EP0428332A1 - Farbhologramme - Google Patents

Farbhologramme Download PDF

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Publication number
EP0428332A1
EP0428332A1 EP90312219A EP90312219A EP0428332A1 EP 0428332 A1 EP0428332 A1 EP 0428332A1 EP 90312219 A EP90312219 A EP 90312219A EP 90312219 A EP90312219 A EP 90312219A EP 0428332 A1 EP0428332 A1 EP 0428332A1
Authority
EP
European Patent Office
Prior art keywords
formula
holographic material
holographic
dye
dyes
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Withdrawn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
EP90312219A
Other languages
English (en)
French (fr)
Inventor
Anthony John Bond
Geoffrey Ernest Ficken
Julie Elizabeth Parsonage
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.)
Ilford Imaging UK Ltd
Original Assignee
Ilford Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ilford Ltd filed Critical Ilford Ltd
Publication of EP0428332A1 publication Critical patent/EP0428332A1/de
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/22—Methine and polymethine dyes with an even number of CH groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain

Definitions

  • This invention relates to holographic material.
  • a multicolour hologram by incorporating a plurality of optical sensitising dyes in the silver halide emulsion and exposing the material holographically to three laser exposures, one in the blue, one in the green and one in the red regions of the spectrum. After processing to develop the latent silver image followed by a rehalogenating bleach, on white light reconstruction a multi-colour hologram should be visible.
  • a mixture of optical sensitizing dyes which can be used to prepare such a multicolour hologram.
  • the crystal size of the silver halide crystals in the emulsion is required to be less than 0.1 ⁇ m, that is to say a Lippmann emulsion, only a limited number of optical sensitizing dyes are able to be used.
  • at least two optical sensitizing dyes are required to be present in the mixture often one dye is adsorbed preferentially on to the silver halide and the optical sensitizing effect of the non-adsorbed dye is almost completely negated. Thus it is necessary to choose two dyes which are adsorbed equally well on to the silver halide crystals.
  • holographic material which comprises coated on a photographic supporting base at least one silver halide emulsion which has a mean grain size of less than 0.1 ⁇ m and at least one emulsion of which has been optically sensitized with at least one green sensitizing dye of the following general formula I:- wherein R1 is an optionally substituted alkyl group, R2 is hydrogen or an alkyl group having 1 to 6 carbon atoms and D represents the atoms needed to complete an optionally substituted 5- or 6- membered heterocyclic ring and at least one emulsion of which has been optically sensitized with at least one red sensitizing dye of the general formula II :- wherein R1 is an alkyl group having 1 to 4 carbon atoms, R2 and R3 are each hydrogen, alkyl groups having 1 to 4 carbon atoms or aryl, R4 is an optionally substituted alkyl group and Y represents the atoms necessary to complete a benzothiazole or benzosele
  • silver halide emulsion layer which has been sensitised with at least one dye of formula I and with at least one dye of formula II.
  • the dyes of formula I R1 is a sulphor-alkyl group and most preferably a sulpho-butyl group.
  • the dyes of formula I R2 is hydrogen or methyl.
  • dyes of formula I D completes an unsubstituted rhodanine or thiohydantoin ring.
  • Y represent the atoms necessary to complete an unsubstituted benzothiazole ring.
  • R1 is methyl or ethyl.
  • R2 and R3 are each methyl.
  • R4 is an optionally substituted alkylene chain -Z-CO2H, wherein Z is an alkyl moiety of from 1 to 4 carbon atoms.
  • the optional substitution on the benzene ring of the benzothiazole or benzoselenazole ring is preferably selected from at least one alkyl or alkoxy group having from 1 to 4 carbon atoms and a halogen atom.
  • Very useful substituents are (one or more) methyl or methoxy groups or chlorine atoms.
  • Optional substitution on the alkylene chain Z preferably is selected from an alkyl group having from 1 to 4 carbon atoms, preferably a butyl radical such as -CH2CH(CH3)2, an aryl group, preferably phenyl and an aralkyl group wherein the alkyl moiety has from 1 to 4 carbon atoms such as benzyl, phenylethyl, phenylpropyl.
  • these groups are substitutents on a methylene group Z.
  • the dyes of formula I are included in the dyes described in British Patent Specification No. 1317139.
  • the dyes of formula I have an absorption which stretches from 440 nm to 550 nm.
  • An argon ion laser can be tuned to emit at 458 nm and also at 528 nm (as well as other wavelengths).
  • the dyes of formula II are red sensitizing dyes and their absorption stretches from 600 nm to 710 nm.
  • a helium-neon laser has its emission at 633 nm.
  • the silver halide emulsion used in the holographic material of the present invention can be used to produce a record of a holographic exposure which has been made using a laser which emits in the blue, green or red regions of the spectrum. If three exposures are made to the three regions of the visible spectrum a record of all three exposures can be obtained.
  • a process for the production of a hologram which on reconstruction exhibits a multi-colour holographic image comprises exposing the holographic material hereinbefore described which comprises at least one dye of formula I and at least one dye of formula II to three holographic laser exposures one in the blue region of the visible spectrum, one in the green region and one in the red region developing the latent silver image using a silver halide developing agent and removing the developed silver using a rehalogenating bleach bath.
  • the binder for the silver halide emulsion or emulsions is gelatin.
  • the laser exposures can be sequentially in any order or simultaneously.
  • the holographic image obtained on reconstruction comprises a blue image which represents the object of the holographic exposure when using the blue light emitting laser, a green image which represents the object of the holographic exposure when using the green light emitting laser and a red image which represents the object of the holographic exposure when using the red light emitting laser.
  • a tuned Krypton laser can be used to effect all three exposures. Such a laser emits at 476.5 nm in the blue region of the spectrum, at 520.8 nm in the green region of the spectrum and at 647.1 nm in the red region of the spectrum.
  • a holographic record can be obtained which on white light reconstruction exhibits a hologram which is in all three colours blue, green and red.
  • a bathochromic shift in the replay wavelength of a hologram can be effected by treating the emulsion after silver halide development with a gelatin swelling agent such as triethanolamine however this is not a lasting effect thought to be due to evaporation of the triethanolamine. Certain gelatin hardening agents such as aluminium salts have also been used but with very unpredictable results.
  • a method of preparing a hologram which is of the silver halide in gelatin binder type which method comprises holographically exposing the material by use of coherent light, developing the holographic image by a chemical process and before processing, simultaneously or subsequently, treating the material with a solution of a compound which has a molecular weight of over a 100 and which reacts with the gelatin to form covalent bonds therewith to increase the molecular bulk of gelatin.
  • a compound of this type is hereinafter referred to as a gelatin reactive compound.
  • the solvent for the gelatin reactive compound is water.
  • a large number of compounds can be used in the process, but particularly useful compounds are those compounds which are used to treat fibrous materials of animal origin such as wool and silk. Such compounds are used to treat wool and silk to increase their dye-ability and to render fabrics treated with them more crease resistant.
  • a particularly useful class of compounds are the aldehyde condensation compounds described in European patent application 225 852.
  • a particularly useful range of condensation compounds are obtained when the aldehyde used in the first stage condensation and in the second stage condensation is in each case formaldehyde.
  • the salt of an alphatic amine used is a salt of ethylene diamine.
  • the water-soluble ammonium salt used in the second stage condensation is ammonium chloride.
  • non-cyclic compounds which contain at least once the grouping there may be used, guanidine, acetoguanidine, biguanide or substitution products of those compounds such as alkyl-biguanides or aryl-biguanides.
  • the non-cyclic compund used is dicyandiamide.
  • Condensate 1 An especially useful compound is obtained which is the reaction product of formaldehyde, ammonium chloride, dicyandiamide and ethylene diamine in a molar ration of 2:1:1:0.1. This compound is hereinafter referred to as Condensate 1 and is used in the Examples which follow.
  • Another useful class of compounds are the so-called reactive dyestuffs which comprise at least one hydrophilic group and at least one group which can react with a textile such as wool, cotton or silk.
  • Reactive dyes comprise both a chromophore group and a reactive group and there are also described in E.P. 225 852.
  • reactive groups are substituted mono-azine, diazine, triazine- oxazine- pyridine-, pyrimidine-, pyridazine-, pyrazine- and thriazine-rings of this type which are annelated for example, phthalazine, quinoline, quinazoline, quainoxaline and acridine rings.
  • rehalogenating bleach bath By rehalogenating bleach bath is meant a bath which oxidises the developed silver to a silver halide. It appears that this silver halide deposits on the undeveloped silver halide present in the material so reinforcing the holographic image on reconstruction.
  • Examples of useful rehalogenating bleach baths are aqueous solutions of ferric ammonium E.D.T.A. together with potassium bromide or p-benzoquinone and potassium bromide.
  • a process for the production of a hologram which on reconstruction exhibits a multi-colour holographic image comprises exposing the holographic material hereinbefore described which comprises at least one dye of formula I and at least one dye of formula II the silver halide emulsion or emulsions having a gelatin binder to three holographic laser exposures one in the blue region of the visible spectrum, one in the green region of the visible spectrum and one in the red region of the visible spectrum, developing the latent silver image using a silver halide developing agent, removing the developed silver using a rehalogenating bleach bath and before the bleach step, at the same time as the bleach step or after the bleach step treating the holographic material with an aqueous solution of a compound which causes a permanent swelling of the gelatin.
  • this compound has a molecular weight of over 100 and reacts with the gelatin to form covalent bonds therewith to increase the molecular bulk of the gelatin.
  • the strength of the solution of this compound and the length of treatment are just sufficient to counteract the shrinkage of the gelatin due to the photographic processing so that no appreciable shift is observed on reconstruction of the hologram and the blue, green and red parts of the hologram when reconstructed exhibit substantially the same wavelengths as those of the three laser exposures. It requires some experimentation to enable this to be done.
  • the holographic material of the present invention has been described in particular for the production of reflection holograms however, it is also of use for the production of transmission holograms.
  • a gelatino silver iodobromide emulsion having a median crystal size of 0.04 ⁇ m was prepared having a gelatin content of 162g/mole of silver.
  • the emulsion was gold and sulphur sensitised and 0.8g/mole of silver of the green sensitizer A of the formula set forth below was added, followed by 0.4g/mole of silver of the red sensitizer B of the formula set forth below was added.
  • the emulsion was stabilized using a tetrazaindene stabilizer and wetting agents and coating aids added.
  • the emulsion was then coated on 100 ⁇ m polyester base, which had been subbed, at a silver coating weight of 3.0g/m2.
  • a gelatin supercoat of 1.1g/m2 was coated on the dried emulsion layer.
  • a strip of the thus prepared holographic material was exposed in three separate areas to three laser exposures performed by a tuned Krypton laser, the first exposure being at 647.1 nm in the red region of the visible spectrum, the second being at 520.8 nm in the green region of the visible spectrum and the third being at 476.5 nm in the blue region of the visible spectrum.
  • the intensity of exposure in each case was between 300 - 600 ⁇ J/cm2.
  • the object of the holographic exposure was a plane mirror positioned parallel to the holographic material plane.
  • Each exposure was made in the Denisyuk mode.
  • the hologram in the holographic material was reconstructed using white light. This reconstruction showed that in the area of the first laser exposure a red hologram of the mirror was seen in the area of the second laser exposure a green hologram of the mirror was seen and in the area of the third exposure a blue hologram of the mirror was seen.
  • Table 1 shows the exposing and replay wavelengths of these three exposures at maximum reflectivity.
  • Table 1 Exposure Number Exposing nm Replay nm first 647.1 647.9 second 520.8 525.9 third 476.5 478.6
  • This example illustrates the effect of not treating the material with a swelling agent and with using a red sensitizing dye not of formula II or using a green sensitizing dye not of formula I.
  • Example 1 There was used in this example a strip of the holographic material as prepared in Example 1 called emulsion 1.
  • emulsion 2 comprised 0.4 g/mole silver of the red sensitizing dye C as hereinafter formulated and emulsion 3 comprised 0.4 g/mole silver of the red sensitizing dye D as hereinafter formulated instead of red dye B.
  • Both dyes C and D are well known red sensitizing dyes for photographic silver halide emulsions.
  • Emulsion 4 comprised 0.8 g/mole silver of green sensitizing dye E as hereinafter formulated instead of dye A.
  • Dye E is a well known green sensitizing dye for use in photographic silver halide emulsions.
  • Holographic evaluation was carried out by making a Denisyuk exposure of a brushed aluminium plate using a HeNe laser with an emitting wavelength of 633 nm.
  • the holographic materials were developed in the developer used in Example 1 and bleached in the same ferric EDTA rehalogenating bleach.
  • the reflectivity of the holograms and replay wavelengths were determined in a spectro-photometer. Relative reflectivity is expressed as a percentage of the reflectivity of the brushed aluminium target. The results of evaluation are given in the table below.
  • the replay wavelength shows how much the replay has shifted to a shorter wavelength from the exposing wavelenth of 633 nm.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Holo Graphy (AREA)
EP90312219A 1989-11-14 1990-11-08 Farbhologramme Withdrawn EP0428332A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB898925677A GB8925677D0 (en) 1989-11-14 1989-11-14 Colour holograms
GB8925677 1989-11-14

Publications (1)

Publication Number Publication Date
EP0428332A1 true EP0428332A1 (de) 1991-05-22

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Application Number Title Priority Date Filing Date
EP90312219A Withdrawn EP0428332A1 (de) 1989-11-14 1990-11-08 Farbhologramme

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EP (1) EP0428332A1 (de)
JP (1) JPH03203765A (de)
GB (1) GB8925677D0 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004051366A2 (de) * 2002-11-05 2004-06-17 Technische Fachhochschule Berlin Verfahren zur herstellung von holografischen aufzeichnungsmaterialien und holografische aufzeichnungsmaterialien
EP1624337A3 (de) * 2004-08-02 2006-04-19 Fuji Photo Film Co., Ltd. Holographisches empfindliches Silberhalogenidmaterial und System zur holographischen Bildaufnahme mit Hilfe desselben

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4500710B2 (ja) * 2004-08-02 2010-07-14 富士フイルム株式会社 ハロゲン化銀ホログラフィ−感光材料

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1317139A (en) * 1969-05-17 1973-05-16 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsions
GB2057153A (en) * 1979-08-08 1981-03-25 Fuji Photo Film Co Ltd Silver halide photographic materials
GB2162855A (en) * 1984-08-09 1986-02-12 Ciba Geigy Ag New optical sensitising dyes for holographic material
EP0225852A2 (de) * 1985-12-11 1987-06-16 ILFORD Limited Behandlung von Hologrammen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1317139A (en) * 1969-05-17 1973-05-16 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsions
GB2057153A (en) * 1979-08-08 1981-03-25 Fuji Photo Film Co Ltd Silver halide photographic materials
GB2162855A (en) * 1984-08-09 1986-02-12 Ciba Geigy Ag New optical sensitising dyes for holographic material
EP0225852A2 (de) * 1985-12-11 1987-06-16 ILFORD Limited Behandlung von Hologrammen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
P.Hariharan: "Optical Holography" 27 April 1984, Cambridge University Press, Cambridge,GB *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004051366A2 (de) * 2002-11-05 2004-06-17 Technische Fachhochschule Berlin Verfahren zur herstellung von holografischen aufzeichnungsmaterialien und holografische aufzeichnungsmaterialien
WO2004051366A3 (de) * 2002-11-05 2004-07-29 Tech Fachhochschule Berlin Verfahren zur herstellung von holografischen aufzeichnungsmaterialien und holografische aufzeichnungsmaterialien
EP1624337A3 (de) * 2004-08-02 2006-04-19 Fuji Photo Film Co., Ltd. Holographisches empfindliches Silberhalogenidmaterial und System zur holographischen Bildaufnahme mit Hilfe desselben
US7241564B2 (en) 2004-08-02 2007-07-10 Fujifilm Corporation Silver halide holographic sensitive material and system for taking holographic images by using the same

Also Published As

Publication number Publication date
JPH03203765A (ja) 1991-09-05
GB8925677D0 (en) 1990-01-04

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