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Title:
SILVER HALIDE MATERIAL FOR OPTICAL MEMORY DEVICES WITH LUMINESCENT READING AND METHODS FOR THE TREATMENT THEREOF
Document Type and Number:
WIPO Patent Application WO/1998/037456
Kind Code:
A1
Abstract:
This invention concerns a luminescent optical memory material and method of forming this material, including the encoding of information by a photographic process. The method involves the use of silver halide crystals of a defined size range, with the optional use of sensitizers, emulsion stabilizers, and other agents followed by the absorption of luminescent dyes on the developed silver particles to form a luminescent optical memory system. The method involves synthesis of a photographic emulsion with silver halide crystals of a defined size range, applying photographic emulsion to a substrate, exposing to light photochemical treatment and a process of transformation of the silver particles formed in the places exposed by light into luminescent particles. The method involves obtaining a multi-layer luminescent material for three-dimensional optical memory devices.

Inventors:
LEVICH EUGENE B (US)
MALKIN JACOB N (US)
ALPEROVICH MARK A (IL)
SHAPIRO BORIS M (RU)
Application Number:
PCT/US1998/003540
Publication Date:
August 27, 1998
Filing Date:
February 24, 1998
Export Citation:
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Assignee:
TRID STORE INC (US)
LEVICH EUGENE B (US)
MALKIN JACOB N (US)
ALPEROVICH MARK A (IL)
SHAPIRO BORIS M (RU)
International Classes:
G03C1/005; G03C9/00; G11B7/244; G11B7/245; G11B7/251; G03C1/015; G03C1/09; G03C1/12; (IPC1-7): G03C1/005; G03C5/29
Foreign References:
US4876183A1989-10-24
Attorney, Agent or Firm:
Cohen, Herbert (Cohen Leitner & Myers, P.C., Suite 1000, 900 - 17th Stree, Washington DC, US)
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Claims:
IN THE CLAIMS:
1. A luminescent material for an optical memory device comprising insoluble microparticles dispersed in a water soluble polymer, said microparticles having a particle size less than about 0.2 microns, said microparticle having a sorbed luminescent dye wherein said water soluble polymer and dispersed microparticles are applied to a substrate.
2. The microparticle material of claim 1, wherein the insoluble microparticles comprise silver grains and insoluble metal salts.
3. The microparticles material of claims 1 and 2 wherein the water soluble polymer is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, gelatine, gelatine modified with polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl sulphate, carboxymethylcellulose, cellulose acetophthalate, phthaloylgelatine or graft polymers of gelatine with polymethoxydiethyleneglycol acrylate or with polydiacetoneacrylamide or with polyN, N'methylenediacrylamide, and mixtures thereof.
4. A method for making a luminescent material for an optical memory devices comprising the steps of : applying a photographic emulsion comprising microcrystals of silver halide salts and a water soluble polymer to a substrate to form a photoplate; exposing said photoplate to light; developing said photoplate with fixation of the exposed silver halide to form particles; treating the photoplate with a luminescing dye and allowing the luminescing dye to be sorbed onto the particles.
5. The method of claim 4, wherein the silver halide is selected from AgCl, AgBr, AgI, AgCl (Br), AgCl (Br, I) and AgBr (I).
6. The method of claims 4 and 5, wherein the microcrystals of silver halide are less than about 0.2 microns.
7. The method of claim 6, wherein the microcrystals are about 0.02 to 0.08 microns.
8. The method of claims 47, wherein the water soluble polymer is selected from the group consisting of polyvinyl alcohol polyvinyl pyrrolidone, gelatine, gelatine modified with polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl sulphate, carboxymethylcellulose, cellulose acetophthalate, phthaloylgelatine or graft polymers of gelatine with polymethoxydiethyleneglycol acrylate or with polydiacetoneacrylamide or with polyN, N' methylenediacrylamide, and mixtures thereof.
9. The method of claims 48, additionally comprising the step of chemically sensitizing the photoplate with a photoreducer before exposure to light.
10. The method of claim 9, wherein the photo reducer is selected from gold, sulphur and mixtures thereof.
11. The method of claims 410, additionally comprising the step of adding a spectral sensitizer to the photoplate before exposure to light, said spectral sensitizer being selected from the group of sensitizers where in the case of the benzothiazole derivatives (X, Y=S); benzoxazole derivative (X, Y=O) ; benzimidazole derivative (X, Y=NR); quinoline derivative (X, Y=CH=CH); indolenine derivative (X, Y=C (R2)) and so on; for the nonsymmetrical dyes X does not equal Y (X*Y). for example, X=O, and Y=S and are independently selected; wherein, for each derivative R, and R3 are independently selected from H, CH3,OCH3,SCH3,N (CH3),N (Et) 2, N (propyl) 2,N (isopropyl) 2,N (butyl) 2,N (isobutyl) 2,N (secbutyl) 2,NCO (CH2) kH wherein k is 1 to 5, F, Cl, Br, I,CN,CO2H,CO2 (CH2) jCH3 where j is 0 to 4,CONH2, CF3, SOCF3, SO2CF3,C6H5, and benzyl; n is 0,1 or 2 and m is 0 or 1 ; when n is 0 and m is 1 then R6 is independently selected from H, CH3, C2H5, C6H5,NH2,NHCOCH3, OCH3, CO2CH3 ; when n is 1 and m is 1 then R4 and R6 are H and R5 H, CH3, CH ;, NHCOCH3, when R4 and R6 are linked together and R4 and R6 are (CH2) 2, (CH2) 3, or CH2C (CH3) 2CH2then R5 is H, Cl, and C6H5 ; when n is 2 and m is 1 then R4, R5 and R6 are H or R4 and R6 are H and R5 and R5 is linked together and R5 is (CH2) 3,CH2C (CH3) 2CH, and when R and R, are independently selected from alkyl then Zis an anion and when R and R, are independently selected from(CH2) 3SO3then Z+ is a cation; merocyanines and merocyaninocyanines and others can be used and mixtures thereof.
12. The method of claims 411, additionally comprising the step of oxidizing the surface of the silver particles in the photoplate.
13. The method of claim 12, additionally comprising the step of adding a solution of at least one multivalent ion to the photoplate after the surface of the silver particles is oxidized.
14. The method of claim 13, wherein the multivalent ions are selected from the group consisting of Ba+2, Co+2, Zn+2, Cd+2 and mixtures thereof.
15. The method of claims 414, additionally comprising the step of treating the oxidized silver particle with metal salts to form insoluble metal complexes.
16. The method of claim 15, wherein the metal salts are selected from the group consisting of Zn2+, Cd2+, Sr2, Ni2, Co2, Fe3, Cr3, In3, Bi3, La3, Gd3, V4, Ce4, Th, and mixtures thereof.
17. The method of claim 15, wherein the insoluble metal complexes have a solubility constant less than about 108 mole/liter at 25 °C.
18. The method of claim 17, wherein the solubility constant is less than 10'° mole/liter at 25°C.
19. A luminescent optical memory material made by the process of claims 418.
20. The method of claims 418, wherein the photographic emulsion is applied to the base so that there are layers of photographic emulsion separated by layers of a water soluble polymer.
21. The luminescent optical memory material of claim 19, wherein the photographic emulsion is applied to the base so that there are layers of photographic emulsion separated by layers of a water soluble polymer.
22. The material or methods of claims 121 wherein the luminescent dye is selected from the xanthene dyes of the eoscin type including eosins, fluoresceins, erythrosins, and dichlorofluorescein of general structure I : wherein R is independently selected from H, Cl, Br, I, NO2, alkyl and others; R, is H, Na, K, and alkyl ; R2 is independently selected from H, Cl. NH2, Br, I, isocyanate, isothiocyanate, alkyl and others; and R3 is independently selected from H, Cl, Br, I, NO2, NH2, alkyl and others; (2) The xanthene dyes of the rhodamine type including the rhodamines B, 3B, C, G, 6G, 101,123 and others having the general structure II : wherein R is H, CH3, C2H,, CH2COOH, C2H4OH and others; R, is H, Na, K, CH3, C2H5, Ar, Alkyl and others; R2 is independently selected from H, Cl, Br, I, NO2, alkyl and others, R3 is independently selected from H, Cl, Br, I, NO2, isothiocyanate, isocyanate, amines and others and X is an anion selected from Cl, Bi, I, C104and others; (3) The acridine dyes, including aurazine, trypaflovine, ethoxydiaminoacridine lactate and others of general structure III: wherein R is H, CH3, C2H5, and others; R, is H, C6H5, CO2H and others; R2 is H, CH, CH2OH, alkyl and others; R3 is independently selected from H, CH3, alkyl and others; and X is a anion ofF, Cl, Br, I, HCOO, CH3CHOHCOO, C104and others; (4) The oxazine dyes, including the oxazines 1,4,9,17,118, nile blue, capry blue A and others having the general structure IVa and IVb : where R is selected from H, CH3, and others; R, is independently selected from H, CH3, CH3CH2 alkyl and others and X is an anion selected from F, Cl, Br, I, C104, sulfates, phosphates and others; (5) The azine dyes, including magdala red, lactoflavine. of general structure V: wherein R is phenyl, naphthyl; R, is H, alkyl, C6H5, and others; R2 is H, alkyl, benzyl, O benzyl; R3 is H, S03H and others; and X is an anion; (6) The indigo dyes, in the form of indigozoles, of general structure VI: wherein, Y is NH, S and R is independently selected from H, Cl, Br, 0alkyl, NO2, sulfate, alkyl and others; (7) The polycyclic vat dyes, including aminoanthropyrimidines, anthropyridones, oxaand tiadiazoloaminoantroquinones, dyes from the group of benzanthrones in the form of sulfuric esters of leuco compounds of general structure VIIXI: where R is H, NHC6Hs, R, is H, NHCOAr, where R is H, alkyl, or aromatic, where R is H, C6H11, C2H5, C2H4OH: where R is H, Ar, SO2Ar and others, where R is independently selected from H, Cl, Br, OH, the structure: and others; (8) The dyes which are forming both the luminescent and nonluminescent complexes with polyvalent metal ions, selected from the hydroxyantraquinone derivatives: calcein, calcein blue, xanthocomplexan, methylcalcein, methylcalcein blue as shown in general structures XIIXVII: Where R is CH3, CH2COOH (9) The cyanine dyes of general structure XVIII: wherein n is 1,2,3; R is H, SO3H and others; R1 is alkyl, (CH2) mSO3H and others m is 3,4 or 5 and X is a anion.
Description:
INTERNATIONAL SEARCH REPORT International application No. PCT/US98/03540 Box I Observations where certain claims were found unsearchable (Continuation of item 1 of first sheet) This international report has not been established in respect of certain claims under Article 17 (2) (a) for the following reasons: 1. ! Claims Nos. : because they relate to subject matter not required to be searched by this Authority, namely: 2. 1 Claims Nos. : because they relate to parts of the international application that do not comply with the prescribed requirements to such an extent that no meaningful international search can be carried out, specifically: 3.51 Claims Nos.: 8-22 because they are dependent claims and are not drafted in accordance with the second and third sentences of Rule 6.4 (a). Box 11 Observations where unity of invention is lacking (Continuation of item 2 of first sheet) This International Searching Authority found multiple inventions in this international application, as follows : 1. ! t As all required additional search fees were timely paid by the applicant, this international search report covers all searchable u claims. 2. jt As all searchable claims could be searched without effort justifying an additional fee, this Authority did not invite payment of any additional fee. 3. As only some of the required additional search fees were timely paid by the applicant, this international search report covers only those claims for which fees were paid, specifically claims Nos.: 4. j No required additional search fees were timely paid by the applicant. Consequently, this international search report is restricted to the invention first mentioned in the claims ; it is covered by claims Nos.: Remark on Protest ! j The additional search fees were accompanied by the applicant's protest. nô No protest accompanied the payment of additional search fees.



 
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