EP4291951A1 - Système à deux composants - Google Patents

Système à deux composants

Info

Publication number
EP4291951A1
EP4291951A1 EP22708501.6A EP22708501A EP4291951A1 EP 4291951 A1 EP4291951 A1 EP 4291951A1 EP 22708501 A EP22708501 A EP 22708501A EP 4291951 A1 EP4291951 A1 EP 4291951A1
Authority
EP
European Patent Office
Prior art keywords
kit
mixture
dye
parts
liquid
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.)
Pending
Application number
EP22708501.6A
Other languages
German (de)
English (en)
Inventor
Frank Knocke
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.)
Xetos AG
Original Assignee
Xetos 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 Xetos AG filed Critical Xetos AG
Publication of EP4291951A1 publication Critical patent/EP4291951A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/02—Homopolymers or copolymers of esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/12—Esters of phenols or saturated alcohols
    • C08F22/20—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • 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
    • C09B21/00—Thiazine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings
    • G02B5/1847—Manufacturing methods
    • G02B5/1857—Manufacturing methods using exposure or etching means, e.g. holography, photolithography, exposure to electron or ion beams
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • 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
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/32—Holograms used as optical elements
    • 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 two-component system (kit-of-parts) and elements produced therefrom and their use.
  • kit-of-parts The photopolymerizable compositions produced from the kit-of-parts are particularly suitable as recording materials for optical elements with refractive index modulation, in particular holograms.
  • holograms such as reflection holograms, embossed holograms or transmission holograms or volume holograms are known.
  • Omnidex materials belong to the class of self-developing photopolymer films based on radical polymerisation and monomer diffusion (see EP 0 324 480 A2).
  • the binder for the coating must be liquid.
  • a solvent is used for this purpose, the evaporation of which after coating leads to a significant reduction in the layer thickness.
  • the wet layer to be applied is therefore significantly thicker than the resulting film layer, depending on the solvent content.
  • the proportion of solvent is usually around 80%.
  • a wet layer of 100pm must be applied in this case.
  • the necessary high thickness of the wet layer prevents or complicates the use of known printing processes such as flexographic or gravure printing. With screen printing, the use of fast-drying solvents can cause the mesh to stick.
  • the film can only be further processed or wound up once all the solvent has evaporated. In production, therefore, a long drying section with health- and environmentally-friendly extraction, as well as such as a dust and explosion-proof environment. This effort means that film production and holographic exposure usually take place at separate locations and times.
  • tempering In the case of the binder-containing materials, thermal post-treatment ("tempering") of the exposed and UV-fixed photopolymer is also necessary in order to achieve the maximum refractive index contrast (see DE 68905610 T2). Tempering is an additional, time-consuming processing step that hampers the production of the hologram slows down, complicates and increases the cost of film production, and also limits the choice of carrier materials to non-temperature-sensitive ones.
  • the user cannot freely choose the carrier material and coat it himself, but must process the supplied film structure.
  • the carrier film there is also a laminating film on the light-sensitive film layer to prevent sticking and soiling. Peeling off this film can cause static electricity that attracts dust particles. Since the film has to be laminated to either glass or a master for exposure, where every particle of dust creates a void, an extremely dust-free environment is required for clean and flawless processing.
  • methylene blue is used as a dye or additives such as NPG (N-phenylglycine) to increase photosensitivity or thermally activatable initiators such as peroxides (tert-butyl peroxybenzoates) to increase reaction rates are used respond to higher temperatures, enter into chemical reactions, decompose, fade, cause turbidity or initiate radical polymerisation.
  • NPG N-phenylglycine
  • thermally activatable initiators such as peroxides (tert-butyl peroxybenzoates) to increase reaction rates
  • peroxides tert-butyl peroxybenzoates
  • kit-of-parts for the production of a photopolymerizable composition by means of UVA/is irradiation comprising: I) a dye concentrate comprising
  • the solvent components have a boiling point of >100° C. at standard pressure.
  • the percentages result from the weight ratio of the components to the total weight of the solvent.
  • a dye concentrate A (also called I)) with a solvent, in particular one with a proportion of more than 50% by weight, preferably more than 65% by weight, particularly preferably more than 80% by weight, has proven to be advantageous for the kit-of-parts Wt .-% high molecular weight, non-volatile components, including Pho toinitiatoren to use.
  • This is added to the liquid composition II) (also called II)) in order to obtain a photopolymerizable composition (also called photopolymer) which can be applied and exposed immediately after mixing.
  • a photopolymerizable composition also called photopolymer
  • the separate storage of the dye concentrate A as I) and the liquid composition B as II) improves durability and storage can be simplified since components A) and B) are less sensitive to light and heat than the photopolymerizable compositions.
  • liquid composition II can be heated and stirred for a long period of time without any problems in order, for example, to redissolve undissolved or crystallized components such as the borate salt.
  • the liquid composition II) is preferably not sensitive to light at all and can be inspected visually, heated and stirred without any problems, such as maintaining a certain ambient lighting. This facilitates quality control and the detection of undissolved or crystallized components, as well as processing.
  • the color is used to set the light to which the kit of parts is sensitive.
  • the complementary hue of the exposure wavelength is usually chosen. For example, a magenta hue is used for a green light, a blue hue for red and a yellow hue for blue. Combinations are also possible for exposure to different wavelengths.
  • the kit-of-part preferably consists of the liquid composition II), which is very particularly preferably a clear, colorless and liquid monomer-containing mixture, and the dye concentrate I).
  • the dye concentrate is preferably used in amounts of 0.5-50% by weight, preferably 1-10% by weight and particularly preferably 1-5% by weight, based on the total amount of the kit-of-parts , in particular the liquid composition II), and mixed by stirring, shaking or swirling.
  • the resulting photopolymerizable composition can be exposed to light immediately after application to a substrate.
  • the wet application of the composition to the carrier material can be done by doctor blade, doctor blade or slot nozzles (slot-dye coating).
  • Known printing methods such as screen, gravure, gravure, pad or flexographic printing can also be used for thin layers of less than 20 ⁇ m.
  • the material is preferably laminated directly onto the template (master) to be copied using a transparent and clear film.
  • the layer thickness is set either by the contact pressure and the laminating speed or by the slot width.
  • a spin coating process can be used to coat thick and rigid substrates such as glass plates.
  • Application with an inkjet printing process or with a CNC-controlled dosing device is also possible. Direct injection into cavities is also possible.
  • the liquid material is also suitable for application to curved surfaces. It can also be pressed between two matching bodies and used as a kit or glue at the same time.
  • kit-of-parts components can take place in the coating system. All mixing techniques and methods known to those skilled in the art, such as, for example, stirred tanks, magnetic stirrers, stirring rods, speed mixers and both dynamic and static mixers, can be used for mixing.
  • the dye concentrate A is diluted to the desired ratio with a dilution mixture.
  • the dilution mixture contains the components and monomers known from the liquid composition II) without the critical components which, like the borate salt, are redissolved by heating after prolonged storage have to. Instead, the monomer-containing liquid mixture B must then contain a multiple of the otherwise customary amount of the critical components or the borate salts, which corresponds to the ratio.
  • the layer After exposure, the layer is solid.
  • no thermal or chemical post-treatment is preferably required after exposure.
  • the user is also free to choose which carrier materials and layer structures he would like to use, since the coating takes place in the exposure system. After the order can be exposed immediately. Multi-layer exposures are also no problem, since after curing a new layer can be applied and holographically exposed according to the same principle. This can be used, for example, to build true-color holograms from three layers for the primary colors red, green and blue.
  • the photopolymerizable composition from the kit-of-parts is particularly suitable for making contact copies. Because the liquid photopolymerizable composition from the kit-of-parts is printed directly onto the master, there is no need for index matching. This means the application of a liquid between the master and the hologram film with approximately the same refractive index of the two layers.
  • Index matching prevents the occurrence of disturbing interference phenomena (Newton rings) in the normal contact copying process. These are caused by reflections, which occur particularly at the points where the two layers do not touch directly, for example because of dust inclusions or a small unevenness, and bubbles or air pockets occur.
  • the compensation of scratches and other irregularities in the substrate and master improves the optical quality of the copy. Small dust particles with a smaller dimension than the layer thickness are embedded in the liquid and do not create any significant pressure or voids as with the film materials. This significantly reduces rejects and clean room demands on the production environment.
  • the liquid photopolymerizable composition from the kit-of-parts can thus advantageously also be used as an index match material for the exposure of holographic film materials. Because it hardens when exposed to light, there is no need for cleaning or evaporation.
  • the holographic recording is supported and strengthened by the combination of the two holographic recording materials, since a hologram is created in both layers. Due to the free choice of the dye concentrate used, the user can decide which wavelength or color range is pushed in the combination.
  • surface structures can be molded and complex-shaped surfaces can be used at the same time in addition to the hologram exposure.
  • the surface structures can in particular be embossed holograms or Fresnel structures. This makes it possible to physically and holographically copy both the surface structure and the volume holographic or optical information of the master in a single processing step.
  • the dye serves as a sensitizer for the co-photoinitiator.
  • suitable materials are methylene blue and those described in U.S. Patents 3,554,753, 3,563,750, 3,563,751, 3,647,467, 3,652,275, 4,162,162, 4,268,667, 4,454,218 , 4,535,052 A and 4,565,769 A, disclosed sensitizers, as well as the dyes and co-photoinitiators mentioned in the application WO 2012062655 A2, to which express reference is made herein.
  • sensitizers include the following: DBC, i.e., 2,5-bis[(4-diethylamino-2-methylphenyl)methylene]cyclopentanone; DEAW, i.e., 2,5-bis[(4-diethylaminophenyl)methylene]cyclopentanone; Dimethoxy-JDI, i.e., 2,3-dihydro-5,6-dimethoxy-2-[(2,3,6,7-tetrahydro-1H,5H-benzo[i,j]quinolizin-9-yl)me - ethylene]-1 FI-inden-1-one; and Safranin O, i.e., 3,7-diamino-2,8-dimethyl-5-phenyl-phenazinium chloride.
  • DBC i.e., 2,5-bis[(4-diethylamino-2-methylphenyl)methylene]cyclopentanone
  • DEAW i.e., 2,
  • the dye in the kit-of-parts according to the invention is preferably a fluorescent dye, which can consist, for example, of a cationic dye and an anion.
  • the cationic dye can be represented by the formula F + .
  • a cationic dye of the formula F + is therefore preferably understood to mean those of the following formulas: wherein
  • X 1 is 0, S, NR 6 or CR 6a R 6b ,
  • R 5 is hydrogen, cyano, C 1 to C 4 alkyl, C 4 to cycloalkyl, a C 1 to C 10 aryl optionally substituted by C 1 to C 4 alkoxycarbonyl or NR 7 R 8 , a heterocyclic radical or stands for Ce- to Cio-aryl substituted with a carboxyl group,
  • R 6 is hydrogen, Ci to Ci6-alkyl, C 4 - to cycloalkyl, C 7 - to Ci6-aralkyl, Ce to Cio-aryl or a heterocyclic radical,
  • R 6a and R 6b are independently substituted for methyl, ethyl or together for a -CH 2 -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 -CH 2 bridge or for Ce to Cio aryl with a carboxyl group,
  • NR 1 R 2 , NR 7 R 4 and NR 7 R 8 independently represent a five- or six-membered saturated ring attached via N, which may additionally contain N or 0 and/or may be substituted by nonionic radicals, or R 1 to R 4 , R 7 and R 8 independently form a two- or three-membered bridge with a carbon atom of the benzene ring adjacent to the N atom, which can contain 0 or N and/or can be substituted by nonionic radicals ,
  • R 9 , R 9a , R 9b , R 10 , R 10a and R 10b independently represent hydrogen, halogen or Ci to C4-alkyl, wherein
  • NR 11 R 12 , NR 13 R 14 and NR 18 R 19 independently represent a five- or six-membered saturated ring attached via N, which may additionally contain N or 0 and/or may be substituted by nonionic radicals, or R12 ; R17b , R13 ; R17c and R18 ; R 17a independently form a two- or three-membered bridge which can contain 0 or N and/or can be substituted by non-ionic radicals,
  • R 16 is hydrogen, chlorine, methyl, methoxycarbonyl or ethoxycarbonyl
  • R 16a is hydrogen, chlorine or methyl
  • R i 7a , R 17b and R 17c independently represent hydrogen, chlorine, methyl or methoxy.
  • Alkyl, alkoxy, cycloalkyl, aryl and heterocyclic radicals can optionally carry further radicals such as alkyl, halogen, nitro, cyano, CO—NH 2 , alkoxy, trialkylsilyl, trialkylsiloxy or phenyl, which can have alkyl and alkoxy radicals be straight-chain or branched, the alkyl radicals can be partially or perhalogenated, the alkyl and alkoxy radicals can be ethoxylated or propoxylated or silylated, adjacent alkyl and/or alkoxy radicals on aryl or heterocyclic radicals can together form a three- or four-membered bridge and the heterocyclic radicals can be benzfused and/or quaternized.
  • further radicals such as alkyl, halogen, nitro, cyano, CO—NH 2 , alkoxy, trialkylsilyl, trialkylsiloxy or phenyl, which can have al
  • aralkyl examples include benzyl, phenethyl or phenylpropyl.
  • fletaryl radicals in particular five- or six-membered heterocyclic radicals, are indolyl, pyridyl, quinolyl and benzothiazolyl.
  • substituted heterocyclic radicals are 1,2-dimethylindol-3-yl, 1-methyl-2-phenylindol-3-yl.
  • Anions for the cationic dyes of the formula F + can be, for example, anions from the flalogens, sulfates, carbonates or nitrates.
  • rhodamine B rhodamine 6G or violamine R
  • sulforhodamine B also sulforhodamine B or sulforhodamine G as listed below.
  • Other suitable dyes are fluorones, as z. B. von Neckers et al. in J. Polym. Sci., Part A, Poly. Chem, 1995, 33, 1691-1703. is particularly interesting
  • Triethanolamine (TEA), castor oil, castor oil glycidyl ether (ricinus oil glycidyl ether), octanoic acid, tert-butyl peroxybenzoate, 2-dimethylaminoethanol, anisole, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) , benzyl alcohol, tetrachlorethylene, dipropylene glycol dimethyl ether, dichloromethane, acetic anhydride, propylene carbonate, n-butyl acetate, cyclohexane, cyclopentanone, ethylene glycol, polyethylene glycols, toluene, eucalyptus oil, butyl glycolate (Polysolvan-O), N-methyl-2-pyrrolidone (NMP ), propylene glycol monomethyl ether acetate (PGMEA), poly(bisphenol-A-co-epichloro
  • the solvent preferably contains polymer which is liquid under standard pressure.
  • the polymer that is liquid under standard pressure can advantageously be selected from the group consisting of polyethylene glycols (PEGs), polycaprolactones, acrylate block copolymers (EFKA) and poly(bisphenol-A-co-epichlorohydrins) (EPI).
  • Free radical polymerization initiators are known, see, e.g., Timpe, H.J. and S. Neuenfeld, "Dyes in photoinitiator Systems", Victor (1990), pp. 28-35 and Jakubiak, J. and J.F. Rabek, "Photoinitiators for visible light polymerization", Polimery (Warsaw) (1999), 44, pp. 447-461.
  • photoinitiators which are also useful, although some are thermally active at temperatures as low as 85°C, are described in U.S. Patent 2,760,663 and include vicinal ketaldonyl alcohols such as benzoin, pivaloin, acyloin ethers, e.g., benzoin me ethyl and ethyl ethers, a-hydrocarbyl-substituted aromatic acyloins including a-methylbenzoin, a-allylbenzoin and a-phenylbenzoin.
  • vicinal ketaldonyl alcohols such as benzoin, pivaloin, acyloin ethers, e.g., benzoin me ethyl and ethyl ethers, a-hydrocarbyl-substituted aromatic acyloins including a-methylbenzoin, a-allylbenzoin and a-phenylbenzoin.
  • photoinitiator Useful as the photoinitiator are photoreducible dyes and reducing agents such as those described in U.S. Patents 2,850,445 A, 2,875,047 A, 3,097,096 A, 3,097,097, 3,145,104 and 3,579,339, as well as dyes from the class of phenazines, oxazines and quinones; Michler's ketone, benzophenone, 2,4,5-triphenylimidazolyl dimers with hydrogen donors and mixtures thereof as described in U.S. Patents 3,427,161, 3,479,185, 3,549,367, 4,311,783, 4,622,286A and 3,784,557A.
  • Useful photoinitiators include CDM-FIABI, ie, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)imidazole dimer; o-CI-HABI, ie, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole; and TCTM-FIABI, ie, 2,5-bis(o-chlorophenyl)-4-(3,4-dimethoxy-phenyl)-1 FI-imidazole dimer, each typically used with a hydrogen donor, eg 2 -mercaptobenzoxazole.
  • CDM-FIABI ie, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)imidazole dimer
  • o-CI-HABI ie, 2,2'-bis(o-chlorophenyl)-4
  • the photoinitiators mentioned above can be used alone or in combination.
  • the photoinitiator is preferably liquid and/or is selected from the group consisting of 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(0-benzoyloxime), (1-[9 - Ethyl 6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-0-acetyloxime, methyl benzoyl formate), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl )-phenylphosphinate), 2-hydroxy-2-methyl-1-phenylpropanone, a mixture of 2-hydroxy-2-methyl-1-phenylpropanone (80%) and 1-hydroxycyclohexyl-phenylketone (20%), 1 - hydroxycyclohexyl phenyl ketone,
  • Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide a mixture of 2-hydroxy-2-methyl-1-phenylpropanone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and ethyl(2,4,6-trimethylbenzoyl)- phenyl phosphinate), and 4,4'-dimethyl diphenyl iodonium hexafluorophosphate.
  • solid photoinitiators are used in the liquid composition and liquid photoinitiators in the dye concentrate.
  • the monomer M1 comprising at least one ethylenically unsaturated group, can have the following general structural units.
  • Suitable monomers M1 are substituted or unsubstituted styrene monomers, acrylic acid, a-alkylacrylic acid, acrylic acid esters, a-alkylacrylic acid esters whose alcohol component can be a substituted or unsubstituted aliphatic or aromatic radical having 2-50 carbon atoms, acrylamides, a- Alkyl acrylamides, where alkyl has the meaning given above, vinyl esters, vinyl alcohol, vinyl ethers and other substituted vinylic monomers substituted with substituted or unsubstituted aliphatic or aromatic radicals having 2-50 carbon atoms.
  • suitable monomers M1 are (meth)acrylic acid butyl ester, (meth)acrylic acid phenyl ester, (meth)acrylic acid benzyl ester, (meth)acrylic acid isobornyl ester, (meth)acrylic acid cyclohexyl ester, (meth)acrylic acid 2-phenoxyethyl ester, (meth) acrylic acid I H, 1 H,2H,2H-perfluorooctyl ester, 2,2,2-trifluo- ethyl (meth)acrylate, heptafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexyfluoroisopropyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate), 2,2 ,3,3,4,4,4-heptafluorobutyl (meth)acrylate, 2,2,3,3,4,4,5,5-octafluoropenty
  • the monomer M1 preferably comprises at least two ethylenically unsaturated groups, therefore the monomer is preferably difunctional.
  • the monomer M1 in the monomer-containing liquid mixture B according to the invention can consist exclusively of one or more difunctional or higher-functional monomers, ie the composition can be free from monofunctional ethylenically unsaturated monomers.
  • the content of monomers M1 with at least two ethylenically unsaturated th groups in the mixture B is more than 10% by weight, and the content of monomers M1 having at least two ethylenically unsaturated groups is particularly preferably more than 20% by weight.
  • difunctional or higher functional monomers leads in particular to a particularly high thermal and mechanical stability of the holographic elements produced and is particularly advantageous in the production of reflection holograms.
  • Preferred monomers M1 having at least two ethylenically unsaturated groups are ethoxylated bisphenol A diacrylates, in particular compounds of the following formula wherein Ri, Q and Ar are as defined above.
  • a particularly preferred monomer M1 is the compound of the following structural formula:
  • the viscosity of the monomer M1 or monomer mixture at room temperature is preferably at least 900 mPa ⁇ s.
  • the viscosity of the liquid composition II) is also at 20° C. at least 900 mPa s, preferably 1500 mPa s and particularly preferably at least 2000 mPa s.
  • the viscosity can be determined using a plate-plate rotational rheometer (for example from Haake, type 006-2805).
  • the material is located between two coaxial, circular plates, one of which rotates.
  • the plates have, for example, a distance of 1 mm and a diameter of 35 mm.
  • the viscosity can be determined by measuring the torque and the speed (e.g. 10 revolutions/s) (DIN53018, ISO3210).
  • R ⁇ C is hydrogen, Ci-Ci 2 -alkyl, phenyl-Ci-C6-alkyl which is unsubstituted or mono- to penta-substituted by C1-C6-alkyl, Ci-Ci- 2 -alkoxy or halogen, or phenyl-Ci-C6-alkyl which is unsubstituted or mono- to penta-substituted by Ci -Ce-alkyl, Ci-Ci 2 -alkoxy or halogen-substituted phenyl;
  • Rec and R 7C unsubstituted or substituted by halogen Ci-Ci 2 alkyl, unsub stituted or mono- to penta-substituted by Ci-Ce-alkyl, Ci-Ci 2 -alkoxy or halogen substituted phenyl-Ci-C6-alkyl or unsubstituted or phenyl which is mono- to penta-substituted by C 1 -C 1-4 alkyl, C 1 -C 2 -alkoxy or halogen;
  • Ree, R9C, RIOC, Riic, Ri2c, Ri3c, RUC, Ri5c and Ri6c independently of one another C1-Ci 2 -alkyl, C 3 -Ci 2 -cycloalkyl, unsubstituted or mono- to pentafold with C 1 -C 6 -AI- kyl, Ci-Ci 2 -alkoxy or halogen-substituted phenyl-Ci-C 6 -alkyl or unsubsti tuated or mono- to five-fold with Ci-Ce-alkyl, Ci-C- 12 -alkoxy or halogen substituted phenyl, or Rsc and R 9 c together with the N atom to which they are bonded form a 6-membered aliphatic ring which can also contain oxygen or sulfur as a further heteroatom;
  • Ri7c ', Ri8c, Ri9c and R 20C are independently hydrogen, unsubstituted or substituted by Ci-Ci 2 -alkoxy Ci-Ci 2 -alkyl, phenyl or phenyl-Ci-C 6 -alkyl, where the radicals are phenyl or phenyl -Ci-C 6 -alkyl unsubstituted o- which are mono- to penta-substituted by Ci-Ce-alkyl, Ci-Ci 2 -alkoxy or halogen; p is a number from 0 to 2; r is a number from 0 to 5;
  • R 21C is hydrogen or Ci-Ci 2 -alkyl
  • R 22C , R 22 a, R 23C and R 24C are independently hydrogen, unsubstituted or substituted by Ci-Ci 2 alkoxy, OH or halogen Ci-Ci 2 alkyl or unsubstituted or substituted by Ci-Ci 2 alkoxy, OH or Halogen substituted phenyl mean; q represents either 0 or 1; and
  • G stands for a group which can form positive ions.
  • the co-photoinitiator in the kit-of-parts according to the invention is preferably selected from the group consisting of tetrabutylammonium tetrahexylborate, tetrabutylammonium triphenylhexylborate, tetrabutylammonium tris-(3-fluorophenyl)hexylborate and tetrabutylammonium tris-(3-chloro-4 -methylphenyl)hexylborate or mixtures thereof.
  • a co-photoinitiator with the structural formula Ia which was developed by Ciba Specialty Chemicals Inc. under the name “CGI 7460” and is now available from BASF AG under the name SEC LCA 1460, is very particularly preferred, is shown as follows :
  • the liquid composition or the first mixture A can be different in order to adapt to the selected processing method or the field of application of the kit-of-parts and to improve the printability, surface adhesion, viscosity, film formation, flexibility, hardness, and resistance to cold, flashing and weathering contain known additives.
  • the colorant concentrate or liquid composition optionally includes an additive.
  • the additives include fillers, dyes, plasticizers, surfactants, customary components used in photopolymer systems, polymeric binders, wetting agents, leveling agents, defoamers, flattening agents, surface additives, nanoscale particles, optical brighteners or mixtures thereof.
  • Non-volatile substances can even permanently improve the diffraction efficiency in thin layers, in particular by choosing additives that increase the refractive index difference between the ethylenically unsaturated monomer and the other components.
  • additives that increase the refractive index difference between the ethylenically unsaturated monomer and the other components.
  • polymers with a low Refractive index such as polyvinyl acetate particularly fluorinated or silanized poly mers into consideration.
  • the molecular weight of the additives under consideration should not be too high.
  • the kit-of-parts may contain a plasticizer to enhance the refractive index modulation of the imaged composition.
  • Plasticizers can be used in amounts ranging from about 0.01 to about 10% by weight, preferably 5 to about 10% by weight, based on the total amount of the kit-of-parts.
  • Suitable plasticizers include triethylene glycol, triethylene glycol diacetate, triethylene glycol dipropionate, triethylene glycol dicaprylate, triethylene glycol dimethyl ether, triethylene glycol bis(2-ethylhexanoate), tetraethylene glycol diheptanoate, polyethylene glycol, polyethylene glycol methyl ether, isopropyl naphthalene, diisopropyl naphthalene, polypropylene glycol, glyceryl tributyrate, diethyl adipate, diethyl sebacate, dibutyl suberinate, tributyl phosphate, tris(2-ethylhexyl) phosphate, Brij ® 30 [C ⁇ F OCFteCFte ⁇ OH], Brij ® 35 [Ci2H25(OCH2CH2)2oOH], and n-butyl acetate.
  • plasticizers are polyethylene glycol, triethylene glycol diethylhexanoate (3G8), triethylene glycol dicaprylate, tetraethylene glycol diheptanoate, diethyl adipate, Brij® 30 and tris(2-ethylhexyl) phosphate.
  • compositions and elements of this invention can be employed with other conventional components used in photopolymer systems.
  • these components include: optical brighteners, ultraviolet absorbers, thermal stabilizers, hydrogen donors, oxygen scavengers, and release agents.
  • optical brighteners include those disclosed in US Patent 3,854,950.
  • a preferred optical brightener is 7-(4'-chloro-6'-diethylamino-1',3',5'-triazin-4'-yl)amino-3-phenylcoumarin.
  • Ultraviolet radiation absorbing materials useful in this invention are also disclosed in the US patent
  • thermal stabilizers include: hydroquinone, phenidone, p-methoxyphenol, alkyl and aryl substituted hydroquinones and quinones, tert-butyl catechol, pyrogallol, copper resinate, naphthylamines, beta-naphthol, copper(I) chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluquinone and chloranil. Also useful are those in US Patent
  • a thermal polymerization inhibitor is also usually present to increase storage stability of the photopolymerizable composition.
  • Hydrogen donor compounds useful as chain transfer agents include: 2-mercaptobenzoxazole, 2-mercaptobenzothioazole, etc. as well as various types of compounds, e.g., (a) ethers, (b) esters, (c) alcohols, (d) compounds containing allylic or benzylic hydrogen such as cumene, (e) acetals, (f) aldehydes, and (g) amides as disclosed at column 12, lines 18-58 of US Patent 3,390,996, which is incorporated herein by reference .
  • a preferred release agent is polycaprolactone.
  • the kit-of-parts can also contain nanoscale particles such as T1O2, S1O2 or Au, which can optionally be coupled to monomers (such materials are available, for example, under the trade name “Nanocryl”).
  • the additive can be an amine synergist.
  • an amine synergist can increase the curing speed of UV coatings (see DE 60216490 T2).
  • the additive can be a peroxide.
  • a thermally activatable peroxide can improve the curing of UV coatings, particularly in shadowed areas (see US Pat. No. 5,017,406 A or DE 60030223 T2).
  • the liquid composition may also comprise a triglyceride and/or a modified triglyceride.
  • Hedipin R/2000 can include polyoxyethylene ricinoleates, free polyethylene glycols and ethoxylated glycerines.
  • the photopolymerizable composition has reduced surface adhesion and flexibility, since the triglyceride or the modified triglyceride acts simultaneously as a release agent and plasticizer.
  • An exposed flologram can therefore be easily removed from a substrate such as glass or metal without leaving any residue.
  • This property is also very favorable for mass production because it means that wear-free copy masters, such as conventional nickel shims with a fine holographic surface structure or volume holograms sealed with thin glass, can be used for the production of contact copies. By completely removing the non-sticky layer the cleaning effort remains low. If the liquid photopolymerizable composition is printed directly onto the master, there is no index matching either.
  • the liquid composition may also include at least one aromatic aldehyde and/or aliphatic aldehyde.
  • the aromatic aldehyde is selected from the group consisting of vanillin, coniferyl aldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3 -dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde , 4-Hydroxy-2,3-dimethyl- benzaldehyde, 4-hydroxy-2,5-dimethyl-benzaldehyde, 4-hydroxy-2,6-dimethyl-benzaldehyde, 4-hydroxy-3,5-dimethoxy-benzaldehyde, 4-hydroxy-3,5-dime
  • the aromatic aldehyde is selected from the group consisting of 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, and 3,5-dihydroxybenzaldehyde.
  • a kit-of-parts for the production of a photopolymerizable composition by means of UVA/is irradiation is particularly preferred, comprising:
  • a dye concentrate comprising A) a first mixture A, in particular liquid mixture A, comprising f) at least one dye selected from the group consisting of acriflavins, diaminoacridines, rhodamine B, safranine-O, diethylsafranines and methylene blue and h) at least one solvent selected from the group , consisting of dimethyl sulfoxide (DMSO), N,N'-dimethylpropylene urea, N-hydroxyethylacrylamide (HEAA), N-methyl-2-pyrrolidone (NMP), benzaldehyde, polyethylene glycols (PEGs), polycaprolactones, acrylate block copolymers ( EFKA) and poly(bisphenol-A-co-epichlorohydrins). and
  • DMSO dimethyl sulfoxide
  • HEAA N-hydroxyethylacrylamide
  • NMP N-methyl-2-pyrrolidone
  • a monomer-containing liquid mixture B comprising: a) at least one monomer M1, comprising at least one ethylenically unsaturated group, c) at least one co-photoinitiator selected from the group consisting of tetrabutylammonium tetrahexylborate, tetrabutylammonium triphenylhexylborate, tetrabutylammonium tris- (3-fluorophenyl)hexyl borate and tetrabutylammonium tris-(3-chloro-4-methylphenyl)hexyl borate or mixtures thereof.
  • a kit-of-parts for the production of a photopolymerizable composition by means of UVA/is irradiation is particularly preferred, comprising:
  • a monomer-containing liquid mixture B comprising: a) at least one monomer M1 comprising at least one ethylenically unsaturated group, c) at least one co-photoinitiator selected from the
  • the kit-of-parts preferably comprises at most 10% by weight of a first mixture A, based on the total amount of mixture B.
  • a kit-of-parts for the production of a photopolymerizable composition by means of UV/Vis irradiation is very particularly preferred, comprising:
  • a dye concentrate comprising A) a first mixture A comprising f) at least one dye selected from the group consisting of acriflavins, diaminoacridines, rhodamine B, safranine-O, diethylsafranines and methylene blue, g) at least one photoinitiator and h) at least one solvent and
  • a liquid composition comprising: B) a monomer-containing liquid mixture B, comprising: a) at least one monomer M1 comprising at least one ethylenically unsaturated group, c) at least one co-photoinitiator selected from the group consisting of tetrabutylammonium tetrahexylborate, tetrabutylammonium triphenylhexylborate, tetrabutylammonium tris- (3-fluorophenyl)hexylborate and tetrabutylammonium tris-(3-chloro-4-methylphenyl)hexylborate or mixtures thereof, the total amount of I) and II) being 100% by weight.
  • the kit-of-parts preferably comprises at most 10% by weight of a first mixture A, based on the total amount of mixture B.
  • a kit-of-parts for the production of a photopolymerizable composition by means of UV/Vis irradiation is very particularly preferred, comprising:
  • a monomer-containing liquid mixture B comprising: a) 49.9 to 99.9% by weight of at least one monomer M1, comprising at least one ethylenically unsaturated group, c) 0.1 to 10% by weight of at least one Co -Photoinitiators selected from the group consisting of tetrabutylammonium tetrahexylborate, tetrabutylammonium triphenylhexylborate, Tetrabutylammonium tris-(3-fluorophenyl)hexylborate and tetrabutylammonium tris-(3-chloro-4-methylphenyl)hexylborate or mixtures thereof, the total amount of a) and c) being at least 50% and not more than 100% by weight -% and the total amount of I) and II) being 100% by weight.
  • Another subject of the invention is an element containing a component which is obtainable by the action of (actinic) UV/VIS radiation on the photopolymerizable composition produced from the kit-of-parts according to the invention.
  • an element comprising a hologram which is obtainable by the action of a modulated radiation carrying holographic information on the photopolymerizable composition of the kit-of-parts according to the invention is preferred.
  • the photopolymerizable composition from the kit-of-parts can advantageously be applied to a substrate, for example a mirror sheet, a surface mirror, a nickel shim with holographic or optical surface structures or to a master hologram, and exposed with a laser beam, so that a hologram is formed.
  • the photopolymerizable composition from the kit-of-parts is then advantageously also cured with UV light.
  • Another object of the invention is the use of the element according to the invention as a film, lens, grid, prism, mirror, beam splitter, diffuser, surface relief, membrane, filter or sensor.
  • the use of the element according to the invention is preferred for a head-up display, data glasses, a light-guiding system, a spectrometer, a detection system, a security element or a label.
  • the dye concentrate does not attack or alter previously exposed hologram layers.
  • the photopolymerizable compositions that can be produced from the kit of parts can be individually adapted to the type of exposure and the desired results depending on the application. By choosing the right dye concentrate and varying the amount, the optimal color intensity can be set depending on the layer thickness, the desired sensitivity and the tolerable color shade in the finished product
  • UV initiators Liquid UV initiators
  • UV initiators that are in powder form at room temperature can also be used if they are melted or dissolved in a second component.
  • example games solvent for example games solvent
  • a mixture of polycaprolactone and a liquid UV photoinitiator is preferably used to dissolve the dyes.
  • a liquid UV photoinitiator eg Omnicure 1173 or MBF
  • a UV initiator that is solid at room temperature such as Omnicure TPO, Omnicure 819 and Omnicure 189, can also be dissolved in the low molecular weight polycaprolactone.
  • the ratio is chosen so that the UV initiator and the dye later with the desired concentration present in the photopolymerizable composition from the kit-of-parts.
  • the UV initiator concentration in the resulting photopolymerizable composition from the kit-of-parts is 1%. If a different concentration were desired, then the ratio of PCL triol and UV initiator would have to be adjusted accordingly. In this example, a maximum photoinitiator concentration of 3% would be possible, please include.
  • liquid compositions MM1 to MM4 were prepared using the same procedure as described for the dye concentrates.
  • a photopolymerizable composition is formed from the previously described dye concentrates and the monomer-containing liquid compositions, which together form a corresponding kit-of-parts, by mixing (for example by shaking with a speed mixer or stirring with a stirring rod).
  • the following photopolymerizable compositions are described: Photopolymerizable composition A
  • Photopolymerizable composition F Photopolymerizable composition G
  • Exposure was carried out with a wavelength of 577 nm at a temperature of 20°C. The material was stored in an oven at 120°C. Exposure was carried out approximately every 15 minutes until no more hologram could be imprinted and the BWG value was 0%. The values given are from the first exposure.
  • FIG. 1 shows a photo of two mixtures of the liquid composition II).
  • the left beaker (1) is a liquid composition II) which has been stored at room temperature for more than three months.
  • the right-hand beaker (2) is a liquid composition II) which had just been stirred on a hotplate with a magnetic stirrer (3) at 120° C. for three hours. It can be clearly seen that this mixture (2) is clearer than the one stored untreated (1) with the crystallizations (4).
  • FIG. 3 shows the schematic exposure setup.
  • FIG. 4 shows the beam path.
  • the photopolymer layer is located between the mirror plate and a transparent carrier material, e.g. PET film or glass.
  • a transparent carrier material e.g. PET film or glass.
  • Figure 5 shows the measurement curve with the corresponding measurement points of the first exposure of sample H.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Materials Engineering (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Holo Graphy (AREA)

Abstract

La présente invention concerne un système à deux composants pour mélanger des compositions photopolymérisables et des éléments produits à partir de celui-ci et leur utilisation. Les compositions photopolymérisables sont particulièrement appropriées en tant que matériau d'enregistrement pour des éléments optiques ayant une modulation d'indice de réfraction, en particulier des hologrammes.
EP22708501.6A 2021-02-11 2022-02-11 Système à deux composants Pending EP4291951A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21156623.7A EP4043961B1 (fr) 2021-02-11 2021-02-11 Système 2k
PCT/EP2022/053408 WO2022171814A1 (fr) 2021-02-11 2022-02-11 Système à deux composants

Publications (1)

Publication Number Publication Date
EP4291951A1 true EP4291951A1 (fr) 2023-12-20

Family

ID=74591893

Family Applications (2)

Application Number Title Priority Date Filing Date
EP21156623.7A Active EP4043961B1 (fr) 2021-02-11 2021-02-11 Système 2k
EP22708501.6A Pending EP4291951A1 (fr) 2021-02-11 2022-02-11 Système à deux composants

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP21156623.7A Active EP4043961B1 (fr) 2021-02-11 2021-02-11 Système 2k

Country Status (9)

Country Link
US (1) US20240150569A1 (fr)
EP (2) EP4043961B1 (fr)
JP (1) JP2024510875A (fr)
KR (1) KR20230145123A (fr)
CN (1) CN116830036A (fr)
DE (1) DE102022103301A1 (fr)
ES (1) ES2963992T3 (fr)
MX (1) MX2023009437A (fr)
WO (1) WO2022171814A1 (fr)

Family Cites Families (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2760663A (en) 1953-12-22 1956-08-28 John F Tatum Automatic hold down structure for fork lift trucks
US2875047A (en) 1955-01-19 1959-02-24 Oster Gerald Photopolymerization with the formation of coherent plastic masses
US2850445A (en) 1955-01-19 1958-09-02 Oster Gerald Photopolymerization
US3097097A (en) 1959-02-12 1963-07-09 Gisela K Oster Photo degrading of gel systems and photographic production of reliefs therewith
NL254306A (fr) 1959-08-07
BE635804A (fr) 1962-03-21
US3390996A (en) 1964-04-29 1968-07-02 Du Pont Photosensitive composition comprising an organic nitrogen-containing color-generator, a photo-oxidant and a redox couple
GB1090142A (en) 1965-02-26 1967-11-08 Agfa Gevaert Nv Photochemical insolubilisation of polymers
US3479185A (en) 1965-06-03 1969-11-18 Du Pont Photopolymerizable compositions and layers containing 2,4,5-triphenylimidazoyl dimers
US3579339A (en) 1967-05-23 1971-05-18 Du Pont Photopolymerizable dispersions and elements containing nonmigratory photoreducible dyes
US3554753A (en) 1967-07-20 1971-01-12 Du Pont Hexaarylbimidazole-carbocyanine dye compositions
US3563751A (en) 1967-07-20 1971-02-16 Du Pont Hexaarylbiimidazole-acridine dye compositions
US3563750A (en) 1967-07-20 1971-02-16 Du Pont Hexaarylbiimidazole hydroxyphthalein compositions
US3549367A (en) 1968-05-24 1970-12-22 Du Pont Photopolymerizable compositions containing triarylimidazolyl dimers and p-aminophenyl ketones
US3647467A (en) 1969-05-22 1972-03-07 Du Pont Hexaarylbiimidazole-heterocyclic compound compositions
US3652275A (en) 1970-07-09 1972-03-28 Du Pont HEXAARYLBIIMIDAZOLE BIS (p-DIALKYL-AMINOPHENYL-{60 ,{62 -UNSATURATED) KETONE COMPOSITIONS
BE788560A (fr) 1972-06-09 1973-03-08 Du Pont Protection contre le halo dans la formation d'images dans des photopolymeres en couches multiples
US3993485A (en) 1975-05-27 1976-11-23 Bell Telephone Laboratories, Incorporated Photopolymerization process and related devices
US4168982A (en) 1976-06-01 1979-09-25 E. I. Du Pont De Nemours And Company Photopolymerizable compositions containing nitroso dimers to selectively inhibit thermal polymerization
US4162162A (en) 1978-05-08 1979-07-24 E. I. Du Pont De Nemours And Company Derivatives of aryl ketones and p-dialkyl-aminoarylaldehydes as visible sensitizers of photopolymerizable compositions
US4326010A (en) 1979-06-15 1982-04-20 E. I. Du Pont De Nemours And Company Additive in a photopolymerizable composition for reducing its adhesion to a support film
US4311783A (en) 1979-08-14 1982-01-19 E. I. Du Pont De Nemours And Company Dimers derived from unsymmetrical 2,4,5,-triphenylimidazole compounds as photoinitiators
US4268667A (en) 1980-04-21 1981-05-19 E. I. Du Pont De Nemours And Company Derivatives of aryl ketones based on 9,10-dihydro-9,10-ethanoanthracene and p-dialkyl-aminoaryl aldehydes as visible sensitizers for photopolymerizable compositions
US4341860A (en) 1981-06-08 1982-07-27 E. I. Du Pont De Nemours And Company Photoimaging compositions containing substituted cyclohexadienone compounds
US4454218A (en) 1982-09-13 1984-06-12 E. I. Du Pont De Nemours And Company N-Alkylindolylidene and N-alkylbenzo-thiazolylidene alkanones as sensitizers for photopolymer compositions
US4476125A (en) 1983-03-24 1984-10-09 Usv Pharmaceutical Corporation Benzobisoxazinetetrones and anti-allergic use thereof
US4535052A (en) 1983-05-02 1985-08-13 E. I. Du Pont De Nemours And Company Constrained n-alkylamino aryl ketones as sensitizers for photopolymer compositions
US4565769A (en) 1984-11-21 1986-01-21 E. I. Du Pont De Nemours And Company Polymeric sensitizers for photopolymer composition
CA1270089A (fr) 1985-08-01 1990-06-05 Masami Kawabata Composition photopolymerisable
US4622286A (en) 1985-09-16 1986-11-11 E. I. Du Pont De Nemours And Company Photoimaging composition containing admixture of leuco dye and 2,4,5-triphenylimidazolyl dimer
DE68905610T2 (de) 1988-01-15 1993-10-07 Du Pont Verfahren zur Herstellung von Reflexionshologrammen in photopolymerisierbaren Schichten.
US4942112A (en) 1988-01-15 1990-07-17 E. I. Du Pont De Nemours And Company Photopolymerizable compositions and elements for refractive index imaging
US5017406A (en) 1988-12-08 1991-05-21 Dow Corning Corporation UV curable compositions cured with polysilane and peroxide initiators
US4963471A (en) 1989-07-14 1990-10-16 E. I. Du Pont De Nemours And Company Holographic photopolymer compositions and elements for refractive index imaging
WO1997013183A1 (fr) 1995-10-06 1997-04-10 Polaroid Corporation Support et procede holographique
US6482551B1 (en) 1998-03-24 2002-11-19 Inphase Technologies Optical article and process for forming article
US6245827B1 (en) 1999-10-12 2001-06-12 Elementis Specialties, Inc. Ultraviolet curable resin compositions having enhanced shadow cure properties
GB0125098D0 (en) 2001-10-18 2001-12-12 Coates Brothers Plc Multi-functional thioxanthone photoinitiators
DE10153028A1 (de) 2001-10-26 2003-05-08 Xetos Ag Holographisches Aufzeichnungsmaterial und Verfahren zur Bildung eines lichtbeständigen Hologramms
KR20050006751A (ko) 2003-07-10 2005-01-17 현대자동차주식회사 실린더라이너
EP1510862A3 (fr) 2003-08-25 2006-08-09 Fuji Photo Film Co., Ltd. Procédé d'enregistrement d'hologrammes et matériau pour l'enregistrement d'hologrammes
JP3978729B2 (ja) 2003-09-26 2007-09-19 康生 富田 ホログラム記録材料組成物及びホログラム記録媒体
GB0413366D0 (en) 2004-06-15 2004-07-21 Heeschen Andreas Binder-free photopolymerizable compositions
DE102004030019A1 (de) * 2004-06-22 2006-01-19 Xetos Ag Photopolymerisierbare Zusammensetzung
EP2218744A1 (fr) 2009-02-12 2010-08-18 Bayer MaterialScience AG Procédé de fabrication de photopolymères holographiques sur des films polymères
EP2219073B1 (fr) 2009-02-17 2020-06-03 Covestro Deutschland AG Supports holographiques et compositions de photopolymère
EP2497081B1 (fr) * 2009-11-03 2013-10-16 Bayer Intellectual Property GmbH Procédé de fabrication de supports holographiques
EP2372454A1 (fr) 2010-03-29 2011-10-05 Bayer MaterialScience AG Formulation photopolymère destinée à la fabrication d'un hologramme visible
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
EP3084765B8 (fr) * 2013-12-20 2020-10-28 Covestro Intellectual Property GmbH & Co. KG Supports holographiques à photosensibilité améliorée
FR3018077B1 (fr) * 2014-02-28 2017-06-30 A Et A Mader Composition polymerisable dual-cure-cationique et procede de fabrication d'un revetement ou d'un materiau composite mettant en oeuvre ladite composition
KR20180019114A (ko) * 2015-06-23 2018-02-23 코베스트로 도이칠란트 아게 치환된 트리아진

Also Published As

Publication number Publication date
CN116830036A (zh) 2023-09-29
ES2963992T3 (es) 2024-04-03
EP4043961B1 (fr) 2023-08-16
JP2024510875A (ja) 2024-03-12
MX2023009437A (es) 2023-08-15
WO2022171814A1 (fr) 2022-08-18
DE102022103301A1 (de) 2022-08-11
KR20230145123A (ko) 2023-10-17
EP4043961A1 (fr) 2022-08-17
EP4043961C0 (fr) 2023-08-16
US20240150569A1 (en) 2024-05-09

Similar Documents

Publication Publication Date Title
JPS5956403A (ja) 光重合性組成物
EP1759246A2 (fr) Composition photopolymerisable
JPS6060104A (ja) 光重合性組成物
DE2041072B2 (de) Gegenüber aktinischen Strahlen beständige, ein Phasenhologramm bildende Aufzeichung
DE69501865T2 (de) Fotopolymerisierbare Zusammensetzung und fotoempfindliche lithographische Druckplatte
DE3007212A1 (de) Lichtempfindliche masse
EP0115021B1 (fr) Procédé pour la réalisation de reliefs et de plaques d'impression positives
EP4043961B1 (fr) Système 2k
JPH01112237A (ja) 光重合可能の記録材料ならびにこの記録材料を主体とするフォトレジスト層及び平版印刷版体
EP4043962B1 (fr) Composition photopolymérisable
DE1952804A1 (de) Fotoaktivierbare farbbildende Massen
EP4043502B1 (fr) Composition hoe photopolymérisable
EP4043963B1 (fr) Blanchissement amélioré
Tanigawa et al. Photopolymer for Recording Holograms
DE1952804C (de) Farbbildendes fotopolymerisierbares Gemisch
WO2011089157A2 (fr) Substance photosensible comprenant des thioxanthones comme photo-initiateur photodésactivable pour la fabrication de petites structures
DE2357440A1 (de) Verfahren zur unmittelbaren entwicklung eines reliefbildes
JPH0413172A (ja) ホログラム用感光材料
DE2533073A1 (de) Dimere nitrosoverbindungen enthaltende photopolymerisierbare massen

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

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

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20230830

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

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)