2K Series

Abstract

The present invention relates to a two-component system for mixing photopolymerizable compositions, and elements prepared therefrom, and their use. The photopolymerizable compositions are particularly suitable as recording materials for optical elements with refractive index modulation, in particular holograms.

Description

[Technical field]

[0001] The present invention relates to a two-component system (kit-of-parts) and elements made therefrom, as well as their uses. The photopolymerizable compositions made from the kit-of-parts are particularly suitable as recording materials for optical elements with refractive index modulation, in particular for holograms. [Background technology]

[0002] Various types of holograms are known, such as reflection holograms, embossing holograms, transmission holograms or volume holograms.

[0003] For example, a volume hologram is created by interfering two light waves of the same wavelength (also called the object and reference waves) and exposing a holographic recording medium (usually photographic film) to produce interference fringes (usually patterns of intensity). The hologram exposure process and hologram duplication (reproduction) are technically complex optical processes that require special application knowledge. The theory and methods of creating holograms are described in detail in the following literature: Howard M. Smith, “Principles of Holography”, Wiley (1969); Fred Unterseher et al., “Holography Handbook: Making Holograms the Easy Way”, Ross Books (1982); and Graham Saxby, “Practical Holography”, Inst. of Physics Pub. (2004).

[0004] Known materials with different performance profiles include silver halide emulsions, hardened dichromated gelatin, ferroelectric crystals, photochromic dichroid materials, and photopolymers [Howard M. Smith, “Principles of Holography”, Wiley (1969)]. For large volume applications, materials of interest are those that can be easily incorporated into hologram creation and replication equipment to allow easy exposure and development of holograms. Photopolymers are considered particularly preferred if they have high efficiency, easy handling, and good storage stability. The best known photopolymer is, for example, Omnidex HRF 600 manufactured by DuPont [S.M. Schultz et al., “Volume grating preferential-order focusing waveguide coupler”, Opt. Lett., vol. 24, pp. 1708-1710, Dec. 1999]. Omnidex materials belong to a type of self-developing photosensitive polymer films based on radical polymerization and monomer diffusion (see EP 0 324 480 A2).

[0005] Omnidex photopolymers have been further developed over the years, primarily to improve the refractive index contrast in the film and achieve high diffraction efficiency (see US Pat. No. 4,942,112A and DE Pat. No. 69,032,682T2). Nevertheless, well over two-thirds of the coating-related diffraction efficiency is provided by the high proportion of thermoplastic binder.

[0006] To produce a film, the binder for the coating must be liquid. For this purpose, solvents are used, which after coating lead to a significant reduction in the layer thickness due to the evaporation of the solvent. The wet layer applied is therefore considerably thicker than the film layer thus obtained, depending on the solvent content. The solvent content is usually about 80%. In order to achieve a 20 μm layer that can be exposed by volume holography, a wet layer of 100 μm must be applied in this case. The high thickness required for the wet layer makes known printing processes, such as flexographic or gravure printing, impossible or complicated. In screen printing, the use of fast-drying solvents can cause the meshes to stick to each other.

[0007] Moreover, the film can only be further processed and wound up once the solvent has completely evaporated. Its production therefore requires the installation of long drying lines and extraction systems that are health-conscious, environmentally friendly and at the same time dust- and explosion-proof. These difficulties mean that film production and hologram exposure are usually carried out in different locations and at different times.

[0008] In the case of binder-containing materials, post-treatment by heating ("annealing") of the exposed and UV-fixed photopolymer is also necessary to achieve maximum refractive index contrast (see DE 68905610T2). Annealing is an additional time-consuming processing step that slows, complicates and costs hologram production in addition to the time-consuming film preparation, and further limits the choice of substrate materials to those that are less temperature sensitive.

[0009] Other photopolymer materials for volume holography are manufactured by Polaroid (see U.S. Pat. No. 5,759,721 A), Fujifilm (see European Patent Application Publication No. 1 510 862 A2), Konica Minolta Medical and Graphics (see U.S. Pat. No. 200505891 A1), Dai Nippon Printing (see European Patent Application Publication No. 123151 A1), Nippon Paint (see European Patent Application Publication No. 021 1615 A2), Nissan Chemical Industries, Ltd. (see U.S. Pat. No. 20050068594 A1), Bayer (see WO 2010091795 A1), Xetos (see WO 2003036389 A1), and InPhase. Technologies (see US Patent Publication No. 2002142227A1). The prior art features photopolymers that differ from Omnidex in their holographic performance or processing. The technological advances described are: reduced oxygen sensitivity, reduced shrinkage of the material upon exposure to light, spectral sensitivity, solvent-free film formation, high diffraction efficiency without annealing, and / or better temperature and storage stability.

[0010] A newer commercially available holographic photopolymer is the "Bayfol HX" film developed by Bayer Materialscience. It does not contain a thermoplastic binder, but instead contains polyurethane as the polymer matrix, which holds the holographically exposable write monomers. The polyurethane is formed by a polyaddition reaction of a polyisocyanate and a polyol mixture. The reactants are mixed together just before coating and cured on a carrier film. Although they do not have a high solvent content compared to the binder-containing materials mentioned above, the curing time of up to an hour presents the same problem of having to provide a sufficiently long, dust-free drying and curing section in the coating system.

[0011] As with all commercially available photopolymer films, the user cannot choose and coat the carrier material of his own free will, but must process the film structure provided. In addition to the carrier film, there is a laminating film on the light-sensitive film layer to prevent adhesion and contamination. When peeling this film, static electricity can be generated, which attracts dust particles. The film must be laminated to the glass or master for exposure, and since any dust particle will cause defects, an extremely dust-free environment is required for clean and defect-free processing.

[0012] Photopolymer systems that contain a polymeric binder or polymeric matrix form a substantially solid film layer. In contrast, binder-free systems that are substantially liquid until exposed to light have also been proposed (see, for example, U.S. Pat. No. 3,993,485 A, or N. Smirnova, "Optics in Information Systems", February 2004, p. 9, or Xetos (see WO 2003036389 A1)).

[0013] In almost substantially solid monomer-binder / matrix photopolymers, the unexposed write monomers located in the areas of the dark interference lines diffuse into the exposed and polymerized areas after holographic laser exposure. This creates refractive index differences, the spatial modulation of which corresponds to the recorded interference fringes. However, the diffusion of the write monomers in the solid matrix takes time. This process can be accelerated by increasing the temperature. For the OmniDex® material mentioned above, DuPont specifies an annealing time of 1 hour at 120° C. For the Bayfol HX material, in its patent applications (EP 2 372 454 A1, p. 13,

[0127] ; EP 2 219 073 A1, p. 15,

[0102] ) specifies a waiting time of 5 minutes before the material is finally fully cured with UV light.

[0014] However, when it comes to creating holograms, many fabrication processes require the shortest possible time or maximum throughput, and simple, cost-effective process control, making cumbersome and time-consuming post-processing and waiting times inconvenient. For this reason, photopolymerizable compositions have been developed which form an effective refractive index modulation already upon laser exposure and can be fixed immediately using UV light, as described in EP 1 779 196 B1, where various triglycerides, for example castor oil, are used. The photosensitivity and the storability associated with the polymerization initiator play an important role in known photopolymerizable compositions, since it is important to always obtain the same quality.

[0015] A drawback of the liquid photopolymerizable composition mentioned above (EP 1 779 196 B1) is that the borate used as copolymerization initiator, SEC-LCA 1460 (BASF) (formerly CGI 7460 (Ciba)), is prone to crystallization over time. It has a melting point of 80° C. Although it is possible to return the borate to solution by heating and stirring, there is a risk of heat-initiated polymerization and loss of photosensitivity due to thermal reaction of the dye. In particular, if methylene blue is used as a dye, additives such as NPG (N-phenylglycine) are used to increase the photosensitivity, or heat-activatable polymerization initiators such as peroxides (tert-butylperoxybenzoate) are used to increase the reaction rate, they may be sensitive to higher temperatures and initiate chemical reactions, decompose, fade, become turbid, or undergo radical polymerization.

[0016] Adding higher amounts of solvent in an attempt to keep the borate in solution for longer periods is counterproductive because it can compromise the holographic quality and rapid reactivity of the photopolymerizable composition. Summary of the Invention [Problem to be solved by the invention]

[0017] The present invention is therefore based on the object of providing a holographic system which avoids the disadvantages of known recording materials and in particular allows for improved longer storage or usable times as well as simple and extremely fast processing, the holographic elements produced from which recording materials should have the highest possible refractive index modulation and high long-term stability as well as thermal and mechanical stability, and in particular should be transparent, clear and free of haze.

[0018] In addition, it must be ensured that the photopolymerizable composition made from the part kit is capable of successive layer-by-layer exposure without the underlying previously cured layers being attacked by the freshly applied wet layer and their mechanical, optical, and holographic qualities being degraded. In particular, the invention is aimed at enabling a user to coat his own carrier materials or products and then immediately expose them holographically, without the need for waiting periods. [Means for solving the problem]

[0019] The object is solved in the present invention by a kit of parts for preparing a photopolymerizable composition by means of UV / Vis radiation, which comprises: I) A dye concentrate comprising: A) a first mixture A, in particular a liquid mixture A, which comprises: (f) at least one dye; and (h) at least one solvent and II) A liquid composition comprising: B) a monomer-containing liquid mixture B comprising: a) at least one monomer M1 containing at least one ethylenically unsaturated group, c) at least one co-photoinitiator.

[0020] This object is also solved according to the invention by a kit of parts for preparing a photopolymerizable composition by means of UV / Vis radiation, which comprises: I) A dye concentrate comprising: A) a first mixture A, in particular a liquid mixture A, which comprises: (f) at least one dye (g) at least one photoinitiator; and (h) at least one solvent and II) A liquid composition comprising: B) a monomer-containing liquid mixture B comprising: a) at least one monomer M1 containing at least one ethylenically unsaturated group, c) at least one co-photoinitiator. [Brief description of the drawings]

[0021] [Figure 1] Photographs of two mixtures of liquid composition II) are shown. [Diagram 2] 1 shows an apparatus for producing holograms made from the claimed kit of parts. 2 shows a schematic configuration of a compact roll-to-roll machine for producing sealed holographic contact transfers from the claimed kit of parts. [Diagram 3] 1 shows a schematic diagram of an exposure apparatus. [Figure 4] The path of the beam is shown. [Diagram 5] The measurement curves at the corresponding measurement points for the first exposure of sample H are shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Of all the solvent components in the kit of parts or dye concentrate of the present invention, preferably more than 80%, preferably more than 90%, more preferably more than 98% have a vapor pressure at 20°C of 2 hPa or less, preferably 1.3 hPa or less, more preferably 0.2 hPa or less. In addition, more than 80%, preferably more than 90%, and most preferably 95% of the solvent components have a boiling point above 100° C. at standard pressure, the percentages being determined by weight ratio of those components to the total weight of the solvent.

[0023] The solvent preferably comprises a polymer that is liquid at standard pressure, the polymer preferably being from the group consisting of: polyethylene glycol (PEG), polycaprolactone, acrylate block copolymer (EFKA), and poly(bisphenol A-co-epichlorohydrin) (EPI).

[0024] By providing a kit of parts in the present invention, the photopolymerizable composition is preferably processable and exposable immediately after mixing. The monomer-containing liquid mixture B is preferably in a liquid state at standard pressure in the range of 15°C to 120°C. In said kit of parts, it has been found to be advantageous to use a dye concentrate A (also called I)) together with a solvent, in particular a solvent having a content of high molecular weight, non-volatile components, including photoinitiators, of more than 50% by weight, preferably more than 65% by weight, particularly preferably more than 80% by weight. This is added to a liquid composition II) (also called II)) to obtain a photopolymerizable composition (also called photopolymer), which can be applied and exposed even immediately after mixing. In addition, there is advantageously no waiting time, no change in physical properties over time due to evaporation, no change in concentration of solvent components, and no generation of fumes harmful to health and the environment.

[0025] By keeping the dye concentrate A as I) and the liquid composition B as II) separate, shelf life can be improved and storage can be simplified since components A) and B) are less susceptible to the effects of light and heat than photopolymerizable compositions. In particular, for example, liquid composition II) can be heated and stirred for longer periods of time without problems in order to bring undissolved or crystallized components, such as borates, back into solution.

[0026] Preferably, the liquid composition II) is completely unaffected by light, easily observable by the naked eye, and can be heated and stirred without any precautions, e.g. while maintaining some ambient light, which allows for easy quality control and detection of undissolved or crystallized components as well as processing. Color is advantageously used to adjust the light to which the kit of components is susceptible. Complementary hues of the exposure wavelengths are usually selected to absorb the light energy. For example, magenta shades are used for green light, blue shades for red, and yellow shades for blue. Exposures using multiple wavelengths can be combined.

[0027] The kit of parts preferably comprises liquid composition II), which is most preferably a clear, colorless, liquid monomer-containing mixture, and dye concentrate I), which is preferably added in an amount of 0.5 to 50% by weight, preferably 1 to 10% by weight, and particularly preferably 1 to 5% by weight, based on the total amount of the kit of parts, specifically liquid composition II), and mixed by stirring, shaking, or swirling.

[0028] The photopolymerizable composition thus obtained can be exposed immediately after being applied to the substrate. The wet application of the composition onto the substrate can be carried out by squeegee, doctor blade or slot die coating. If the layer is thinner than 20 μm, known printing processes such as screen printing, gravure printing, intaglio printing, pad printing or flexographic printing can also be used. It is preferable to laminate the material directly onto the master to be copied using a transparent clear film. The layer thickness is controlled either by the contact pressure and the lamination speed or via the slit width. When coating a thick and hard substrate, such as a glass plate, a spin-coating process can also be used. It is also possible to apply using an inkjet printing process or using a CNC-controlled dispersion device. It is also possible to directly inject into the cavity.

[0029] In particular, the liquid material is also suitable for application to curved surfaces. It can also be used as a kit or adhesive at the same time by applying pressure between two counterparts. The mixing of the kit of parts components can be carried out in a coating plant. For mixing, all mixing techniques and processes known to those skilled in the art can be used, such as: stirred tanks, magnetic stirrers, stirring bars, high-speed mixers, as well as dynamic and static mixers.

[0030] After mixing, additional conventional processes known to those skilled in the art, such as filtration and degassing, may be carried out. If technically advantageous, it is also possible to provide modified types, for example (1:1) or (1:2). In this case, the dye concentrate A is made up to the desired ratio with a dilute mixture, which contains the components and monomers known from the liquid composition II), but does not contain dangerous components, such as borates, which must be put back into solution by heating after long-term storage. Conversely, the monomer-containing liquid mixture B can then contain the dangerous components or borates in several times the usual amount, depending on the ratio.

[0031] After exposure, the layer is solid. Photopolymerizable compositions prepared from the part kits preferably do not require any thermal or chemical post-treatment after exposure. By avoiding the need for substances that must first be evaporated or chemically reacted after addition or application, it is ensured that times of less than 30 minutes, preferably less than 10 minutes, particularly preferably less than 2 minutes are used between mixing, application and exposure. On the other hand, this makes it possible that the layer does not have to be applied in the open, but rather in an intermediate area or laminated with a cover film. In this environment, the process for creating a hologram is significantly simplified and the device can be made extremely compact.

[0032] The short processing times, short transport distances, and ability to rapidly expose immediately after coating also reduce ambient light requirements, simplifying the setup and operation of the equipment, since it does not need to be extensively protected from light intrusion, nor does it need to be placed in an extremely darkened room.

[0033] Since the coating is carried out in the exposure unit, the user is further free to choose the substrate material and the structure of the layers used. After application, the exposure can be carried out immediately. According to the same principle, a new layer can be applied after curing and exposed holographically, so there are no problems with multi-layer exposures. This can also be used to build up true-color holograms, for example from three layers for the primary colors red, green and blue.

[0034] The photopolymerizable composition from the kit of parts is particularly suitable for producing contact copies. Since the liquid photopolymerizable composition from the kit of parts is printed directly onto the master, no refractive index matching is required. This is because a liquid having approximately the same refractive index as the master and the holographic layer is applied between them. In conventional contact transfer methods, the refractive index matching prevents the occurrence of disturbing interference phenomena (Newton's rings) caused by reflections that occur where the two layers are not in close contact, for example due to dust inclusions or microscopic irregularities resulting from air bubbles or air inclusions. In addition, scratches and other irregularities on the substrate and master are compensated for, improving the optical quality of the copy. Microscopic dust particles with dimensions smaller than the layer thickness are embedded in the liquid and do not cause noticeable stains of prints or defects, as they do with film materials. This significantly reduces waste and the need for clean rooms in the manufacturing environment.

[0035] Therefore, the liquid photopolymerizable composition from the kit of parts can advantageously also be used as an index match material for the exposure of holographic film materials. It cures upon exposure without the need for cleaning or evaporation. In addition, the combination of the two hologram recording materials preserves and strengthens the holographic recording because holograms are created in both layers. The freedom to choose the dye concentrate allows the user to decide which wavelengths and color ranges to work with in the combination.

[0036] Since the photopolymerizable composition from the kit of parts can be adapted to any surface, unlike film materials, it is possible to mold a surface structure simultaneously with the exposure of the hologram, and to use surfaces with complex shapes. The surface structure can be, in particular, an embossed hologram or a Fresnel structure. This allows the physical and holographic duplication of both the surface structure and the volume holographic or optical information of the master in a single processing step. In this way it is also possible to create optical elements such as prisms or lenses, which have integrated holographic structures.

[0037] pigment The dye acts as a sensitizer for the co-photoinitiator. Suitable for this purpose are, for example, methylene blue and the sensitizers disclosed in US Pat. No. 3,554,753A, US Pat. No. 3,563,750A, US Pat. No. 3,563,751A, US Pat. No. 3,647,467A, US Pat. No. 3,652,275A, US Pat. No. 4,162,162A, US Pat. No. 4,268,667A, US Pat. No. 4,454,218A, US Pat. No. 4,535,052A and US Pat. No. 4,565,769A, as well as the dyes and co-photoinitiators described in WO2012062655A2, which are also expressly incorporated herein by reference. Particularly preferred sensitizers include DBC, 2,5-bis[(4-diethylamino-2-methylphenyl)methylene]cyclopentanone; DEAW, 2,5-bis[(4-diethylaminophenyl)methylene]cyclopentanone; dimethoxy-JDI, 2,3-dihydro-5,6-dimethoxy-2-[(2,3,6,7-tetrahydro-1H,5H-benzo[i,j]quinolizin-9-yl)methylene]-1H-inden-1-one; and Safranine O, 3,7-diamino-2,8-dimethyl-5-phenyl-phenazinium chloride.

[0038] The dyes in the kit of parts of the present invention are preferably fluorescent dyes, which may, for example, consist of a cationic dye and an anion. The cationic dye may be represented by the formula F + It can be expressed as: Therefore, the formula F + It is to be understood that the cationic dye is preferably one of the following formulae:

[0039] [ka] [In the formula, X 1 are O, S, and NR 6 , or CR 6a R 6b represents X 2 is N or CR 5 represents R 5 is hydrogen, cyano, C1-C4-alkyl, C4-C7-cycloalkyl, C6-C 10 -aryl (optionally C1-C4-alkoxycarbonyl or NR 7 R 8 C6-C substituted by a heterocyclic group or a carboxyl group 10 -aryl, R 6 is hydrogen, C1-C 16 -Alkyl, C4-C7-Cycloalkyl, C7-C 16 -Aralkyl, C6~C 10 -aryl or heterocyclic group, R 6a and R 6b are independently of one another methyl, ethyl or together represent a -CH2-CH2-CH2- or -CH2-CH2-CH2-CH2- bridge or a C6-C substituted with a carboxyl group. 10 -aryl, R 1 ~R 4 , R 7 , and R 8 are each independently hydrogen, C1-C 16 -Alkyl, C4-C7-Cycloalkyl, C7-C 16 -Aralkyl, C6~C 10 - an aryl or heterocyclic group, or NR 1 R 2 , N.R. 7 R 4 and N.R. 7 R 8 represent, independently of each other, a 5- or 6-membered saturated ring, which is bonded via N and which may further contain N or O and / or which may be substituted by nonionic groups, or R 1 ~R 4 , R 7 , and R 8form, independently of one another, a 2- or 3-membered bridge with a C atom of the benzene ring adjacent to the N atom, which bridge may contain O or N and / or may be substituted by a nonionic group, R 9 , R 9a , R 9b , R 10 , R 10a , and R 10b represent, independently of one another, hydrogen, halogen or C1-C4-alkyl,

[0040] [ka] (In the formula, R 15 is hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy, or NR 18 R 19 represents R 11 ~R 14 , R 18 , and R 19 , independently of each other, hydrogen, C1-C 16 -Alkyl, C4-C7-Cycloalkyl, C7-C 16 -Aralkyl, C6~C 10 - an aryl or heterocyclic group, or NR 11 R 12 , N.R. 13 R 14 and N.R. 18 R 19 represent, independently of each other, a 5- or 6-membered saturated ring, which is bonded via N and which may further contain N or O and / or which may be substituted by nonionic groups, or R 12 ;R 17b , R 13 ;R 17c ; and R 18 ;R 17a form, independently of one another, a 2- or 3-membered bridge, which may contain O or N and / or be substituted by nonionic groups, R 16 represents hydrogen, chlorine, methyl, methoxycarbonyl, or ethoxycarbonyl; R 16a represents hydrogen, chlorine, or methyl; R 17a , R 17b , and R 17c represent, independently of each other, hydrogen, chlorine, methyl, or methoxy).

[0041] The nonionic groups are C1-C4-alkyl, C1-C4-alkoxy, halogen, cyano, nitro, C1-C4-alkoxycarbonyl, C1-C4-alkylthio, C1-C4-alkanoylamino, benzoylamino, mono- or di-C1-C4-alkylamino. The alkyl, alkoxy, cycloalkyl, aryl, and heterocyclic groups may optionally carry further groups such as alkyl, halogen, nitro, cyano, CO-NH2, alkoxy, trialkylsilyl, trialkylsiloxy, or phenyl; the alkyl and alkoxy groups may be linear or branched; the alkyl groups may be partially or fully halogenated; the alkyl and alkoxy groups may be ethoxylated, propoxylated, or silylated; adjacent alkyl and / or alkoxy groups on an aryl or heterocyclic group may combine to form a 3- or 4-membered bridge; and the heterocyclic group may be benzo-fused or quaternized. The term "halogen" means fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

[0042] Examples of substituted alkyl groups are trifluoromethyl, chloroethyl, cyanomethyl, cyanoethyl, methoxyethyl, examples of branched alkyl groups are isopropyl, tert-butyl, 2-butyl, neopentyl, examples of alkoxy groups are methoxy, ethoxy, methoxyethoxy. Preferred optionally substituted C1-C4-alkyl groups are: methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, perfluorinated methyl, perfluorinated ethyl, 2,2-trifluoroethyl, 3,3,3-trifluoroethyl, perfluorobutyl, cyanoethyl, methoxyethyl, chloroethyl. Suitable aralkyls are, for example, benzyl, phenethyl, or phenylpropyl.

[0043] C6~C 10 Examples of -aryl are phenyl and naphthyl. Examples of substituted aryl groups are tolyl, chlorophenyl, dichlorophenyl, methoxyphenyl, nitro-phenyl, cyanophenyl, dimethylaminophenyl, diethylaminophenyl. Examples of heteroaryl groups, especially 5- or 6-membered heterocyclic groups, are indolyl, pyridyl, quinolyl, benzthiazolyl. Examples of substituted heterocyclic groups are 1,2-dimethylindol-3-yl, 1-methyl-2-phenylindol-3-yl.

[0044] formula F + The anion for the cationic dyes may be, for example, a halogen, sulfate, carbonate, or nitrate anion. Particularly preferred cationic dyes are malachite green, methylene blue, safranine O, rhodamine of formula III. [ka] (In the formula, R a , R b , R c , R d , R e , R f , and R g Each represents H or an alkyl group, X -stands for chloride ion, trifluoromethanesulfonate, naphthalenedisulfonate, para-toluenesulfonate, hexafluorophosphate, perchlorate, meta-nitrobenzenesulfonate or meta-aminobenzenesulfonate, for example Rhodamine B, Rhodamine 6G or Violamine R, as well as Sulforhodamine B or Sulforhodamine G, as shown below.

[0045] [ka]

[0046] Other suitable dyes are fluorones, such as those described by Neckers et al., J. Polym. Sci., Part A, Poly. Chem., 1995, 33, 1691-1703. Particularly preferred are those of the formula: [ka]

[0047] Other examples of suitable dyes are the cyanines of formula IV: [ka] (IV) (In the formula, R IV = alkyl; n 1 =0, 1, 2, 3, or 4, and Y1 =CH=CH, N-CH3, C(CH3)2, O, S, or Se. Preferred are cyanines in which Y1 in formula IV is C(CH3)2 or S.

[0048] The dye in the kit of parts of the present invention is preferably selected from the group consisting of: acriflavine, diaminoacridine, rhodamine B, safranine-O, diethylsafranine, and methylene blue.

[0049] Solvent for dyes Ethanol, propanol, iso-propanol, butanol, iso-butanol, tert-butanol, pentanol, iso-pentanol, tert-pentanol, hexanol, heptanol, glycol, diglycol, triglycol. Water, methanol, ethanol, propanol, butanol, ketones, acetone, methyl ethyl ketone, ether, tetrahydrofuran, 1,4-dioxane, trioxane. Triethanolamine (TEA), castor oil, castor oil glycidyl ether, octanoic acid, tert-butyl peroxybenzoate, 2-dimethylaminoethanol, anisole, poly(ethylene glycol) block-poly(propylene glycol) block-poly(ethylene glycol), benzyl alcohol, tetra-chloroethylene, dipropylene glycol dimethyl ether, dichloromethane, acetic anhydride, propylene carbonate, n-butyl acetate, cyclohexane, cyclopentanone, ethylene glycol, polyethylene glycol, toluene, eucalyptus oil, glycolic acid butyl ester (Polysolvan-O), N-methyl-2-pyrrolidone (NMP), propylene glycol monomethyl ether acetate (PGMEA), poly(bisphenol A-co-epichlorohydrin), trimethylolpropane ethoxy triacrylate (TMPEOTA), trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TrPGDA), N,N-dimethylacrylamide.

[0050] Preferred are dimethylsulfoxide (DMSO), N,N'-dimethylpropyleneurea, N-hydroxyethylacrylamide (HEAA), benzaldehyde, polycaprolactone (PlyCLO, Capromer PT-05), polycaprolactone triol, polyethylene glycol (PEG-200), acrylic block copolymer (Efka PX 4701). Surprisingly, it has been found to be particularly advantageous that the UV photoinitiator which is required anyway in the photosensitive polymerizable composition can also be used as a good solvent for the dye.

[0051] It is preferred to use liquid photoinitiators, which are described below: Omnirad 1173, Omnirad MBF, Omnirad 1000, and Omnirad TPO-L. However, the addition of a UV initiator that is in powder form at room temperature to the solvent mixture can also increase the solubility of the dye. Preferably, the solvent comprises a polymer that is liquid at standard pressure. Advantageously, the polymer that is liquid at standard pressure may be selected from the group consisting of polyethylene glycol (PEG), poly-caprolactone, acrylate block copolymer (EFKA), and poly(bisphenol A-co-epichlorohydrin) (EPI). It is particularly advantageous if the above-mentioned substances do not impair the performance, e.g., diffraction efficiency, of the substances mixed together from the two components of the kit of parts. They can also be used as additives into the monomer-containing liquid mixture B if they further contribute to the improvement.

[0052] Photoinitiator It is preferable that the photopolymerization initiator in the parts kit of the present invention is capable of generating radicals when irradiated with light having a wavelength between 100 nm and 480 nm, preferably between 150 nm and 460 nm, and particularly preferably between 200 nm and 380 nm. These photoinitiators may be present in either the first mixture A (dye concentrate) or in the monomer-containing liquid mixture B in the kit of parts of the present invention.

[0053] The kit of parts according to the invention comprises a first mixture A, preferably a first liquid mixture A, which contains at least one photoinitiator, which preferably activates the polymerization of the monomers M1 or M2 by exposure to (actinic) radiation, which is preferably a radical-forming polymerization initiator. Actinicity is to be understood as the photochemical activity of electromagnetic radiation of various wavelengths.

[0054] The term is used, for example, to evaluate the physiological effects of laser light of various colors, or the spectral sensitivity of photographic film and paper. In photochemistry, an actinic chemical is one that is sensitive to the effects of light or radiation. Radical-forming polymerization initiators are known, see, for example, the following literature: HJ Timpe and S. Neuenfeld, "Dyes in Photoinitiator Systems", Kontakte (1990), pp. 28-35, and J. Jakubiak and JF Rabek, "Photoinitiators for visible light polymisation", Polymery (Warsaw) (1999), 44, pp. 447-461.

[0055] Suitable radical-forming polymerization initiators that can be activated by UV radiation and are generally inactive at temperatures up to 185° C. include substituted or unsubstituted polynuclear quinones, which are compounds having two ring carbon atoms in a conjugated carbocyclic ring system, such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,4-naphthoquinone, 9,10- Phenanthrenequinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dichloronaphthoquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, sodium salt of anthraquinone alpha-sulfonic acid, 3-chloro-2-methylanthraquinone, lethenquinone, 7,8,9,10-tetrahydronaphthacenequinone, and 1,2,3,4-tetrahydrobenz[a]anthracene-7,12-dione. Other photoinitiators which are also useful (although some of them are thermally activated at temperatures as low as 85° C.) are described in U.S. Pat. No. 2,760,663 A and include, for example, vicinal ketoaldonyl alcohols such as benzoin, pivaloin, acyloin ethers such as the methyl and ethyl ethers of benzoin, α-hydrocarbon-substituted aromatic acyloins such as α-methylbenzoin, α-allylbenzoin, and α-phenylbenzoin.

[0056] Photoreducible dyes and reducing agents such as those disclosed in U.S. Pat. Nos. 2,850,445A, 2,875,047A, 3,097,096A, 3,097,097A, 3,145,104A, and 3,579,339A can be used as photoinitiators, as well as phenazine, oxazine, and quinone type dyes. Michler's ketone, benzophenone, 2,4,5-triphenylimidazolyl dimers with hydrogen donors, and mixtures thereof, as described in U.S. Pat. Nos. 3,427,161A, 3,479,185A, 3,549,367A, 4,311,783A, 4,622,286A, and 3,784,557A. A useful discussion of dye-sensitized photopolymerization can be found in D.F. Eaton, "Dye Sensitized Photopolymerization", Adv. in Photochemistry, vol. 13 (D.H. Volman, G.S. Hammond and K. Gollnick, eds, Wiley-Interscience, New York, 1986), p. 427-487. Similarly, the cyclohexadienone compounds of U.S. Pat. No. 4,341,860 are also useful as polymerization initiators.Suitable photoinitiators also include: CDM-HABI, i.e., 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)-imidazole dimer; o-Cl-HABI, i.e., 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole; and TCTM-HABI, i.e., 2,5-bis(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-1H-imidazole dimer, each typically used with a hydrogen donor, such as 2-mercaptobenzoxazole.

[0057] Particularly preferred UV photoinitiators for the liquid composition B) and / or the dye concentrate are IRGACURE® OXE-01 (1,2-octanedione-1-[4-(phenylthio)-phenyl]-2-(O-benzoyloxime) and IRGACURE® OXE-02 (1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-O-acetyloxime (BASF AG), as well as OMNIRAD-MBF (methylbenzoyl formate), OMNIRAD-TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), OMNIRAD-TPO-L (ethyl-(2,4,6-trimethylbenzoyl)-phenylphosphinate), OMNIRAD-1173 (2-hydroxy-2-methyl-1-phenylpropanone), OMNIRAD OMNIRAD 1000 (a mixture of 2-hydroxy-2-methyl-1-phenylpropanone (80%) and 1-hydroxycyclohexyl-phenyl ketone (20%)), OMNIRAD 184 (1-hydroxycyclohexyl-phenyl ketone), OMNIRAD 819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), OMNIRAD 2022 (a mixture of 2-hydroxy-2-methyl-1-phenylpropanone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate), and OMNICAT 440 (4,4'-dimethyl-diphenyl-iodonium-hexafluorophosphate), available from IGM Resins, are preferably used in amounts of 0.1 to 10% by weight.

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] The above-mentioned photoinitiators may be used alone or in combination. Preferably, the photoinitiator is in liquid form and / or is selected from the group consisting of 1,2-octanedione-1-[4-(phenylthio)-phenyl]-2-(O-benzoyloxime), (1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-O-acetyloxime, methylbenzoyl formate), 2,4,6-trimethylbenzoyldiphenylphosphine 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-phenyl ketone (20%), a mixture of 1-hydroxycyclohexyl-phenyl ketone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, and 4,4'-dimethyl-diphenyl-iodonium hexafluorophosphate. Preferably, a solid photoinitiator is used in the liquid composition and a liquid photoinitiator is used in the dye concentrate.

[0062] Monomer M1 The liquid composition II) of the kit of parts comprises a mixture B comprising at least one monomer M1 comprising at least one ethylenically unsaturated group, and preferably a monomer M2 comprising at least two ethylenically unsaturated groups, where M2 preferably differs from M1 only in the second ethylenically unsaturated group. Monomers M1 containing at least one ethylenically unsaturated group have the following general structural unit:

[0063] [ka]

[0064] During the ceremony, [ka] (wherein n and m=0-12, preferably 1-12; o=0, 1, and Ar is a mononuclear or polynuclear, substituted or unsubstituted aromatic or heterocyclic aromatic group). The group R1 is H, methyl or ethyl, and The groups R2 and R3 are independently selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, acyl, and acyloxy groups, which may be linear or branched, unsubstituted or substituted, substituted or unsubstituted aryloxy groups, substituted or unsubstituted aromatic or heterocyclic groups, unsubstituted or substituted alicyclic hydrocarbon groups, aliphatic, aromatic and aliphatic-aromatic amino, carboxylic acid, amido, and imido groups, hydroxy, amino, cyano, nitro, halogen atoms or hydrogen atoms, and combinations of the abovementioned groups, where the substituted groups are C1 to C6 12 Alkyl, C1-C 12 It may be substituted with alkoxy, hydroxy, carboxy, carbonyl, amino, amido, imido groups, halogen atoms, aromatic groups, or combinations thereof.

[0065] Examples of suitable monomers M1 include: substituted or unsubstituted styrene monomers, acrylic acid, α-alkylacrylic acids, acrylic acid esters, alkylacrylic acid esters (whose alcohol component may be a substituted or unsubstituted aliphatic or aromatic group containing from 2 to 50 carbon atoms), acrylamides, α-alkylacrylamides (wherein alkyl is as defined above), vinyl esters, vinyl alcohols, vinyl ethers, and other substituted vinyl monomers substituted with substituted or unsubstituted aliphatic or aromatic groups having from 2 to 50 carbon atoms.

[0066] Preferred examples of suitable monomers M1 include: (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 1H,1H,2H,2H-perfluorooctyl ester, (meth)acrylic acid 2,2,2-trifluoroethyl ester, (meth)acrylic acid heptafluoropropyl ester, (meth)acrylic acid 1,1,1,3,3,3-hexafluoroisopropyl ester, (meth)acrylic acid 2,2,3,3-tetrafluoropropyl ester, (meth)acrylic acid 2,2,3,3,4,4,4-heptafluorobutyl ... ,2,3,3,4,4,5,5-Octafluoropentyl, acrylic acid N,N-diethylaminoethyl ester, acrylic acid ethoxyethoxyethyl ester, acrylic acid 2-(p-chlorophenoxy)ethyl ester, p-chlorophenyl acrylate, 2-phenylethyl (meth)acrylate, pentachlorophenyl acrylate, phenyl acrylate, p-chlorostyrene, N-vinylcarbazole, 1-vinyl-2-pyrrolidone, 2-chlorostyrene, 2-bromostyrene, methoxystyrene, phenol ethoxylate acrylate, 2-(p-chlorophenoxy)ethyl acrylate, 2-(1-naphthyloxy)ethyl acrylate, hydroquinone monomethacrylate, and 2-[β-(N-carbazolyl)propionyloxy]ethyl acrylate.

[0067] Particularly preferred monomers M1 include N-vinylcarbazole, ethoxyethoxyethyl acrylate, 2-naphthyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, phenol ethoxylate acrylate, 2-(p-chlorophenoxy)ethyl acrylate, p-chlorophenyl acrylate, phenyl acrylate, 2-phenylethyl acrylate, 2-(1-naphthyloxy)ethyl acrylate, t-butyl acrylate, isobornyl acrylate, cyclohexyl acrylate, N,N-diethylaminoethyl acrylate, acrylamide, ethoxyethoxyethyl acrylate, 1H,1H,2H,2H-perfluorooctyl methacrylate, and pentafluoroethyl acrylate. It is preferred that the monomer M1 contains at least two ethylenically unsaturated groups and therefore the monomer is preferably difunctional.

[0068] Difunctional ethylenically unsaturated monomers have two C-C double bonds in their molecule, i.e., they contain, for example, two of the structural units shown above. Difunctional ethylenically unsaturated monomers may, for example, contain two acrylate or methacrylate groups.

[0069] The monomers M1 in the monomer-containing liquid mixture B according to the invention may consist exclusively of one or more difunctional or higher functional monomers, i.e. the composition should be free of monofunctional ethylenically unsaturated monomers. It is preferred that the content of monomers M1 having at least two ethylenically unsaturated groups in mixture B is greater than 10% by weight, particularly preferably greater than 20% by weight.

[0070] The use of difunctional or higher functional monomers in particular results in particularly high thermal and mechanical stability of the holographic elements produced therewith, which is particularly advantageous in the production of mirror holograms. Preferred monomers M1 having at least two ethylenically unsaturated groups are ethoxylated bisphenol A diacrylates, in particular compounds of the formula:

[0071] [ka] (wherein R1, Q and Ar have the meanings given above). Particularly preferred monomers M1 are compounds of the following structural formula: [ka] The viscosity of the monomer M1 or monomer mixture is preferably at least 900 mPa·s at room temperature.

[0072] The viscosity of the liquid composition II) is furthermore at least 900 mPa·s, preferably at least 1500 mPa·s, particularly preferably at least 2000 mPa·s at 20° C. The viscosity can be measured using a plate-plate rotational rheometer (e.g., Haake, type 006-2805). The material is placed between two coaxial circular plates, one of which rotates. The distance between the plates is, for example, 1 mm, and the diameter is 35 mm. The viscosity can be determined from the measurement of the torque and the speed (e.g., 10 revolutions / second) (DIN 53018, ISO 3210).

[0073] Co-photoinitiator Preferably, the co-photoinitiator used in the kit of parts of the present invention comprises a compound of formula (I). [ka] [In the formula, R 1c is C1~C 20 -Alkyl, C3-C 12 -cycloalkyl, C2-C8-alkenyl, phenyl-C1-C6-alkyl, or naphthyl-C1-C3-alkyl, where these groups C1-C20 -Alkyl, C3-C 12 -cycloalkyl, C2-C8-alkenyl, phenyl-C1-C6-alkyl or naphthyl-C1-C3-alkyl is selected from one or more groups O, S(O) p , or NR 5c or the groups C1-C 20 -Alkyl, C3-C 12 -cycloalkyl, C2-C8-alkenyl, phenyl-C1-C6-alkyl or naphthyl-C1-C3-alkyl is unsubstituted or 12 -Alkyl, OR6, R 7c S(O) p , R 7c S(O)2O, NR 8c R 9c , SiR 10c R 11c R 12c , B.R. 13c R 14c , or R 15c R 16c P(O) q Replaced by; R 2c , R 3c and R 4c are, independently of each other, phenyl or biphenyl, the phenyl or biphenyl group being unsubstituted or substituted by the following groups: OR 6c , N.R. 8c R 9c or halogen-substituted C1-C 12 -Alkyl, OR 6c , R 7c S(O) p , R 7c S(O)2O, R 8c R 9c NS(O)2, NR 8c R 9c , N.R. 3c R 8c CO,

[0074] [ka] SiR 10c R 11cR 12c , B.R. 13c R 14c , halogen, R 15c R 16c P(O) q ,

[0075] [ka] R 5c is hydrogen, C1-C 12 -alkyl, phenyl-C1-C6-alkyl (which may be unsubstituted or C1-C6-alkyl, C1-C 12 -alkoxy or halogen), or phenyl (which is unsubstituted or substituted 1-5 times by C1-C6-alkyl, C1-C 12 -substituted 1 to 5 times by alkoxy or halogen; R 6c and R 7c is C1~C 12 -alkyl (which is unsubstituted or substituted by halogen), phenylC1-C6-alkyl (which is unsubstituted or substituted by halogen), C1-C6-alkyl, C1-C 12 -alkoxy or halogen), or phenyl (which is unsubstituted or substituted 1-5 times by C1-C6-alkyl, C1-C 12 -substituted 1 to 5 times by alkoxy or halogen; R 8c , R 9c , R 10c , R 11c , R 12c , R 13c , R 14c , R 15c , and R 16c are independent of each other, C1 to C 12 -Alkyl, C3-C 12 -cycloalkyl, phenyl-C1-C6-alkyl (which is unsubstituted or C1-C6-alkyl, C1-C 12-alkoxy or halogen), or phenyl (which is unsubstituted or substituted 1-5 times by C1-C6-alkyl, C1-C 12 -alkoxy or halogen) 8c and R 9c combine with the N-atom to which they are attached to form a 6-membered aliphatic ring, which may further contain oxygen or sulfur as additional heteroatoms; R 17c ', R 18c , R 19c , and R 20c are each independently hydrogen, C1-C 12 - alkyl (which is unsubstituted or C1-C 12 -alkoxy or phenyl), or phenyl-C1-C6-alkyl, the group phenyl or phenyl-C1-C6-alkyl (unsubstituted or C1-C6-alkyl, C1-C 12 - mono- to penta-substituted by alkoxy or halogen; p is a number from 0 to 2; r represents a number from 0 to 5; R 21c is hydrogen or C1-C 12 - represents alkyl; R 22c , R 22a , R 23c , and R 24c are each independently hydrogen, C1-C 12 - alkyl (which is unsubstituted or C1-C 12 -alkoxy, OH or halogen), or phenyl (which is unsubstituted or substituted with C1-C 12 -substituted by alkoxy, OH or halogen; q represents either 0 or 1; and G represents a residue capable of forming a positive ion.

[0076] The co-photoinitiator in the kit of parts of the present 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 a mixture thereof. Highly preferred is a co-photoinitiator having structural formula Ia, developed by Ciba Specialty Chemicals Inc. under the designation "CGI 7460" and currently available from BASF AG under the designation SEC LCA 1460, which is represented by the following formula: [ka]

[0077] Additives In order to adapt the component kit to a selected processing method or application field and to improve printability, surface adhesion, viscosity, film-forming property, flexibility, hardness, cold resistance, heat resistance, and weather resistance, the liquid composition or first mixture A may contain various additives known per se. Thus, the dye concentrate, or liquid composition, optionally includes additives. Additives can include; fillers, pigments, plasticizers, surfactants, common components used in photopolymer systems, polymeric binders, wetting agents, leveling agents, defoamers, adhesion promoters, surface additives, nanoscale particles, optical brighteners, or mixtures thereof.

[0078] They should be easily mixed in and should not impair the diffraction efficiency. Non-volatile substances can even improve the diffraction efficiency in thin layers permanently, especially by choosing additives that increase the refractive index difference between the ethylenically unsaturated monomer and the other components. Thus, in addition to known polymers with low refractive index, such as polyvinyl acetate, in this case, especially fluorinated or silanized polymers can also be taken into account. In order to achieve good diffusion performance, the molecular weight of the additives considered should not be too high. The additives mentioned above and described below can be used in an amount of 0.01 to 20% by weight, preferably 0.01 to 10% by weight, based on the total weight of the kit of parts.

[0079] The kit of parts may include a plasticizer to increase the modulation of the refractive index of the imaged composition. The plasticizer may be used in an amount ranging from about 0.01% to about 10% by weight, preferably from 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 sebacinate, dibutyl suberinate, tributyl phosphate, tris(2-ethylhexyl) phosphate, Brij® 30 [C 12 H 25 (OCH2CH2)4OH], Brij® 35 [C 12 H 25 (OCH2CH2) 20 OH], and n-butyl acetate.

[0080] Particularly preferred plasticizers are: polyethylene glycol, triethylene glycol diethylhexanoate (3G8), triethylene glycol dicaprylate, tetraethylene glycol diheptanoate, diethyl adipate, Brij® 30, and tris(2-ethylhexyl) phosphate. Other components commonly used in photopolymer systems may be used with the compositions and devices of the present invention, if desired. Such components include optical brighteners, ultraviolet light absorbing materials, heat stabilizers, hydrogen donors, oxygen scavengers, and release agents. These additives may further include polymers or copolymers. Useful optical brighteners include those disclosed in U.S. Patent No. 3,854,950A. A preferred optical brightener is 7-(4'-chloro-6'-diethylamino-1',3',5'-triazin-4'-yl)amino-3-phenylcoumarin. Ultraviolet absorbing materials useful in the present invention are also disclosed in U.S. Patent No. 3,854,950A.

[0081] Useful heat stabilizers include hydroquinone, phenidone, p-methoxyphenol, alkyl- and aryl-substituted hydroquinones and quinones, tert-butylcatechol, pyrogallol, copper resinate, naphthylamine, β-naphthol, copper(I) chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluquinone, and chloranil. Dinitroso-dimers, as described in U.S. Pat. No. 4,168,982A, are also useful. Typically, a thermal polymerization inhibitor is also present to improve the stability of the photopolymerizable composition during storage. Hydrogen donor compounds useful as chain transfer agents include 2-mercaptobenzoxazole, 2-mercaptobenzothioazole, and the like, as well as various types of compounds such as those disclosed in U.S. Pat. No. 3,390,996, column 12, lines 18-58, which are specifically incorporated herein by reference, such as (a) ethers, (b) esters, (c) alcohols, (d) compounds containing allylic or benzylic hydrogens, such as cumene, (e) acetals, (f) aldehydes, and (g) amides. Compounds which have been found to be useful as release agents are described in U.S. Patent No. 4,326,010 A. A preferred release agent is polycaprolactone.

[0082] The kit of parts may further include one or more polymeric binders selected from the group including: polymethyl methacrylate and polyethyl methacrylate, polyvinyl esters such as polyvinyl acetate, polyvinyl acetate / acrylate, polyvinyl acetate / methacrylate, and partially hydrolyzed polyvinyl acetate, ethylene / vinyl acetate copolymers, vinyl chloride / carboxylic acid ester copolymers, vinyl chloride / acrylic acid ester copolymers, polyvinyl butyral and polyvinyl formal, polymers and copolymers of butadiene and isoprene. Polymers, and polyglycols having an average molecular weight of about 1,000 to 1,000,000 g / mol, polyethylene oxides, such as epoxides containing acrylate or methacrylate residues, polystyrene, cellulose esters, such as cellulose acetate, cellulose acetate succinate, and cellulose acetate butyrate, cellulose ethers, such as methyl cellulose and ethyl cellulose, polycondensates, such as polycarbonates, polyesters, polyamides, such as N-methoxymethyl polyhexamethylene adipamide, polyimides, polyurethanes. The above-mentioned polymeric binders can be used in an amount of, for example, 0.001 to 10% by weight, based on the total weight of the kit of parts.

[0083] The kit of parts may further include one or more wetting agents (e.g., a fluorocarbon polymer, such as Schwego-Fluor 8038™, or a fluorosurfactant, such as 3M Fluorad FC-4430™), a leveling agent (e.g., a glycolic acid n-butyl ester or a polyether modified polydimethylsiloxane, such as ADDID 130™), a defoamer (e.g., a fluorosilicone oil based defoamer, such as ADDID 763™), an adhesion promoter (e.g., a diamino-trimethoxy functional silane adhesion promoter, such as ADDID 900™, or a glycidyl trimethoxy trifunctional silane coupling agent, such as ADDID 911™, vinyl triethoxy silane, or 3-methacryloxypropyl trimethoxy silane), or a surface additive (e.g., a polyether modified acryl functional polydimethylsiloxane, such as BYK-UV 3500™, polyether modified polydimethylsiloxanes such as BYK-UV 3510™, or polyether modified acryl functional polydimethylsiloxanes such as BYK-UV 3530™. Products bearing the trade names "ADDID" or "BYK" are available from Wacker Chemie and BYK Chemie, respectively.

[0084] The kit of parts may further include nanoscale particles, such as TiO2, SiO2, or Au, which may be combined with a monomer (such materials are available, for example, under the trade name "Nanocryl"). Preferably, the additive can be an amine synergist, which in combination with other photoinitiators can increase the curing speed of UV coatings (see DE 60216490T2). Preferably, the additive can be a peroxide, which can be heat activated in combination with other photoinitiators to improve the curability of UV coatings, especially in shaded areas (see US Pat. No. 5,017,406 A or DE Pat. No. 6,003,023 T2). Preferably, the additive may be a marker selected from fluorescent pigments or lanthanide compounds, for example europium or terbium trisdipicolinate complexes may be used as lanthanide compounds.

[0085] For the purposes of the present invention, a marker is understood to be a forensically detectable entity that can be used to determine the authenticity or origin of a product or its manufacturer or distributor. It is also possible to introduce small individualized particles, colored microplastics (known as forensic additives), if the layer made is thick enough to allow the embedding of corresponding microparticles. The liquid composition may further comprise a triglyceride and / or a modified triglyceride.

[0086] Suitable triglycerides are generally compounds of the following general structural formula: [ka] wherein each R, independently of the other, represents a residue of a fatty acid, preferably each R containing from 6 to 22, more preferably from 8 to 18, carbon atoms.

[0087] Naturally occurring fats and oils, such as castor oil, coconut oil, palm kernel oil, and mixtures thereof, can also be used as triglycerides. It is also possible to use derivatives of such natural fats and oils, such as hydrogenated products. Such naturally occurring fats and oils generally include mixtures of various triglycerides. A particularly preferred triglyceride is the triglyceride of ricinoleic acid, which is the main component of castor oil. The triglyceride is preferably selected such that the difference between the refractive index (n) of the ethylenically unsaturated monomer or monomer mixture and the refractive index of the triglyceride at 20° C. (i.e., |n(monomer)-n(triglyceride)|) is at least 0.02, more preferably at least 0.05, and most preferably at least 0.07.

[0088] For example, ethoxylated castor oil or its ricinoleic acid are considered as modified triglycerides. The modified triglycerides preferably include ethoxylated triglycerides having 25 to 250 units of ethylene oxide. For example, Hedipin R / 2000 (known as "PEG-200 castor oil") may be used. Hedipin R / 2000 is produced by reacting castor oil with ethylene oxide in a molar ratio of 1:200. Castor oil is a mixture of triglycerides obtained from the seeds of Ricinus communis. The major component of castor oil (>80%) is the triglyceride of ricinoleic acid. Hedipin R / 2000 contains a mixture of polyethoxylated triglycerides, but the major component is the polyethoxylated reaction products of triglycerides of ricinoleic acid. The polyethoxylated reaction products of triglycerides of ricinoleic acid include one or more of the compounds of formula A, B, and C, as well as mixtures thereof and all their stereoisomers. Other components of Hedipin R / 2000 may include polyoxyethylene ricinoleate, free polyethylene glycol, and ethoxylated glycerol.

[0089] [ka] In formula (A), n1, n2, and n3 are independently an integer of 0 to 200, more preferably 10 to 180, more preferably 20 to 150, more preferably 30 to 130, more preferably 40 to 110, more preferably 50 to 90, and more preferably 60 to 75, where n1+n2+n3=150 to 250.

[0090] [ka] In formula (B), m1, m2, and m3 are independently an integer of 0 to 200, more preferably 10 to 180, more preferably 20 to 150, more preferably 30 to 130, more preferably 40 to 110, more preferably 50 to 90, and more preferably 60 to 75, where m1+m2+m3=150 to 250.

[0091] [ka] In formula (C), n1', n2', and n3' each independently represent an integer of 0 to 200, more preferably 5 to 175, more preferably 10 to 150, more preferably 15 to 125, more preferably 20 to 100, more preferably 20 to 75, and more preferably 25 to 40, where n1'+n2'+n3'=50 to 150. In formula (C), m1', m2', and m3' each independently represent an integer of 0 to 200, more preferably 5 to 175, more preferably 10 to 150, more preferably 15 to 125, more preferably 20 to 100, more preferably 20 to 75, and more preferably 25 to 40, where n1'+n2'+n3'=50 to 150. Preferably, in formula (C), n1', n2', n3', m1', m2', and m3' are each independently an integer of 10 to 150, more preferably an integer of 15 to 125, more preferably an integer of 20 to 100, more preferably an integer of 20 to 75, and more preferably an integer of 25 to 40, where n1'+n2'+n3'+m1'+m2'+m3'=150 to 250.

[0092] The use of triglycerides or modified triglycerides has the further advantage that the photopolymerizable composition exhibits low surface adhesion and flexibility, since the triglycerides or modified triglycerides simultaneously function as a release agent and a plasticizer. Thus, the exposed hologram can be easily and completely removed from the substrate, e.g., glass or metal. This property is also highly desirable in mass production, since it allows wear-free copy masters, e.g., nickel shims with a fine holographic surface structure, which are customary, or volume holograms sealed with thin glass, which are used to create contact transfers. The non-adhesive layer is removed without leaving any residue, so that cleaning is hardly required. If the liquid photopolymerizable composition is printed directly on the master, the adjustment of the refractive index can also be omitted. This is because a liquid having approximately the same refractive index as the master and the hologram layer is applied between them. In the conventional contact transfer method, the adjustment of the refractive index prevents the occurrence of disturbing interference phenomena (Newton's rings). These are due to reflections that occur where the two layers are not in tight contact, for example due to dust inclusions or microscopic irregularities. The optical quality of the reproduction is improved because scratches and other irregularities in the substrate and on the master are compensated for. Tiny dust particles, with dimensions smaller than the layer thickness, are embedded in the liquid and do not cause noticeable stains of the print or defects, as they do in film materials. This significantly reduces waste and the need for clean rooms in the production environment.

[0093] It is also possible to use tight contact between the recording material and the master to form a pre-existing surface structure on the master. Such a surface structure can in particular be an embossed hologram or a Fresnel structure. This makes it possible to replicate both the surface structure and the volume holographic or optical information of the master in a single processing step. The liquid composition may further comprise at least one aromatic aldehyde and / or an aliphatic aldehyde.

[0094] The aromatic aldehyde is preferably 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-dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxy-benzaldehyde, 4-hydroxy-2,6-dimethoxy-benzaldehyde, 4-hydroxy-2-methyl-benzaldehyde, 4- Hydroxy-3-methyl-benzaldehyde, 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-dimethyl-benzaldehyde, 3,5-diethoxy-4-hydroxy-benzaldehyde, 2,6-diethoxy-4-hydroxy-benzaldehyde, 3-hydroxy-4-methoxy-benzaldehyde, 2-hydroxy-4-methoxy-benzaldehyde aldehyde, 2-ethoxy-4-hydroxy-benzaldehyde, 3-ethoxy-4-hydroxy-benzaldehyde, 4-ethoxy-2-hydroxy-benzaldehyde, 4-ethoxy-3-hydroxy-benzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methyl-benzaldehyde, 2,4-dihydroxy-5-methyl-benzaldehyde, 2,4-dihydroxy-6-methyl-benzaldehyde, 2,4-Dihydroxy-3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxy-benzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methyl-benzaldehyde, 3,4-dihydroxy-5-methyl-benzaldehyde, 3,4-dihydroxy -6-Methyl-benzaldehyde, 3,4-dihydroxy-2-methoxy-benzaldehyde, 3,4-dihydroxy-5-methoxy-benzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenza aldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-Dimethoxy-1-naphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 4-dimethylamino-cinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylamino-benzaldehyde, 4-diphenylamino-benzaldehyde, 4-dimethylamino 4-(1-imidazolyl)-benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H,5H-benzo[ij]quinolizine-9-carboxaldehyde, N-ethylcarbazol-3-aldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or trisalt) aldehyde), 2-indole aldehyde, 3-indole aldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2-(1',3',3'-trimethyl-2-indolinylidene)-acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoroacetone, chromone-3-aldehyde, 3-(5'-nitro-2'-furyl)-acrolein, 3-(2'-furyl)-acrolein, and imidazole-2-aldehyde.

[0095] Particularly preferred are aromatic aldehydes selected from the group consisting of 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methyl-benzaldehyde, 2,4-dihydroxy-5-methyl-benzaldehyde, 2,4-dihydroxy-6-methyl-benzaldehyde, 2,4-dihydroxy-3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methyl-benzaldehyde, Methoxy-benzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methyl-benzaldehyde, 3,4-dihydroxy-5-methyl-benzaldehyde, 3,4-dihydroxy-6-methyl-benzaldehyde, 3,4-dihydroxy-2-methoxy-benzaldehyde, 3,4-dihydroxy-5-methoxy-benzaldehyde, 3,5-dihydroxybenzaldehyde. Highly preferably, the aromatic aldehyde is selected from the group consisting of: 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, and 3,5-dihydroxybenzaldehyde.

[0096] Particularly preferred is a kit of parts for preparing a photosensitive polymerizable composition by UV / Vis irradiation, comprising: I) A dye concentrate comprising: A) a first mixture A, in particular a liquid mixture A, which comprises: f) at least one dye selected from the group consisting of acriflavine, diaminoacridine, rhodamine B, safranine-O, diethylsafranine, and methylene blue; and h) at least one solvent selected from the group consisting of dimethylsulfoxide (DMSO), N,N'-dimethylpropyleneurea, N-hydroxyethylacrylamide (HEAA), N-methyl-2-pyrrolidone (NMP), benzaldehyde, polyethylene glycol (PEG), polycaprolactone, acrylate block copolymer (EFKA), and poly(bisphenol A-co-epichlorohydrin);

[0097] and II) A liquid composition comprising: B) a monomer-containing liquid mixture B comprising: a) at least one monomer M1 containing 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.

[0098] Particularly preferred is a kit of parts for preparing a photosensitive polymerizable composition by UV / Vis irradiation, comprising: I) A dye concentrate comprising: A) a first mixture A, in particular a liquid mixture A, which comprises: f) at least one dye selected from the group consisting of acriflavine, diaminoacridine, rhodamine B, safranine-O, diethylsafranine, and methylene blue; (g) at least one photoinitiator; and (h) at least one solvent

[0099] and II) A liquid composition comprising: B) a monomer-containing liquid mixture B comprising: a) at least one monomer M1 containing 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.

[0100] The kit of parts preferably contains at most 10% by weight of the first mixture A, based on the total amount of mixture B. Very particular preference is given to a kit of parts for preparing a photosensitive polymerizable composition by UV / Vis irradiation, comprising: I) 0.1 to 5% by weight of a dye concentrate comprising: A) a first mixture A comprising: f) at least one dye selected from the group consisting of acriflavine, diaminoacridine, rhodamine B, safranine-O, diethylsafranine, and methylene blue; (g) at least one photoinitiator; and (h) at least one solvent

[0101] and II) A liquid composition comprising 95 to 99.9% by weight of: B) a monomer-containing liquid mixture B comprising: a) at least one monomer M1 containing 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, [wherein the sum of I) and II) is 100% by weight].

[0102] The kit of parts preferably contains at most 10% by weight of the first mixture A, based on the total amount of mixture B. Very particular preference is given to a kit of parts for preparing a photosensitive polymerizable composition by UV / Vis irradiation, comprising: I) 0.1 to 5% by weight of a dye concentrate comprising: A) a first mixture A comprising: f) 0.5 to 5% by weight of at least one dye selected from the group consisting of acriflavine, diaminoacridine, rhodamine B, safranine-O, diethylsafranine, and methylene blue; (g) 9.5 to 99.5% by weight of at least one photoinitiator; and h) 0 to 90% by weight of at least one solvent, [the total amount of f) to h) being 100% by weight]

[0103] and II) A liquid composition comprising 95 to 99.9% by weight of: B) a monomer-containing liquid mixture B comprising: a) 49.9 to 99.9% by weight of at least one monomer M1 containing at least one ethylenically unsaturated group, c) 0.1 to 10% by weight of 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 a mixture thereof, [the total amount of a) and c) is at least 50% by weight and not more than 100% by weight] and wherein the sum of I) and II) is 100% by weight.

[0104] Another object of the invention is an element comprising a component obtainable by exposing a photopolymerizable composition prepared from the kit of parts of the invention to (actinic) UV / VIS radiation. Preferred is an element containing a hologram that can be obtained by exposing the photopolymerizable composition of the component kit of the present invention to modulated radiation containing holographic information.For this purpose, advantageously, the photopolymerizable composition from the component kit can be applied to a substrate, such as a mirror sheet, a surface mirror, a nickel shim with a photographic or optical surface structure, or a master hologram, and exposed to a laser beam to form a hologram.The photopolymerizable composition from the component kit is then advantageously cured using UV light.

[0105] Another object of the invention is the use of the element according to the invention as a film, lens, grating, prism, mirror, beam splitter, diffuser, surface relief, membrane, filter or sensor. Preferred is the use of the element according to the invention for head-up displays, data glasses, optical guidance systems, spectrometers, detection systems, safety elements or labels. Advantageously, the dye concentrate does not attack or pre-alter the exposed holographic layer.

[0106] Benefits of component kits · Can be exposed immediately after mixing No waiting time and no change in properties over time due to solvent evaporation and concentration changes No fumes harmful to health and the environment · No explosion protection required Good compatibility, no deterioration of holographic properties No attack or alteration of previously exposed holographic layers Improved shelf life and simplified storage by storing the dye concentrate and holographic material separately so that the materials are less susceptible to the effects of light and heat. Photopolymerizable compositions made from this material kit can be individually tailored to the type of exposure and the desired result depending on the application. By choosing the appropriate dye concentrate and varying its amount, the optimum color strength can be set depending on the layer thickness, the desired sensitivity and the acceptable color tone of the final product. The substances used do not diminish the holographic properties of the photopolymerizable composition, but rather improve them. The quality of the component kit can be evaluated in normal ambient light · Low requirements for ambient light color and brightness due to short time intervals between mixing, application, and exposure. EXAMPLES

[0107] [Table 1]

[0108] pigment Molecular structures having a main framework of three benzene rings have been found to be particularly suitable dyes.

[0109] [Table 2]

[0110] UV polymerization initiator Liquid UV polymerization initiator The dyes are in powder form. To add them to the mixture, they must be dissolved. It was found that they dissolve well in the liquid UV photoinitiator. This is advantageous because after the laser exposure, the UV photoinitiator is required for the final UV cure in some way.

[0111] [Table 3]

[0112] Powder UV polymerization initiator UV polymerization initiators that are in powder form at room temperature can also be used, provided that they melt or dissolve in the second component.

[0113] [Table 4]

[0114] solvent Volatility

[0115] [Table 5]

[0116] High boiling point

[0117] [Table 6]

[0118] high molecular weight

[0119] [Table 7]

[0120] Dye Concentrate A mixture of polycaprolactone and a liquid UV photoinitiator (e.g., Omnicure 1173 or MBF) is preferably used to dissolve the dye. Instead of a liquid UV photoinitiator, it is also possible to dissolve a UV initiator that is solid at room temperature, such as Omnicure TPO, Omnicure 819, and Omnicure 189, in a low molecular weight polycaprolactone. The ratio is selected so that the UV initiator and the dye are present in the desired concentration in the photopolymerizable composition from the kit of parts later.

[0121] [Table 8]

[0122] If this total of 3.1 g were added to 96.9 g of the monomer-containing liquid mixture, the resulting photopolymerizable composition from the kit of parts would have a UV initiator concentration of 1%. If a different concentration is desired, the ratio of PCL-triol to UV initiator would have to be adjusted accordingly. In this example, initiator concentrations up to 3% would be possible.

[0123] Other Ingredients Depending on the dye and UV initiator used, it may also be useful to add further copolymerization initiators such as N-phenylglycine (NPG), amine synergists such as PHOTOCRYL A101 (Miwon), or monomers such as N-hydroxyethylacrylamide.

[0124] Color concentrates FK1 to FK5 (component kit I) Dye concentrates FK1 to FK5 were prepared similarly to dye concentrate 1. The components are added one after the other in a beaker with magnetic stirring. For this purpose, the beaker is placed on a balance so that the liquid substances can be added in precise amounts. The whole is then heated to 120°C, with stirring, on a heatable stirring table. Powdered substances are weighed using a weighing tray and added to the mixture with stirring. The mixture is stirred at 120°C for about 1 hour, then the solution is filtered and filled into bottles.

[0125] [Table 9]

[0126] [Table 10]

[0127] [Table 11]

[0128] [Table 12]

[0129] [Table 13]

[0130] Liquid composition (component kit II) Liquid compositions MM1-MM4 were prepared using the same procedure as described for the dye concentrates.

[0131] [Table 14]

[0132] [Table 15]

[0133] [Table 16]

[0134] [Table 17]

[0135] Parts Kit The dye concentrate and the monomer-containing liquid composition described above are used to form a photopolymerizable composition, which is then mixed (e.g., by shaking with a high-speed mixer or stirring with a stirring rod) to form the corresponding kit of parts. The photopolymerizable composition is described below.

[0136] [Table 18]

[0137] [Table 19]

[0138] [Table 20]

[0139] [Table 21]

[0140] [Table 22]

[0141] [Table 23]

[0142] [Table 24]

[0143] [Table 25]

[0144] exposure

[0145] [Table 26]

[0146] Exposure was performed at a wavelength of 577 nm at a temperature of 20° C. The material was kept in an oven at 120° C. Exposures were performed every 15 minutes until no more holograms could be exposed and the BWG value (diffraction efficiency) was 0%. The values ​​given are from the first exposure. The monomer-containing mixtures, i.e., the liquid compositions of the component kit II, were stored at room temperature for at least 3 months. Before use, they were kept in an oven at 120° C. for 4 hours to bring the crystallized borates back into solution. Mixture MM2 is from a particularly old batch; it is more than 5 years old and has been frequently reheated to 120° C. during that time without any deterioration in quality. Dye concentrate FK3 is also particularly old, more than 3 years old. The dye concentrates can be stored at room temperature for at least 1 year as the component kits, as well as the monomer-containing liquid compositions, provided they are stored away from light.

[0147] Figure 1 shows a photograph of two mixtures of liquid composition II). The left beaker (1) contains liquid composition II) that has been stored for a long period of time, for more than 3 months, at room temperature. The right beaker (2) contains liquid composition II) that has been recently stirred with a magnetic stirrer (3) on a hot plate at 120°C for 3 hours. It can be clearly seen that this mixture (2) is clearer than the untreated stored one (1) that contains crystallization (4).

[0148] Exposure Equipment The laser beam, with a measured output of 1.43 W, was expanded horizontally using a polygon mirror scanner and focused by a cylindrical lens so that it covered an exposure width of 23 cm. Figure 3 shows a schematic of the exposure apparatus. References in Figure 3: 1 Laser 577nm 2. Mirror 3. Polygonal Scanner 4 Cylindrical Lenses 5 Scanning Beam 6 Scanner Mirror Each sample was scanned and exposed along this line using a moving mirror. The moving speed was set at 9 mm / sec. The laser beam struck the sample surface at an angle of 22 degrees to the vertical. Figure 4 shows the path of the beam.

[0149] References in Figure 4: 1 Scanning beam 577nm 2 Scanner Mirror 3 Exposure direction 4 Exposure angle, 22 degrees 5 Substrate, glass or film 6. Photosensitive polymers (photopolymerizable compositions) 7 Original plate, mirror sheet

[0150] To create a reflection hologram, a sample of material is applied to a mirror sheet that reflects laser light. Interference between the incident and reflected beams creates a line pattern of light and dark spots parallel to the mirror's surface. This interference pattern is recorded in the object in the form of refractive index modulation, creating a so-called Lippmann-Bragg hologram. When laser exposure is used, the photosensitive polymer layer is located between a mirror sheet and a transparent substrate, such as a PET film or glass.

[0151] After laser exposure, the material is further cured using UV light. For the first curing step, we use a UV flash with a power of 3000WS. This is enough to remove the hologram together with the carrier from the sheet. To ensure adhesion to glass, it should be pre-treated with a primer. Optionally, the holographic layer can then be further cured and bleached under a standard UV lamp equipped with a mercury vapor bulb. For this, we use a UV bridge with an arc length of 70 mm and a power of 120 W / cm. Samples B, D, and H were irradiated with this for 30 seconds, whereas the other samples were left untreated and measured after flashing. FIG. 2 illustrates an apparatus for producing holograms made from the claimed kit of parts.

[0152] Measuring Equipment The sample was measured in transmitted light using a spectrometer (CAS 140B, Instrument Systems). This was done with perpendicular illumination. At this point, the spectral curve shows a clear absorption peak, since the hologram reflects only those wavelengths that satisfy the Bragg condition. Peak value T Peak and the reference value T of the upper baseline in the neighborhood Ref From this, the diffraction efficiency (BWG) η is calculated as follows: η = (T Ref -T Peak ) / T Ref FIG. 5 shows the measurement curves at the corresponding measurement points for the first exposure of sample H. The exposure table figures show that all sample mixtures achieve high diffraction efficiency on the first exposure, but the longer the exposable material is held at high temperature the worse the results become, until after a certain time no holograms can be written at all.

[0153] create FIG. 2 shows a schematic configuration of a compact roll-to-roll machine for producing sealed holographic contact transfers from the presently claimed kit of parts. Symbols in Figure 2: 1 Storage container for component A 2 Storage container for component B 3. Mixer 4 Dosing unit 5. Photosensitive polymers (photopolymerizable compositions) 6. Support film 7 Hologram-bearing film 8 Film unwinder 9 Film winder 10 Original version 11 Laser light 12 UV light

Claims

1. A kit of parts for preparing a photopolymerizable composition by means of UV / Vis radiation, comprising: I) A dye concentrate comprising: A) a first mixture A comprising: (f) at least one dye; and (h) at least one solvent and II) A liquid composition comprising: B) A monomer-containing liquid mixture B comprising: a) at least one monomer M1 containing at least one ethylenically unsaturated group, c) at least one co-photoinitiator; Parts kit including:

2. A kit of parts for preparing a photopolymerizable composition by means of UV / Vis radiation, comprising: I) A dye concentrate comprising: A) a first mixture A comprising: (f) at least one dye; (g) at least one co-photoinitiator, and (h) at least one solvent and II) A liquid composition comprising: B) A monomer-containing liquid mixture B comprising: a) at least one monomer M1 containing at least one ethylenically unsaturated group, c) at least one photoinitiator; Including, Preferably, the photopolymerization initiator is capable of generating radicals upon irradiation with a wavelength between 100 nm and 480 nm.

3. The photoinitiator is in liquid form and / or is selected from the group consisting of 1,2-octanedione-1-[4-(phenylthio)-phenyl]-2-(O-benzoyloxime), (1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-O-acetyloxime, methylbenzoyl formate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate), 2-hydroxy-2-methyl-1-phenylpropanone, 2-hydroxy-2-methyl-1-phenylpropanone (80%) and 1- 3. The kit of parts according to claim 1, wherein the component is selected from the group consisting of a mixture of 1-hydroxycyclohexyl-phenylketone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, and 4,4'-dimethyl-diphenyl-iodonium hexafluorophosphate.

4. The kit of parts according to any one of claims 1 to 3, wherein the dye is a fluorescent dye.

5. The kit of parts according to any one of claims 1 to 4, wherein the dye is selected from the group consisting of acriflavine, diaminoacridine, rhodamine B, safranine-O, diethylsafranine, and methylene blue.

6. The kit of parts according to any one of claims 1 to 5, wherein the co-photoinitiator is selected from the group consisting of tetrabutylammonium tetrahexylborate, tetrabutylammonium triphenylhexylborate, tetrabutylammonium tris-(3-fluorophenyl)-hexylborate, and tetrabutylammonium tris-(3-chloro-4-methylphenyl)-hexylborate, or a mixture thereof.

7. The kit of parts according to any one of claims 1 to 6, wherein the monomer-containing liquid mixture B is liquid at standard pressure in the range of 15°C to 120°C.

8. The kit of parts according to any one of claims 1 to 7, wherein more than 80% of all components of the solvent in the kit of parts or in the dye concentrate have a vapor pressure of 2 hPa or less at 20°C and a boiling point of 100°C or more at standard pressure.

9. The kit of parts according to any one of claims 1 to 8, wherein the solvent contains a polymer that is liquid under standard pressure.

10. The kit of parts of any one of claims 1 to 9, wherein the polymer that is liquid under standard pressure is selected from the group consisting of polyethylene glycol (PEG), polycaprolactone, acrylate block copolymer (EFKA), and poly(bisphenol A-co-epichlorohydrin) (EPI).

11. The kit of parts according to any one of claims 1 to 10, comprising I) 10% by weight or less of the first mixture A based on the total amount of the mixture B.

12. An element comprising a component obtainable by the action of (actinic) UV / VIS radiation on the photopolymerizable composition from the kit of parts according to any one of claims 1 to 11.

13. The element of claim 12, comprising a hologram obtainable by exposing the photopolymerizable composition from the kit of parts of any one of claims 1 to 11 to modulated radiation containing holographic information.

14. 14. Use of the element according to any one of claims 12 or 13 as a film, lens, grating, prism, mirror, beam splitter, diffuser, surface relief, membrane, filter or sensor.

15. Use of the element according to any one of claims 12 or 13 for a head-up display, a data glass, a light guidance system, a spectrometer, a detection system, a safety element or a label.

Images