EP1759246A2 - Composition photopolymerisable - Google Patents

Composition photopolymerisable

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Publication number
EP1759246A2
EP1759246A2 EP05770246A EP05770246A EP1759246A2 EP 1759246 A2 EP1759246 A2 EP 1759246A2 EP 05770246 A EP05770246 A EP 05770246A EP 05770246 A EP05770246 A EP 05770246A EP 1759246 A2 EP1759246 A2 EP 1759246A2
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EP
European Patent Office
Prior art keywords
ethylenically unsaturated
composition
composition according
unsaturated monomer
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05770246A
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German (de)
English (en)
Inventor
Frank Knocke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xetos AG
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Xetos AG
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Filing date
Publication date
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Publication of EP1759246A2 publication Critical patent/EP1759246A2/fr
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/001—Phase modulating patterns, e.g. refractive index patterns
    • 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

Definitions

  • the present invention relates to photopolymerizable compositions and elements made therefrom.
  • the photopolymerizable compositions are particularly suitable as recording material for optical elements with refractive index modulation, in particular holograms.
  • the present invention relates to a method for forming a light-resistant hologram.
  • a phase hologram is characterized by a pattern of areas of different refractive indices within a recording material.
  • holograms e.g. Silver halide emulsions or hardened dichromate-treated gelatin.
  • a useful discussion about well-known materials can be found e.g. in "Holography Recording Materials” by H.M. Smith, Ed. (Topics in Applied Physics, Vol. 20, Springer Verlag, 1977).
  • Photopolymers as recording material have also been known for some time. In principle, they can be divided into those that have to be developed by wet chemistry and those that do not require any chemical development step. The latter systems were described by Haugh in 1969 in U.S. Patent 3,658,526 describe. They essentially consist of polymeric binder, monomer and an initiator system and are suitable for holding high-resolution holograms. Since then, further monomer-binder photopolymers have been described in the prior art which have improved properties compared to the material originally presented. In the meantime, DuPont has commercially sold a holography material under the brand name OmniDex ® (see EP 0 324 480).
  • binder-free systems have also been presented which are essentially liquid until exposure (see, for example, US Pat. No. 3,993,485 or N. Smirnova, Optics in Information Systems, February 2004, p. 9).
  • holograms with a diffraction efficiency of over 80% have essentially only been possible with a photopolymer composition be produced that contains a high proportion of a thermoplastic binder (eg PVAC, PMMA).
  • a thermoplastic binder eg PVAC, PMMA
  • Post-treatment times after exposure (DuPont specifies a drying time of one hour at 120 ° C for the OmniDex material mentioned) ensures long distances at fast production speeds and leads to complex and large machine designs.
  • the present invention is therefore based on the object of providing a holographic recording material which avoids the disadvantages mentioned of known recording materials and in particular enables a high processing speed.
  • the holographic elements produced from the recording material should also show the highest possible refractive index modulation and high long-term stability, in particular thermal and mechanical stability.
  • a photopolymerizable composition comprising (a) 75 to 99% by weight of a an ethylenically unsaturated monomer or a monomer mixture composed of various ethylenically unsaturated monomers, (b) 0.5 to 25% by weight of a triglyceride or a mixture of various triglycerides and (c) 0.1 to 10% by weight of a pho - to initiator system, which activates the polymerization of the ethylenically unsaturated monomer or monomers upon exposure to actinic radiation; the composition being a homogeneous, clear, liquid mixture at 20 ° C.
  • the present invention furthermore provides an element containing a component which can be obtained by the action of actinic radiation on a photopolymerizable composition according to the invention.
  • the present invention also provides a method of forming a lightfast hologram in a photopolymerizable layer on a substrate surface, comprising the
  • the invention is based on the knowledge that photopolymerizable compositions as holographic recording materials can advantageously be produced using triglycerides. As a result, an increased refractive index modulation can be achieved compared to photopolymerizable compositions without triglycerides, without the need for time-consuming thermal aftertreatment. In contrast to conventional materials, such self-developing recording materials are suitable for very fast and inexpensive manufacturing processes.
  • the holograms produced in this way are also distinguished by a very high long-term stability, in particular by improved thermal, mechanical and chemical stability (eg resistance to solvents).
  • no solvent and also no thermal aftertreatment is required. It can be exposed immediately after applying the composition to a substrate. Since the wet application of the composition only has to take place in a thickness of approximately 8 to 15 micrometers, known printing methods such as screen, gravure, tampon or flexographic printing can also be used.
  • the layer is solid after exposure.
  • the use of triglycerides in the production of photopolymerizable compositions as holographic recording materials has further significant advantages:
  • the exposed photopolymer has a reduced surface adhesion, since the triglyceride also acts as a release agent.
  • the exposed hologram can therefore be easily and completely removed from a substrate such as glass. This property is also very favorable for mass production because it allows wear-free copy masters with a glass surface to be used to make contact copies. Due to the complete removal of the non-sticky layer, the cleaning effort remains low. If the liquid photopolymerizable composition is printed directly on the master, index matching is also eliminated. This means the application of a liquid between the master and the hologram layer with approximately the same refractive index of the two layers.
  • Index matching prevents the occurrence of disturbing interference phenomena (Newton rings) in normal contact copying. These are caused by reflections, which occur particularly at those places where the two layers do not touch directly, for example due to dust inclusion or a small unevenness.
  • the gapless contact between the recording material and the master can also be used to cast surface structures on the master. Such surface structures can be embossed holograms in particular. This makes it possible to copy both the surface structure and the volume holographic information of the master in a single processing step.
  • the photopolymerizable composition according to the invention contains an ethylenically unsaturated monomer or a monomer mixture of various ethylenically unsaturated monomers.
  • the ethylenically unsaturated monomers can have the following general structural units:
  • radicals R 2 and R 3 are selected independently of one another from the group comprising alkyl, alkenyl, alkynyl, alkoxy, acyl and acyloxy radicals, which can be straight or branched chain, unsubstituted or substituted, substituted or un - substituted aryloxy residues, substituted or unsubstituted aromatic residues or heterocyclic residues, unsubstituted or substituted alicyclic hydrocarbon residues, aliphatic, aromatic and aliphatic-aromatic amino, carboxylic acid, amido and imido residues, hydroxy, amino, cyano, nitro,
  • halogen atoms or hydrogen atoms and combinations wherein the substituted moieties may be substituted with C 1 -C 1 2 alkyl, C 1 -C 12 boxy- alkoxy, hydroxy, carboxylic, carbonyl, amino, amido -, Imidorrest, halogen atoms, aromatic residues or combinations thereof.
  • Suitable ethylenically unsaturated monomers are substituted or unsubstituted styrene monomers, acrylic acid, ⁇ -alkyl acrylic acid, acrylic acid esters, alkyl acrylates, the alcohol component of which can be a substituted or unsubstituted aliphatic or aromatic radical having 2-50 carbon atoms, acrylamides, ⁇ -alkyl acrylamides, alkyl being the has the meaning given above, vinyl esters, vinyl alcohol, vinyl ether and other substituted vinyl monomers, substi tuiert with substituted or unsubstituted aliphatic or aromatic residues with 2-50 carbon atoms.
  • Preferred examples of suitable ethylenically unsaturated monomers are (meth) acrylic acid butyl ester, (meth) acrylic acid phenyl ester, (meth) acrylic acid benzyl ester,
  • ethylenically unsaturated monomers are 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-phenyl acrylate, 2-phenyl acrylate, 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
  • the ethylenically unsaturated monomer is preferably at least difunctional.
  • Difunctional ethylenically unsaturated monomers have two CC double bonds in the molecule, ie they contain, for example, two of the structural units specified above.
  • a different ethylenically unsaturated monomer can contain, for example, two acrylate or methacrylate groups.
  • the component of the ethylenically unsaturated monomer in the photopolymerizable composition according to the invention can essentially consist exclusively of one or more difunctional or higher functional monomers, i.e. the composition can be substantially free of monofunctional ethylenically unsaturated monomers.
  • the content of monofunctional ethylenically unsaturated monomers in the composition according to the invention is preferably less than 10% by weight, more preferably less than 5% by weight.
  • difunctional or higher functional monomers leads in particular to a particularly high thermal and mechanical stability of the holographic elements produced and is particularly advantageous in the production of reflection holograms.
  • Preferred difunctional ethylenically unsaturated monomers are ethoxylated bisphenol A diacrylates, in particular compounds of the following formula
  • a particularly preferred difunctional ethylenically unsaturated monomer is the compound of the following structural formula:
  • epoxy acrylates in particular epoxy acrylates based on difunctional bisphenol A, such as, for example, that from Sartomer Company, Inc. (USA) epoxy acrylate available under the trade name CN124
  • fatty acid-modified epoxy acrylates such as, for example, the fatty acid-modified epoxy acrylate available from Sartomer Company, Inc. (USA) under the trade name CN2101.
  • the viscosity of the ethylenically unsaturated monomer or monomer mixture at room temperature is preferably at least 900 mPas.
  • the photopolymerizable composition according to the invention further contains a triglyceride or a mixture of different triglycerides.
  • the suitable triglycerides are generally compounds of the following general structural formula
  • each R independently, represent a fatty acid residue; each R preferably contains 6 to 22, more preferably 8 to 18, carbon atoms.
  • Naturally occurring oils or fats such as castor oil, coconut oil, palm kernel oil and mixtures thereof can also be used as the triglyceride.
  • Derivatives (eg hydrogenation products) of such natural fats and oils can also be used.
  • Such na- Naturally occurring oils or fats are or generally contain mixtures of different triglycerides.
  • Alkoxylated triglycerides preferably ethoxylated triglycerides, such as e.g. alkoxylated castor oil, especially ethoxylated castor oil, can be used.
  • a particularly preferred triglyceride is the triglyceride of ricinoleic acid, which is a major component of castor oil.
  • the triglyceride is preferably selected such that the amount of the difference between the refractive index (n) of the ethylenically unsaturated monomer or monomer mixture and the refractive index of the triglyceride (ie
  • the photopolymerizable composition according to the invention also contains a photoinitiator system which activates the polymerization of the ethylenically unsaturated monomer (s) when exposed to actinic radiation.
  • a photoinitiator system which activates the polymerization of the ethylenically unsaturated monomer (s) when exposed to actinic radiation.
  • An essential component of such a system is preferably at least one radical-forming polymerization initiator.
  • Photoinitiators are preferably used which are activated by visible light, ie by light with a wavelength of> 300 nm, preferably light with a wavelength in the range of 400-800 nm. Such initiators preferably have an absorption coefficient of 1000 or more for light with wavelengths of more than 300 nm. Such photoinitiators can control the polymerization reaction of the ethylenically unsaturated monomer when irradiated with visible light (ie light with a wavelength of> 300 nm, preferably light with initiate a wavelength in the range of 400-800 nm). Radical-forming polymerization initiators are known, cf. e.g. Timpe, HJ and S.
  • Suitable radical-forming polymerization initiators which can be activated by UV radiation and are generally inactive at temperatures up to 185 ° C. include the substituted or unsubstituted polynuclear quinones; these are compounds with two intracyclic carbon atoms in a conjugated carbocyclic ring system, e.g.
  • photoinitiators that are also useful, although some are thermally active at temperatures as low as 85 ° C, are described in U.S. Patent 2,760,663, and include vicinal ketal allyl alcohols such as benzoin, pivaloin, acyloin ethers, e.g. Benzoin methyl and ethyl ether, hydrocarbon-substituted aromatic acyloins, including ⁇ -methylbenzoin, ⁇ -allylbenzoin and ⁇ -phenylbenzoin.
  • vicinal ketal allyl alcohols such as benzoin, pivaloin, acyloin ethers, e.g. Benzoin methyl and ethyl ether, hydrocarbon-substituted aromatic acyloins, including ⁇ -methylbenzoin, ⁇ -allylbenzoin and ⁇ -phenylbenzoin.
  • photoreducible dyes and reducing agents such as those in US Patents 2,850,445, 2,875,047, 3,097,096, 3,074,974, 3,097,097, 3,145,104 and 3,579,339 and dyes from the class of phenazines, oxazines and quinones; Michler's ketone, benzophenone, 2,4,5-triphenylimidazolyl dimers with hydrogen donors and mixtures thereof, as described in U.S. Patents 3,427,161, 3,479,185, 3,549,367, 4,311,783, 4,622,286 and 3 784 557.
  • Suitable photoinitiators include CDM-HABI, ie 2- (o-chlorophenyl) ) -4, 5-bis (m-methoxyphenyl) imidazole dimer; o-Cl-HABI, ie, 2, 2 'bis (o-chlorophenyl) -4, 4', 5, 5 '-tetraphenyl-1 , 1 '-biimidazole; and TCTM-HABI, ie, 2, 5-bis (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -IH-imidazole dimer, each typically used with a hydrogen donor , e.g. 2-mercaptobenz oxazole.
  • a hydrogen donor e.g. 2-mercaptobenz oxazole.
  • a particularly preferred photoinitiator is 2-benzyl-2-dimetylamino-1- (4-morpholinophenyl) butanone-1, which is available under the name "irgacure 369" from Ciba and preferably in an amount of 0.1 to 10% by weight. % is used.
  • photopolymerization initiators of the formula SLA can also be used, as are described in US patent application 2005/0026081, wherein in the formula S mentioned, for a light-absorbing group with a chromophoric group, the absorption coefficients of 1000 or more for wavelengths of more is 300 nm; A stands for an active grouping which interacts with the light-absorbing grouping S to form a free radical; and L stands for a connecting group which connects the light-absorbing group S and the active group A.
  • A stands for an active grouping which interacts with the light-absorbing grouping S to form a free radical
  • L stands for a connecting group which connects the light-absorbing group S and the active group A.
  • the above photoinitiators can be used alone or in combination.
  • Sensitizing agents can be used together with the photoinitiators mentioned, e.g. Methylene blue, and those in U.S. Patents 3,554,753, 3,563,750, 3,563,751, 3,647,467, 3,652,275, 4,162,162, 4,268,667, 3,351,893, 4,454,218, 4,535,052, and 4th 565,769 disclosed sensitizers, expressly incorporated herein by reference.
  • the most preferred sensitizers include the following: DBC, i.e., 2,5-bis [(4-diethylamino-2-methylphenyl) methylene] cyclopentanone; DEAW, i.e., 2, 5-bis [(4-diethylaminophenyl) methylene] cyclopentanone; Dimethoxy-JDI, ie, 2, 3-dihydro-5, 6-dimethoxy-2- [(2, 3, 6, 7-tetrahydro-1H, 5H-benzo [i, j] quinolizin-9-yl) methylene] -IH-inden-1- one; and safranin 0, i.e. 3, 7-diamino-2, 8-dimethyl-5-phenylphenazinium chloride.
  • DBC i.e., 2,5-bis [(4-diethylamino-2-methylphenyl) methylene] cyclopentanone
  • DEAW i.
  • a particularly preferred photoinitiator comprises the compound of the following structural formula, which is referred to as
  • CGI 7460 is available from Ciba Specialty Chemicals Inc.:
  • the composition can contain various additives known per se. These should be able to be mixed in well and should not impair the diffraction efficiency. Non-volatile substances can even permanently improve the diffraction efficiency in thin layers, in particular by choosing additives which increase the difference in refractive index between the ethylenically unsaturated monomer and the other components of the photopolymerizable composition.
  • the additive or the additives should also have the lowest possible refractive index.
  • the additive or the additives should also have the lowest possible refractive index.
  • polymers with a low refractive index such as polyvinyl acetate, fluorinated or silanized polymers are particularly suitable.
  • the molecular weight of the additives under consideration should not be too high.
  • additives mentioned above and specified in detail below can generally be used in an amount of 0.01 to 25% by weight, preferably 0.01 to 10% by weight.
  • the photopolymerizable compositions may contain a plasticizer to enhance modulation of the refractive index of the imaged composition.
  • Plasticizers can be used in amounts ranging from about 2 to about 25
  • Suitable plasticizers include triethylene glycol, triethylene glycol diacetate, triethylene glycol dipropionate, triethylene glycol dicapryate, triethylene glycol dimethyl ether, triethylene glycol bis (2-ethylhexanoate), tetraethylene glycol diaphthylate, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol ladipat, diethyl sebacinate, dibutyl suberinate, tributyl phosphate, tris (2-ethylhexyl) phosphate, Brij ® 30 [C ⁇ 2 H 25 (OCH 2 CH 2 ) 4 0H], Brij ® 35 [C ⁇ 2 H 25 (OCH 2 CH 2 ) 2 ⁇ OH ], as well as n-butyl acetate.
  • plasticizers are Triethylenglycoldicapry- methacrylate, tetraethylene glycol diheptanoate, diethyl adipate, Brij ® 30, and tris (2-ethylhexyl) phosphate.
  • compositions and elements of this invention can be used with the compositions and elements of this invention.
  • these components include: optical brighteners, ultraviolet radiation absorbing material, thermal stabilizers, hydrogen donors, oxygen scavengers or antioxidants and release agents.
  • optical brighteners ultraviolet radiation absorbing material
  • thermal stabilizers thermal stabilizers
  • hydrogen donors oxygen scavengers or antioxidants and release agents.
  • antioxidants antioxidants
  • release agents can also include polymers or copolymers.
  • Optical brighteners useful in the method of the present invention include those disclosed in US Patent 3,854,950, cited herein.
  • a preferred optical brightener is 7- (4 '-chloro-6' -diethylamino-1 ', 3', 5 '-triazin-4' -yl) amino-3-phenylcoumarin.
  • Ultraviolet radiation absorbing materials useful for this invention are also disclosed in U.S. Patent 3,854,950.
  • Useful thermal stabilizers include: hydroquinone, phenidone, p-methoxyphenol, alkyl- and aryl-substituted hydroquinones and quinones, tert-butylcatechol, pyrogallol, copper resinate, naphthylamines, ⁇ -naphthol, copper (I) chloride, 2, 6- di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, di-nitrobenzene, p-toluchinone and chloranil.
  • the dinitroso dimers described in U.S. Patent 4,168,982 are also useful.
  • a thermal polymerization inhibitor is usually also present in order to increase the stability during storage of the photopolymerizable composition.
  • Hydrogen donor compounds useful as chain transfer agents in the photopolymer compositions include: 2-mercaptobenzoxazole, 2-mercaptobenzothioazole, etc., and various types of compounds, such as (a) ethers, (b) esters, (c) alcohols, (d) compounds containing allylic or benzylic hydrogen such as Cu ol, (e) acetals, (f) aldehydes, and (g) amides as disclosed in column 12, lines 18-58 in US Patent 3,390,996, to which expressly incorporated herein by reference.
  • the photopolymerizable composition preferably contains one or more antioxidants such as e.g. Vitamin C (ascorbic acid) or vitamin E.
  • Vitamin C can be used as such or in a modified form.
  • Ascorbyl palmitate can be used as a modified, fat-soluble vitamin C.
  • a form of vitamin C (ascorbic acid) solubilized with the aid of polysorbate and medium-chain triglycerides as micelles or vesicles approximately 50 nm in size can be used; such a solubilisate is available under the trade name Solu C 10 from BASF.
  • a preferred release agent is polycaprolactone.
  • the photopolymerizable composition can also contain one or more polymeric binders which are selected from the group comprising 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, butadiene and isoprene polymers and copolymers and polyethylene oxides from polyglycols with an average molecular weight molecular weight of about 1,000 to 1,000,000 g / mol, epoxides, such as epoxides containing acrylate or methacrylate residues, polystyrenes, cellulose esters, such as
  • Polyamides such as N-methoxymethylpolyhexamethylene adipamide, polyimides, polyurethanes.
  • the polymeric binders mentioned can e.g. be used in an amount of 0.001 to 10 wt .-%.
  • the photopolymerizable composition can also contain one or more wetting agents (in particular fluorocarbon polymers, such as, for example, Schwego-Fluor 8038 TM, or fluorosurfactants, such as, for example, 3M Fluorad FC-4430 TM), leveling agents (in particular n-butyl glycolate or polyether -modified polydimethylsiloxanes, such as, for example, ADDID 130 TM), defoamers (in particular defoamers based on fluorosilicone oil, such as, for example, ADDID 763 TM), adhesion promoters (in particular diamino-trimethoxy-functional silane coupling agents, such as, for example, ADDID 900 TM or glycidyl-trimethoxy trifunctional silane coupling agents) , such as ADDID 911 TM, vinyltriethyoxysilane or 3-methacryloxypropyltrimethoxysilane), or surface additives (in
  • the photopolymerizable composition can also contain nanoscale particles (nanoparticles), for example made of Ti0 2 , Si0 2 or Au, which can optionally be coupled to monomers (such materials are available, for example, under the trade name "Nanocryl”).
  • nanoparticles for example made of Ti0 2 , Si0 2 or Au
  • monomers such materials are available, for example, under the trade name "Nanocryl”
  • the photopolymerizable composition can also contain polyethylene glycol.
  • the photopolymerizable composition according to the invention is essentially free of organic solvents.
  • the composition preferably contains at most 5% by weight, more preferably at most 1% by weight, of organic solvents.
  • optical elements in particular those with refractive index modulation, can be produced. These are especially holograms. Both transmission holograms and reflection holograms can be produced.
  • the holograms are generally produced by allowing a modulated radiation carrying holographic information to act on a layer of the photopolymerizable composition which is applied to a carrier substrate.
  • the photopolymerizable composition can e.g. between two glass plates.
  • Residual monomers which have not yet reacted after the holographic exposure can be polymerized as a whole by subsequent UV irradiation of the layer.
  • the holographic exposure and / or the mentioned UV radiation of the layer as As with other radical systems, the whole process is preferably carried out with the exclusion of oxygen.
  • the optical element according to the invention can be a film which is obtained directly by the holographic exposure of a layer of the composition according to the invention on one or between two inert carrier substrates and optionally subsequent UV irradiation of the layer as a whole.
  • Such an element can e.g. can be used as a security feature.
  • the element can be produced in particular using the contact copying method.
  • the photopolymerizable composition is applied directly to a holographic master copy with a glass surface. Due to the complete removal of the non-sticky layer, the cleaning effort remains low.
  • index matching can also be omitted.
  • the photopolymerizable compositions according to the invention can furthermore be used for molding surface structures, in particular surface holograms (embossed holograms).
  • the photopolymerizable compositions according to the invention can also be used to produce optical elements with a refractive index gradient structure, such as e.g. photonic crystals, optical fibers, diffusers, angle-selective diffusers, data memories, head-up displays, planar gradient index lenses, antireflection layers or Fabry-Perot filters.
  • a refractive index gradient structure such as e.g. photonic crystals, optical fibers, diffusers, angle-selective diffusers, data memories, head-up displays, planar gradient index lenses, antireflection layers or Fabry-Perot filters.
  • the photopolymerizable composition according to the invention can be used for the production of optical elements such as, for example: directionally selective focusing screens, photonic crystals, plastic lasers, color filters, dichroic filters Beam splitters, dielectric and dichroic mirrors, optical heat and pressure sensors (depending on pressure and temperature, the layer thickness and thus the color or the angle-dependent reflection and transmission spectrum can vary) or chemical sensors (by doping with corresponding absorbing substances or capture molecules (receptors) chemical substances can be detected which, by coupling to the receptors, change either the thickness or the refractive index modulation and thus the diffraction efficiency, the diffraction angle or the measurable color spectrum).
  • optical elements such as, for example: directionally selective focusing screens, photonic crystals, plastic lasers, color filters, dichroic filters Beam splitters, dielectric and dichroic mirrors, optical heat and pressure sensors (depending on pressure and temperature, the layer thickness and thus the color or the angle-dependent reflection and transmission spectrum can vary) or chemical sensors (by doping with
  • Elements according to the invention without a gradient structure can e.g. for rapid prototyping, for optical lithography, as a membrane filter, as a film, as a semi-permeable film, as a diffractive optical element or as a casting compound.
  • a coating solution was prepared from the components shown in the following table.
  • the monomer "SR-349” is an ethoxylated bisphenol A diacrylate of the following structural formula:
  • CGI 7460 is a compound of the following structural formula:
  • the sensitizer "Safranin 0" is the compound 3, 7-diamino-2, 8-dimethyl-5-phenyl-phenazinium chloride.
  • the wetting agent Schwego-Fluor 8038 TM is a fluorocarbon polymer.
  • the coating solution was prepared as follows:
  • the oil mixture was filled.
  • the monomer was then added and mechanically stirred until a clear solution had formed (about 1 minute).
  • the solution of the photoinitiator was added dropwise and also stirred well.
  • the solution of the photosensitizer and the wetting agent were stirred in.
  • the coating solution was heated in an oven at 120 ° C. for a further 5-10 minutes and was then ready for use.
  • a drop of the coating solution described under 1. was placed on a glass slide and covered with a second glass slide. By pressing lightly and after a waiting time of a few minutes, the drop was distributed between the plates into a layer with a thickness of about 15 micrometers.
  • This sample was placed in an exposure setup where it was exposed to coherent laser light from both sides.
  • the light of a neodymium-YAG laser (COMPASS model from Coherent) with the wavelength of 532 nm was expanded into a parallel beam and split into two beams using a beam splitter cube.
  • the beams are deflected via mirrors so that one beam strikes the top of the sample perpendicularly and the second beam hits the back at an angle of 45 degrees.
  • By overlaying the Both coherent beams create an interference pattern of light and dark lines with a line spacing of approximately 183 nm within the material.
  • the lines or planes lie obliquely at an angle of approximately 14 degrees in the recording layer.
  • the brightness pattern leads to a locally different polymerization, so that a corresponding pattern with different refractive indices is created.
  • the beams each had an intensity of 1.3 mW / cm 2 .
  • the exposure time was 15 seconds.
  • the sample was then exposed to UV light (120 mW / cm 2 at 365 nm) for 1 minute to complete the polymerization process.
  • the diffraction efficiency is calculated from the ratio of the intensity of the laser beam (I ⁇ ) reflected or diffracted by the hologram structure to the continuous non-reflected portion (I 0 ) according to the following equation:
  • the sample was illuminated with the unexpanded laser beam (532 nm) and the angle of incidence was chosen so that the reflected beam reached its maximum intensity.
  • the refractive index amplitude ( ⁇ n) of the grating structure can be determined using the Kogelnik theory (see “Coupled Wave Theory for Thick Hologram Grätings", The Bell System Technical Journal of May 23, 1969) calculate the following formula:
  • ⁇ 0.5 ( ⁇ m - ß m )
  • ß m aresine (sin (ß) / n)
  • ⁇ angle of incidence of the 1st ray
  • ß Angle of incidence of the 2nd beam
  • n refractive index of the recording material

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  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une composition photopolymérisable comprenant (a) 75 à 99 % en poids d'un monomère éthyléniquement insaturé ou d'un mélange de monomères constitué de différents monomères éthyléniquement insaturés, (b) 0,5 à 25 % en poids d'un triglycéride ou d'un mélange de différents triglycérides et (c) 0,1 à 10 % en poids d'un système photoamorceur qui active la polymérisation du (des) monomère(s) éthyléniquement insaturé(s) sous l'action d'un rayonnement actinique, ladite composition étant un mélange homogène, clair et fluide à 20 °C. Ladite invention concerne également des éléments fabriqués à partir de ces compositions photopolymérisables et un procédé pour former un hologramme résistant à la lumière. Ces compositions photopolymérisables sont appropriées pour être utilisées, en particulier, comme matériau d'enregistrement pour des éléments optiques à modulation d'indice de réfraction, en particulier des hologrammes.
EP05770246A 2004-06-22 2005-06-22 Composition photopolymerisable Withdrawn EP1759246A2 (fr)

Applications Claiming Priority (2)

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DE102004030019A DE102004030019A1 (de) 2004-06-22 2004-06-22 Photopolymerisierbare Zusammensetzung
PCT/EP2005/006768 WO2005124456A2 (fr) 2004-06-22 2005-06-22 Composition photopolymerisable

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EP1759246A2 true EP1759246A2 (fr) 2007-03-07

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US (1) US8603730B2 (fr)
EP (1) EP1759246A2 (fr)
JP (1) JP5058790B2 (fr)
CA (1) CA2571951C (fr)
DE (1) DE102004030019A1 (fr)
WO (1) WO2005124456A2 (fr)

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CA2571951A1 (fr) 2005-12-29
WO2005124456A3 (fr) 2006-04-13
JP2008503780A (ja) 2008-02-07
US8603730B2 (en) 2013-12-10
DE102004030019A1 (de) 2006-01-19
CA2571951C (fr) 2012-08-14
WO2005124456A2 (fr) 2005-12-29
JP5058790B2 (ja) 2012-10-24
US20100112458A1 (en) 2010-05-06

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