EP3721292A1 - Structure multicouche photopolymère exempte d'adhésif - Google Patents

Structure multicouche photopolymère exempte d'adhésif

Info

Publication number
EP3721292A1
EP3721292A1 EP18815978.4A EP18815978A EP3721292A1 EP 3721292 A1 EP3721292 A1 EP 3721292A1 EP 18815978 A EP18815978 A EP 18815978A EP 3721292 A1 EP3721292 A1 EP 3721292A1
Authority
EP
European Patent Office
Prior art keywords
layer
photopolymer
substrate layer
hologram
composite
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
EP18815978.4A
Other languages
German (de)
English (en)
Inventor
Thomas Fäcke
Therese Klobutowski
Enrico Orselli
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 EP3721292A1 publication Critical patent/EP3721292A1/fr
Pending legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • G03H1/0252—Laminate comprising a hologram layer
    • G03H1/0256—Laminate comprising a hologram layer having specific functional layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/18—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of discrete sheets or panels only
    • B32B37/182—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of discrete sheets or panels only one or more of the layers being plastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • 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
    • G03F7/032—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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B32B2310/0837—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using actinic light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2554/00—Paper of special types, e.g. banknotes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • 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
    • 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
    • G03H1/0005—Adaptation of holography to specific applications
    • G03H1/0011—Adaptation of holography to specific applications for security or authentication
    • 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

  • Photopolymer layers for producing holographic media are known in principle from WO 2011/054797 and WO 2011/067057. Advantages of these holographic media are their high diffractive light diffraction efficiency and that no post-processing steps after the holographic exposure, such as, e.g. chemical or thermal development steps are needed.
  • the patent application WO2017 / 081078 A1 describes a process for the production of a layer structure in which first a sealing layer is applied to a photopolymer layer and then cured with the aid of actinic radiation. With this method, only exposed photopolymer layers can be sealed because the actinic radiation used to cure the protective layer inactivates an unexposed photopolymer layer.
  • WO 2014/114654 A1 and DE 10 2013 200 980 A1 disclose a method for subsequent holographic labeling.
  • the composite body used in this process consists of several polycarbonate layers in which an unexposed photopolymer layer is integrated.
  • the integration of the photopolymer layer is carried out at temperatures in the range of 120 ° C to 220 ° C, preferably by lamination.
  • the disadvantage is that it can come at such Ho hen temperatures to damage the photopolymer layer and the substrate layers of polycarbonate.
  • the object of the present invention was thus to provide a sealing method for coated and unexposed photopolymer films which produces a stable bond between the photopolymer layer and the protective layer, without damaging the photopolymer layer or protective layer and / or impairing its properties , Furthermore, for sealed photopolymer films prepared by the process of the present invention, post-processing steps after holographic exposure are no longer required.
  • the object is achieved by a method for producing an at least partially bonded layer structure comprising a photopolymer layer B containing a hologram, and a substrate layer C made of (co) polycarbonate, characterized in that the method comprises the fol lowing steps:
  • step d) is always performed as a last step.
  • the photopolymer layer B is bonded in the inventive method adhesive-free with the substrate layer C.
  • the advantage of the inventive method is that it allows in a simple way the Versie gelung a partially exposed or unexposed photopolymer, which requires no elaborate ended machines or specially trained personnel and wherein the components B and C are coordinated so that they on the one hand a good Allow adhesion and at the same time ensure frequency stability / lattice stability of the hologram and protection against chemical, physical and mechanical stress.
  • a high compatibility is achieved by the adhesive-free connection of the substrate layer C with the photopolymer layer B and a general improved handling of the exposed or unexposed photopolymer layer, such.
  • B. a protection against dustiness by eliminating residual tackiness or protection against chemical and physical influences.
  • the layer structures produced by the process according to the invention have a high adhesive force between the photopolymer layer B and the substrate layer C, so that the Schichtver bund can be processed well, for. B. in an injection molded article, another Lamina tion step can be subjected or applied to a casting lens. It is also possible to process the resulting layer structure both on the substrate layer A and the substrate layer C by a further lamination or gluing step without influence on the hologram. V explanatory steps with liquid lacquers, which usually contain solvents or reactive diluents, can now also be used without these being able to penetrate into the photopolymer layer B and thus changing the hologram.
  • the process steps a) -d) are carried out in the sequence a), b), c) and d) or in the order a), c), b) and d) or in the order c) , a), b) and d), preferably in the order c), a), b) and d).
  • the method comprises the following steps:
  • step b) heating the layer composite BC from step a) to a temperature of from 70 ° C. to 110 ° C., c) imprinting a hologram, preferably a volume hologram, into the unexposed photopolymer layer B of the chromatographic compound b from step b), wherein the Photopolymer layer B contains matrix polymers, writing monomers, photoinitiators, if appropriate at least one non-photopolymerizable component and, if appropriate, catalysts, radical stabilizers, solvents, additives and other auxiliaries and / or additives,
  • step d) subjecting layer composite B-C from step c) to actinic radiation, preferably containing UV radiation,
  • the method comprises the following steps:
  • a hologram preferably a volume hologram
  • the photopolymer layer B comprising matrix polymers, writing monomers, photoinitiators, optionally at least one non-photopolymerizable component and optionally catalysts, radical stabilizers, solvents Contains additives and other auxiliaries and / or additives,
  • step c) heating the layer composite B-C from step b) to a temperature of from 70 ° C. to 110 ° C., d) subjecting the layer composite B-C from step c) to actinic radiation, preferably containing UV radiation,
  • the method comprises the following steps:
  • step b) directly contacting the photopolymer layer B, containing a hologram, from step a) with the substrate layer C, so that a layer composite B-C is formed,
  • step c) heating the layer composite B-C from step b) to a temperature of from 70 ° C. to 110 ° C., d) subjecting the layer composite B-C from step c) to actinic radiation, preferably containing UV radiation,
  • the layer composite BC in step b) or the heating step is heated to a temperature of 70 ° C. to 110 ° C. for 0.2 seconds to 60 minutes, preferably from 0.5 seconds to 30 minutes, preferably 75 ° C to 110 ° C, more preferably at 80 ° C to 110 ° C, even more preferably at 90 ° C to 110 ° C he is heated.
  • the layer composite after passing through step b) or the heating step has an adhesive force in accordance with ISO / IEC 10373 using a Switzerlandprüfmachinene according to DIN EN ISO 527-1 between the layer B and C of at least 0 , 5 N / 10mm, preferably at least 0.8 N / 10mm, more preferably 0.9 N / 10mm, even more preferably 1.2 N / 10mm.
  • the layer composite after passing through step b) or the heating step has an adhesive force in accordance with ISO / IEC 10373 using a Switzerlandprüfmachinene according to DIN EN ISO 527-1 between the layer B and C of at least 0.5 N / 10mm, preferably at least 0.8 N / 10mm, more preferably at least 0.9 N / 10mm, more preferably at least 1.2 N / 10mm, wherein in the heating step for 30 seconds at least 70 ° C was heated.
  • the temperature in step b) is 75 ° C to 110 ° C, preferably 80 ° C to 110 ° C, more preferably 90 ° C to 110 ° C.
  • step b) or the heating step is carried out in a heated room, preferably an oven, or a laminator.
  • step a) or the step of directly contacting the photopolymer layer and the substrate layer C and step b) or the heating step are carried out in a common step.
  • the photopolymer layer B is present on a substrate layer A, the layers A and B being adhesively bonded together, the substrate layer A preferably being a transparent thermoplastic substrate layer or glass.
  • the substrate layer C is present on a substrate layer D and is at least partially connected thereto, preferably adhesively-free, wherein the substrate layer D preferably consists of a transparent thermoplastic material or a composite material.
  • the glass transition temperature T g of the substrate layer C is higher than the temperature in the process steps a) -d) for producing the layered composite BC according to the invention.
  • actinic radiation electro-magnetic radiation which has a wavelength in the visible (400 nm to 800 nm) spectral range and is in the UV-C, UV-B and / or in the UV-A range. Preference is given to actinic radiation in the spectral range of UV Be rich, preferably in the UV-A and / or UV-B range. It is also preferred to combine UV and visible range, as can typically be generated in mercury vapor lamps. It is also possible to produce such a blend of visible light with white LEDs and UV light with UV LEDs (e.g., 360-370 nm emitting LEDs).
  • the substrate layer C is an aromatic polycarbonate layer, preferably an aromatic homopolycarbonate layer.
  • Substrate layer A materials or composite materials are based on polycarbonate (PC), polyethylene terephthalate (PET), amorphous polyesters, polybutylene terephthalate, polyethylene, polypropylenes, cellulose acetate, cellulose hydrate, cellulose nitrate, cycloolefin polymers, polystyrene, hydrogenated polystyrene, polyepoxides, polysulfone, thermoplastic polyurethane ( TPU), cellulose triacetate (CTA), polyamide (PA), polymethyl methacrylate (PMMA), polyvinyl chloride, polyvinyl acetate, polyvinyl butyral or polydicyclopentadiene or mixtures thereof.
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PET amorphous polyesters
  • polybutylene terephthalate polyethylene
  • polypropylenes polypropylenes
  • cellulose acetate cellulose hydrate
  • cellulose nitrate
  • 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.
  • Particularly preferred are PC / PMMA, PC / PA, PC / PET, PET / PC / PET and PC / TPU.
  • Substrate layer A is preferably transparent in the spectral range of 400-800 nm.
  • the photopolymer layer B comprises matrix polymers, writing monomers and photoinitiators.
  • matrix polymers it is possible to use amorphous thermoplastics such as, for example, polyacrylates, polymethyl methacrylates or copolymers of methyl methacrylate, methacrylic acid or other alkyl acrylates and alkyl methacrylates and also acrylic acid such as polybutyl acrylate, polyvinyl acetate and polyvinylbiryrate its partially hydrolyzed derivatives such as polyvinyl alcohols and copolymers with ethyl and / or further (meth) acrylates, gelatin, cellulose esters and cellulose ethers such as methylcellulose, cellulose acetobutyrate, silicones such as polydimethylsilicone, polyurethanes, polybutadienes and polyisoprenes, as well as polyethylene oxides, epoxy resins, especially aliphatic epoxy resins, polyamides, polycarbonates and those described in US 4994347A
  • the matrix polymers are polyurethanes.
  • the matrix polymers are crosslinked. It is particularly preferred if the matrix polymers are crosslinked three-dimensionally.
  • Epoxy resins can be cationically crosslinked with themselves. Furthermore, it is also possible to use acid / anhydrides, amines, hydroxyalkylamides and thiols as crosslinkers.
  • Silicones can be crosslinked both as one-component systems by condensation in the presence of water (and, if appropriate, under broenstic acid catalysis) or as two-component systems by addition of silicic acid esters or organotin compounds. Likewise, the hydro rosilylations in vinyl silane systems is possible.
  • Unsaturated compounds e.g. Acryloyl functional polymers or unsaturated esters can be crosslinked with amines or thiols.
  • a cationic vinyl ether polymerization is also possible.
  • the matrix polymers are crosslinked, preferably crosslinked three-dimensionally and most preferably are three-dimensionally crosslinked polyurethanes.
  • Polyurethane matrix polymers are obtainable in particular by reacting at least one polyisocyanate component a) with at least one isocyanate-reactive component b).
  • the polyisocyanate component a) comprises at least one organic compound having at least two NCO groups. These organic compounds may in particular be mono-mer 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 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. organic compounds with an NCO group include.
  • 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'-diisocyanato) isocyanatocyclohexyl) methane and / or bis (2 ', 4-isocyanatocyclohexyl) methane and / or mixtures thereof of any isomer content, 1,4-cyclohexane diisocyanate, the isomeric bis (isocyanatomethyl) cyclohexanes, 2,4- and / or 2,6 Diisocyanato-1-methylcyclohexane (hexahydro-2,4- and / or 2,6-toluene diisocyanate, He-TDI), 1,4-phenylene diisocyanate, 2,4- and /
  • Suitable polyisocyanates are compounds having urethane, urea, carbodiimide, acylurea, amide, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione and / or iminooxadiazinedione structures which are selected from the abovementioned di- or tri- Triisocyanates are available.
  • the polyisocyanates are particularly preferably oligomerized aliphatic and / or cycloaliphatic di- or triisocyanates, it being possible in particular for the abovementioned aliphatic and / or cycloaliphatic di- or triisocyanates to be used.
  • Suitable prepolymers contain urethane and / or urea groups and optionally further structures formed by modification of NCO groups as mentioned above.
  • Derar term prepolymers are obtainable for example by reacting the above monomeric di- and triisocyanates and / or polyisocyanates al) with isocyanate-reactive compounds bl).
  • 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, decandicarbon, phthalic, terephthalic, isophthalic T etrahydrophthal- or trimellitic acid and acid anhydrides such as phthalic, trimellitic or Succinic anhydride or any mixtures thereof.
  • the polyester polyols can also be based on natural raw materials such as castor oil. It is likewise possible for the polyesterpolyols to be based on homopolymers or copolymers of lactones, which preferably by addition of lactones or lactone mixtures such as butyrolactone, e-caprolactone and / or methyl-e-caprolactone to hydroxy-functional compounds such as polyhydric alcohols of an OH -Functionality> 2, for example, the type mentioned below who can get.
  • suitable alcohols are all polyhydric alcohols, such as, for example, the C2-Cn-diols, the isomeric cyclohexanediols, glycerol or any desired 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 known per se in the context of the polyester segments. Also polyester polyols can be converted to polycarbonate polyols vice.
  • 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 exclusively based on Propy lenoxid 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, preferably at least 45 wt .-% makes up.
  • Oxypropylene and oxybutylene here include all respective linear and branched C 3 - and C-C isomers.
  • isocyanate-reactive compounds are also low molecular weight, i. with molecular weight ⁇ 500 g / mol, short chain, i.
  • these may include neopentyl glycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, positionally 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-functionality alcohols are di- (trimethylolpropane), pen taerythritol, dipentaerythritol or sorbitol. It is particularly preferred if the polyol component is a di functional polyether, polyester or a polyether-polyester-block copolyester or a polyether-Po lyester block copolymer with primary OH functions.
  • isocyanate-reactive compounds bl) amines are ethylenediamine, propyl endiamin, diaminocyclohexane, 4,4'-Dicylohexyl- menthanediamine, isophoronediamine (IPDA), difunctional polyamines such as Jeffamine ®, amine terminated polymers, and 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 it is also possible to use as isocyanate-reactive compounds bl) amino alcohols.
  • the isomeric aminoethanols, the isomeric aminopropanols are 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 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 partially organic compound whose NCO groups have been completely or partly reacted with blocking agents known from coating technology.
  • blocking agents are alcohols, lactams, oximes, malonic esters, pyrazoles and amines, such as e.g. Butanoxime, diisopropylamine, diethyl malonate, acetoacetic ester, 3, 5-dimethylpyrazole, e-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 cyano-reactive component b) preferably comprises at least one organic compound which has on average at least 1.5 and preferably 2 to 3 isocyanate-reactive groups. In the context of the present invention, hydroxy, amino or mercapto groups are preferably considered as isocyanate-reactive groups.
  • the isocyanate-reactive component may, in particular, comprise compounds which have at least 1.5 and preferably 2 to 3 isocyanate-reactive groups in the number average.
  • Suitable polyfunctional, isocyanate-reactive compounds of component b) are, for example, the compounds described above bl).
  • polyurethanes are based on polyester C 4 -polyether polyols.
  • Photoinitiators of the component are usually compounds which can be activated by actinic radiation and which can initiate polymerization of the sulfur monomers.
  • photoinitiators a distinction can be made between unimolecular (type I) and bimolecular (type II) initiators.
  • type I unimolecular
  • type II bimolecular
  • photoinitiators for radical, anionic, cationic or mixed type of polymerization.
  • Type I photoinitiators for radical photopolymerization form free radicals when irradiated by unimolecular bond cleavage.
  • type I photo initiators are triazines, oximes, benzoin ethers, benzil ketals, bis-imidazoles, Aroylphosphinoxide, sulfonium and iodonium salts.
  • Radical polymerization type II 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. It releases the polymerization-inducing radicals by electron or proton transfer or direct hydrogen abstraction.
  • type II photoinitiators are preferably used.
  • photoinitiator systems are described in principle in EP 0 223 587 A and preferably consist of a mixture of one or more dyes with ammonium alkylaryl borate (s).
  • Suitable dyes which form a type II photoinitiator together with an ammonium alkylaryl borate are the cationic dyes described in WO 2012062655 in combination with the anions just described there.
  • Cationic dyes are preferably understood to mean those of the following classes: acridine dyes, xanthene dyes, thioxanthene dyes, phenazine dyes, phenoxazine dyes, phenothiazine dyes, tri (het) arylmethane dyes - in particular diamino- and Triamino (het) arylmethane dyes, mono-, di-, tri- and pentamethine cyanine dyes, hemocyanin dyes, externally cationic merocyanine dyes, externally cationic neutrocyanine dyes, zero methine dyes - especially naphtholactam dyes, streptocyanin Dyes.
  • Such dyes are described, for example, in H. Bemeth in Ullmann's Encyclopedia of Industrial Chemistry, Azine Dyes, Wiley-VCH Verlag, 2008, H. Bemeth in Ullmann's Encyclopedia of Industrial Chemistry, Methine Dyes and Pigments, Wiley-VCH Verlag, 2008, T. Gessner, U. Mayer in Ullmann's Encyclopedia of Industrial Chemistry, Triarylmethane and Diarylmethane Dyes, Wiley-VCH Verlag, 2000.
  • phenazine dyes particularly preference is given to phenazine dyes, phenoxazine dyes, phenothiazine dyes, tri (het) arylmethane dyes-in particular diamino and triamino (het) arylmethane dyes, mono-, di-, tri- and pentamethinecyanine dyes.
  • cationic dyes are Astrazon Orange G, Basic Blue 3, Basic Orange 22, Basic Red 13, Basic Violet 7, Methylene Blue, New Methylene Blue, Azure A, 2,4-diphenyl-6- (4-methoxyphenyl) pyrylium, Safranine O, Astraphloxin, Brilliant Green, Crystal Violet, Ethyl Violet and Thionin.
  • Preferred anions are particularly Cs to C25 alkane, preferably C B - to C 25 - alkane, C 3 - to C perfluoroalkanesulfonate, C 4 - to C perfluoroalkanesulfonate, which kylkette in the Al carries at least 3 hydrogen atoms, C 9 - to C25 alkanoate, C 9 - to C 25 -Alkenoat, Cs to C 25 alkyl sulfate, preferably C 13 - to C 25 alkyl sulfate, Cs to C 25 -Alkenylsulfat, preferably C B - to C 25 - Alkenyl sulfate, C 3 - to C 1 s perfluoroalkyl sulfate, C 4 - to C l s -perfluoroalkyl sulfate which carries at least 3 hydrogen atoms in the alkyl chain, polyether sulfates
  • the anion A of the dye has an AClogP in the range from 1 to 30, particularly preferably in the range from 1 to 12 and particularly preferably in the range from 1 to 6.5.
  • the AClogP is named after J. Comput. Aid. Mol. Des. 2005, 19, 453; Virtual Computational Chemistry Laboratory, http: // www. vcclab .org calculated.
  • Suitable ammonium alkylaryl borates are, for example, (Cunningham et al., RadTech'98 North America UV / EB Conference Proceedings, Chicago, Apr. 19-22, 1998): T etrabutylammonium triphenylhexyl borate, T etrabutylammonium triphenyl butylborate, T etrabutylammonium trinapthyl hexyl borate, T etrabutylammonium tris (4-tert-butyl) -phenylbutylborate, T etrabutylammonium tris (3-fluorophenyl) hexylborate hexylborate ([191726-69-9], CGI 7460, product of BASF SE, Basel, Switzerland), 1-methyl- 3-octyl imidazolium dipentyl diphenyl borate and T etrabutyl ammonium tris (3-chloro-4-methylphen
  • 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.
  • the photopolymer layer B contains at least two laser light colors selected from blue, green and red depending on a suitable photoinitiator.
  • the photopolymer layer B comprises an acrylate or methacrylate functional writing monomer.
  • Particularly preferred are monofunctional writing monomers and in particular those monofunctional urethane (meth) acrylates which are described in US 2010/0036013 A1.
  • Suitable acrylate writing monomers are in particular compounds of the general formula (I)
  • esters of acrylic acid or methacrylic acid are referred to as acrylates or methacrylates.
  • acrylates or methacrylates examples include phenyl acrylate, phenyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxyethoxyethyl acrylate, phenoxyethoxyethyl methacrylate, phenylthioethyl acrylate, phenylthioethyl methacrylate, 2-naphthyl acrylate, 2-naphthyl methacrylate, 1,4-bis (2-thionaphthyl) -2 Butyl acrylate, 1, 4-bis (2-thionaphthyl) - 2-butyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, and their ethoxylated analogues, N-carbazolyl.
  • 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 methacrylates with an isocyanate-functional compound.
  • isocyanate-functional compounds which can be used for this purpose are monoisocyanates and the monomeric diisocyanates, triisocyanates and / or polyisocyanates mentioned under a).
  • suitable monoisocyanates are phenylisocyanate, isomeric methylthiophenyl isocyanate.
  • Di-, tri- or polyisocyanates are mentioned above, and diphenylmethane-4,4 ', 4 "-triisocyanate and tris (p-isocyanatophenyl) thiophosphate or their derivatives with urethane, urea, carbodiimide, acylurea, isocyanurate, Allophanate, biuret, oxadiazinetrione, uretdione, iminooxadiazinedione, and mixtures thereof.
  • Aromatic di-, tri- or polyisocyanates are preferred.
  • Poly (8-caprolactone) mono (meth) acrylates such as Tone ® Ml 00 (Dow, Schwalbach, Germany), 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, hydroxypropyl (meth) acrylate, acrylic acid - (2-hydroxy-3-phenoxypropyl ester ), the hydroxy-functional mono-, di- or tetraacrylates of polyhydric alcohols, such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or technical mixtures thereof.
  • hydroxyl-containing epoxy (meth) acrylates known per se having OH contents of from 20 to 300 mg KOH / g or hydroxyl-containing polyurethane (meth) acrylates having OH contents of from 20 to 300 mg KOH / g or acrylated polyacrylates having 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 o-phenylthiophenyl acrylate and / or o-biphenyl acrylate 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 semi-monomer further unsaturated compounds such as a, b -un saturated carboxylic acid derivatives such as maleates, fumarates, maleimides, acrylamides, further vinyl ethers, propenyl ethers, allyl ethers and dicyclopentadienyl units containing compounds and olefinically unsaturated compounds such.
  • Styrene, a-methyl styrene, Vi nyltoluol and / or olefins comprises or consists thereof.
  • the photopolymer additionally comprises monomeric fluorourethanes.
  • the fluorourethanes comprise at least one compound of the formula (II)
  • n> 1 and n ⁇ 8 and R 3 , R 4 , R 5 are independently hydrogen, linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted with hetero atoms organic radicals, preferably at least one of the radicals R 3 , R 4 , R 5 is substituted by at least one fluorine atom and more preferably R 3 is an organic radical having at least one fluorine atom.
  • photopolymers containing from 20 to 70% by weight of matrix polymers, from 20 to 50% by weight of semi-monomers, from 0.001 to 5% by weight of photo initiators, from 0 to 2% by weight of catalysts, from 0.001 to 1% by weight.
  • % Radical stabilizers optionally 10 to 30 wt .-% fluorourethanes and optionally used from 0.1 to 5 wt .-% of other additives.
  • urethanization catalysts e.g. organic or inorganic derivatives of bimuth, tin, zinc or iron (see also the compounds mentioned in US 2012/062658).
  • Particularly preferred catalysts are butyltin tris (2-ethylhexanoate), iron (III) tris-acetylacetonate, bismuth (III) tris (2-ethylhexanoate), and stannous bis (2-ethylhexanoate).
  • sterically hindered A- mine can be used as catalysts.
  • additives which can be used are starting aids and / or antistatic agents and / or thixotropic agents and / or thickeners and / or biocides.
  • the photopolymer layer B is in particular one which, after exposure to UV radiation, has a mechanical modulus Guv in the range between 0.1 and 160 MPa.
  • the exposed holographic media may have a modulus Guv in the range between 0.3 and 40, preferably between 0.7 and 15 MPa.
  • the substrate layer C comprises (co) polycarbonates, in particular aromatic polycarbonates or copolycarbonates are particularly suitable in preferred embodiments.
  • the polycarbonates or copolycarbonates may be linear or branched in a known manner.
  • the substrate layer C may be a composite material such as a film laminate or co-extrudate which consists on one side of (co) polycarbonate. If a (co) polycarbonate film laminate or coextrudate is used in the process according to the invention, the side of the substrate layer C facing the photopolymer layer B is always the (co) polycarbonate side.
  • Preferred composite materials are duplex and triplex films constructed according to one of the schemes A / B, A / B / A or A / B / C.
  • the (co) polycarbonate of the substrate layer C may be untreated (native) or pretreated, for example by a flame, corona, plasma and / or UV treatment.
  • Suitable dihydroxyaryl compounds may be, for example, dihydroxyaryl compounds of the general formula (III)
  • Z is an aromatic radical having 6 to 34 C atoms, which may contain one or more optionally substituted aromatic nuclei and aliphatic or cycloaliphatic radicals or alkylaryl or heteroatoms as bridge members.
  • dihydroxyaryl compounds examples include: dihydroxybenzenes, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, bis (hydroxyphenyl) -aryls, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) -ketones, Bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, 1, 1 'bis (hydroxyphenyl) diisopropyl benzenes, and their kemalkyltechnisches, and their kemalkyltechnisches, and their kemalkyltechnisches, and their kemalkyltechnisches, and their kemalkyltechnisches, and their kemalkyltechnisches, and their kemalkyltechnisches, and their kemalkyltechnisches, and their kemalkyltechnisches, and their ke
  • Preferred dihydroxyaryl compounds are, for example, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane , 1,1-bis (4-hydroxyphenyl) -1-phenyl-ethane, 1,1-bis (4-hydroxyphenyl) -1- (1-naphthyl) ethane, 1,1-bis- (4- hydroxyphenyl) -1- (2-naphthyl) ethane, 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis - (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis (4-hydroxyphenyl) -1-phenylpropane, 2,2-bis (4-hydroxyphenyl) hex
  • R 6 and R 7 independently of one another are hydrogen, halogen, preferably chlorine or bromine, C 1 -C 8 -alkyl, C 1 -C 12 -cycloalkyl, C 1 -C 10 -aryl, preferably phenyl, and C 7 -C 12 -aralkyl, preferably phenylC C 1 -C 4 -alkyl, in particular benzyl,
  • n is an integer from 4 to 7, preferably 4 or 5
  • R 8 and R 9 are individually selectable for each X, independently of one another hydrogen or C 1 -C 6 -alkyl and
  • Preferred alkyl radical for the radicals R 8 and R 9 in formula (IIIa) is methyl.
  • the X atoms in the alpha position to the diphenyl-substituted C atom (Cl) are preferably not dialkyl-substituted, whereas alkyl disubstitution in the beta position to Cl is preferred.
  • a most preferred dihydroxydiphenylcycloalkane of formula I (IIIa) is 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (formula (IIIa-1) where R 6 and R 7 are H).
  • Such polycarbonates can be prepared according to EP-A 359 953 from dihydroxydiphenylcycloalkanes of the formula (IIIa).
  • dihydroxyaryl compounds are resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) -diphenyl-methane, 1,1-bis- (4-hydroxyphenyl) -1-phenyl-ethane, bis- (4-hydroxyphenyl) - 1 - (1-naphthyl) ethane, bis (4-hydroxyphenyl) -1- (2-naphthyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3 , 5-dimethyl-4-hydroxyphenyl) -propane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, 1, 1 - Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1'-bis (4-hydroxyphenyl) -3-diisopropyl
  • dihydroxyaryl compounds are 2,2-bis (4-hydroxyphenyl) propane (BP-A) and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BP-TMC) , Both a dihydroxyaryl compound to form homopolycarbonates and various dihydroxyaryl compounds to form copolycarbonates can be used. It is possible to use both a dihydroxyaryl compound of the formula (III) or (IIIa) to form homopolycarbonates and also a plurality of dihydroxyaryl compounds of the formula (III) and / or (IIIa) to form copolycarbonates.
  • the various dihydroxyaryl compounds can be linked to one another both statistically and in blocks.
  • the molar ratio of dihydroxyaryl compounds of the formula (IIIa) to the optionally used other dihydroxyaryl compounds of the formula (III) is preferably from 99 mol% (IIIa) to 1 mol -% (III) and 2 mol% (IIIa) to 98 mol% (III), preferably between 99
  • a very particularly preferred copolycarbonate can be prepared by using 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 2,2-bis (4-hydroxyphenyl) propane dihydroxyaryl compounds of the formula ( purple) and (III).
  • Suitable carbonic acid derivatives may be, for example, diaryl carbonates of the general formula (IV)
  • R, R 'and R are each, independently of one another or different, hydrogen, linear or branched C 1 -C 4 -alkyl, C 7 -C 34 -alkylaryl or C 6 -C 34 -aryl, R furthermore also -COO-R'" where R '"is hydrogen, linear or branched Ci-C 34 alkyl, C7-C34 alkylaryl or Ce-C 34 -aryl.
  • Preferred diaryl carbonates are, for example, diphenyl carbonate, methylphenyl phenyl carbonates and di (methylphenyl) carbonates, 4-ethylphenyl phenyl carbonate, di (4-ethylphenyl) carbonate, 4-n-propylphenyl phenyl carbonate, di- (4-n-propylphenyl) carbonate, 4-iso-Propylphenyl- phenyl carbonate, di- (4-iso-propylphenyl) carbonate, 4-n-butylphenyl-phenyl carbonate, di- (4-n-butylphenyl ) carbonate, 4-isobutylphenyl phenyl carbonate, di (4-isobutylphenyl) carbonate, 4-tert-butylphenyl phenyl carbonate, di- (4-tert-butylphenyl) carbonate, 4- n-pentylphenyl phenyl carbonate, di
  • diaryl compounds are diphenyl carbonate, 4-tert-butylphenyl phenyl carbonate, di- (4-tert-butylphenyl) carbonate, biphenyl -4-yl phenyl carbonate, di (biphenyl-4-yl) carbonate, 4- (1-methyl-1-phenylethyl) -phenyl-phenyl carbonate, di- [4- (1-methyl-1-phenylethyl) -phenyl] -carbonate and di (methyl salicylate) carbonate.
  • one or more monohydroxyaryl compound (s) may be used as a chain terminator for controlling or changing the end groups, which was not used for the preparation of the diaryl carbonate (s) used (s).
  • These may be those of the general formula (V),
  • R A is linear or branched Ci-C34-alkyl, C7-C34-alkylaryl, C6-C34-aryl or -COO-R D , where R D is hydrogen, linear or branched Ci-C34-alkyl, C7-C34 -Alkylaryl or C6-C34-aryl, and
  • R b , R c independently of one another are identical or different for hydrogen, linear or branched
  • Such monohydroxyaryl compounds are, for example, 1-, 2- or 3-methylphenol, 2,4-dimethylphenol 4-ethylphenol, 4-n-propylphenol, 4-iso-propylphenol, 4-n-butylphenol, 4- Isobutylphenol, 4-tert-butylphenol, 4-n-pentylphenol, 4-n-hexylphenol, 4-iso-octylphenol, 4-n-nonylphenol, 3-pentadecylphenol, 4-cyclohexylphenol, 4- (1-methyl-1-phenyl ethyl) -phenol, 4-phenylphenol, 4-phenoxyphenol, 4- (1-naphthyl) -phenol, 4- (2-naphthyl) -phenol, 4-tritylphenol, methyl salicylate, ethyl salicylate, n-propyl salicylate, iso-propyl salicylate, n Butyl salicylate, iso-butyl salicylate,
  • Suitable branching agents may be compounds having three or more functional groups, preferably those having three or more hydroxyl groups.
  • Suitable compounds having three or more phenolic hydroxyl groups are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tri (4-hydroxyphenyl) -phenylmethane, 2,2-bis (4,4-bis (4-hydroxyphenyl) -cyclohexyl] -propane,
  • Preferred branching agents are 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tri (4-hydroxyphenyl) -ethane.
  • the substrate layer C may also consist of a mixture or a copolymer of different bisphenol units.
  • polycarbonates or copolycarbonates in particular having average molecular weights Mw of from 500 to 100,000, preferably from 10,000 to 80,000, more preferably from 15,000 to 40,000, or blends comprising at least one such polycarbonate or copolycarbonate.
  • Suitable blends are blend of polycarbonate or copolycarbonate with acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate or copolycarbonate with polyester (s) such as polyalkyl enter ephthalate, especially polyethylene terephthalate and polybutylene terephthalate, poly carbonate or copolycarbonate with vinyl (co) polymers such as Polystyrene-acrylonitrile (SAN), polymethyl methacrylate (PMMA) or copolymers of two monomers, such as, for example, methyl methacrylate / styrene acrylonitrile and methyl methacrylate / styrene.
  • ABS acrylonitrile-butadiene-styrene copolymer
  • polyester such as polyalkyl enter ephthalate, especially polyethylene terephthalate and polybutylene terephthalate
  • poly carbonate or copolycarbonate with vinyl (co) polymers such
  • Such a blend of polycarbonate or copolycarbonate with one of the abovementioned polymeric blend partners may be preferably one having from 1 to 90% by weight of polycarbonate or copolycarbonate and from 99 to 10% by weight of polymeric blend partner, preferably from 1 to 90% by weight of polycarbonate and 99 to 10% by weight of polymeric blend partners, the proportions adding to 100% by weight.
  • the blend is transparent in the spectral range of 400-800 nm.
  • Materials or composite materials of the substrate layer D are based on polycarbonate (PC), polyethylene terephthalate (PET), amorphous polyesters, polybutylene terephthalate, polyethylene, polypropylenes, cellulose acetate, cellulose hydrate, cellulose nitrate, cycloolefin polymers, polystyrene, hydrogenated polystyrene, polyepoxides, polysulfone, thermoplastic polyurethane (TPU), cellulose triacetate (CTA), polyamide (PA), polymethyl methacrylate (PMMA), polyvinyl chloride, polyvinyl acetate, polyvinyl butyral or polydicyclopentadiene or mixtures thereof.
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PET amorphous polyesters
  • polybutylene terephthalate polyethylene
  • polypropylenes polypropylenes
  • cellulose acetate cellulose hydrate
  • cellulose nitrate
  • 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.
  • Particularly preferred are PC / PMMA, PC / PA, PC / PET, PET / PC / PET and PC / TPU.
  • Substrate layer D is preferably transparent in the spectral range of 400-800 nm.
  • Another object of the invention is layer structure comprising a photopolymer layer B containing a hologram, and a substrate layer C of (co) polycarbonate available or obtained th ten by the inventive method.
  • the layer composite has an adhesive force based on ISO / IEC 10373 using a Switzerlandprüfmachinene according to DIN EN ISO 527-1 between the layer B and C of at least 0.5 N / 10mm, preferably of at least 0.8 N / 10mm , more preferably at least 0.9 N / 10mm, more preferably at least 1.2 N / 10mm.
  • the layer composite has an adhesive force according to ISO / IEC 10373 using a Switzerlandprüfmachinene according to DIN EN ISO 527-1 between rule the layer B and C of at least 0.5 N / 10mm, preferably of at least 0.8 N / 10mm, more preferably at least 0.9N / 10mm, more preferably at least 1.2N / 10mm, when the laminate has been heated to at least 70 ° C for 30 seconds.
  • the photopolymer layer B is present on a substrate layer A, where in the layers A and B are adhesively bonded together, wherein the substrate layer A is preferably a transparent thermoplastic substrate layer or glass.
  • the substrate layer C is present on a substrate layer D and is at least partially connected thereto, preferably adhesively-free, wherein the substrate layer D preferably consists of a transparent thermoplastic material or a composite material.
  • the substrate layer C is an aromatic polycarbonate layer, preferably an aromatic homopolycarbonate layer, in particular a polycarbonate layer as defined and explained above.
  • Another object of the invention is a sealed holographic medium containing a layer structure according to the invention.
  • the holographic medium contains a a hologram or a holographic optical element-containing photopolymer layer having a layer thickness of 0.3 mih to 500 mih, preferably from 0.5 mih to 200 mih and particularly preferably be from 1 mm to 100 mih.
  • Possible optical functions of the holograms correspond to the optical functions of light elements such as lenses, mirrors, deflecting mirrors, filters, diffusers, scattered scattering elements, diffraction elements, optical fibers, waveguides, projection disks and / or masks.
  • several such optical functions can be combined in such a hologram, e.g. so that, depending on the incidence of light, the light is deflected in a different direction.
  • autostereo Skopische or holographic electronic displays that allow a stereoscopic rule visual impression without further aids such.
  • Polarizer or shutter glasses the use in automotive head-up displays or head-mounted displays.
  • these optical elements exhibit specific frequency selectivity depending on how the holograms have been exposed and what dimensions the hologram has. This is especially important when using monochromatic light sources such as LED or laser light. So you need a hologram per complementary color (RGB) to direct light frequency selective and simultaneously to enable full-color displays. Therefore, certain display structures of several holograms are to be exposed to one another in the medium.
  • RGB complementary color
  • holo graphic images or representations such as for personal portraits, biometric representations in security documents, or generally of images or image structures for advertising, security labels, trademark protection, brand branding, labels, design elements, Dekoratio, by means of the sealed holophaphic media according to the invention, Illustrations, trading cards, pictures and the like, as well as pictures, the representative of digital data representative may also be produced in combination with the products previously shown who the.
  • 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.
  • holograms in particular volume holograms, represent an attractive technical solution for the above-mentioned application. It is also possible to use such holograms for the storage of digital data, using a variety of B (shift, spatial or angular multiplexing) become.
  • B shift, spatial or angular multiplexing
  • the invention likewise provides an optical display comprising a sealed holographic medium according to the invention.
  • autostereoscopic and / or holographic displays projection screens, projection screens, displays with switchable restricted beams, for privacy filters and bidirectional multi-user screens, virtual screens, head-up displays, head-mounted displays, illuminated symbols, warning lamps, signal lamps, Headlamps and display panels comprising a holographic medium according to the invention.
  • a holographic medium according to the invention for the production of chip cards, ID documents, 3D images, product protection labels, Lab a, banknotes or holographic optical elements in particular for optical displays are Ge subject matter of the invention.
  • Desmodur® RFE [141-78-6] tris (p-isocyanatophenyl) thiophosphate, 27% in ethyl acetate, product of Covestro GmbH AG, Le verkusen, Germany
  • Hexane diisocyanate-based polyisocyanate proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%.
  • Trimethylhexamethylene diisocyanate [28679-16-5] - ABCR GmbH & Co KG, Düsseldorf, Germany
  • Tinuvin 292 - light stabilizer A sterically hindered amine from BASF SE, Ludwigs hafen, Germany.
  • Irganox 1135 - Antioxidant A phenolic antioxidant from BASF SE, Ludwigshafen, Germany.
  • Methoxypropanol (MP) 1 -methoxy-2-propanol from Brenntag GmbH, Mülheim an der Ruhr, Germany.
  • MPA-EEP M / E
  • DOWANOL TM PMA GLYCOL ETHER ACETATE 1-methoxy-2-propanol acetate
  • Makrofol DE 1-1 A bisphenol A (BP-A-PC) based polycarbonate film from Covestro GmbH AG, Leverkusen, DE, with a smooth surface on the front and back.
  • BP-A-PC bisphenol A
  • BP-A-PC bisphenol A
  • PET polyethylene glycol terephthalate
  • Urethane acrylate 1 phosphorothioyl tris (oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) tris acrylate
  • this solution was in a roll to roll coating system on a 66 mih thick Po lycarbonate carrier film, where by means of a doctor blade, the product was applied in a wet layer thickness of 19 mih. At a drying temperature of 85 ° C. and a drying time of 5 minutes, the coated film was dried and then protected with a 40 mih thick polyethylene film. Subsequently, this film was packed light-tight.
  • Test holograms were prepared as follows: the photopolymer films were cut to the desired size in the dark and laminated to a 50 mm x 70 mm (3 mm thick) glass plate by means of a rubber roller.
  • T est holograms are produced by a test apparatus which generates Denisyuk reflection holograms by means of green (532 nm) laser radiation.
  • the test apparatus consists of a laser source, an optical beam guidance system and a holder for the glass coupons.
  • the holder for the glass coupons is mounted at an angle of 13 ° relative to the beam axis.
  • the laser source generated the radiation, which was guided over a special optical beam path to about 5 cm expanded to the glass coupon, which was in optical contact with the mirror be.
  • the holographed object was an approximately 2 cm x 2 cm large mirror, so that the wavefront of the mirror was reconstructed during the reconstruction of the hologram. All 15 examples were exposed to a green 532nm laser (Newport Corp, Irvine, CA, USA, stock no. EXLSR-532-50-CDRH). The recording film was exposed for 2 seconds by means of a cover plate.
  • UV Spotlight was an iron-doped Hg lamp type Fusion UV type "D Bulb" no. 558434 ICR 85 with 80 W / cm 2 total power density used.
  • the parameters corresponded to a dose of 2 ⁇ 2.5 J / cm 2 (measured with a ILT 490 light bug).
  • This diffractive reflection can be analyzed in transmission due to the high efficiency of the volume hologram with visible light with a VI S spectrometer (USB 2000, Ocean Optics, Dunedin, FL, USA) and appears in the transmission spectrum as a peak with reduced transmission.
  • the quality of the hologram can be determined by evaluating the transmission curve: the width of the peak was determined as "full width at half maximum” (FWHM) in nanometers (nm), the depth of the peak (Tmin) being 30 as 100% Tmin in percent (1- T mm ), the lowest transmission range indicates the wavelength ( pea k) of highest diffraction efficiency.
  • FWHM full width at half maximum
  • Non-inventive examples A-C, inventive example 1 are non-inventive examples A-C, inventive example 1
  • a 5 cm x 7 cm piece of film of photopolymer film was cut in the dark (5x7cm) and the PE liner was removed.
  • the photopolymer surface was then covered with a polycarbonate film (Makrofol DE 1-1, thickness 125 ⁇ m) by means of a roll laminator (Dormer Trident 46, lamination speed: 0.3 m / min, roll end pressure setting: high, contact time: approx sec) laminated together at various roll entempatures. Thereafter, a reflection hologram was written at 532 nm and the sample completely bleached with UV light (5 J / cm 2).
  • Examples 7 to 12 a small, acceptable hologram shift was measured while the adhesion between photopolymer and polycarbonate film increased with temperature. In the non-inventive example L, a strong blistering was shown. Examples 9-12 are preferred (storage time> 50 seconds at 100 ° C. oven temperature), with particular preference being given to Example 1 1-12 (storage time of> 90 seconds at 100 ° C. oven temperature).
  • Table 5 Adhesion between the photopolymer layer and various laminated thermoplastic films and glass.
  • a 15 cm x 20 cm piece of film of 25 mm thick photopolymer film was cut in the dark (15x20 cm) and the PE liner was removed.
  • the photopolymer surface was then laminated to a polycarbonate film (Makrofol DE 1-1, thickness 125mih) (Dumor Trident 46, lamination rate: 0.3 m / min, roller pressure setting: high) at room temperature.
  • a polycarbonate film Mokrofol DE 1-1, thickness 125mih
  • Dumor Trident 46 lamination rate: 0.3 m / min, roller pressure setting: high
  • the structure was annealed at different temperatures and times in the oven.
  • the samples were completely bleached with UV light (5 J / cm 2).
  • Each film was cut into at least 6 different 10 mm wide strips.
  • Example 17 In Examples 17 to 19, a very good adhesion was obtained and this increased as a function of the oven temperature and the time. In Example 19, a very high adhesive force of 13 N / 10 mm was obtained, so that the layer structure can no longer be separated without destruction.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Holo Graphy (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une structure multicouche liée sans adhésif, une structure multicouche comprenant une couche photopolymère B exposée à la lumière et une couche substrat C à base de (co)polycarbonate, un moyen optique scellé contenant la structure multicouche et un affichage optique et un document de sécurité comprenant le moyen optique scellé.
EP18815978.4A 2017-12-06 2018-12-03 Structure multicouche photopolymère exempte d'adhésif Pending EP3721292A1 (fr)

Applications Claiming Priority (2)

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EP17205629.3A EP3495886A1 (fr) 2017-12-06 2017-12-06 Structure en couches en photopolymère sans adhésif
PCT/EP2018/083347 WO2019110505A1 (fr) 2017-12-06 2018-12-03 Structure multicouche photopolymère exempte d'adhésif

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EP3721292A1 true EP3721292A1 (fr) 2020-10-14

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KR (1) KR20200090250A (fr)
CN (1) CN111465898A (fr)
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WO2020219029A1 (fr) * 2019-04-23 2020-10-29 Bemis Company, Inc. Procédé de production de stratifiés exempts d'adhésif

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Publication number Priority date Publication date Assignee Title
NL152889B (nl) 1967-03-10 1977-04-15 Gen Electric Werkwijze ter bereiding van een lineair polycarbonaatcopolymeer, alsmede orienteerbare textielvezel van dit copolymeer.
DE3650107T2 (de) 1985-11-20 1995-05-24 Mead Corp Ionische Farbstoffe.
US4994347A (en) 1988-01-15 1991-02-19 E. I. Du Pont De Nemours And Company Storage stable photopolymerizable composition and element for refractive index imaging
US4965152A (en) * 1988-01-15 1990-10-23 E. I. Du Pont De Nemours And Company Holographic notch filters
DE3832396A1 (de) 1988-08-12 1990-02-15 Bayer Ag Dihydroxydiphenylcycloalkane, ihre herstellung und ihre verwendung zur herstellung von hochmolekularen polycarbonaten
NO170326C (no) 1988-08-12 1992-10-07 Bayer Ag Dihydroksydifenylcykloalkaner
EP0439050B1 (fr) * 1990-01-18 1996-04-03 E.I. Du Pont De Nemours And Company Méthode de fabrication de milieux lisibles par voie optique avec des informations en relief
EP2154128B1 (fr) 2008-08-08 2010-12-29 Bayer MaterialScience AG Uréthane acrylates à base de phénylisocyanate ayant un index de rupture élevé
CN102667935B (zh) 2009-11-03 2016-01-20 拜尔材料科学股份公司 具有不同书写共聚单体的光聚合物制剂
RU2542984C2 (ru) 2009-11-03 2015-02-27 Байер Матириальсайенс Аг Способ изготовления голографической пленки
JP5752906B2 (ja) 2010-09-14 2015-07-22 エスアイアイ・プリンテック株式会社 液体噴射ヘッドの製造方法
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
US9195215B2 (en) * 2011-11-29 2015-11-24 Bayer Intellectual Property Gmbh Holographic medium having a protective layer
EP2613319A1 (fr) * 2012-01-05 2013-07-10 Bayer MaterialScience AG Composite en couche à partir d'une pellicule photopolymère et d'une couche d'adhésif
DE102013200980B4 (de) 2013-01-22 2021-11-18 Bundesdruckerei Gmbh Verfahren zur nachträglichen holografischen Beschriftung sowie Vorrichtung zur nachträglichen holografischen Beschriftung
TWI640428B (zh) * 2013-02-27 2018-11-11 拜耳材料科學股份有限公司 以丙烯酸酯為基底之保護塗層與黏著劑
EP3166109A1 (fr) 2015-11-09 2017-05-10 Covestro Deutschland AG Ensemble de pieces comprenant une couche couvre-n uds et photo-polymere

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CN111465898A (zh) 2020-07-28
JP2021505946A (ja) 2021-02-18
EP3495886A1 (fr) 2019-06-12
WO2019110505A1 (fr) 2019-06-13
US20200387110A1 (en) 2020-12-10
KR20200090250A (ko) 2020-07-28
TW201936406A (zh) 2019-09-16

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