EP2766903A1 - Réactifs de transfert de chaîne dans des formulations photopolymères à base de polyuréthane - Google Patents

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

Info

Publication number
EP2766903A1
EP2766903A1 EP12770136.5A EP12770136A EP2766903A1 EP 2766903 A1 EP2766903 A1 EP 2766903A1 EP 12770136 A EP12770136 A EP 12770136A EP 2766903 A1 EP2766903 A1 EP 2766903A1
Authority
EP
European Patent Office
Prior art keywords
mercaptopropionate
compounds
formulation according
photopolymer formulation
photopolymer
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Withdrawn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
EP12770136.5A
Other languages
German (de)
English (en)
Inventor
Marc-Stephan Weiser
Friedrich-Karl 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 EP12770136.5A priority Critical patent/EP2766903A1/fr
Publication of EP2766903A1 publication Critical patent/EP2766903A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • 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 preparation of a holographic medium using it according to the invention en photopolymer formulation.
  • Photopolymer formulations of the type mentioned above for the preparation of holographic media are known from WC ) 2011/054797 and WO 2011/067057.
  • the respective sensitivity ie the minimum dose required to achieve the full diffraction efficiency (DE) or the maximum refractive index modulation (An) is determined by the photoinitiator, i. the combination of dye and initiator specified. This combination is often determined by other conditions of preparation or later use of the holographic media prepared from the described photopolymer formulations and is not readily variable.
  • the object of the present invention was therefore to provide a photopolymer formulation from which holographic media with a low sensitivity can be produced, into which holograms can be imprinted with a lower dose rate, which have the full diffraction efficiency (DE).
  • DE full diffraction efficiency
  • a chain transfer agent is understood as meaning a compound which has at least one covalent bond which can be cleaved homolytically with formation of free radicals.
  • Chain transfer agents have already been used in other photopolymer formulations. This is described, for example, in CN 101320208 (here preferably 2-mercaptobenzoazole, mercaptobenzothiazole and dodecylthiol) and in US Pat. No. 4,917,977 A (in conjunction with initiator systems based on HABIs as initiators).
  • the chain transfer agents were used here as a necessary ("requisite") component of the initiator system.
  • the cited photopolymer formulations have in common that holographic exposure produces only a latent image, the full diffraction efficiency (DE) or maximum refractive index modulation (An).
  • DE total diffraction efficiency
  • An maximum refractive index modulation
  • the photopolymer formulations according to the invention are purely photonic materials in which the total diffraction efficiency ( DE) or the maximum refractive index modulation (An) is already generated during the laser exposure of the photopolymer, a subsequent (eg thermoactivated) process step is not necessary, so that the exposure time and required amount of energy of the laser and not the heat step as in the materials Stan
  • the technique is the decisive cost and speed-determining step for the production of the hologram.
  • the chain transfer agent E) may contain one or more compounds selected from the group consisting of 1,3-diketo compounds, thiols, sulfides, disulfides, thioethers, peroxides, amino compounds, ethers, esters, alcohols, acetals, aldehydes, amides. organic chlorides, organic bromides and organic iodides.
  • the chain transfer agent E comprises one or more compounds selected from the group consisting of monofunctional and polyfunctional thiols, more preferably mono-, di- and multifunctional primary thiols and / or difunctional secondary thiols, Disulfides, thiophenols, esters, amines, aromatic alcohols, preferably phenols and naphthols, benzylic alcohols, compounds with benzylic hydrogen atoms, benzylic halides, 1, 3-diketo compounds, peroxides, acetals and et al.
  • the primary thiols alkylthiols in particular with linear or branched alkyl radicals, preferably with 6 - 18 C atoms and more preferably one or more compounds from the group 1-octylthiol, 1-decylthiol, 1 -dodecylthiol and 1 1, 1 1 -dimethyldodecane-1-thiol, di-, tri- and higher erfunktionelle thiols having at least one primary Sl [group, in particular pentaerythritol tetrakis (3 -mercaptopropionat), pentaerythritol tetrakis (mercaptoacetate), Trimethyl olpr op tris (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), octane-1, 8-dithiol, 3,6-dioxa-1, 8-octanedith
  • esters have a primary or secondary amino function and are in particular N-phenylglycine ethyl esters or esters which carry at least one -SRo group, where Ro can be hydrogen, a linear or branched alkyl radical or an aryl radical and the esters in particular one or more compounds from the group consisting of 3-methoxybutyl 3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, 3-methoxybutyl 3-mereapto-propionate. ⁇ -octyl thioglycolate, 2-ethylhexyl thioglycolate.
  • the peroxides for a half-life of 1 hour have a half-life temperature of greater than 80 ° C and in particular one or more compounds from the group di-tert-butyl peroxide, dicumyl peroxide. Dilauryl peroxide and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane.
  • thiols in particular primary or multi-functional secondary thiols, esters and peroxides as chain transfer agents.
  • examples of particularly preferred compounds of the substance classes listed here are "-octylthiol,
  • Ethyl 3-mercaptopropionate glycol dimercaptoacetate, pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), Trimethylolpropane tris (2-mercaptoacetate), trimethylolpropur tris (3-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), methyl furfurylmercaptopropionate, 1, 4-bis (3-mercaptobutylyloxy) butane, 1, 3, 5-tris ( 3-mercaptobutyloxyethyl) - 1, 3, 5-triazine
  • this comprises less than 2.5% by weight, preferably 0.05-1.01% by weight, and particularly preferably 0.09-0.55% of the chain transfer agent E) , based on the photopolymer formulation.
  • polyisocyanate component (ea) it is possible to use all compounds or mixtures thereof which are well known to the person skilled in the art and which on average have two or more NC (s) 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.
  • butylene diisocyanate hexamethyl endiisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatomethyl) -octane, 2,2,4- and / or 2,4,4- are suitable.
  • HDI hexamethyl endiisocyanate
  • IPDI isophorone diisocyanate
  • 1,8-diisocyanato-4- isocyanatomethyl
  • Trimethylhexamethylene diisocyanate containing isomeric bis (4,4'-isocyanatocyclohexyl) methane and mixtures thereof of any desired isomeric isomer, isocyanatomethyl-1,8-octane diisocyanate, 1,4-cyclohexylenediisocyanate, the isomeric cyclohexanedimethyl endiisocyanates, 1, 4- Phenylene diisocyanate, 2,4- and / or 2,6-toluenediyl cyanate, 1,5-naphthylene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate and / or triphenylmethane-4,4 ', 4 " -triiso cyanate.
  • polyisocyanates based on aliphatic and / or cycloaliphatic di- or triisocyanates is preferred.
  • the polyisocyanates of component a) are particularly preferably di- or oligomerized aliphatic and / or cycloaliphatic di- or triisocyanates.
  • Prepolymers of component a) 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.
  • polyisocyanates al are all known in the art per se known aliphatic, cycloaliphatic, aromatic or ar aliphatic di- and triisocyanates, where it is irrelevant whether they were obtained by phosgenation or by phosgene-free processes.
  • Nooxadiazindion Jardine
  • Suitable monomeric di- or triisocyanates which can be used as component al) are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), 1,8-diisocyanate. 4 - (isocyanatomethyl) octane, isocyanatomethyl-l, 8-octane diisocyanate (TIN), 2,4- and / or 2,6-toluene diisocyanate.
  • isocyanate-reactive compounds a2) for the construction of the prepolymers OFI-functional compounds are preferably used. These are analogous to the oil-functional compounds as described below for component b). Also possible is the use of amines for prepolymer production. Examples which are suitable are ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, diamino cyclohexane, diaminobenzene, diaminobisphenyl, difunctional polyamines such as the Jeffamine *, amine-terminated polymers having number-average molar masses of up to 10,000 g of mol or mixtures thereof with one another.
  • isocyanate is reacted in excess with amine to form a biuret group.
  • 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.
  • 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 from 200 to 10,000 g / mol; particularly preferred are urethanes, allophanates or biurets of aliphatic isocyanate-functional compounds.
  • fertilize 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 HDI or TM DI and difunctional polyether polyols having number average molecular weights of 1000 to 8200 g / mol.
  • the prepolymers described above preferably have residual contents of free monomeric isocyanate of less than 1% by weight, more preferably less than 0.5% by weight and very preferably less than 0.2% by weight.
  • the polyisocyanate component may contain, in addition to the described prepolymers, further isocyanate components in proportion. 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, H examethyl endiisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, 2,2,4- and / or 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 cyclohexane hexanedimethyl endiisocyanate, 1, 4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 1,5-naphthylene diisocyanate, 2,
  • polyisocyanates based on oligomerized and / or derivatized diisocyanates which have been freed of excess diisocyanate by suitable processes, in particular those of hexamethylene diisocyanate.
  • suitable processes in particular those of hexamethylene diisocyanate.
  • Particularly preferred are the oligomeric isocyanurates, uretdiones and Iminooxadiazindione of 1 IDI and mixtures thereof.
  • 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, maleates, fumarates, maleimides, acrylamides, and vinyl ether, propenyl ether, allyl ether and dicyclopentadienyl units containing compounds containing at least one isocyanate-reactive Group have 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 (meth) acrylates, polyalkylene oxide mono (meth) acrylates, poly (e-caprolactone) mono (meth) acrylates, such as. B.
  • isocyanate-reactive oligomeric or polymeric unsaturated acrylate and / or methacrylate group-containing compounds are suitable alone or in combination with the aforementioned monomeric compounds.
  • the proportion of isocyanates in the isocyanate component a) which are partially reacted with isocyanate-reactive ethylenically unsaturated compounds is 0 to 99%, preferably 0 to 50%, more preferably 0 to 25% and most preferably 0 to 15%.
  • 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, for example butanone oxime, diisopropylamine, 1,2,4-triazole, dimethyl-1, 2,4 triazole, imidazole, diethyl malonate, Acetoacetic ester, acetone oxime, 3,5-dimethylpyrazole, ⁇ -caprolactam, N-tert-butylbenzylamine, cyclopentanonecarboxylethylester 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.
  • polyol component b) it is possible to use all polyfunctional, isocyanate-reactive compounds which on average have at least 1.5 isocyanate-reactive groups per molecule.
  • Isocyanate-reactive groups in the context of the present invention are preferably 1-hydroxy, amino or thio groups, with particular preference being given to hydroxyl compounds.
  • Suitable polyfunctional, isocyanate-reactive compounds are, for example, polyester, polyether, polycarbonate, poly (meth) acrylate and / or polyurethane ethane 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.
  • suitable alcohols are ethanediol, di-, tri-, tetraethylene glycol, 1,2-propanediol, di-, tri-, tetrapropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, butyl- tandiol-2,3, pentanediol-1,5, 1,6-hexanediol, 2,2-di-methyl-1, 3-propanediol. 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, octanediol-1,8, decanediol-1,10, dodecanediol-1,12.
  • Trimethylolpropane, glycerol or any mixtures around each other Trimethylolpropane, glycerol or any mixtures around each other.
  • the polyester polyols can also be based on natural raw materials such as castor oil. It is likewise possible for the polyesterpolyols to be based on homopolymers or copolymers of lactones, as is preferred by addition of lactones or lactone mixtures such as butyrolactone, ⁇ -caprolactone and / or methyl-e-caprolactone to hydroxy-functional compounds. fertilize as polyhydric alcohols of an OH functionality> 2, for example, the above-mentioned type can be obtained.
  • Such 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 within the scope of the polyester segments, or also polyester polyols can be used to form polycarbonate polyols be reworked.
  • 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 based solely on propylene oxide or random or block copolymers based on propylene oxide with further 1-alkylene oxides, wherein the 1-alkenoxide is not higher than 80 wt .-%.
  • Particular preference is given to propylene oxide homopolymers and also random or block copolymers which have oxyethylene, oxypropylene and / or oxybutylene units, the proportion of oxypropylene units based on the total amount of all oxyethylene, oxybutylene and oxybutylene units being at least 20% by weight. %, preferably at least 45% by weight power.
  • 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 8,500 g / mol and very particularly preferably from 600 to 4500 g / mol.
  • the OH functionality is preferably 1.5 to 4.0, particularly preferably 1.8 to 3.1.
  • 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 segments X. based on the total amount of X and Y ä segments wt .-% amounts to at least 50th
  • the outer blocks X make up thereby at least 50 wt .-%, preferably 66 wt .-% of the total molar mass of Y (Xi-H) n and consist of monomer units which obey the formula I.
  • Y (X.-I i) t a number from 2 to 6, more preferably 2 or 3, and most preferably equal to 2.
  • Y (X ll) r a number from 1 to 6 , more preferably from 1 to 3, and most preferably equal to 1.
  • R is preferably a hydrogen, a methyl, butyl, hexyl 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 (X.-H) 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 linkages X may be homopolymers of exclusively identical oxyalkylene repeat units. They can also be built up statistically from different oxyalkylene units or, in turn, blockwise from different oxyalkylene units. Preferred are the segments X, based solely on propylene oxide or random or blockwise mixtures of propylene oxide with further 1-alkylene oxides, wherein the proportion of further 1-alkenkenoxiden is not higher than 80 wt .-%.
  • 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) ".
  • the inner block Y which is less than 50% by weight, preferably less than 34% by weight, in Y (X-H) n , consists of di- and / or higher hydroxy-functional polymer structures based on cyclic ethers or is synthesized from di- and / or higher hydroxy-functional polycarbonate, polyester, poly (meth) acrylate, epoxy resin and / or polyurethane structural units or corresponding hybrids.
  • Suitable polyesterpolyols are linear polyesterdiols or branchedpolyesterpolyols, as are known in the art from aliphatic, cyclic or aromatic dicarboxylic or polycarboxylic acids or their anhydrides, such as, for example, polyisocyanates.
  • glutaric, adipic, pimelene, cork, azelaic, sebacic, Nonandicarbon-, Decandicarbon-, terephthalic is ophthalic, o-phthalic, tetrahydrophthalic, hexahydrophthalic or trimellitic acid and acid anhydrides such as o-phthalic, trimellitic or succinic anhydride or any mixtures thereof with polyhydric alcohols such.
  • ethane diol di-, tri-, T etraeth y glycol, 1,2-propanediol, di-, tri-, tetrapropylene glycol, 1, 3-propanediol, 1,4-butanediol.
  • polyester polyols can also be based on natural raw materials such as castor oil.
  • polyesterpolyols are based on homopolymers 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 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 OH functionality of 2, preferably 1,4-butanediol, 1,6-hexanediol and / or 3-methylpandanediol, 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 block-formed polyaddition products of cyclic ethers on Ol 1 or NH-functional starter molecules. As polyether polyols z.
  • Example 2 the polyaddition of styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, and their Mischadditions- and graft products, as well as by condensation of polyhydric alcohols or mixtures thereof and obtained by alkoxylation of polyhydric alcohols, amines and amino alcohols polyether polyols ,
  • Suitable polymers of cyclic ethers are in particular polymers of tetrahydrofuran.
  • the starter may be the polyhydric alcohols mentioned per se in the context of the polyesterpolyols, and also primary or secondary amines and amino alcohols of an Ol.sub.1 or N.sub.U. Functionality of 2 to 8, preferably 2 to 6, more preferably 2 to 3, most preferably equal to 2 are used.
  • Such polyether polyols preferably have number average molecular weights of from 200 to 2000 g / mol, more preferably from 400 to 1400 g, and most preferably from 650 to 1000 g / mol.
  • polyether polyols used for starters the polymers of tetrahydrofuran are preferably used.
  • Preferred components for the inner block Y are polymers of tetrahydrofuran and aliphatic polycarbonate polyols and polyester polyols and polymers of ⁇ -caprolactone having number average molecular weights less than 3100 g / 'mol.
  • Particularly preferred components for the inner block Y are difunctional polymers of tetrahydrofuran and difunctional aliphatic polycarbonate polyols and polyester polyols as well as polymers of ⁇ -caprolactone having number-average molar masses of less than 3100 g / mol.
  • the initiator egment Y is based on difunctional, aliphatic polycarbonate polyols, poly (e-caprolactone) or polymers of tetrahydrofuran having number-average molar masses greater than 500 g mol and less than 2100 g / mol.
  • Biockcopolymere of the structure Y (XII) r consist of more than 50 weight percent of the blocks described above as X. and have a number average total molar mass of greater than 1200 g / mol.
  • Particularly preferred block copolyols consist of less than 50% by weight of aliphatic polyester, aliphatic polycarbonate polyol or polyTHF and more than 50% 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% by weight of aliphatic polycarbonate polyol, poly (e-caprolactone) or polyTHF and more than 50% by weight of the blocks X described above as being according to the invention and have a number-average molecular weight of greater than 1200 g / mol.
  • Very particularly preferred block copolymers consist of less than 34% by weight of aliphatic polycarbonate polyol, poly (e-caprolactone) or polyTHF and more than 66% by weight of the blocks X described above as being according to the invention and have a number average molecular weight of greater than 1950 g / mol and less than 9000 g / moi.
  • the described block copolyols are prepared by Alkylenoxidadditionssupervised.
  • writing monomer B one or more different compounds, which exhibit polymerization-reactive groups (radiation-curing groups) on exposure to 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 multi-functional writing monomer, which may in particular be mono- and multi-functional acrylate writing monomers. More preferably, the semi-monomer may comprise at least one monofunctional and one multifunctional urethane (meth) acrylate.
  • the acrylate writing monomers may in particular be compounds of the general formula (II)
  • R 2 are independently hydrogen, linear, branched, cyclic or heterocyclic unsubstituted or optionally substituted with hetero atoms organic radicals.
  • R 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.
  • acrylates and methacrylates are generally esters of acrylic acid or methacrylic acid.
  • useful acrylates and methacrylates are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert. Butyl acrylate, tert.
  • 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. Examples of suitable di-.
  • Tri- or polyisocyanates are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatoethyl) octane, 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes and mixtures thereof of any desired isomeric isomer, isocyanatomethyl-1,8-octane diisocyanate, 1,4-cyclohexylene diisocyanate, the isomeric cyclohexanedimethylene-diisocyanate.
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • cyanates 1, 4-phenylene diisocyanate, 2,4- and / or 2,6-oluyl endiisocyanate, 1,5-naphthylene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate, 1, 5 Naphthylene diisocyanate, m-methylthiophenyl isocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate and tris (p-isocyanatophenyl) thiophosphate or derivatives thereof with urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate , Biuret, oxadiazinetrione, uretdione, iminooxadiazine structure and mixtures thereof, aromatic or araliphatic di-, tri- or polyisocyanates being 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, polyols ( ⁇ - Capr olactone) mono (meth) acrylates, such as.
  • Tone * M100 (Dow, Schwalbach, DE), 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, hydroxypropyl (meth) acrylate, Acrylic acid (2-hydroxy-3-phenoxypropyl ester), the hydroxy-functional mono-, di- or tetraacrylates of polyhydric alcohols such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or their technical mixtures.
  • polyhydric alcohols such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated, prop
  • isocyanate-reactive oligomeric or polymerc unsaturated acrylate and / or methacrylate groups containing compounds alone or in combination with the aforementioned monomeric compounds are suitable.
  • hydroxyl-containing epoxy (meth) acrylates known per se with OH contents of 20 to 300 mg KOH / g or hydroxyl-containing polyurethane (meth) acrylates having OH contents of 20 to 300 mg KOH / g or acrylated Polyacrylates with Ol [contents of 20 to 300 mg KOH / g and mixtures thereof with one another and mixtures with hydroxyl-containing unsaturated polyesters and mixtures with polyester (meth) acrylates or mixtures of hydroxyl-containing unsaturated polyesters with polyester (meth) acrylates.
  • Urethane acrylates are particularly preferably 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 which can initiate a polymerization of the corresponding groups.
  • actinic radiation compounds which can initiate a polymerization of the corresponding groups.
  • a distinction can be made between unimolecular (type I) and bimolecular (type II) initiators.
  • photoinitiators for radical, anionic, cationic or mixed type of polymerization.
  • Type I photoinitiators for radical photopolymerization form free radicals when irradiated 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 electron or proton transfer or direct hydrogen abstraction forms polymerization initiating radicals.
  • type-ii photoinitiators are quinones, such as. B. camphorquinone, aromatic etotagenen, such as. B. benzophenones in combination with tertiary amines, alkylbenzophenones, halogenated benzophenones, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), anthrone, Metyl-p- (d imet hy lam ino) benzoate, Thioxantho ", ketocoumarine, alpha-aminoalkylphenone, alpha-hydroxyalkylphenone and cationic dyes, such as, for example, methylene blue, in combination with tertiary amines.
  • quinones such as. B. camphorquinone, aromatic etotheticen, such as. B. benzophenones in combination with tertiary amines, alkylbenzophenones, halogenated benzophenone
  • type -! And type II photoinitiators are used; for the longer-wavelength visible light range, predominantly type II photoinitiators are used.
  • ammonium ammonium larylborate examples include tertiary ammoniumammonium triphenylhexylborate, tetraethylammonium triphenylbutylborate, tetraethylammonium trinaphthylborate, hexylborate, tetrabutylammonium tris (4-tert-butyl) -phenylbutylborate, tetrabutylammonium tris- (3-fluorophenyl) -hexylborate, tetramethylammonium triphenylbenzylborate, tetra (n-hexyl) ammonium (sec-butyl) triphen
  • the photoinitiators used for the anionic polymerization are typically Type I systems and are derived from transition metal complexes of the first series.
  • chromium salts e.g. trans-Cr (NH3) 2 (NCSy (Kutal et al, Macromolecules 1991, 24, 6872) or ferrocenyl compounds (Yamaguchi et al., Macromolecules 2000, 33, 33;
  • anionic polymerization is the use of dyes, such as crystal violet leuconitrile or malachite green leuconitrile, which are able to polymerize cyanoacrylates by photolytic decomposition (Neckers et al., Macromolecules 2000, 33, 7761).
  • the chromophore is incorporated into the polymers, so that the resulting polymers are colored through.
  • 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 organometalic compounds.
  • Phenyldiazonium Saize upon irradiation in both the presence and absence of a hydrogen donor, can produce a cation that initiates polymerization.
  • the efficiency of the overall system is determined by the nature of the counterion used for the diazonium compound. Preference is given here to the less reactive but rather expensive SbFe " , AsFe " or F ".
  • these compounds are generally less suitable since the surface quality is reduced by the nitrogen released after the exposure (Pinholes) (Li et al., Polymerie Materials Science and Engineering, 2001, 84, 139 ).
  • 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 undergoes a 1-1 abstraction to form a cation, which finally releases a proton and thereby initiates cationic polymerization (Deklar et al Org. 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.
  • S alz s is it Norrish type II compounds (Crivello et al., Macromolecules, 2000, 33, 825).
  • the choice of counterion has a critical importance, which is essentially determined by the rate of cure of the polymers expresses. the best results are usually achieved with SbFe ⁇ salts.
  • iodonium and sulfonium salts are ⁇ 300 nm, these compounds should be appropriately sensitized for photopolymerization with near UV or short wavelength visible light. This is achieved by the use of longer-wavelength absorbing aromatics such. Anthracene and derivatives (Gu et al., Am. Chem. Soc., Polymer Preprints, 2000, 41 (2), 1266) or phenothiazine or its derivatives (Flua et al, Macromolecules 2001, 34, 2488-2494).
  • Preferred photoinitiators are mixtures of tetrabutylammonium tetrahexylborate, tetraethylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium tris (3-fluorophenyl) hexylborate ([191726-69-9], CGI 7460, product of BASF SE, Basel, Switzerland) and tetrabutylammonium Tris (3-chloro-4-methylphenyl) hexylborate ([1147315-11-4], CGI 909, product of BASF SE, Basel, Switzerland) with cationic dyes, as described, for example, in 11 Berneth in Ulimann's Encyclopedia of Industrial Chemistry, Cationic Dyes, Wiley-VCH Verlag, 2008.
  • 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 thionine. It is particularly preferred if the photopolymer formulation according to the invention contains a cationic dye of the formula F ' An.
  • Cationic dyes of the formula F are preferably understood to mean those of the following classes: acridine dyes, xanthene dyes, thioxanthene dyes, phenazine dyes, phenoxazine dyes, phenothiazine dyes, tri (het) arylmethane dyes - in particular diamino dyes. and triamino (het) arylmethane dyes, mono-, di- and trimethencyanine dyes, hemicyanine dyes, externally cationic merocyanine dyes, externally cationic neutrocyanine dyes, zero methine dyes - in particular naphtholactam dyes, streptocyanin dyes.
  • Such dyes are described, for example, in FL Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Azine Dyes, Wiiey-VCH Verlag, 2008, 1, Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Methine Dyes and Pigments, Wiley-VCH Verlag, 2008, T. Gessner U. Mayer in Ullmann's Encyclopedia of Industrial Chemistry, Triarylmethane and Diarylmethane Dyes, Wiley-VCH Verlag, 2000. An " is an anion.
  • Preferred anions An are, in particular, C 1 to C 25 -alkanesulfonate, preferably C 13 - to C 25 -alkanesulfonate, C 3 - to cis-perfluoroalkanesulfonate, C 4 - to cis-perfluoroalkanesulfonate, which are in the alkyl chain at least 3 hydrogen atoms, C9 to C25 alkanoate, C9 to C25 alkenoate, C5 to C25 alkyl sulfate, preferably C13 to C25 alkyl sulfate, C5 to C25 alkenyl sulfate, preferably C13 to C25 alkenyl sulfate, C3 - to C 18-perfluoroalkyl sulfate, innbaiondoro C 4 to C 18 -P er fluoroalkyl sulfate, which carries at least 3 hydrogen atoms in the alkyl chain,
  • Ci- to Cs-alkyl and / or Ci- to C 12 -alkoxycarbonyl-substituted benzenesulfonate optionally by nitro, cyano, hydroxy, C 1 - to C 25 -alkyl, C 1 - to C 12 -alkoxy, amino, C 1 - to C 12 -alkoxycarbonyl or chlorine-substituted naphthalene or biphenylsulfonate, optionally substituted by nitro, cyano, hydroxy, Ci to C25-alkyl, Ci to Ci2-alkoxy, Ci to Ci2-alkoxycarbonyl or chlorine-substituted benzene, naphthalene or biphenyl disulfonate, by dinitro , C 1 - to C 25 -alkyl, C 4 - to C 12 -alkoxycarbonyl, benzoyl, chlorobenzoyl or toluoyl-substituted benzo
  • Particularly preferred anions are sec-Cn to C 1 g alkanesulfonate, CD to C25 alkyl sulfate, branched Cs to C25 alkyl sulfate, optionally branched bis-CV to C25 alkyl sulfosuccinate, sec- or tert-C4 bis C25-alkylbenzenesulfonate, sulfonated or sulfated, optionally at least monounsaturated Cs to C25-F ettklasteder of aliphatic Ci- to Cs alcohols or glycerol, bis (sulfo-C2 to C6-alkyl) -C3- to Ci2-alkandicarbonklaer , (Sulfo-C 2 to C 6 alkyl) ce- to cis-alkanecarboxylic acid esters, triscacylene phosphate substituted by up to 12 halo radicals, cyanotriphenyl bo
  • the anion An "of the dye has an AClogP in the range of 1 to 30, more preferably in the range of 1 to 12 and particularly preferably in the range of 1-6.5
  • the AClogP is according to J. Comput Mol. Des. 2005, 19, 453; Virtual Computational Chemistry Laboratory, http://www.vcclab.org.
  • Dyes F ' An with a water absorption ⁇ 5% by weight are particularly preferred.
  • the photoinitiator comprises a combination of dyes whose absorption spectrums 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) R 3 Sn (IV) L 3 (III)
  • L 2 Sn (IV) R 3 2 (IV) include, in which
  • R ' is a linear or branched, optionally with heteroatoms, in particular oxygen, also in the chain substituted alkyl radical having 1-30 C atoms and L are each independently O 2 CR 4 groups in which R 4 is a linear or branched, optionally with heteroatoms, in particular with oxygen, also in the chain substituted alkyl radical having 1 - 30 C atoms, an alkenyl radical having 2 - 30 carbon atoms or any substituted or unsubstituted optionally polycyclic aromatic ring with or without heteroatoms, is particularly preferred here, if R 3 is a linear or branched alkyl radical having 1-12 C atoms, particularly preferably a methyl, ethyl, propyl, n-, / -, ⁇ -butyl, n-octyl radical and very particularly preferably one "-, -, / -Butyl radical and / or R 4 is a linear or branched, optionally substituted with heteroatoms, in
  • catalysts are, for example, compounds of the general formula (V) or (VI). Bi (III) M 3 (V),
  • M are each independently OC-R ' groups in which R 5 is a saturated or unsaturated or heteroatom-substituted C 1 to C 19 alkyl radical or C 2 to C 19 alkenyl radical , in particular a Ce to Cn-alkyl radical and particularly preferably a C? to C9-alkyl radical Alkyl radical or an optionally aromatic or oxygen or nitrogen optionally substituted C to Cis alkyl radical, wherein in the formula (V) and (VI) M need not be synonymous.
  • the catalyst D) is selected from the group of the abovementioned compounds of the formulas (III) and / or (IV).
  • photopolymer formulation may be: radical stabilizers or other auxiliaries and additives.
  • the photopolymer formulation additionally contains additives F) and more preferably urethanes as additives, wherein the urethanes may be substituted in particular with at least one fluorine atom.
  • the additives F) may preferably have the general formula (VII)
  • R 7 , 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 7 , R 8 is substituted with at least one fluorine atom and more preferably R "is an organic radical having at least one fluorine atom.
  • Particularly preferred R " is a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms such as fluorine-substituted organic radical.
  • the invention is also a holographic medium containing 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 covering layer and / or a carrier layer, which if appropriate in each case are connected to the film at least in certain areas.
  • a hologram can also be imprinted by conventional methods.
  • Yet another object of the invention is the use of a photopolymer composition according to the invention for the production 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 layer of a material or composite material transparent to light in the visible spectral range may preferably be used.
  • a layer of a material or composite material transparent to light in the visible spectral range may preferably be used.
  • 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 can foil laminates or Be coextrudates.
  • 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, ISSN: 0018-9383).
  • holographic lithography Holographic interference lithography for integrated optics, IEEE Transactions on Electron Devices (1978), ED-25 (10), 1 193-1200, ISSN: 0018-9383.
  • 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 modifications mentioned serve on the photopoly mer side facing the purpose that the photopolymer can be detached from the support substrate destructively.
  • 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. during processing in roll laminators, in particular 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 photopolymer formulation according to the invention and optionally a side of the side facing away from the carrier substrate
  • the layer structure may have one or more covering layers on the film in order to protect it from dirt and environmental influences. You can do this
  • cover layers it is preferred to use film materials analogous to the materials used in the carrier substrate, wherein these may have a thickness of typically 5 to 200 ⁇ m, preferably 8 to 125 ⁇ m, particularly preferably 20 to 50 ⁇ m. Covering layers with as smooth a surface as possible are preferred.
  • the roughness determined according to DIN EN ISO 4288 "Geometrical product specification (GPS) - surface texture ! (English: “Geometrical Product Specifications (GPS) - Surface texture ..."), test condition R3z front and back. Preferred roughnesses are in the range of less than or equal to 2 ⁇ , preferably less than or equal to 0.5 ⁇ .
  • cover layers preferably PE or PET films of a thickness of 20 to 60 ⁇ are used. Particularly preferred is a polyethylene film with a thickness of 40 ⁇ used.
  • a holographic medium according to the invention for producing a hologram, in particular a ⁇ -line, off-axis, full-aperture transfer, white light transmission, denis yuk, off-axis reflection or edge-lit hologram and a holographic stereogram is also the subject of
  • the hermetic 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 every 1 kilogram that can be recorded by methods known to those skilled in the art.
  • in-line (Gabor) holograms include, inter alia, in-line (Gabor) holograms, off-axis holograms, full-aperture holograms, white light tr ansmis sionshol ogr amme ("rainbow holograms"), denisy holograms, off-axis reflection holograms, edge-lit holograms, and more holographic stereograms.
  • In-line (Gabor) holograms include, inter alia, in-line (Gabor) holograms, off-axis holograms, full-aperture holograms, white light tr ansmis sionshol ogr amme (“rainbow holograms”), denisy holograms, off-axis reflection holograms, edge-lit holograms, and more holographic stereograms.
  • 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, deflecting 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.
  • holographic images or representations can also be produced by means of the holographic media according to the invention, for example for personal portraits, biometric representations in security documents, or generally images or images.
  • 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. Because of these diverse design possibilities, holograms, in particular zoom enhancers, represent an attractive technical solution for the above-mentioned application. The invention will be explained in more detail below with reference to examples.
  • 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) Bayer ma- terialScience AG, Leverkusen, Germany, high-NCO-containing aliphatic prepolymer based on hexane diisocyanate, NCO content: about 17%.
  • Polyols 1-2 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 is an experimental product of Bayer MaterialScience AG, Leverkusen, Germany, the preparation is described below.
  • Chain transfer agent 2 is N-phenylglycine ester and was purchased from ABCR GmbH & Co. KG, Düsseldorf, Germany.
  • Chain transfer agent 3 is TMPMA (trimethylolpropane tris (2-mercaptoacetate)) and was purchased from Bruno Bock Chemical Factory GmbH & Co. KG, Marschacht, Germany.
  • Chain transfer agent 4 is pentaerythritol tetrakis (3-mercaptobutylate) and was purchased under the name Karenz MT PE-1 from Showa Denko K.K. Kawasaki, Japan.
  • Chain transfer agent 5 is pentaerythritol tetrakis (3-mercaptopropionate) and was purchased from Bruno Bock Chemical Factory GmbH & Co. KG, Marschacht, Germany.
  • Chain transfer agent 6 is Trigonox B (di-tertiary butyl peroxide) and was obtained from Akzo Nobel Polymer Chemical BV, Emmerich, Germany.
  • Chain transfer agent 7 is peroxan I IX (2,5-dimethyl-2,5-di ('' e -butylperoxy) hexane) and was obtained from Pergan GmbH, Bocholt, Germany.
  • Chain transfer reagent 8 is GDMP (Glykoldi (3-mercaptopropionate)) and was obtained from Bruno Bock Chemische Fabrik GmbH & Co. KG. Marschacht, Germany, based.
  • Chain transfer agent 9 is iso-octylfioglycolate and was obtained from Bruno Bock Chemische Fabrik GmbH & Co. KG. Marschacht, Germany, based.
  • Chain transfer reagent 10 is 2-ethylhexyl thioglycolate and was purchased from Bruno Bock Chemical Factory GmbH & Co. KG, Marschacht, Germany.
  • Chain transfer agent 1 1 is TMPMP (trimethylolpropane tris (3-mercaptopropionate)) and was purchased from Bruno Bock Chemische Fabrik GmbH & Co. KG, Marschacht, Germany.
  • Chain transfer agent 12 is 3,6-dioxa-1,8-octadithiol and was obtained from Sigma-Aldrich Chemie GmbH, Steinheim, Germany.
  • Chain transfer agent 13 is w-dodecylthiol and was purchased from Chempur Feinchemikalien und Anlagens system GmbH, Düsseldorf, Germany.
  • Chain transfer agent 14 is "-decylthiol (1-decanethiol) and was obtained from Alfa Aesar GmbH & CO. KG, Düsseldorf, Germany.
  • Chain transfer reagent 15 is 3-methoxybutyl-3-mercaptopropionate and was obtained from AB CR GmbH & Co. KG. Düsseldorf, Germany.
  • Photoinitiator 1 Neumethylene blue 0.10% with CGI 909 (product of 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 2 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.
  • Catalyst 1 Fomrez® UL28 0.5%, urethanization catalyst, dimethylbis [(1-oxoneodecl) oxy] stannane, commercial product from Momentive Performance Chemicals, Wonton, CT, USA (used as a 10% solution in N-ethylpyrrolidone ).
  • Byk® 310 (silicone-based surface additive from BYK-Chemie GmbH, Wesel, 25% solution in xylene) 0.3%.
  • Substrate 1 Macrofoi DE 1-1 CC 125 ⁇ (Bayer MaterialScience AG, Leverkusen, Germany).
  • DMC catalyst double metal cyanide catalyst based on Zmkhexacyanocobaltate (III), obtainable by the process described in EP 700 949 A.
  • Irganox 1076 is octadecyl 3,5-di- (tert) -butyl-4-hydroxyhydrocinnamate (CAS 2082-79-3).
  • the indicated Ol 1 numbers were determined according to DIN 53240-2.
  • 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:
  • Measurement gap as distance between cone and plate 0.047 • Measuring time: 10 sec.
  • the protective film of the holographic film is peeled off and the holographic film with the photopolymer side is exposed to a 1 mm thick glass plate of suitable length and width with a rubber roller under slight 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 converted into a parallel homogeneous beam by means of the spatial 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 opening is 0.4 cm.
  • the polarization-dependent beam splitters (PBS) divide the laser beam into two coherent identically polarized beams. Through the ⁇ / 2 plates, the power of the reference beam was set to 0.5 mW and the power of the signal beam to 0.65 mW.
  • the 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 ( ⁇ o) of the signal beam is 41.8 °.
  • the angles are measured from the sample standard to the beam direction. According to 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 beams incident on the sample (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. Holograms were written into the medium in the following way:
  • 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 swept over the angular range from ⁇ "to O max with an angular increment of 0.05 °. ⁇ is measured from the sample standard to the reference direction of the turntable.
  • Ot 0 Q 0 + ⁇ recordi "g ⁇ is the half-angle in the laboratory system outside of the medium and it applies when writing the hologram:
  • PD is the power in the detector of the rejected beam and P; is the power in the detector of the transmitted beam.
  • the Bragg curve was described, it describes the diffraction efficiency ⁇ as a function of the rotation angle ⁇ of the written hologram measured 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 Tj max ) of the hologram, ie its peak value, was determined in ⁇ reconstmciion. It may be necessary to change the position of the detector of the diffracted beam to determine this maximum value.
  • the refractive index contrast ⁇ n and the thickness d of the photopolymer layer have now been measured by the Coupled Wave Theory (see Figure 1 ogelnik, The Bell System Technical Journal, Volume 48, November 1969, N around 9 page 2909 - page 2947) to the measured Bragg curve and determines the angle profile of the transmitted intensity. It should be noted that due to the thickness shrinkage occurring due to the photopolymerization, 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.
  • the angle ⁇ o 'or the corresponding angle of the turntable ⁇ reC onsimction is achieved at the maximum diffraction efficiency of ao or the corresponding Q re cordmg differ.
  • the still unknown angle ⁇ ' can be determined from the comparison of the Bragg condition of the interference field during writing of the hologram and the Bragg condition during reading of the hologram under the assumption that only thickness shrinkage takes place. Then follows: v is the lattice strength, ⁇ is the detuning parameter and ⁇ 'is the orientation (slant) of the refractive index lattice written, ⁇ ' and ⁇ 'correspond to the angles ao and ⁇ o of the interference field when writing the hologram, but measured in the medium and for the lattice of the hologram (after thickness shrinkage), n is the mean refractive index of the photopolymer and was set to 1 .504, ⁇ is the wavelength of the laser light in the
  • the detector can detect only a finite angular range for the diffracted light
  • the Bragg curve of broad fathoms (small ef) is not completely detected in a ⁇ scan, but only the central area, with suitable detector positioning. Therefore, the form of the transmitted intensity complementary to the Bragg curve is additionally used to adjust the layer thickness cT.
  • 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 using commercially available white light ethers, such as, for example, US Pat. the device FTM-Lite NIR Coating Thickness Gauge Company Ingenieurs vom
  • 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 writing monomers e B), the stabilizers, which could already have been dissolved in component B), and, where appropriate, the oil and additives in the polyol used (is ocyanatreeptept b)), optionally at 60 10 ° C. were added to Whitehouse Scientific Ltd., Waverton, Chester, ( ⁇ 13 7PB, United Kingdom) and thoroughly mixed, after which the photoinitiator (s) or photoinitiators C) were weighed in the dark or under suitable illumination and again 1 Minute mixed. If appropriate, the mixture was heated to 60 ° C. in the drying oven for a maximum of 10 minutes. Then the isocyanate component a1) was added and mixed again in 1 minute.
  • the writing monomers B), the stabilizers, which could already be pre-dissolved in component B) and optionally the auxiliaries and additives in the polyol used (isocyanate-reactive component b)) were optionally dissolved at 60 ° C. and mixed thoroughly , Thereafter, in the dark or under suitable illumination, the photoinitiator (s) C) and the chain transfer agent (s) E) were added and mixed again for 1 minute to give a clear solution. Then the isocyanate component a) was added and mixed again in 1 minute. The resulting liquid composition was then applied to substrate film 1 and dried at 80 ° C for 4.5 minutes. The dry film thickness was determined.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)
  • Holo Graphy (AREA)

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 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.
EP12770136.5A 2011-10-12 2012-10-11 Réactifs de transfert de chaîne dans des formulations photopolymères à base de polyuréthane Withdrawn EP2766903A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12770136.5A EP2766903A1 (fr) 2011-10-12 2012-10-11 Réactifs de transfert de chaîne dans des formulations photopolymères à base de polyuréthane

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11184771 2011-10-12
EP12770136.5A EP2766903A1 (fr) 2011-10-12 2012-10-11 Réactifs de transfert de chaîne dans des formulations photopolymères à base de polyuréthane
PCT/EP2012/070118 WO2013053792A1 (fr) 2011-10-12 2012-10-11 Réactifs de transfert de chaîne dans des formulations photopolymères à base de polyuréthane

Publications (1)

Publication Number Publication Date
EP2766903A1 true EP2766903A1 (fr) 2014-08-20

Family

ID=47008609

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12770136.5A Withdrawn EP2766903A1 (fr) 2011-10-12 2012-10-11 Réactifs de transfert de chaîne dans des formulations photopolymères à base de polyuréthane

Country Status (7)

Country Link
US (1) US20140295328A1 (fr)
EP (1) EP2766903A1 (fr)
JP (1) JP2014535072A (fr)
KR (1) KR20140082692A (fr)
CN (1) CN103875037A (fr)
BR (1) BR112014008577A2 (fr)
WO (1) WO2013053792A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL2317511T3 (pl) * 2009-11-03 2012-08-31 Bayer Materialscience Ag Formulacje fotopolimerowe z nastawialnym mechanicznym modułem 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
TR201809751T4 (tr) * 2013-10-17 2018-07-23 Covestro Deutschland Ag Holografi ortamlarının üretimi için düşük TG değerine sahip boratları içeren fotopolimer formülasyonu.
EP3234021A1 (fr) * 2014-12-17 2017-10-25 Covestro Deutschland AG Photopolymère comprenant une nouvelle classe de photo-initiateur
CN107223121B (zh) * 2014-12-19 2020-10-27 科思创德国股份有限公司 湿稳定的全息介质
MX2019015445A (es) * 2017-06-27 2020-02-19 Albemarle Corp Espuma de poliuretano retardante de llama.
WO2020172154A1 (fr) * 2019-02-18 2020-08-27 The Regents Of The University Of Colorado, A Body Corporate Polymères de réseau et leurs procédés de fabrication et d'utilisation
CN110016117B (zh) * 2019-04-26 2021-10-01 福建华夏蓝新材料科技有限公司 一种自交联聚氨酯分散体及其制备方法和应用
CN111423529B (zh) * 2020-03-28 2022-05-17 海南师范大学 基于氨基酸衍生物的自由基光聚合引发体系及其引发自由基光聚合的方法
CN111410705B (zh) * 2020-05-21 2021-07-06 北京航空航天大学 多组分光引发体系及光致聚合物材料
CN112876617B (zh) * 2021-01-20 2022-11-01 西北大学 一种多孔分子印迹缓释材料的制备方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0389067B1 (fr) 1985-11-20 1994-10-19 The Mead Corporation Colorants ioniques
US4917977A (en) 1988-12-23 1990-04-17 E. I. Du Pont De Nemours And Company Visible sensitizers for photopolymerizable compositions
US5536529A (en) * 1989-05-11 1996-07-16 Borden, Inc. Ultraviolet radiation-curable coatings for optical fibers and optical fibers coated therewith
US5482908A (en) 1994-09-08 1996-01-09 Arco Chemical Technology, L.P. Highly active double metal cyanide catalysts
JP2006235386A (ja) * 2005-02-25 2006-09-07 Fuji Photo Film Co Ltd ホログラム記録材料およびこれを用いた光記録媒体
US7704643B2 (en) * 2005-02-28 2010-04-27 Inphase Technologies, Inc. Holographic recording medium with control of photopolymerization and dark reactions
TW200702954A (en) * 2005-07-11 2007-01-16 Toagosei Co Ltd Volume hologram recording material, the method of processing thereof and the recording medium
JP2007093688A (ja) * 2005-09-27 2007-04-12 Toshiba Corp ホログラム記録媒体、マスターホログラムの製造方法およびコピーホログラムの製造方法
US20070191506A1 (en) * 2006-02-13 2007-08-16 3M Innovative Properties Company Curable compositions for optical articles
JP4698470B2 (ja) * 2006-03-31 2011-06-08 富士フイルム株式会社 光記録媒体の処理方法及び処理装置、並びに光記録再生装置
EP2110718B1 (fr) * 2007-02-05 2012-10-10 Nippon Steel Chemical Co., Ltd. Matériau d'enregistrement holographique à phase de volume et support d'enregistrement d'information optique
CN101320208B (zh) 2008-07-21 2011-06-01 上海复旦天臣新技术有限公司 反射全息薄膜及其制备方法
JP2010157706A (ja) * 2008-12-03 2010-07-15 Fujifilm Corp 光インプリント用硬化性組成物およびそれを用いた硬化物の製造方法
JP2012111787A (ja) * 2009-03-31 2012-06-14 Nippon Steel Chem Co Ltd 感光性材料、感光性材料前駆体及び感光性材料の製造方法
US8771903B2 (en) 2009-11-03 2014-07-08 Bayer Materialscience Ag Method for producing a holographic film
JP5638085B2 (ja) 2009-11-03 2014-12-10 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ 異なった書込コモノマーを含有する感光性ポリマー組成物
CN102667934B (zh) * 2009-11-03 2015-09-09 拜尔材料科学股份公司 作为光聚合物制剂中的添加剂的氟代氨基甲酸酯
EP2372454A1 (fr) * 2010-03-29 2011-10-05 Bayer MaterialScience AG Formulation photopolymère destinée à la fabrication d'un hologramme visible
EP2766902A1 (fr) * 2011-10-12 2014-08-20 Bayer Intellectual Property GmbH Réactifs de transfert de chaîne soufrés dans des formulations photopolymères à base de polyuréthane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013053792A1 *

Also Published As

Publication number Publication date
US20140295328A1 (en) 2014-10-02
CN103875037A (zh) 2014-06-18
JP2014535072A (ja) 2014-12-25
BR112014008577A2 (pt) 2017-04-18
KR20140082692A (ko) 2014-07-02
WO2013053792A1 (fr) 2013-04-18

Similar Documents

Publication Publication Date Title
EP2172504B1 (fr) Formules de photopolymères ayant une densité de réseau réduite
WO2013053792A1 (fr) Réactifs de transfert de chaîne dans des formulations photopolymères à base de polyuréthane
JP6329600B2 (ja) ホログラフィック媒体を製造するためのフォトポリマー処方物
EP2317511B1 (fr) Formules de photopolymères dotées d'un module mécanique réglable Guv
EP2531889B1 (fr) Utilisation d'une formulation de photopolymère comprenant des monomères d'écriture à base d'ester pour la fabrication des médias holographiques
EP2531892B1 (fr) Utilisation d'une composition de photopolymère contenant des monomères d'écriture à base de triazine
EP2497085B1 (fr) Procédé de fabrication d'un film holographique
EP2496549B1 (fr) Méthacrylates nouveaux non cristallisants, leur fabrication et leur utilisation
EP3230261B1 (fr) Acrylate naphtyle comme monomère d'écriture pour photo-polymères
WO2013053771A1 (fr) Réactifs de transfert de chaîne soufrés dans des formulations photopolymères à base de polyuréthane
EP2372454A1 (fr) Formulation photopolymère destinée à la fabrication d'un hologramme visible
EP2497083A1 (fr) Formulation de photopolymères contenant divers comonomères d'enregistrement
WO2010037515A1 (fr) Supports pour enregistrement holographique en volume, à base d'un polymère autodéveloppant
EP2845195B1 (fr) Nouveaux photo-initiateurs pour photopolymères
EP2962302B1 (fr) Laque de protection pour applications photopolymeriques à base d'acrylate
EP2354845A1 (fr) Monomères d'écriture à base de (méth)acrylate
EP3233791A1 (fr) Milieux holographiques stables à l'humidité
EP2801867A1 (fr) Moyen d'enregistrement holographique avec couche anti-halo et procédé de fabrication de celui-ci
WO2023156485A1 (fr) Sels de triarylalkylborate servant de co-amorceurs dans des compositions de photopolymères nir
TW201331282A (zh) 以聚胺基甲酸酯為主的光聚合物調配物中的鏈轉移劑

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140512

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20140829