 to 6, especially preferably from 1 to 3 and most preferably equal to 1.
  • R is preferably a hydrogen, a methyl, butyl, Hcxyl- or octyl group or an ether group-containing alkyl radical.
  • Preferred ether group-containing alkyl radicals are those based on oxyalkylene units.
  • the multiblock copolymers Y (Xj-! I) "preferably have number average molecular weights of more than 1200 g / mol, more preferably more than 1950 g / mol, but preferably not more than 12000 g / mol, particularly preferably not more than 8000 g mol.
  • the blocks X. may be homopolymers of exclusively identical oxyalkylene repeat units. They can also be constructed statistically from different oxyalkylene units or in turn blockwise from different oxyalkylene units.
  • the X.sup.- segments are based exclusively on propylene oxide or random or blockwise mixtures of propylene oxide with further 1-alkylene oxides, the proportion of further 1-alkylene oxides being not higher than 80% by weight.
  • segments X are as segments X, propylene oxide homopolymers and random or block copolymers, the oxyethylene and / or oxypropylene units, wherein the proportion of oxypropylene units based on the total amount of all oxyethylene and oxypropylene at least 20 wt .-%, preferably at least 40 wt .-%.
  • the blocks X. are added as described below by ring-opening polymerization of the above-described alkylene oxides onto an n-fold hydroxy- or amino-functional starter block Y (H) n .
  • the inner block Y which is contained to less than 50 wt .-%, preferably from less than 34 wt .-% in Y (X - 1 1) n , consists of di- and / or higher hydroxy-functional polymer structures based on cyclic ethers or is constructed from di- and / or higher hydroxy-functional polycarbonate, polyester, poly (meth) acrylate, epoxy resin and / or polyurethane structural units or corresponding hybrids.
  • Suitable polyester polyols are linear polyester diols or branched polyester polyols, as in a known manner from aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or their anhydrides such as.
  • ethanediol di-, tri-, tetraethylene glycol, 1, 2-propanediol, Di-, tri-, tetra-propylene glycol, 1,3-propanediol, butanediol-1, 4, butanediol-1,3, butanediol-2,3, pentanediol-1,5, hexanediol-1,2,6,2,2-dimethyl- l, 3-propanediol, 1, 4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, octanediol-1,8, decanediol-1,10, dodecane-1,12 or mixtures thereof, optionally with the concomitant use of higher functional polyols such as trimethylolpropane or glycerol can be prepared ,
  • higher functional polyols such as trimethylolpropane or glycerol
  • polyesters can also be based on natural raw materials such as castor oil. It is also possible that the polyester polyols are based on homo- or copolymers of lactones, as preferred by addition of lactones or lactone mixtures such as butyrolactone, ⁇ -caprolactone and / or methyl-e-caproiactone to hydroxy-functional compounds such as polyhydric alcohols of an OH functionality of preferably 2, for example of the type mentioned above, can be obtained.
  • Such polyester polyols preferably have number-average molar masses of from 200 to 2000 g / mol, more preferably from 400 to 1400 g / mol.
  • Suitable polycarbonate polyols are obtainable in a manner known per se by reacting organic carbonates or phosgene with diols or diol mixtures.
  • Suitable organic carbonates are dimethyl, diethyl and diphenyl carbonate.
  • Suitable diols or mixtures include the polyhydric alcohols of an OFI functionality of 2, preferably 1,4-butanediol, 1,6-hexanediol and / or 3-methylpentanediol, which are known per se in the context of the polyesterpolyols.
  • Polyester polyols can also be converted into polycarbonate polyols. Particular preference is given to using dimethyl or diethyl carbonate in the reaction of the stated alcohols to form polycarbonate polyols.
  • Such polycarbonate polyols preferably have number average molecular weights of from 400 to 2000 g / mol, particularly preferably from 500 to 1400 g / mol and very particularly preferably from 650 to 1000 g / mol.
  • Suitable polyether polyols are optionally blockwise polyaddition products of cyclic ethers to OH- or NH-functional starter molecules.
  • polyether polyols z.
  • Example the polyaddition of styrene oxides, ethylene oxide, propylene oxide, tetra- hydrofuran, butylene oxide, epichlorohydrins, and their Mischadditions- and grafting products, as well as by condensation of polyhydric alcohols or mixtures thereof and the polyether polyols obtained by alkoxylation of polyhydric alcohols, amines and amino alcohols.
  • Suitable polymers of cyclic ethers are in particular polymers of tetrahydrofuran.
  • polyhydric alcohols mentioned in the context of the polyesterpolyols and primary or secondary amines and amino alcohols of an Ol I or l I functionality of 2 to 8, preferably 2 to 6, particularly preferably 2 to 3, very particularly preferably the same 2 are used.
  • Such polyether polyols preferably have number-average molecular weights of from 200 to 2000 g / mol, particularly preferably from 400 to 1400 g / mol and very particularly preferably from 650 to 1000 g / mol.
  • polyether polyols used for starters the polymers of tetrahydrofuran are preferably used.
  • mixtures of the components described above for the inner block Y can be used.
  • Preferred components for the inner block Y are polymers of tetrahydrofuran and aliphatic polycarbonate polyols and polyester polyols, as well as polymers of ⁇ -caprolactone mi number average molecular weights less than 3100 g / mol.
  • Particularly preferred components for the inner block Y are difunctional polymers of tetrahydrofuran as well as difunctional aliphatic polycarbonate polyols and polyester polyols, as well as polymers of ⁇ -caprolactone having number-average molar masses of less than 3100 g / mol.
  • starter segment Y is based on difunctional, aliphatic polycarbonate polyols, poly (e-caprolactone) or polymers of tetrahydrofuran with number-average molar masses greater than 500 g / mol and less than 2100 g / mol.
  • Preferably used block copolymers of structure Y (.X, -il) consist of more than 50 weight percent of the above-described blocks X, and have a number average total molecular weight of greater than 1200 g / mol.
  • Particularly preferred block copolyols consist of less than 50 percent by weight of aliphatic polyester, aliphatic polycarbonate polyol or polyTHF and more than 50 percent by weight of the blocks X described above according to the invention, and have a number average molecular weight of greater than 1200 g mol.
  • Particularly preferred block copolymers consist of less than 50 weight percent aliphatic polycarbonate polyol, poly (e-caprolactone) or poly-THF and more than 50 weight percent of the blocks described above as X invention and have a number average molecular weight of greater than 1 200 g ' mol.
  • block copolymers consist of less than 34% by weight of aliphatic polycarbonate polyol, poly (e-caprolactone) or polyTHF and more than
  • the described block copolyols are prepared by Alkylenoxidadditionssupervised.
  • writing monomer B one or more different compounds which exhibit polymerization-reactive groups (radiation-curing groups) under the influence of actinic radiation with ethylenically unsaturated compounds and are themselves free of NCO groups are used.
  • the writing monomers are preferably acrylates and / or methacrylates. Very particular preference is given to urethane acrylates and urethane (meth) acrylates.
  • the writing monomer B) comprises at least one mono- and / or one multifunctional writing monomer, which may in particular be mono- and multi-functional acrylate writing monomers. More preferably, the writing monomer may comprise at least one monofunctional and one multifunctional urethane (meth) acrylate.
  • the acrylate random monomers may in particular be compounds of the general formula (I)
  • R 2 are independently hydrogen, linear, branched, cyclic or heterocyclic unsubstituted or optionally substituted with hetero atoms organic radicals.
  • R 2 is particularly preferably hydrogen or methyl and / or R 1 is a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by heteroatom-substituted organic radical.
  • unsaturated compounds such as ⁇ , ⁇ -unsaturated carboxylic acid derivatives such as acrylates, methacrylates, maleinates, fumarates, maleimides, acrylamides, further vinyl ethers, propenyl ethers, A lily lether and dicyclopentadienyl units containing compounds as well as olefinically unsaturated compounds such.
  • Acrylates or methacrylates are generally esters of acrylic acid or methacrylic acid.
  • Examples of acrylates and methacrylates which can be used are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, n-
  • Urethane acrylates are understood as meaning compounds having at least one acrylic acid ester group which additionally have at least one urethane bond. It is known that such compounds can be obtained by reacting a hydroxy-functional acrylic ester with an isocyanate-functional compound.
  • suitable isocyanate-functional compounds are aromatic, araliphatic, aliphatic and cycloaliphatic di-, tri- or polyisocyanates. It is also possible to use mixtures of such di-, tri- or polyisocyanates.
  • suitable di-, tri- or polyisocyanates are butylene diisocyanate, hexamethylene diisocyanate (I lül).
  • Isopho ondi isocyanate (IPDI), l, 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 of any 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-toluene diisocyanate, 1,5- naphthylene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate, 1, 5 -Naphthylendiisocyanat, m- Methy
  • Aromatic or araliphatic di-, tri- or polyisocyanates are preferred.
  • Suitable hydroxy-functional acrylates or methacrylates for the preparation of urethane acrylates 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 (e) caprolactone) mono (meth) acrylates, such as Tone ® Ml 00 (Dow, Schwalbach, Germany), 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyi- ( meth) acrylate, hydroxypropyl (meth) acrylate,
  • polyhydric alcohols such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol
  • oligomeric or polymeric unsaturated acrylate and / or methacrylate groups containing compounds alone or in combination with the aforementioned monomeric compounds are suitable.
  • urethane acrylates obtainable from the reaction of tris (p-isocyanatophenyl) thiophosphate and m-methylthiophenyl isocyanate with alcohol-functional acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.
  • the photoinitiators C) used are usually activatable by actinic radiation compounds that can trigger a polymerization of the corresponding groups.
  • photoinitiators In the photoinitiators, a distinction can be made between unimolecular (type I) and bimolecular (type II) initiators. Furthermore, depending on their chemical nature, they are differentiated into photoinitiators for radical, anionic, cationic or mixed type of polymerization.
  • Type I photoinitiators for radical photopolymerization form free radicals upon irradiation by unimolecular bond cleavage.
  • type I photoinitiators are triazines, such as. Tris (trichloromethyl) triazine, oximes, benzoin ethers, benzil ketals, alpha-alpha-dialkoxyacetophenone, phenylglyoxylic acid esters, bis-imidazoles, aroylphosphine oxides, e.g. 2,4,6-trimethyl-benzoyl-diphenylphosphine oxide, sulfonium and iodonium salts.
  • Tris (trichloromethyl) triazine oximes
  • benzoin ethers benzil ketals
  • alpha-alpha-dialkoxyacetophenone phenylglyoxylic acid esters
  • bis-imidazoles bis-imidazoles
  • aroylphosphine oxides e.g. 2,4,6-trimethyl-benzoyl-diphenylphosphine oxide
  • Radical polymerization type II photoinitiators undergo a bimolecular reaction upon irradiation, the excited state photoinitiator reacting with a second molecule, the coinitiator, and the polymerization initiating by electron or proton transfer or direct hydrogen abstraction Radical forms.
  • type-ii photoinitiators are quinones, such as. B. camphorquinone, aromatic keto compounds, such as. Benzophenones in combination with tertiary amines, alkylbenzophenones, halogenated benzophenones, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), anthrone, methyl p- (dimethylamino) benzoate, thioxanthoe, ketocoum - Arynes, alpha-aminoalkylphenone, alpha-lydt oxyalkylphenon and cationic dyes, such as methylene blue, in combination with tertiary amines.
  • type I and type I For the UV and short-wave visible range, type I and type I
  • Pbotoinitiatoren used, for the longer-wavelength visible light range are mainly type I photoinitiators used.
  • photoinitiator systems described in EP 0 223 587 A consisting of a mixture of an ammonium alkylaryl borate and one or more dyes, can also be used as the photoinitiator of type 11 for free-radical polymerization.
  • ammonium alkylaryl borate for example, tetrabutylammonium triphenylhexyl borate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinapthyl-hexylborate, tetrabutylammonium tris (4-tert-butyl) -phenylbutylborate, tetrabutylammonium tris- (3-fluorophenyl) -hexylborate, tetramethylammonium triphenylbenzylborate, tetra (n-hexyl ) ammonium (sec-butyl) triphenylborate, 1-methyl-3-octylimidazolium dipentyldiphenylborate, and tetrabutylammonium tris (3-chloro-4-methylphenyl) hexylborate (Cunningham et al
  • the photoinitiators used for the anionic polymerization are usually type I
  • chromium salts such as trans-Cr (H3) 2 (NCS) 4 " (Kutal et al, Macromolecules 1991, 24, 6872) or fen ocenyl compounds (Yamaguchi et al., Macromolecules 2000, 33, 1 152
  • anionic polymerization is the use of
  • Dyes such as crystal violet leuconitrile or malachite green leuconitrile, which can polymerize cyanoacrylates by photolytic decomposition (Neckers et al., Macromolecules
  • the photoinitiators which can be used for the cationic polymerization essentially consist of three classes: aryldiazonium salts, onium salts (in particular: iodonium, sulfonium and selenonium salts) and organometallic compounds. Phenyldiazonium salts, upon irradiation in the presence as well as in the absence of a hydrogen donor, can form a cation that initiates polymerization. The efficiency of the overall system is determined by the nature of the counterion used for the diazonium compound.
  • onium salts especially sulfonium and iodonium salts.
  • the photochemistry of these compounds has been studied sustainably.
  • the iodonium salts decompose homolytically after excitation and thus generate a radical and a radical cation, which first passes into a cation through 1 1 abstraction, which finally liberates a proton and thereby initiates cationic polymerization (Dektar et al Chem., 1990, 55, 639; J. Org. Chem., 1991, 56, 1838).
  • This mechanism also allows the use of iodonium salts for radical photopolymerization.
  • the election of the counter-ion is again of great importance.
  • SbtV, ASF ⁇ " or PY, ' are also used, otherwise the choice of aromatic substitution is rather free in this structural class and essentially determined by the availability of suitable starting building blocks for the synthesis. which break down into Norrish type II (Crivello et al., Macromolecules, 2000, 33, 825). Also in the case of the sulfonium salts, the choice of the counterion is of critical importance, which manifests itself essentially in the rate of plating of the polymers Results are usually achieved with Sbl V salts.
  • Preferred photoinitiators are mixtures of tetrabutylammonium tetrahexylborate,
  • cationic dyes are Astrazon Orange G, Basic Blue 3, Basic Orange 22, Basic Red 13, Basic Violet 7, Methylene Blue, New Methylene Blue, Azure A, Pyrillium I, Safranine O, Cyanine, Gallocyanine, Brilliant Green, Crystal Violet, Ethyl violet and thionin.
  • the photopolymer formulation according to the invention contains a cationic dye of the formula I ' An " .
  • Cationic dyes of the formula " are preferably understood to mean those of the following classes: acridine dyes, xanthene dyes, thioxanthene dyes, phenazine dyes,
  • An " is an anion.
  • Preferred anions An " are in particular C 8 to C 25 alkanesulfonate, preferably C 13 to C 25 alkanesulfonate, C 3 to C 8 perfluoroalkanesulfonate, C 4 to C 18 perfluoroalkanesulfonate, which are in the alkyl chain carries at least 3 hydrogen atoms, C9 to C-25 alkanoate, C9 to C25 alkenoate, Cs to C25 alkyl sulfate, preferably C13 to C25 alkyl sulfate, Cs to C25 alkenyl sulfate, preferably CD to C25 alkenyl sulfate , C3-CI8 Perfluoralkylsulfat, C 4 - to C 8-Perfluoralkylsulfat carrying at least 3 hydrogen atoms in the alkyl chain, polyether sulfates ene oxide based on at least 4 equivalents of ethyl
  • Particularly preferred anions are sec-Cn- to Ci 8-alkanesulfonate, CD to C25 alkyl sulfate, branched Cs to C25 alkyl sulfate, optionally branched bis-C6 to C25 alkyl sulfosuccinate, sec- or tert-C4 bis C25 - alkylbenzenesulfonate, sulfonated or sulfated, optionally at least monounsaturated Cs to C25 fatty acid esters of aliphatic C 1 to C 6 -alcohols or glycerol, bis (C 2 to C 6 -alkyl) C 3 to C 12 -alkanedicarboxylic acid esters, ( Sulfo-C 1 -C 6 -alkyl) C 6 -C 18 -alkanecarboxylic acid esters, triscatechol phosphate substituted by up to 12 halogen radicals, cyanotriphenyl
  • the anion An "of the dye has an AClogP in the range from 1 to 30, particularly preferably in the range from 1 to 12 and particularly preferably in the range from 1 to 6.5. Aid Mol. Des., 2005, 19, 453; Virtual Computational Chemistry Laboratory, http://www.vcclab.org.
  • dyes 1 ⁇ “ on “ with a water absorption ⁇ 5% by weight with a water absorption ⁇ 5% by weight.
  • the photoinitiator comprises a combination of dyes whose absorption spectra at least partially cover the spectral range from 400 to 800 nm with at least one co-initiator adapted to the dyes.
  • the catalyst D) may comprise at least one compound of the general formula (III) or (IV)
  • L 2 Sn (IV) R 3 2 (IV) include, in which
  • R 3 is a linear or branched, optionally with heteroatoms, especially with oxygen, also in the chain substituted alkyl radical having 1 to 30 carbon atoms and
  • R 3 is a linear or branched alkyl radical having 1 to 12 carbon atoms, particularly preferably a meth l, ethyl, propyl, n, f-butyl, w-octyl radical and very particularly is preferably a /, -, z-, / -Butyl- radical and / or R 4 is a linear or branched, optionally substituted with fletero atoms, in particular with oxygen, also in the chain substituted tert-alkyl radical having 1-17 carbon atoms or alkenyl radical having 2 to 17 C atoms, particularly preferably a linear or branched alkyl or alkenyl radical having 3 to 13 C atoms. most preferably a linear or branched alkyl or alkenyl radical having 5 - 1 1 carbon atoms. In particular, all I are the same.
  • Further suitable catalysts are, for example, compounds of the general formula (V) or (VI).
  • the urethanization catalyst D) is selected from the group of the abovementioned compounds of the formulas (III) and / or (IV).
  • the photopolymer formulation additionally contains additives F) and particularly preferably urethanes as additives, it being possible for the urethanes in particular to be substituted by at least one fluorine atom.
  • the additives may preferably have the general formula (VII)
  • R, R 8 are independently hydrogen, linear, branched, cyclic or heterocyclic unsubstituted or optionally substituted with hetero atoms organic radicals, preferably wherein at least one of R 6 R 6 , R 8 is substituted by at least one fluorine atom, and more preferably R 6 is an organic radical having at least one fluorine atom R 6 is more preferably a linear, branched, cyclic or heterocyclic organic unsubstituted or optionally also heteroatom-substituted such as fluoro Rest.
  • the invention also provides a holographic medium comprising a photopolymer formulation according to the invention or obtainable using a photopolymer formulation according to the invention.
  • the holgraphic medium may comprise a film of the photopolymer formulation.
  • it may additionally comprise a cover layer and / or a carrier layer, which are optionally in each case connected at least in regions to the film.
  • a hologram can also be imprinted by conventional methods.
  • Yet another object of the invention is the use of a photopolymer formulation according to the invention for the preparation of holographic media.
  • the invention also provides a process for producing a holographic medium, in which
  • (III) is cured in the desired form with urethane formation at a crosslinking temperature above the processing temperature, wherein the processing temperature in particular> 15 and ⁇ 40 ° C and preferably> 18 and ⁇ 25 ° C and the crosslinking temperature> 60 ° C and ⁇ 100 ° C. , preferably> 70 ° C and ⁇ 95 ° C and more preferably> 75 ° C and ⁇ 90 ° C.
  • the photopolymer formulation is placed in the form of a film in step II).
  • the photopolymer formulation can be applied, for example, flat on a carrier substrate, for example, the devices known in the art such as doctoring devices (doctor blade, knife-over-roll, Commabar, etc.) or a slot die can be used.
  • a carrier layer may preferably be a layer which is transparent to light in the visible spectral range (transmission greater than 85% in the wavelength range from 400 to 780 nm) Material or composite materials are used. However, other non-transparent carrier substrates can also be used.
  • Preferred materials or composite materials of the carrier substrate are based on polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene, polypropylene, cellulose acetate, cellulose hydrate, cellulose nitrate, cycloolefin polymers, polystyrene, polyepoxides, polysulfone, cellulose triacetate (CTA), polyamide , Polymethyl methacrylate, polyvinyl chloride, polyvinyl butyral or polydicyclopentadiene or mixtures thereof. Most preferably, they are based on PC, PET and CTA. Composite materials may be film laminates or co-extrudates.
  • Preferred composite materials are duplex and triplex films constructed according to one of the schemes A B.
  • planar glass plates which are used in particular for large-area image-accurate exposures, e.g. for holographic lithography (Holographic interference lithography for integrated optics, IEEE Transactions on Electron Devices (1978), ED-25 (10), 1 193- 1200,
  • the materials or composite materials of the carrier substrate can be equipped on one or both sides with non-sticky, antistatic, hydrophobic or hydrophilized properties.
  • the mentioned modifications serve on the side facing the photopolymer for the purpose that the photopolymer can be detached from the carrier substrate without destruction.
  • a modification of the side of the carrier substrate facing away from the photopolymer serves to ensure that the media according to the invention meet special mechanical requirements, e.g. when processing in roll laminators, especially in roll-to-roll processes.
  • the carrier substrate may be coated on one or both sides.
  • the invention also provides a holographic medium obtainable by the process according to the invention.
  • Yet another object of the invention is a layer structure, comprising a carrier substrate, a film applied thereon from a Phoiopolymer- formulation according to the invention and optionally a covering layer applied on the side facing away from the carrier substrate side of the film.
  • the layer structure may in particular have one or more covering layers on the fi lm in order to protect it from dirt and environmental influences.
  • plastic films or composite film systems, but also clearcoats can be used.
  • film materials analogous to the materials used in the carrier substrate, these having a thickness of typically 5 to 200 ⁇ m, preferably 8 to 125 ⁇ m. particularly preferably 20 to 50 ⁇ may have.
  • cover layers PE or PET films of 20 to 60 ⁇ m in thickness are preferably used. Particularly preferred is a polyethylene film with a thickness of 40 ⁇ used. It is likewise possible for a further covering layer to be applied as a protective layer in the case of a layer structure on the carrier substrate.
  • a holographic medium according to the invention for producing a hologram in particular an in-line, off-axis, full-aperture transfer, white light transmission, denisyuk, off-axis reflection or edge-lit hologram and a holographic stereogram is likewise an object of the invention ..
  • the holographic media according to the invention can be processed into holograms by appropriate exposure processes for optical applications in the entire visible and near UV range (300-800 nm).
  • Visual holograms include all holograms that can be recorded by methods known to those skilled in the art. These include, inter alia, in-line (Gabor) holograms, off-axis holograms, full
  • Aperture transfer holograms white-light transmission holograms ("rainbow holograms"), Denisyuk holograms, off-axis reflection holograms, edge-lit flolograms, and holographic stereograms. Preference is given to reflection holograms, denisy-holograms, transmission holograms.
  • Possible optical functions of the holograms that can be produced with the media according to the invention correspond to the optical functions of light elements such as lenses. Mirrors, deflection mirrors, filters, diffusers, diffractive elements, light guides, waveguides, projection screens and / or masks. Frequently, these optical elements exhibit frequency selectivity depending on how the holograms were exposed and the dimensions of the hologram.
  • the holographic media according to the invention also holographic
  • Images or representations such as for personal portraits, biometric representations in security documents, or generally of images or image structures for advertising, security labels, trademark protection, branding, labels, design elements, decorations, illustrations, trading cards, images and the like, as well as images that can represent digital data, among others also in combination with the products shown above.
  • Holographic images can have the impression of a three-dimensional image, but they can also represent image sequences, short films or a number of different objects, depending on which angle, with which (even moving) light source etc. this is illuminated. Due to these diverse design possibilities, holograms, in particular volume holograms, represent an attractive technical solution for the above-mentioned application.
  • Isocyanate component 1 is a commercial product (Desmodur ® N 3900) of Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%.
  • Isocyanate component 2 is a test product (Desmodur ® E VP XP 2747) from Bayer MaterialScience AG, Leverkusen, Germany, high-NCO-containing aliphatic prepolymer based on hexane diisocyanate, NCO content: about 17%.
  • Polyols 1-3 are experimental products of Bayer MaterialScience AG, Leverkusen, Germany, the preparation methods are described below.
  • Writing Monomer 1 is an experimental product of Bayer MaterialScience AG, Leverkusen, Germany, the preparation is described below.
  • Writing Monomer 2 is an experimental product of Bayer MaterialScience AG, Leverkusen, Germany, the preparation is described below.
  • Additive 1 is an experimental product of Bayer MaterialScience AG, Leverkusen, Germany, the preparation is described below.
  • Chain transfer reagent 2 is 3-methoxybutyl-3-mercaptopropionate and was obtained from AB CR. GmbH & Co. KG, Düsseldorf, Germany.
  • Chain transfer agent 3 is pentaerythritol tetrakis (3-mercaptobutylate) and was purchased under the name Karenz MT PH-1 from Showa Denko K.K., Kawasaki, Japan.
  • Chain transfer reagent 4 is pentaerythritol tetrakis (3-mercaptopropionate) and was purchased from Bruno Bock Chemical Factory GmbH & Co. KG, Marschacht, Germany.
  • Chain transfer agent 5 is dodecylthiol and was obtained from Chempur Feinchemikalien und Anlagens personal GmbH, Düsseldorf, Germany.
  • Photoinitiator 1 Neumethylenblau 0, 10% with CGI 909 (product of the company ASF SE, Basel,
  • Photoinitiator 2 Safranine O 0.10% with CGI 909 (product of Fa.BASF SE, Basel, Switzerland) 1.0%, dissolved as a solution in N-ethylpyrrolidone (NEP), proportion of NEP 3.5%. Percentages refer to the overall formulation of the medium.
  • Photoinitiator 3 Neumethylene blue (resalted with dodecylbenzenesulfonate) 0.20%, safranine 0 (resalted with dodecylbenzenesulfonate) 0.10%, and Astrazon Orange G (resalted with
  • Dodecylbenzenesulfonate 0.10% with CGI 909 (product of BASF SE, Basel, Switzerland) 1.5%, dissolved as a solution in N-ethylpyrrolidone (NEP), proportion of NEP 3.5%. Percentages refer to the overall formulation of the medium.
  • Byk® 310 (silicone-based surface additive from BYK-Chemie GmbH, Wesel, 25% solution in xylene) 0.3%.
  • Substrate 1 polyethylene terephthalate film, 36 ⁇ . Type Hostaphan ® RNK from Mitsubishi Chemicals, Germany.
  • Substrate 2 Makrofol DE 1 - 1 CC 125 ⁇ (Bayer MaterialScience AG, Leverkusen, Germany).
  • DMC Catalyst Zinc hexacyanocobaltate (III) double metal cyanide catalyst obtainable by the process described in EP 700 949A.
  • Irganox 1076 is octadecyl 3,5-di (tert-butyl) -4-hydroxyhydrocinnamate (CAS 2082-79-3).
  • the component or mixture to be investigated For the determination of the viscosity, the component or mixture to be investigated, unless otherwise stated, at 20 ° C in a cone-plate measuring system of a rheometer (Anton Paar Physica model MCR 51) applied. The measurement was carried out under the following conditions:
  • the protective film of the holographic film is peeled off and the holographic film with the photopolymer side is laminated on a 1 mm thick glass plate of suitable length and width with a rubber roller under light pressure.
  • This sandwich of glass and photopolymer film can now be used to determine the holographic performance parameters DE and An.
  • the beam of a He-Ne laser (emission wavelength 633 nm) was transformed into a parallel homogeneous with the help of the space filter (SF) and together with the collimation lens (CL)
  • the final cross sections of the signal and reference beam are defined by the iris diaphragms (I).
  • the diameter of the iris aperture is 0.4 cm.
  • the polarization-dependent beam splitters (PBS) divide the laser beam into two coherent identically polarized beams.
  • the power of the reference beam was set to 0.5 mW and the power of the signal beam to 0.65 mW.
  • the performances were determined with the semiconductor detectors (D) with the sample removed.
  • the angle of incidence (ao) of the reference beam is -21.8 °
  • the angle of incidence ( ⁇ 0 ) of the signal beam is 41.8 °. The angles are measured from the sample standard to the beam direction.
  • Figure 1 therefore has ao a negative sign and ßo a positive sign.
  • the interference field of the two overlapping beams produced a lattice of light and dark stripes perpendicular to the bisector of the two on the sample incident rays lie (reflection hologram).
  • the stripe distance ⁇ also called the grating period, in the medium is ⁇ 225 nm (the refractive index of the medium assumed to be -1.504).
  • FIG. 1 shows the holographic experimental setup with which the diffraction efficiency (DE) of the media was measured.
  • the written holograms have now been read out in the following way.
  • the shutter of the signal beam remained closed.
  • the shutter of the reference beam was open.
  • the iris diaphragm of the reference beam was closed to a diameter ⁇ 1 mm. It was thus achieved that for all rotation angles ( ⁇ ) of the medium, the beam was always located completely in the previously written hologram.
  • the turntable computer controlled now the angular range of ⁇ to ⁇ , ⁇ : ⁇ with an angular increment of 0.05 °. ⁇ is measured from the sample standard to the reference direction of the turntable.
  • a 0 - () "+ ⁇ 'recording ⁇ o is the half-angle in the laboratory system outside the medium and the following applies when writing the hologram:
  • ⁇ -31.8 °.
  • 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 deflected into the first order by means of the detector. sector D measured.
  • the diffraction efficiency was found at each approached angle ⁇ as the quotient of:
  • PD is the power in the detector of the diffracted beam and / 'is the power in the detector of the transmitted beam.
  • the Bragg curve was measured, it describes the diffraction efficiency ⁇ as a function of the angle of rotation ⁇ of the written hologram and stored in a computer.
  • the intensity transmitted in the zeroth order was recorded against the angle of rotation ⁇ and stored in a computer.
  • the maximum diffraction efficiency (DE rj max ) of the hologram, ie its peak value, was determined in ⁇ reconstmction. It may be necessary to change the position of the detector of the diffracted beam to determine this maximum value.
  • the refractive index contrast ⁇ and the thickness d of the photopolymer layer has now been measured by means of the coupled wave theory (see: II ogelnik, The Bell System Technical Journal, Volume 48, November 1969, Number 9 page 2909 - page 2947) to the measured Bragg curve and the angle curve the transmitted intensity determined.
  • the strip spacing ⁇ 'of the hologram and the orientation of the strips (slant) can deviate from the strip spacing ⁇ of the interference pattern and its orientation. Accordingly, the angle ⁇ o 'or the corresponding angle of the turntable ⁇ reconstmction, in which maximum diffraction efficiency is achieved by o and the corresponding differ. This changes the Bragg condition. This change is taken into account in the evaluation process.
  • the evaluation method is described below: All geometrical quantities which relate to the written hologram and not to the interference pattern are represented as canceled sizes.
  • sm 1 • [sin ( 0 ) + sin ( ⁇ 0 ) - sin (0 0 + n recomtrudy v is the lattice strength
  • ⁇ is the detuning parameter
  • ⁇ ' is the orientation (slant) of the refractive index lattice written 'a' and ⁇ 'correspond to the angles ao and ⁇ o of the interference field when writing the hologram, but measured in the medium and valid for the lattice of the hologram (after thickness shrinkage)
  • n is the average refractive index of the photopolymer and set to 1.504
  • ⁇ is the wavelength of the laser light in a vacuum
  • FIG. 2 shows the representation of the Bragg curve ⁇ according to the Coupled Wave Theory (dashed line), the measured diffraction efficiency (filled circles) and the transmitted power (black solid line) against the angle tuning ⁇ .
  • this procedure may be repeated several times for different exposure times t on different media to determine at which average absorbed dose of the incident laser beam when writing the hologram DE changes to the saturation value.
  • the powers of the partial beams have been adjusted so that the same power density is achieved in the medium at the angles ao and ⁇ o used.
  • the physical layer thickness was determined with commercially available white light interferometers, e.g. the device FTM-Lite NIR Coating Thickness Gauge from Ingenieurs supra Fuchs.
  • the determination of the layer thickness is based in principle on interference phenomena on thin layers.
  • light waves are superimposed, which have been reflected at two interfaces of different optical density.
  • the undisturbed superposition of the reflected sub-beams now results in periodic lightening and cancellation in the spectrum of a white continuum radiator (e.g., halogen lamp). This superposition is called the expert interference.
  • These interference spectra are measured and evaluated mathematically.
  • the detection unit is mounted on a swivel arm that can cover a surface quadrant.
  • the scattering angle ⁇ in the laboratory coordinate system can be varied by means of the swivel arm between 0 ° and 90 °.
  • the linear polarization direction of the red laser light (657 ⁇ m) is parallel to the z axis in the laboratory system (S polarization). For the blue laser, the linear polarization direction is parallel to the x, y
  • the bidirectional scattering function BSDF is defined:
  • Psc is the power incident on the solid angle element u measured with the photodiode on the lock-in amplifier.
  • Pi " c is the laser power incident on the sample and 1 / cos ( ⁇ ) corrects the cross section of the scattering volume defined by the detector as a function of the scattering angle in the laboratory system ⁇ .
  • the BSDF is given in 1 / srad and is a measure of the scattering power of the sample. To determine the BSDF, the samples were previously homogeneously photopolymerized under a UV lamp from Hoenle (illuminant: MH emitter UV-400 i I, dose 5 J / cm 2 ).
  • the protective film of the hoiografischen film was peeled off on film samples and the holographic film with the photopolymer side on a 1 mm thick glass plate of suitable length and width with a Rubber roller laminated under light pressure.
  • This sandwich of glass and photopolymer film can now be used to determine the BSDF after UV exposure.
  • the coupon samples were used for UV exposure and later BSDF determination as prepared. A sample that forms high random concentration fluctuations and high molecular weights during homogeneous UV exposure then show a high BSDF.
  • the Angle Scan measuring mode measures the BSDF per angular increment at a point over an angular range ⁇ of 10 ° to 90 °. The average value of the BSDF is then determined between 50 ° and 90 °.
  • I n a 500 m L round bottom flask 0 1 g of 2,6-di-tert-butyl-4-methylphenol, 0.05 g of di-butyl tin 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) and heated to 60 ° C.
  • TMDI 2,4,4-trimethyihexane-1,6-diisocyanate
  • the substrate used also has an influence on the scatter in the holographic medium. Therefore, in the examples, in each case media having the same substrate film were compared with one another. Comparative Example 4
  • Example 6 6.6 g of polyol 1 were added stepwise with 3.0 g of writing monomer 1, 3.0 g of writing monomer 2, 5.0 g of additive 1 and 0.02 g of additive 6, then 0.020 g of catalyst 1 and 0.060 g of Byk® 310, and finally 1, 06 g of photoinitiator 3 in the dark and mixed, so that a clear solution was obtained. Subsequently, at 30 ° C., 1, 265 g of isocyanate component 1 were added and mixed again. The resulting liquid mass was then applied to substrate 1 and dried at 80 ° C. for 7.7 minutes. Dry film thickness: 17 ⁇ m; On (max.) (633 nm)

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Abstract

L'invention concerne une formulation photopolymère contenant des polymères matriciels (A), qui peuvent être obtenus par mise en réaction d'au moins un composant polyisocyanate (a) et d'un composant réactif aux isocyanates (b), un monomère d'enregistrement (B), un photoamorceur (C), un catalyseur (D) et un réactif de transfert de chaîne soufré (E). L'invention concerne également un support holographique qui comprend une formulation photopolymère selon l'invention ou qui peut être obtenu en utilisant une telle formulation, l'utilisation d'une formulation photopolymère selon l'invention pour fabriquer des supports holographiques, et un procédé de fabrication d'un support holographique mettant en oeuvre une formulation photopolymère selon l'invention.
EP12770130.8A 2011-10-12 2012-10-10 Réactifs de transfert de chaîne soufrés dans des formulations photopolymères à base de polyuréthane Withdrawn EP2766902A1 (fr)

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EP12770130.8A EP2766902A1 (fr) 2011-10-12 2012-10-10 Réactifs de transfert de chaîne soufrés dans des formulations photopolymères à base de polyuréthane

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EP2317511B1 (fr) * 2009-11-03 2012-03-07 Bayer MaterialScience AG Formules de photopolymères dotées d'un module mécanique réglable Guv
EP2450893A1 (fr) 2010-11-08 2012-05-09 Bayer MaterialScience AG Formule photopolymère pour la fabrication de supports holographiques dotés de polymères à matrice hautement réticulés
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US20140255824A1 (en) 2014-09-11

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