EP3314607A1 - Supports holographiques contenant des colorants de cyanine substitués par une chaîne - Google Patents

Supports holographiques contenant des colorants de cyanine substitués par une chaîne

Info

Publication number
EP3314607A1
EP3314607A1 EP16733368.1A EP16733368A EP3314607A1 EP 3314607 A1 EP3314607 A1 EP 3314607A1 EP 16733368 A EP16733368 A EP 16733368A EP 3314607 A1 EP3314607 A1 EP 3314607A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
independently
alkyl
methyl
cyano
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Withdrawn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
EP16733368.1A
Other languages
German (de)
English (en)
Inventor
Horst Berneth
Thomas Fäcke
Thomas RÖLLE
Serguei Kostromine
Friedrich-Karl Bruder
Dennis Hönel
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.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
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 Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP3314607A1 publication Critical patent/EP3314607A1/fr
Withdrawn legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/001—Phase modulating patterns, e.g. refractive index patterns
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • 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
    • 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
    • G03H1/04—Processes or apparatus for producing holograms
    • G03H1/0402—Recording geometries or arrangements
    • G03H1/0404—In-line recording arrangement
    • 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
    • G03H1/04—Processes or apparatus for producing holograms
    • G03H1/0402—Recording geometries or arrangements
    • G03H1/0408—Total internal reflection [TIR] holograms, e.g. edge lit or substrate mode holograms
    • 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
    • G03H1/26—Processes or apparatus specially adapted to produce multiple sub- holograms or to obtain images from them, e.g. multicolour technique
    • G03H1/268—Holographic stereogram
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • 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
    • G03H1/04—Processes or apparatus for producing holograms
    • G03H1/0402—Recording geometries or arrangements
    • G03H2001/0413—Recording geometries or arrangements for recording transmission holograms
    • 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
    • G03H1/04—Processes or apparatus for producing holograms
    • G03H1/0402—Recording geometries or arrangements
    • G03H2001/0415—Recording geometries or arrangements for recording reflection holograms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2222/00—Light sources or light beam properties
    • G03H2222/33—Pulsed light beam
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2260/00—Recording materials or recording processes
    • G03H2260/12—Photopolymer

Definitions

  • the present invention relates to a photopolymer composition
  • a photopolymer composition comprising a photopolymerizable component and a photoinitiator system containing a chain-substituted cyanine colorant.
  • Further objects of the invention are a photopolymer comprising a photopolymer composition according to the invention, a holographic medium containing a photopolymer according to the invention, the use of a holographic medium according to the invention and a method for producing a holographic medium using the photopolymer according to the invention and the exposure of the corresponding holographic medium with the help of pulsed laser radiation.
  • Photopolymer compositions of the type mentioned above are known in the art.
  • WO 2008/125229 A1 describes a photopolymer composition and a photopolymer obtainable therefrom which comprise polyurethane matrix polymers, an acrylate-based writing monomer and photoinitiators comprising a coinitiator and a dye.
  • the refractive index modulation ⁇ produced by the holographic exposure plays the decisive role.
  • the interference field of signal and reference light beam (in the simplest case, that of two plane waves) is converted by the local photopolymerization of random monomers, e.g.
  • diffraction efficiency The strength of the thus reconstructed signal in relation to the intensity of the incident reference light.
  • the DE results from the quotient of the intensity of the light diffracted during the reconstruction and the sum of the intensities of non-diffracted and diffracted light.
  • the matrix polymers and the writing monomers of a photopolymer composition should in principle be chosen such that they differ as much as possible in their refractive indices.
  • a possibility To realize is to use matrix polymers with the lowest possible and writing monomers with the highest possible refractive index.
  • Suitable low refractive index matrix polymers are, for example, polyurethanes obtainable by reaction of a polyol with a polyisocyanate component.
  • the matrix polymers are highly crosslinked in the finished medium. If the degree of crosslinking is too low, the medium does not have sufficient stability. This can lead to a significant reduction in the quality of holograms written in the media. In the worst case, the holograms can even be destroyed later.
  • the photosensitivity is sufficient to be able to expose a large area and without loss of index modulation for a given laser light source.
  • the choice of a suitable photoinitiator is of crucial importance for the properties of the photopolymer.
  • holographic exposure with a continuous laser source encounters technical limitations in the case of large-area exposure, since it is always necessary to irradiate a certain light dose per unit area in order to ensure efficient formation of the hologram and limit the technically available laser power.
  • large-area exposures at relatively low dose require long exposure times, which in turn make very high demands on the mechanical vibration damping of the exposure setup.
  • holograms can be written point by point. Since pulsed lasers or fast optical shutters are technically available and such an exposure structure has very low requirements with respect to the mechanical vibration damping, it is a good technical alternative to the above-described constructions with continuous lasers for large-area exposure of holograms.
  • the photopolymers known from WO 2008/125229 Al have, because of the photoinitiators used there, too low photosensitivity in order to be able to use them when writing holograms with pulsed lasers.
  • the object of the present invention was to provide a photopolymer composition with the aid of which it is possible to produce photopolymers into which holograms can be written with pulsed lasers because of their higher photosensitivity.
  • a photopolymer composition comprising a photopolymerizable component and a photoinitiator system comprising a chain-substituted cyanine dye of the formula (I)
  • K is a radical of the formula (II)
  • X 1 is O, S, NR 7 , CR 9 or CR U R 12 ,
  • X 2 is O, S, NR 8 , CR 10 or CR 13 R 14 ,
  • Q 1 is hydrogen, cyano or methyl
  • Q 2 is hydrogen or cyano
  • Q 3 is hydrogen or a radical of the formula (V) Air
  • X 4 is N or CR 6 ,
  • X 5 is N, O or CR 20
  • R 20 , R 1 , R 2 , R 7 , R 8 , R 15 and R 19 independently of one another are C 1 - to C 6 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalk I or C 7 - to Ci- Aralkyl stand and
  • R 15 can additionally be hydrogen
  • R 9 and R 10 independently of one another represent hydrogen or C 1 - to C 2 -alkyl
  • R 11 , R 12 , R 13 , R 14 and R 20 independently of one another are C 1 - to C 4 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalkyl or C 7 - to Cio-aralkyl or R 11 and R 12 together and / or R 13 and R 14 together are a -CH2-CH2-CH2- or -CH 2 form -CH2-CH2-CH2-CH 2 bridge, and in addition
  • R 7 , R 9 or R 12 together with Q 1 can form a -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 -bridge,
  • R 3 and R 4 independently of one another are C 1 - to C 6 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalkyl, C 7 - to C 10 -aralkyl or C - to C 10 -aryl or
  • R 3 , R 4 is a -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -O-CH 2 -CH 2 -, -CH 2 -CH 2 --NH-CH 2 Form -CH 2 - or -CH 2 -CH 2 -N (alkyl) -CH 2 -CH 2 - bridge, R 5 and R 16 independently of one another represent hydrogen, C 1 - to C 8 -alkyl, C 4 - to C 7 -cycloalkyl or
  • R 6 is hydrogen, alkyl or cyano
  • R 17 and R 18 independently of one another represent hydrogen, chlorine, methyl, ethyl, methoxy or ethoxy
  • n and m independently of one another denote 0 or 1, where m is only 1, even if n stands for 1, and
  • Q 1 is cyano or together with R 12 forms a -Cfb-Cfb-CI-b bridge
  • Q 2 is hydrogen or cyano, preferably hydrogen
  • Q 3 is hydrogen, the ring A together with R 1 , N and X 1 and the atoms connecting them for a remainder of the
  • R 1 is C 1 -C 8 -alk, C 3 -C -alkenyl, C 4 -C 7 -cycloalk 1 or C 7 -C 10 -arylalkyl,
  • R 11 and R 12 are independently C 1 to C 4 alkyl, C 3 to C 6 alkenyl, C 4 to C 7 cycloalk I or C 7 to C 10 aralkyl, or together represent a -CH 2 -CH 2 -CH 2 -CH 2 - or -CH2-CH2- CH 2 -CH 2 -CH 2 bridge form,
  • R 21 and R 22 are independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen,
  • R 23 and R 24 are independently hydrogen, chloro, cyano, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen, ring B together with R 2 , N and X 2 and the atoms connecting them for a rest of the formulas
  • R 2 is C 1 -C 8 -alk, C 3 -C 6 -alkenyl, C 4 -C 7 -cycloalkyl or C 7 -C 10 -arylalkyl,
  • R 13 and R 14 independently of one another are C 1 - to C 4 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalk I or C 7 - to C 10 -aralkyl, or together form a -CH 2 -CH 2 -CH 2 -CH 2 - or -CH2-CH2- CH 2 -CH 2 -CH 2 bridge form,
  • R 25 and R 26 are each independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen,
  • R 27 and R 28 independently represent hydrogen, chlorine, cyano, methyl, ethyl, methoxy or
  • X 3 stands for S
  • X 4 is N or CR 6 , preferably N,
  • R 3 and R 4 independently of one another are C 1 - to C 6 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalkyl, C 7 - to C 10 -aralkyl or C 1 - to C 10 -aryl, or
  • R 3 , R 4 form a -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 - or -CH 2 -CH 2 -O-CH 2 -CH 2 -bridge,
  • R 5 is Ci- to Cs-alkyl or Ce- to Cio-aryl
  • R 6 is hydrogen or cyano
  • R 15 is hydrogen, C 1 - to C 8 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalkyl or C 7 - to Cio- aralkyl,
  • R 16 is hydrogen, C 1 -C 4 -alkyl, C 5 -C 6 -cycloalkyl or C 6 -aryl,
  • R 17 and R 18 are each independently hydrogen, chloro, methyl or methoxy, preferably only one of which is not hydrogen, n and m are independently 0 or 1, where m is 1 only, albeit n stands for 1, and
  • a further embodiment of the invention is characterized in that Q 1 and Q 2 are hydrogen,
  • Q 3 is a radical of the formula (V), the ring A together with R 1 , N and X 1 and the atoms connecting them is a radical of
  • R 1 and R 19 independently of one another represent C 1 - to C 6 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalkyl or C 7 - to C 10 -aralkyl
  • R 11 and R 12 independently of one another are C 1 - to C 4 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalk I or C 7 - to C 1 -alkenyl or together form a -CH 2 -CH 2 -CH 2 -CH 2 - or -CH2-CH2- CH 2 -CH 2 -CH 2 bridge form,
  • R 21 and R 22 are independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen,
  • R 23 and R 24 are independently hydrogen, chloro, cyano, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen, ring B together with R 2 , N and X 2 and the atoms connecting them for a rest of the formulas
  • R 2 is Ci- to Cs-alkyl, C3- to Ce-alkenyl, C4- to C7-cycloalk I or C7- to Cio-aralkyl,
  • R 13 and R 14 independently of one another are C 1 - to C 4 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalkyl or C 7 - to C 10 -aralkyl or together form a -CH 2 -CH 2 -CH 2 -CH 2 - or - Form CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -bridge,
  • R 25 and R 26 are each independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen,
  • R 27 and R 28 independently of one another are hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, preferably only one of which does not represent hydrogen,
  • X 5 is S or C (CH 3 ) 2 , X 3 stands for S,
  • X 4 is N or CR 6 , preferably N,
  • R 3 and R 4 independently of one another are C 1 - to C 6 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalkyl, C 7 - to C 10 -aralkyl or C 1 - to C 10 -aryl, or
  • R 3 , R 4 form a -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 - or -CH 2 -CH 2 -O-CH 2 -CH 2 -bridge,
  • R 5 is C 1 -C -alkyl or C 6 -C 10 -aryl
  • R 6 is hydrogen or cyano
  • R 15 represents hydrogen, C 1 - to C 6 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalkyl or C 7 - to C 10 -aralkyl,
  • R 16 is hydrogen, C 1 - to C 4 -alkyl, C 5 - to Ce-cycloalkyl or Ce-aryl,
  • R 17 and R 18 are independently hydrogen, chloro, methyl or methoxy, preferably only one of which is not hydrogen, n and m are both 1 and
  • Q 1 is cyano or together with R 12 forms a -Ctb-Ctb-CI-b bridge
  • Q 2 and Q 3 are hydrogen, the ring A together with R 1 , N and X 1 and the atoms connecting them for a remainder of
  • R 1 is methyl, ethyl, 1-propyl, 1-butyl, benzyl or cyanoethyl,
  • R 11 and R 12 are, independently of one another represent methyl, ethyl or benzyl together a - CH2-CH2-CH2-CH2- or -CH 2 -CH2-CH2-CH2-CH 2 bridge form,
  • R 21 represents hydrogen, chlorine, cyano, methoxycarbonyl, ethoxycarbonyl, methyl or methoxy,
  • R 22 and R 24 are hydrogen
  • R 23 is hydrogen, chlorine, cyano, methyl or methoxy, with R 2 , N and X 2 and the atoms connecting them, a radical of the formula
  • R 2 is methyl, ethyl, 1-propyl, 1-butyl, benzyl or cyanoethyl,
  • R 13 and R 14 are, independently of one another represent methyl, ethyl or benzyl together a - CH2-CH2-CH2-CH2- or -CH 2 -CH2-CH2-CH2-CH 2 bridge form,
  • R 25 is hydrogen, chlorine, cyano, methoxycarbonyl, ethoxycarbonyl, methyl or methoxy,
  • R 26 is hydrogen, X 3 stands for S,
  • R 3 and R 4 independently of one another are methyl, ethyl, 1-propyl, 1-butyl, 1-octyl, cyclohexyl or benzyl or
  • R 3 , R 4 form a -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 - or -CH 2 -CH 2 -O-CH 2 -CH 2 -bridge,
  • R 5 is methyl, ethyl, tert-butyl, phenyl, 4-methylphenyl or 4-methoxyphenyl,
  • R 15 is hydrogen, methyl, ethyl, 1-propyl-1-butyl, 1-octyl or benzyl,
  • R 16 is hydrogen, methyl or phenyl
  • R 17 is hydrogen, chlorine or methyl
  • R 18 stands for hydrogen and stands on "the equivalent of an anion.
  • Alkyl and alkoxy radicals can be unbranched or branched. They may also carry further radicals such as fluorine, chlorine, alkoxy, cyano or alkoxycarbonyl. Examples are methyl, ethyl, 1- or 2-propyl, 1- or 2-butyl, tert-butyl, 1-octyl, chloroethyl, cyanoethyl, methoxyethyl or trifluoromethyl.
  • Cycloalkyl radicals are preferably cyclopentyl or cyclohexyl.
  • Aralkyl radicals can be unbranched or branched in the alkyl moiety and carry further radicals in the aryl moiety. Examples are benzyl, phenethyl, 2- or 3-phenylpropyl, 4-chlorobenzyl, 4-methoxybenzyl.
  • Aryl radicals are phenyl or naphthyl, preferably phenyl, and may carry further radicals such as fluorine, chlorine, alkoxy, nitro, cyano or alkoxycarbonyl.
  • substituted phenyl radicals are 2-, 3- or 4-fluorophenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4- Methoxyphenyl, 2-, 3- or 4-cyanophenyl, biphenylyl, 3,4-dichlorophenyl, 3,4-dimethylphenyl, 3,4-dimethoxyphenyl.
  • the photopolymer composition according to the invention contains matrix polymers and at least one writing monomer.
  • the photopolymer composition additionally contains a coinitiator.
  • Suitable coinitiators are ammonium alkylarylborates which together with the dyes of the invention form a type II photoinitiator (Norrish type II) are described in principle in EP 0 223 587.
  • ammonium alkylaryl borates are, for example, (Cunningham et al., RadTech'98 North America UV / EB Conference Proceedings, Chicago, Apr. 19-22, 1998): tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinapthylhexylborate, tetrabutylammonium tris (4-tert-butyl ) -phenylbutylborate, tetrabutylammonium tris (3-fluorophenyl) -hexyrborate hexylborate ([191726-69-9], CGI 7460, product of BASF SE, Basel, Switzerland), 1-methyl-3-octylimidazolium dipentyldiphenylborate and tetrabutylammonium tris ( 3-chloro-4-methylphen
  • coinitiators are electron acceptors such.
  • the photoinitiator system can thus be prepared from at least one ammonium alkylaryl borate as described above and / or at least one electron acceptor such as, for.
  • known electron acceptors such as iodonium or sulfonium salts could be part of the photoinitiator system. It is also possible to use any mixtures of said coinitiators.
  • the invention likewise relates to photopolymers which contain a photopolymer composition according to the invention.
  • the matrix polymers of the photopolymer according to the invention may in particular be crosslinked and particularly preferably be crosslinked three-dimensionally. It is also advantageous if the matrix polymers are polyurethanes, where the polyurethanes may be obtainable in particular by reacting at least one polyisocyanate component a) with at least one isocyanate-reactive component b).
  • the polyisocyanate component a) preferably comprises at least one organic compound having at least two NCO groups. These organic compounds may in particular be monomeric di- and triisocyanates, polyisocyanates and / or NCO-functional prepolymers.
  • the polyisocyanate component a) may also contain or consist of mixtures of monomeric di- and triisocyanates, polyisocyanates and / or NCO-functional prepolymers.
  • monomeric di- and triisocyanates it is possible to use all the compounds or mixtures thereof which are well known to the person skilled in the art. These compounds may have aromatic, araliphatic, aliphatic or cycloaliphatic structures. In minor amounts, the monomeric di- and tri-isocyanates may also be monoisocyanates, i. include organic compounds having an NCO group.
  • Suitable monomeric di- and triisocyanates are 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 2,2,4-trimethylhexamethylene diisocyanate and / or 2,4,4-trimethylhexamethylene diisocyanate ( TMDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, bis (4,4'-isocyanatocyclohexyl) methane and / or bis (2 ', 4-isocyanatocyclohexyl) methane and / or their mixtures any isomer content, 1, 4-cyclohexane diisocyanate, the isomeric bis (isocyanatomethyl) cyclohexanes, 2,4- and / or 2,6-diisocyanato
  • Suitable polyisocyanates are compounds having urethane, urea, carbodiimide, acylurea, amide, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione and / or iminooxadiazinedione structures which are obtainable from the abovementioned di- or triisocyanates.
  • the polyisocyanates are particularly preferably oligomerized aliphatic and / or cycloaliphatic di- or triisocyanates, it being possible in particular to use the abovementioned aliphatic and / or cycloaliphatic di- or triisocyanates.
  • Suitable prepolymers contain urethane and / or urea groups and optionally further structures formed by modification of NCO groups as mentioned above.
  • Such prepolymers are obtainable, for example, by reacting the abovementioned monomeric diisocyanates and triisocyanates and / or polyisocyanates a1) with isocyanate-reactive compounds b1).
  • isocyanate-reactive compounds bl it is possible to use alcohols, amino or mercapto compounds, preferably alcohols. These may in particular be polyols. Very particular preference is given to using as the isocyanate-reactive compound bl) polyester, polyether, polycarbonate, poly (meth) acrylate and / or polyurethane polyols.
  • Suitable polyester polyols are, for example, linear polyester diols or branched polyester polyols which can be obtained in a known manner by reacting aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or their anhydrides with polyhydric alcohols having an OH functionality> 2.
  • suitable di- or polycarboxylic acids are polybasic carboxylic acids such as succinic, adipic, cork, sebacic, decanedicarboxylic, phthalic, terephthalic, isophthalic-tetrahydr-ophthalic or trimellitic acid, and also acid anhydrides such as phthalic, trimellitic or succinic anhydride or their mixtures with each other.
  • 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 homopolymers or copolymers of lactones, which preferably by addition of lactones or lactone mixtures such as butyrolactone, ⁇ -caprolactone and / or methyl-s-caprolactone to hydroxy-functional compounds such as polyhydric alcohols of an OH functionality > 2, for example of the type mentioned below can be obtained.
  • suitable alcohols are all polyhydric alcohols such as the C2 - Cn-diols, the isomeric cyclohexanediols, glycerol or any mixtures thereof.
  • 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. Polyester polyols can also be converted to polycarbonate polyols.
  • Suitable polyether polyols are optionally block-formed polyaddition of cyclic ethers to OH 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 OH functionality> 2 mentioned in the context of the polyesterpolyols and also primary or secondary amines and amino alcohols.
  • 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. 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.
  • isocyanate-reactive compounds are also low molecular weight, i. with molecular weights ⁇ 500 g / mol, short chain, i. 2 to 20 carbon atoms containing aliphatic, araliphatic or cycloaliphatic di-, tri- or polyfunctional alcohols suitable.
  • neopentyl glycol 2-ethyl-2-butylpropanediol, trimethylpentanediol, positional isomeric diethyloctanediols, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2- and 1, 4 Cyclohexanediol, hydrogenated bisphenol A, 2,2-bis (4-hydroxy-cyclohexyl) -propane or 2,2-dimethyl-3-hydroxypropionic acid, 2,2-dimethyl-3-hydroxypropyl ester.
  • triols examples are trimethylolethane, trimethylolpropane or Glycerol.
  • Suitable higher functional alcohols are di (trimethylolpropane), pentaerythritol, dipentaerythritol or sorbitol.
  • the polyol component is a difunctional polyether, polyester or a polyether-polyester block copolyester or a polyether-polyester block copolymer having primary OH functions.
  • isocyanate-reactive compounds bl) amines are ethylene diamine, propylene diamine, diaminocyclohexane, 4,4'-Dicylohexylmethandiamin, isophoronediamine (IPDA), difunctional polyamines such as Jeffamine ®, amine-terminated polymers, in particular having number average molecular weights of ⁇ 10000 g / mol. Mixtures of the aforementioned amines can also be used.
  • isocyanate-reactive compounds bl) amino alcohols are also possible to use as isocyanate-reactive compounds bl) amino alcohols.
  • suitable amino alcohols are the isomeric aminoethanols, the isomeric aminopropanols the isomeric aminobutanols and the isomeric aminohexanols or any mixtures thereof.
  • All of the aforementioned isocyanate-reactive compounds B1) can be mixed with one another as desired.
  • the isocyanate-reactive compounds bl) have a number average molecular weight of> 200 and ⁇ 10000 g / mol, more preferably> 500 and ⁇ 8000 g / mol and very particularly preferably> 800 and ⁇ 5000 g / mol.
  • the OH functionality of the polyols is preferably 1.5 to 6.0, particularly preferably 1.8 to 4.0.
  • the prepolymers of the polyisocyanate component a) may in particular have a residual content of free monomeric di- and triisocyanates ⁇ 1% by weight, more preferably ⁇ 0.5% by weight and most preferably ⁇ 0.3% by weight.
  • the polyisocyanate component a) may comprise completely or proportionally organic compound whose NCO groups have been completely or partially reacted with blocking agents known from coating technology.
  • blocking agents are alcohols, lactams, oximes, malonates, pyrazoles and amines, such as butanone oxime, diisopropylamine, diethyl malonate, acetoacetic ester, 3,5-dimethylpyrazole, ⁇ -caprolactam, or mixtures thereof.
  • the polyisocyanate component a) comprises compounds having aliphatically bonded NCO groups, aliphatic NCO groups being understood to mean those groups which are bonded to a primary carbon atom.
  • the isocyanate-reactive component b) preferably comprises at least one organic compound which has on average at least 1.5 and preferably from 2 to 3 isocyanate-reactive groups.
  • hydroxy, amino or mercapto groups are preferably considered as isocyanate-reactive groups.
  • the isocyanate-reactive component may in particular comprise compounds which have a number average of at least 1.5 and preferably 2 to 3 isocyanate-reactive groups.
  • Suitable polyfunctional, isocyanate-reactive compounds of component b) are, for example, the compounds bl) described above.
  • the writing monomer c) comprises or consists of at least one mono- and / or one multifunctional writing monomer. More preferably, the writing monomer may comprise or consist of at least one mono- and / or a multifunctional (meth) acrylate random monomer. Most preferably, the writing monomer may comprise or consist of at least one mono- and / or a multifunctional urethane (meth) acrylate.
  • Suitable acrylate Schreibmonomere are in particular compounds of the general formula (VI)
  • R 100 is a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radical and / or R 101 is hydrogen, a linear, branched, cyclic or heterocyclic unsubstituted or optionally also with Heteroatoms substituted organic radical is.
  • R 101 is preferably hydrogen or methyl and / or R 100 is a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radical.
  • esters of acrylic acid or methacrylic acid are referred to.
  • preferably usable acrylates and methacrylates are phenyl acrylate, phenyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxyethoxyethyl acrylate,
  • Urethane acrylates in the present context are understood as meaning compounds having at least one acrylic acid ester group and at least one urethane bond. Such compounds can be obtained, for example, by reacting a hydroxy-functional acrylate or methacrylate with an isocyanate-functional compound.
  • Suitable isocyanate-functional compounds are monoisocyanates and the monomeric diisocyanates, triisocyanates and / or polyisocyanates mentioned under a).
  • suitable monoisocyanates are phenyl isocyanate, the isomeric Methylthiophenylisocyanate, the isomeric Phenylthiophenylisocyanate.
  • Aromatic di-, tri- or polyisocyanates are preferred as hydroxy-functional acrylates or methacrylates for the preparation of urethane acrylates, for example compounds such as 2-hydroxyethyl (meth) acrylate , polyethylene oxide mono (meth) acrylates, Polypropylenoxidmono (meth) acrylates, Polyalkylenoxidmono (meth) acrylates, poly (s- caprolactone) mono (meth) acrylates, such as Tone ® Ml 00 (Dow, Schwalbach, Germany), 2- Hydroxypropyl (meth) acrylate, 4-hydroxybutyl
  • hydroxyl-containing epoxy (meth) acrylates known per se with OH contents of 20 to 300 mg KOH / g or hydroxyl-containing polyurethane (meth) acrylates with OH contents of 20 to 300 mg KOH / g or acrylated polyacrylates with OH Contents of 20 to 300 mg KOH / g and mixtures thereof and mixtures with hydroxyl-containing unsaturated polyesters and mixtures with polyester (meth) acrylates or mixtures of hydroxyl-containing unsaturated polyester with polyester (meth) acrylates.
  • urethane acrylates are obtainable from the reaction of tris (p-isocyanatophenyl) thiophosphate and / or m-methylthiophenyl isocyanate and / or m- or o-phenylthiophenyl isocyanates with alcohol-functional acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and / or hydroxybutyl (meth) acrylate.
  • alcohol-functional acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and / or hydroxybutyl (meth) acrylate.
  • the writing monomer further unsaturated compounds such as ⁇ , ⁇ -unsaturated carboxylic acid derivatives such as maleinates, fumarates, maleimides, acrylamides, vinyl ethers, propenyl ethers, allyl ether and dicyclopentadienyl units containing compounds and olefinically unsaturated compounds such.
  • unsaturated compounds such as ⁇ , ⁇ -unsaturated carboxylic acid derivatives such as maleinates, fumarates, maleimides, acrylamides, vinyl ethers, propenyl ethers, allyl ether and dicyclopentadienyl units containing compounds and olefinically unsaturated compounds such.
  • Photoinitiators of component d) are usually activatable by actinic radiation compounds which can initiate a polymerization of the writing monomers.
  • actinic radiation compounds which can initiate a polymerization of the writing monomers.
  • a distinction can be made between unimolecular (type I) and bimolecular (type II) initiators.
  • photoinitiators for radical, anionic, cationic or mixed type of polymerization.
  • Radical polymerization type ⁇ photoinitiators consist of a dye as a sensitizer and a coinitiator and undergo a bimolecular reaction upon irradiation with dye-adapted light. First, the dye absorbs a photon and transfers energy to the coinitiator from an excited state. This releases the polymerization-initiating radicals by electron or proton transfer or direct hydrogen abstraction.
  • Preferred anions on "in the inventive chain substituted cyanine dyes are particularly Cs to C25 alkane, preferably C - to C25-alkane, C3 to Cis perfluoroalkanesulfonate, C4 to Cis-perfluoroalkanesulfonate, which in the alkyl chain, at least 3 Hydrogen, C9 to C25 alkanoate, C9 to C25 alkenoate, C5 to C25 alkyl sulphate, preferably C13 to C25 alkyl sulphate, C5 to C25 alkenyl sulphate, preferably C6 to C25 alkenyl sulphate, C3 bis Cis perfluoroalkyl sulfate, C4 to C18 perfluoroalkyl sulfate bearing at least 3 hydrogen atoms in the alkyl chain, polyether sulfates based on at least 4 equivalents of ethylene oxide and / or equivalents 4 propylene oxide, B1S
  • 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 to 6.5 ., 2005, 19, 453; Virtual Computational Chemistry Laboratory, http://www.vcclab.org.
  • the counter anions may be arbitrary, excluding dibenzylsulfosuccinate as the anion.
  • photoinitiators it may be advantageous to use mixtures of these photoinitiators.
  • the type and concentration of photoinitiator must be adapted in a manner known to the person skilled in the art. Further details are described, for example, in P.K.T. Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 3, 1991, SITA Technology, London, pp. 61-328.
  • 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.
  • At least one suitable for a laser light color selected from blue, green, yellow and red photoinitiator is included in the photopolymer composition.
  • the photopolymer composition contains at least two laser light colors selected from blue, green, yellow and red, each containing a suitable photoinitiator.
  • the photopolymer composition in each case contains a suitable photoinitiator for each of the laser light colors blue, green and red.
  • the photopolymer composition additionally contains urethanes as additives, wherein the urethanes may be substituted in particular with at least one fluorine atom.
  • the urethanes may preferably have the general formula (VIII) have in which p> l and m ⁇ 8 and R 200 , R 201 and R 202 are linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radicals and / or R 201 , R 202 are independently hydrogen, wherein preferably at least one of the radicals R 200 , R 201 , R 202 is substituted by at least one fluorine atom and more preferably R 200 is an organic radical having at least one fluorine atom.
  • R 201 is particularly preferably a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by heteroatoms such as fluorine organic radical.
  • a further subject of the present invention is a photopolymer comprising matrix polymers, a writing monomer and a photoinitiator, wherein the photoinitiator contains a coinitiator and a cationic dye and the cationic dye contains a chain-substituted cyanine dye of the formula (I)
  • Dyes of the formula (I) in which K is a radical of the formula (III) can be prepared, for example, by reacting aldehydes of the formula the formula
  • the reaction can be carried out, for example, under acidic conditions in the presence of protic acids or inorganic acid chlorides.
  • suitable protic acids are sulfuric acid and sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid
  • inorganic acid chlorides are, for example, phosgene, thionyl chloride or phosphoroxychloride.
  • Solvents in the case of the use of protic acids are polar solvents, for example alcohols such as ethanol, carboxylic acids such as glacial acetic acid, aprotic solvents such as dimethyl sulfoxide, N-ethylpyrrolidone, dimethylformamide.
  • solvents are aromatics such as toluene, xylene, chlorinated solvents such as trichloromethane, chlorobenzene.
  • the reaction takes place at room temperature to the boiling point of the medium, preferably at 30 to 90 ° C.
  • the matrix polymers of the photopolymer according to the invention may in particular be crosslinked and particularly preferably be crosslinked three-dimensionally.
  • the matrix polymers are polyurethanes, where the polyurethanes may be obtainable in particular by reacting at least one polyisocyanate component with at least one isocyanate-reactive component.
  • the invention also provides a holographic medium, in particular in the form of a film, comprising a photopolymer according to the invention or obtainable using a photopolymer composition according to the invention.
  • a holographic medium in particular in the form of a film, comprising a photopolymer according to the invention or obtainable using a photopolymer composition according to the invention.
  • Yet another object of the invention the use of a photopolymer composition according to the invention for the production of holographic media.
  • holographic information is imprinted therein.
  • 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).
  • the invention likewise relates to holograms comprising a holographic medium according to the invention.
  • Visual holograms include all holograms that can be recorded by methods known to those skilled in the art.
  • in-line (Gabor) holograms include 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 holograms, and holographic stereograms, particularly for the production of optical elements, images or image representations. Preference is given to reflection holograms, denisy-holograms, transmission holograms.
  • Possible optical functions of the holograms which can be produced with the photopolymer compositions according to the invention correspond to the optical functions of light elements such as lenses, mirrors, deflection mirrors, filters, diffusers, diffractive elements, diffusers, light guides, waveguides, projection screens and / or masks. Also, combinations of these optical functions may be unified independently in a hologram. 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 media according to the invention, for example for personal portraits, biometric representations in security documents, or generally for 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, including in combination with the previously presented products.
  • 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 volume holograms, an attractive technical solution for the above application is.
  • the present invention furthermore relates to the use of a holographic medium according to the invention for recording in-line, off-axis, full-aperture transfer, white-light transmissions, denisyuk, off-axis reflection or edge-lit holograms and holographic stereograms, in particular for Production of optical elements, images or image representations.
  • a further subject of the present invention is also a process for producing a holographic medium using the photopolymer composition or the photopolymer composition according to the invention.
  • the holographic medium is exposed using laser light, wherein the exposure is effected by pulsed laser radiation.
  • a method for producing a hologram in which pulsed laser radiation is used for the exposure of the medium.
  • the pulse duration is ⁇ 200 ns, preferably ⁇ 100 ns, particularly preferably ⁇ 60 ns.
  • the pulse duration must not be less than 0.5 ns. Particularly preferred is a pulse duration of 4 ns.
  • the photopolymer compositions can be used in particular for producing holographic media in the form of a film.
  • a layer of a material or composite material transparent to light in the visible spectral range is coated on one or both sides and optionally a cover layer applied to the photopolymer layer (s).
  • Preferred materials or composite materials of the carrier 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, A / B / A or A / B / C.
  • PC / PET, PET / PC / PET and PC / TPU Thermoplastic Polyurethane.
  • the materials or composite materials of the carrier may be unilaterally or bilaterally anti-adhesive, antistatic, hydrophobed or hydrophilated.
  • the modifications mentioned serve on the photopolymer layer side facing the purpose that the photopolymer layer can be detached from the carrier nondestructive.
  • a modification of the side of the carrier facing away from the photopolymer layer serves to ensure that the media according to the invention satisfy specific mechanical requirements which are required, for example, in processing in roll laminators, in particular in roll-to-roll processes.
  • Another object of the invention are dyes of the formula (I) wherein
  • K is a radical of the formula (III), and the further radicals have the abovementioned meaning.
  • K is a radical of formula (III), n and m are 0, cyano or together with R 12 forms a CEb-CEb-CEb bridge, the ring A together with R 1 , N and X 1 and the atoms connecting them for a remainder of the formulas
  • R 1 is C 1 -C 8 -alk, C 3 -C 6 -alkenyl, C 4 -C 7 -cycloalkyl or C 7 -C 10 -arylalkyl,
  • R 11 and R 12 are independently C 1 to C 4 alkyl, C 3 to C 6 alkenyl, C 4 to C 7 cycloalk I or C 7 to C 10 aralkyl, or together represent a -CH 2 -CH 2 -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - bridge, R 21 and R 22 are independently hydrogen, chlorine, nitro, cyano, methoxycarbonyl, ethoxycarbonyl,
  • Methyl, ethyl, methoxy or ethoxy preferably only one of which is not hydrogen
  • R 23 and R 24 are independently hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, preferably only one of which is not hydrogen,
  • X 3 stands for S
  • X 4 is N or CR 6 , preferably N,
  • R 3 and R 4 independently of one another are C 1 - to C 6 -alkyl, C 3 - to C 6 -alkenyl, C 4 - to C 7 -cycloalkyl, C 7 - to C 10 -aralkyl or C 1 - to C 10 -aryl, or
  • R 3 , R 4 form a -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 - or -CH 2 -CH 2 -O-CH 2 -CH 2 -bridge,
  • R 5 is C 1 -C -alkyl or C 6 -C 10 -aryl
  • R 6 is hydrogen or cyano and An "represents the equivalent of an anion. Particular preference is given to dyes of the formula (I) in which
  • K is a radical of the formula (III), n and m are 0,
  • Q 1 is cyano, the ring A together with R 1 , N and X 1 and the atoms connecting them for a remainder of the
  • R 1 is methyl, ethyl, 1-propyl, 1-butyl, benzyl or cyanoethyl,
  • R 11 and R 12 independently represent methyl, ethyl or benzyl or together form a - CH 2 -CH 2 -CH 2 -CH 2 or -CH 2 CH 2 -CH 2 -CH 2 CH 2 bridge form,
  • R 21 represents hydrogen, chlorine, cyano, methoxycarbonyl, ethoxycarbonyl, methyl or methoxy,
  • R 22 and R 24 are hydrogen
  • R 23 is hydrogen, chlorine, cyano, methyl or methoxy
  • X 3 stands for S
  • X 4 is N or C-CN, preferably N
  • R 3 and R 4 independently of one another are methyl, ethyl, 1-propyl, 1-butyl, 1-octyl, cyclohexyl or benzyl or
  • R 3 is a -CH 2 -CH 2 -CH 2 -CH2-, -CH2-CH2-CH2-CH2- or -CH 2 -CH 2 form -0-CH 2 -CH 2 Bmcke,
  • R 5 is methyl, ethyl, tert-butyl, phenyl, 4-methylphenyl or 4-methoxyphenyl, preferably tert-butyl or phenyl and
  • Q 1 is cyano, with R 1 , N and X 1 and the atoms connecting them to a radical of the formula
  • R 1 is methyl or benzyl
  • R 11 and R 12 are methyl
  • R 21 is hydrogen, methoxycarbonyl or ethoxycarbonyl
  • R 22 is hydrogen, X 3 is S, X 4 is N,
  • R 3 and R 4 are the same and are methyl or ethyl or
  • R 3 , R 4 form a -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 - or -CH 2 -CH 2 -O-CH 2 -CH 2 -bridge,
  • R 5 is phenyl
  • FIG. 1 describes a film coating installation for producing holographic media on films.
  • FIG. 2 describes a holographic measuring arrangement for determining the diffraction efficiency after exposure, in particular laser pulse exposure.
  • the Denisyuk hologram of a mirror was recorded in a sample consisting of a glass plate with laminated photopolymer film.
  • the substrate of a photopolymer film pointed to the laser source and the glass substrate to the mirror.
  • the sample was aligned with the plane of its exposure perpendicular to the laser beam.
  • the distance sample to the mirror was 3 cm.
  • the laser used was a pulse laser from Quantel, France, model Brilliant b. It was a Q-switched Nd-YAG laser with a module for frequency doubling to 532 nm. The single frequency mode was guaranteed by a seed laser. The calculated coherence length was about 1 m. The pulse duration 4 ns and the average output power 3 watts at a pulse repetition rate of 10 Hz.
  • the electronically controlled shutter ensured single pulse exposure.
  • the wave plate allowed the rotation of the polarization plane of the laser light and with the following polarizer, the S-polarized portion of the laser light was reflected towards the sample.
  • the beam expansion allowed adjustment of the exposed area.
  • the wave plate and the beam spread were adjusted so that the sample reached an exposure dose of 100 mJ / cm 2 / pulse.
  • the samples were each exposed exactly with one pulse. After exposure, the sample was bleached on a light table. The hologram of the bleached sample was used to measure a transmission spectrum. A spectrometer from Ocean Optics, Model HR4000 was used. The sample was placed perpendicular to the light beam. The transmission spectrum showed a breakdown in transmission at the wavelength at which the Bragg condition was met. The depth of the transmission dip to the baseline was evaluated as the diffraction efficiency DE of the Denisyuk hologram of the mirror.
  • the solvents used were purchased in the chemicals trade.
  • Hexane diisocyanate-based polyisocyanate proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%.
  • the two-phase mixture was stirred for 1 h and then transferred to a separatory funnel.
  • the aqueous phase was drained off and the organic phase was washed four times with 40 ml of water.
  • the organic phase was diluted with 250 mL of butyl acetate and distilled on a rotary evaporator in vacuo anhydrous. In this case, about 200 mL of butyl acetate were distilled off, so that finally 150.1 g of a red solution of the dye of the formula
  • the concentration of the above solution could be determined to be 10.0%.
  • Comparative Dyes (Known from EP 2 638 544 A2): Comparative Dye 1:
  • TMDI 2,4,4-trimethylhexane 1,6-diisocyanate
  • FIG. 1 shows the schematic structure of the coating system used.
  • the individual components have the following reference numerals:
  • the photopolymer composition 53.7 g of the polyol 1 (OH number 59.7) was added stepwise with a mixture of 30.0 g of the urethane acrylate 1 and 30.0 g of the urethane acrylate 2, 22.5 g of the additive 1, 0.15 g of the triazine 1 or 2, 1.5 g borate, 0.075 g of Fomrez UL 28, and 1.35g of the surface-active additive BYK ® 310 and 50 g of ethyl acetate and mixed. Subsequently, 0.3 g of a dye of the invention was added to the mixture in the dark and mixed to obtain a clear solution.
  • the composition was heated at 60 ° C for a short time to more quickly dissolve the feeds.
  • This mixture was introduced into one of the two reservoirs 1 of the coating system.
  • the polyisocyanate component (Desmodur ® N 3900, commercial product of Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of hninooxadiazindion at least 30%, NCO content: 23.5%) was filled.
  • Both components were then each by the metering devices 2 in the ratio of 18.2 (component mixture) to 1.0 (isocyanate) to Vacuum degassing 3 funded and degassed. From here, they were then each passed through the filters 4 in the static mixer 5, in which the mixing of the components for photopolymer composition took place. The resulting liquid mass was then fed to the coating device 6 in the dark.
  • the coating device 6 in the present case was a doctor blade known to the person skilled in the art. Alternatively, however, a slot nozzle can also be used.
  • the photopolymer composition was applied at a processing temperature of 20 ° C to a carrier substrate 8 in the form of a 36 ⁇ thick polyethylene terephthalate and dried for 5.8 minutes at a crosslinking temperature of 80 ° C in a circulating air dryer 7.
  • a medium in the form of a film was obtained, which was then provided with a 40 ⁇ thick polyethylene film as a cover layer 9 and wound up. All these steps were in the dark.
  • the desired target layer thickness of the film was preferably 1 to 60 ⁇ , preferably 5 to 25 ⁇ , more preferably 10 to 15 ⁇ .
  • the production rate was preferably in the range of 0.2 m / min to 300 m / min and more preferably in the range of 1.0 m / min to 50 m / min.

Abstract

L'invention concerne une composition photopolymère comprenant un constituant photopolymérisable et un système photoamorceur qui contient un colorant de cyanine substitué par une chaîne. D'autres objets de l'invention sont un photopolymère comprenant une composition photopolymère de l'invention, un support holographique qui contient un photopolymère de l'invention, l'utilisation d'un support holographique de l'invention ainsi qu'un procédé de fabrication d'un support holographique faisant appel au photopolymère de l'invention ainsi que l'exposition du support holographique correspondant au moyen d'un rayonnement laser pulsé.
EP16733368.1A 2015-06-23 2016-06-21 Supports holographiques contenant des colorants de cyanine substitués par une chaîne Withdrawn EP3314607A1 (fr)

Applications Claiming Priority (2)

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EP15173234 2015-06-23
PCT/EP2016/064302 WO2016207155A1 (fr) 2015-06-23 2016-06-21 Supports holographiques contenant des colorants de cyanine substitués par une chaîne

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EP (1) EP3314607A1 (fr)
JP (1) JP2018526475A (fr)
KR (1) KR20180020162A (fr)
CN (1) CN107743595A (fr)
TW (1) TW201710405A (fr)
WO (1) WO2016207155A1 (fr)

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EP3470466A1 (fr) * 2017-10-13 2019-04-17 LANXESS Deutschland GmbH Nouveaux colorants méthyne
CN111982884A (zh) * 2020-09-15 2020-11-24 江苏师范大学 一种紧凑型266nm短波紫外拉曼光谱仪

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DE2214054A1 (de) * 1972-03-23 1973-09-27 Agfa Gevaert Ag Sensibilisierte elektrophotographische schichten
TW467933B (en) * 1995-11-24 2001-12-11 Ciba Sc Holding Ag Photopolymerizable compositions comprising borate photoinitiators from monoboranes and the use thereof
DE102004058584A1 (de) * 2004-12-03 2006-06-08 Basf Ag Strahlungshärtbare Beschichtungsmassen
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
JP5475244B2 (ja) * 2007-03-30 2014-04-16 株式会社Ａｄｅｋａ シアニン化合物、該化合物を用いた光学フィルター及び光学記録材料
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
CN103309157B (zh) * 2012-03-08 2015-06-17 中国科学院理化技术研究所 基于聚乙烯吡咯烷酮共聚物树脂的可阳离子光聚合成像组合物

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TW201710405A (zh) 2017-03-16
CN107743595A (zh) 2018-02-27
JP2018526475A (ja) 2018-09-13
US20180223100A1 (en) 2018-08-09
KR20180020162A (ko) 2018-02-27

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