PHOTOPOLYMER FORMULATION FOR PRODUCING HOLOGRAPHIC MEDIA HAVING HIGHLY CROSSLINKED MATRIX POLYMERS

• US 20130224634A1
• Filed: 11/04/2011
• Published: 08/29/2013
• Est. Priority Date: 11/08/2010
• Status: Active Grant

• Current Assignee: Bayer Materialscience AG (Covestro AG)
• Original Assignee: Bayer Intellectual Property GmbH (Bayer AG)
• Inventors: Berneth, Horst, Rlle, Thomas, Bruder, Friedrich-Karl, Fcke, Thomas, Weiser, Marc-Stephan, Hnel, Dennis
• Granted Patent: US 9,146,456 B2
• Time in Patent Office: Days
• US Class Current: 430/2
• CPC Class Codes: C09B 11/12 without any OH group bound to an aryl nucleus
• CPC Class Codes: C09B 17/00 Azine dyes
• CPC Class Codes: C09B 21/00 Thiazine dyes
• CPC Class Codes: C09B 23/04 one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
• CPC Class Codes: C09B 23/06 three >CH- groups, e.g. carbocyanines
• CPC Class Codes: C09B 23/083 five >CH- groups
• CPC Class Codes: C09B 23/105 two >CH- groups
• CPC Class Codes: C09B 23/166 containing two or more nitrogen atoms hydrazon dyes -CH=N-N- C09B26/02
• CPC Class Codes: C09B 49/12 from other compounds , e.g. other heterocyclic compounds
• CPC Class Codes: C09B 55/009 Azomethine dyes, the C-atom of the group -C=N- being part of a ring (Image)
• CPC Class Codes: C09B 57/00 Other synthetic dyes of known constitution
• CPC Class Codes: C09B 69/06 of cationic dyes with organic acids or with inorganic complex acids
• CPC Class Codes: C09B 69/065 of cationic azo dyes
• CPC Class Codes: G03C 1/00 Photosensitive materials photosensitive materials for multicolour processes G03C7/00; for diffusion transfer processes G03C8/00; photosensitive glass C03C4/04
• CPC Class Codes: G03F 7/0045 with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• CPC Class Codes: G03F 7/035 the binders being polyurethanes
• CPC Class Codes: G03H 1/00 Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
• CPC Class Codes: G03H 1/024 Hologram nature or properties
• CPC Class Codes: G03H 2260/12 Photopolymer
• CPC Class Codes: G03H 2260/14 Photoresist
• CPC Class Codes: G11B 7/24044 : for storing optical interference patterns, e.g. holograms; for storing data in three dimensions, e.g. volume storage G11B7/24038 takes precedence
• CPC Class Codes: G11B 7/245 : containing a polymeric component

Abstract

The invention relates to a photopolymer formulation comprising a polyol component, a polyisocyanate component, a writing monomer, and a photoinitiator, containing a coinitiator and a dye having the formula F An, where F stands for a cationic dye and An″ stands for an anion, wherein the dye having the formula F An comprises a water absorption of =5%. The invention further relates to a holographic medium, in particular in the form of a film, containing a photopolymer formulation according to the invention, to the use of such a medium for recording holograms, and to a special dye that can be used in the photopolymer formulation according to the invention.

Claims

1-17. -17. (canceled)

18. A photopolymer formulation comprising a polyol component, a polyisocyanate component, a writing monomer and a photoinitiator containing a coinitiator and a dye of formula

F⁺An⁻

,

where

F⁺ represents a cationic dye, and

An⁻

represents an anion,

wherein the dye of formula F⁺An⁻

has a water imbibition of ≦

5%.

19. The photopolymer formulation according to claim 18, wherein the dye has a water imbibition of ≦

3%.

20. The photopolymer formulation according to claim 18, wherein the dye has a water imbibition of ≦

2%.

21. The photopolymer formulation according to claim 18, wherein the anion An−

has an AClogP in the range of 1-30.

22. The photopolymer formulation according to claim 18, wherein the anion An−

has a molar mass >

150 g/mol.

23. The photopolymer formulation according to claim 18, wherein the anion An−

has an AClogP in the range of 1-4 and the anion An−

has a molar mass >

250 g/mol.

24. The photopolymer formulation according to claim 18, wherein the anion An−

comprises at least a phosphorus, boron or sulphur atom.

25. The photopolymer formulation according to claim 18, wherein the anion An−

has one or more than one linear or branched aliphatic moiety or when it has more than one linear or branched aliphatic moiety, these together have 8 to 36 carbon atoms.

26. The photopolymer formulation according to claim 18, wherein the anion An−

is selected from the group C8- to C25-alkanesulphonate, C3- to C18-perfluoroalkanesulphonate, C9- to C25-alkanoate, C9- to C25-alkenoate, C8- to C25-alkyl sulphate, C8- to C25-alkenyl sulphate, preferably C13- to C25-alkenyl sulphate, C3- to C18-perfluoroalkyl sulphate, polyether sulphates based on 4 or more equivalents of ethylene oxide and/or propylene oxide, bis-C4- to C25-alkyl, C5- to C7-cycloalkyl, C3- to C8-alkenyl or C7- to C11-aralkyl sulphosuccinate, bis-C2- to C10-alkyl sulphosuccinate substituted by 8 or more fluorine atoms, C8- to C25-alkyl sulphoacetates, benzenesulphonate substituted by at least one moiety from the group halogen, C4- to C25-alkyl, perfluoro-C1- to C8-alkyl and/or C1- to C12-alkoxycarbonyl, optionally nitro-, cyano-, hydroxyl-, C1- to C25-alkyl-, C1- to C12-alkoxy-, amino-, C1- to C12-alkoxycarbonyl- or chlorine-substituted naphthalene- or biphenylsulphonate, optionally nitro-, cyano-, hydroxyl-, C1- to C25-alkyl-, C1- to C12-alkoxy-, C1- to C12-alkoxycarbonyl- or chlorine-substituted benzene-, naphthalene- or biphenyldisulphonate, dinitro-, C6- to C25-alkyl-, C4- to C12-alkoxycarbonyl-, benzoyl-, chlorobenzoyl- or toluoyl-substituted benzoate, the anion of naphthalenedicarboxylic acid, diphenyl ether disulphonate, sulphonated or sulphated, optionally mono- or polyunsaturated C8- to C25-fatty acid esters of aliphatic C1- to C8-alcohols or glycerol, bis(sulpho-C2- to C6-alkyl) C3- to C12-alkanedicarboxylic esters, bis(sulpho-C2- to C6-alkyl) itaconic acid esters, (sulpho-C2- to C6-alkyl) C6- to C18-alkanecarboxylic esters, (sulpho-C2- to C6-alkyl) acrylic or methacrylic acid esters, triscatechol phosphate optionally substituted by up to 12 halogen moieties, an anion from the group tetraphenyl borate, cyanotriphenyl borate, tetraphenoxyborate, C4- to C12-alkyltriphenyl borate, the phenyl or phenoxy moieties of which may be halogen, C1- to C4-alkyl and/or C1- to C4-alkoxy substituted, C4- to C12-alkyltrinaphthyl borate, tetra-C1- to C20-alkoxyborate, 7,8- or 7,9-dicarbanidoundecaborate (1-) or (2-), which optionally bear on the B and/or C atoms one or two C1- to C12-alkyl or phenyl substituents, dodecahydrodicarbadodecaborate (2-) or B—

C1- to C12-alkyl-C-phenyldodecahydrodicarbadodecaborate (1-), where An−

in multivalent anions and represents one equivalent of this anion, and where the alkane and alkyl groups may be branched and/or may be halogen, cyano, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl substituted.

27. The photopolymer formulation according to claim 26, where An−

is naphthalenedisulphonate.

28. The photopolymer formulation according to claim 18, wherein the anion An−

is sec-C11- to C18-alkanesulphonate, C13- to C25-alkyl sulphate, branched C8- to C25-alkyl sulphate, optionally branched bis-C6- to C25-alkyl sulphosuccinate, sec- or tert-C4- to C25-alkylbenzenesulphonate, sulphonated or sulphated, optionally mono- or polyunsaturated C8- to C25-fatty acid esters of aliphatic C1- to C8-alcohols or glycerol, bis(sulpho-C2- to C6-alkyl) C3- to C12-alkanedicarboxylic esters, (sulpho-C2- to C6-alkyl) C6- to C18-alkanecarboxylic esters, triscatechol phosphate substituted by up to 12 halogen moieties, cyanotriphenyl borate, or tetraphenoxyborate.

29. The photopolymer formulation according to claim 18, wherein the cationic dye F+ is acridine, xanthene, thioxanthene, phenazine, phenoxazine, phenothiazine, tri(het)arylmethane, diamino(het)arylmethane, triamino(het)arylmethane, monomethinecyanine, dimethinecyanine, trimethinecyanine, hemicyanine, externally cationic merocyanine, externally cationic neutrocyanine, nullmethine, naphtholactam or streptocyanine dyes.

30. The photopolymer formulation according to claim 18, wherein the polyisocyanate component is an aliphatic polyisocyanate or a prepolymer with primary NCO groups.

31. The photopolymer formulation according to claim 18, wherein the polyol component is a difunctional polyether, polyester or a polyether-polyester block copolyester with primary OH functions.

32. The photopolymer formulation according to claim 18, wherein the writing monomer comprises at least a monofunctional and a multifunctional urethane (meth)acrylate.

33. The photopolymer formulation according to claim 18, wherein it additionally comprises a plasticizer which conforms to general formula (CI)

34. A holographic medium containing the photopolymer formulation according to claim 18.

35. A process for recording of in-line, off-axis, full-aperture transfer, white light transmission, Denisyuk, off-axis reflection or edge-lit holograms or holographic stereograms, which comprises utilizing the holographic medium according to claim 34.

36. A dye of formula

F⁺An⁻

,

where

F⁺ represents a cationic dye, and

An⁻

represents an anion,

wherein the anion An⁻

is selected from the group sec-alkylbenzenesulphonates, secondarily and branched alkyl sulphates, n-alkyl sulphates, sec-alkylsuiphonates, sulphosuccinates, triscatechol phosphates, ester sulphates and ester sulphonates.

37. The dye according to claim 36, wherein the cationic dye F⁺ is acridine, xanthene, thioxanthene, phenazine, phenoxazine, phenothiazine, tri(het)arylmethane, diamino(het)arylmethane, triamino(het)arylmethane, monomethinecyanine, dimethinecyanine, trimethinecyanine, hemicyanine, externally cationic merocyanine, externally cationic neutrocyanine, nullmethine, naphtholactam or streptocyanine dyes.