EP0012020B1 - Dry silver photo-sensitive compositions, dyes for use therein and preparation of such dyes - Google Patents

Dry silver photo-sensitive compositions, dyes for use therein and preparation of such dyes Download PDF

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Publication number
EP0012020B1
EP0012020B1 EP79302730A EP79302730A EP0012020B1 EP 0012020 B1 EP0012020 B1 EP 0012020B1 EP 79302730 A EP79302730 A EP 79302730A EP 79302730 A EP79302730 A EP 79302730A EP 0012020 B1 EP0012020 B1 EP 0012020B1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
hydrogen
alkyl
group
dye
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.)
Expired
Application number
EP79302730A
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German (de)
English (en)
French (fr)
Other versions
EP0012020A1 (en
Inventor
Bernard Alan Lea
Ronald William Burrows
Jack E. Reece
Harvey A. Brown
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.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
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Filing date
Publication date
Priority claimed from US05/964,479 external-priority patent/US4197131A/en
Priority claimed from US05/964,480 external-priority patent/US4260676A/en
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0012020A1 publication Critical patent/EP0012020A1/en
Application granted granted Critical
Publication of EP0012020B1 publication Critical patent/EP0012020B1/en
Expired 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
    • G03C1/49854—Dyes or precursors of dyes

Definitions

  • This invention relates to compounds suitable for use as acutance dyes in photosensitive compositions, to the preparation of such compounds and to photosensitive compositions containing the compounds.
  • the invention is particularly concerned with photosensitive compositions of the type known as "dry silver" compositions.
  • Dry silver photosensitive compositions comprise an intimate mixture of a light sensitive silver halide and another silver compound such as a silver salt of an organic acid, e.g. silver behenate or silver saccharine, which upon reduction gives a visible change and which is substantially light-insensitive.
  • a mixture is usually prepared in suspension and the resulting dispersion spread as a layer on a suitable substrate.
  • a reducing agent such as hydroquinone or certain substituted phenols.
  • the silver compound can be reduced by heating with the reducing agent, this reduction being catalysed image-wise by the light exposed silver halide.
  • the reduction of the silver compound can be catalysed in the light exposed areas to give a visible darkening while any slight reduction which occurs in the non-light exposed areas is insufficient to give a marked change.
  • the silver halide acts as a catalyst progenitor, only very small amounts of it can suffice, e.g. 0.1 to 10% by weight of the mixture. However, large amounts, e.g. up to 15 or even 20% may be desirable in some circumstances.
  • a dye known as an acutance dye is often incorporated into photosensitive compositions.
  • the acutance dye will absorb at the wavelengths at which the photosensitive composition is sensitive. The longer the path length of the light in the layer of light sensitive composition the greater the attenuation. Therefore, scattered light is attenuated or absorbed to a larger extent than light which impinges directly on a light-sensitive crystal. As a result therefore, although the overall speed of the composition is reduced slightly, scattered light and other light rays which are liable to produce a blurred image are preferentially absorbed and so the overall definition and sharpness of images produced in the layer are increased.
  • An acutance dye for use in a dry silver composition is preferably heat labile, that is to say, it is destroyed by the heat development of the dry silver composition to one or more compounds which are substantially colour-less.
  • French Patent Specification No. 965 555 discloses a range of benzothiazole and benzoxazole cyanine dyes for use in conventional photographic emulsions and Chem. Ber. 101, 2925-30 (1968) discloses several compounds having a methine chain. There is no indication, in either of these references of the use of the compounds in photothermographic systems.
  • a light-sensitive composition comprising an intimate mixture of a substantially light-insensitive silver compound which upon reduction gives a visible change and sufficient of a silver halide to catalyse said reduction to give a visible change in those areas where the silver halide has been exposed to light and when the mixture is heated in the presence of a reducing agent, the composition containing an acutance dye, characterised in that the acutance dye is a compound of the general formula: in which R 1 represents an alkyl group containing 1 to 12 carbon atoms,
  • the substituents R 3 , R 4 and R 5 independently represent a substituent which, as known in the art, can be present in a cyanine dye type heterocyclic nucleus, defined herein as a "cyanine dye compatible substituent", referring to the broadly art accepted knowledge of substituents. A range of such substituents are disclosed for example in United States Patent Specification No. 2 921 067.
  • substituents for R 3 , R 4 and R 5 include hydrogen or halogen, e.g. chlorine, bromine or iodine, an alkyl group containing 1 to 12 carbon atoms, an alkoxy group containing 1 to 4 carbon atoms, an alkenyl group containing 2 to 4 carbon atoms, -(CH 2 ) p COOH where p is 0, 1,2 or 3, ⁇ NO 2 , -NH 2 or -NHCOCH 3 , or any two of R 3 to R 5 together represent the carbon atoms needed to complete a fused on benzene ring.
  • at least one, more preferably at least two, of the substituents R 3 to R 5 represent hydrogen atoms.
  • the most preferred substituents to be represented by each of R 3 to R 5 are hydrogen, chlorine or bromine atoms, or methyl, ethyl, methoxy or ethoxy groups.
  • dry silver compositions containing one of the above described compounds as an acutance dye can give excellent sharp images and that the acutance dye will be rendered considerably lighter in colour or substantially colourless by the heating required to develop the composition. This is surprising in view of the fact that many of these dyes are found not to be decomposed to a colourless state when they are heated on their own to the temperature at which the dry silver compositions are heated for development.
  • a further group of preferred dyes are 1-alkyl-4-nitromethylene-quinolanes in which the alkyl substituent contains 1 to 4 carbon atoms, particularly those dyes of the general formula (II): in which R 11 represents an alkyl group containing 1 to 4 carbon atoms, each R 12 independently represents a hydrogen or halogen atom, an alkyl or alkoxy group containing 1 to 4 carbon atoms, an alkenyl group containing 2 to 4 carbon atoms, ⁇ (CH 2 ) p COOH wherein p is 0, 1, 2 or 3, ⁇ NO 2 , ⁇ NH 2 or NHCOCH 3 , or two groups R 12 together represent the carbon atoms required to complete a fused on benzene ring.
  • R 11 represents an alkyl group containing 1 to 4 carbon atoms
  • each R 12 independently represents a hydrogen or halogen atom, an alkyl or alkoxy group containing 1 to 4 carbon atoms, an alkenyl group containing 2 to 4 carbon
  • R" represents a methyl or ethyl group
  • at least one group R 12 represents a hydrogen atom and each other R 12 independently represents a hydrogen, chlorine or bromine atom, or a methyl, ethyl, methoxy or ethoxy group.
  • a further series of dyes are those of formula (I) in which R 2 represents: in which X, Z and Z' independently represent a hydrogen or halogen atom, NO 2 , CN or perfluoroalkyl of 1 to 4 carbon atoms, with the proviso that at least one of X and Z is N0 2 and R 3 , R 4 and R 5 independently represent a hydrogen or halogen atom, an alkyl or alkoxy of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, ⁇ (CH 2 ) P COOH wherein p is 0, 1, 2 or 3, ⁇ NO 2 , -NH 2 or -NHCOCH 3 , or any two of the adjacent groups are the atoms necessary to form a fused on benzene ring.
  • Preferred dyes within the group have the general formula (III): in which R' 6 represents an alkyl group of 1 to 8 carbon atoms,
  • the acutance dyes can be incorporated into the dry silver compositions of the invention in an amount from 5 x 10- 4 to 0.1 mole of acutance dye per kilogram of total dry solids in the composition. Preferably, however the dyes are incorporated in an amount of from 2 x 10- 3 to 3 x 10- 2 mole of acutance dye per kilogram of dry solids in the composition.
  • the light-sensitive compositions of the invention will normally be spread for use on a support, suitable supports including, for example, paper, polyester or polyamide film bases, and glass.
  • the composition will normally be prepared as a solution or suspension which is spread as a layer on the support and then the solvent or vehicle is evaporated off to leave a dry photo-sensitive layer.
  • a coating aid or binder such as polyvinyl butyral, polymethyl methacrylate, cellulose acetate, polyvinyl acetate, cellulose acetate-propionate and cellulose acetate butyrate, can be incorporated in the light-sensitive mixture.
  • the substantially light-insensitive silver compound is suitably a silver salt of an organic acid.
  • the organic acid can be a C 12 to C 29 aliphatic acid and is preferably a C 16 to C 25 aliphatic acid. Examples include silver behenate, silver caprate, silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidate and ⁇ silver saccharine.
  • the reducing agent for this substantially light-insensitive silver compound can normally be quite mild. Suitable examples include hydroquinone and substituted phenols such as 1-methyl-4-hydroxynaphthalene, methyl gallate, catechol, phenylene diamine, p-amino-phenol and 1-phenyl-3-pyrazolidone.
  • the reducing agent can be incorporated into the light-sensitive composition.
  • the composition can be placed in contact with the reducing agent after exposure to light.
  • a light-sensitive coating can be exposed to a light image, placed in contact with a layer containing the reducing agent and the image then developed by heating.
  • the reducing agent is incorporated in the light-sensitive composition before this is spread on the support.
  • the storage stability of the composition can be improved by incorporating in the composition a small amount of a stabilizer such as an acid stabilizer, e.g. succinic acid, benzoic acid or salicylic acid.
  • the silver halide can be present in amounts of up to 20% by weight of the mixture of silver compounds or can be present in small amounts, e.g. 0.1 to 10% by weight of the mixture of silver compounds. It can be added as such to the substantially light-insensitive compound or formed in situ by adding a soluble halide, e.g. a mercury or sodium halide, to the substantially light-insensitive silver compound.
  • a soluble halide e.g. a mercury or sodium halide
  • the silver halide can, for example, be chloride, bromide or a mixture of them and/or other silver halides.
  • the light-sensitive compositions of the invention can include one or more sensitising dyes to improve their sensitivity to parts of the spectrum other than the shorter wavelengths.
  • dye sensitized dry silver compositions of the present invention can contain an additional acutance dye such as one of those described in our copending British Patent Nr. 1 565 593.
  • the compounds of general formula (I) may be prepared by a process which comprises reacting a compound of the general formula: wherein X 9 represents an anion,
  • Suitable reagents are well known and fully exemplified in the cyanine/merocyanine dye literature.
  • the reaction is preferably carried out in the presence of C 2 H 5 OH as a solvent and (C 2 H 5 ) 3 N as both catalyst and acid binder.
  • the preparation is analogous to known processes used in the synthesis of merocyanine dyes.
  • the acutance dyes of general formula (II) can be prepared by processes which are well known. Thus, they can be prepared in a manner analogous to the synthesis of simple merocyanine dyes as described, for example, in British Patent No. 426 718, by reacting nitromethane with a 1-alkyl-4-alkylthio-quinolinium salt in a solvent in the presence of a basic catalyst.
  • the dyes of general formula (III) may also be made according to the following reaction scheme A:
  • This method is performed in the presence of a strong tertiary amine such as diisopropylethylamine.
  • a strong tertiary amine such as diisopropylethylamine.
  • 1,4-dihydro-4-(2,4-dinitrophenyl)-nitromethylene-1-methylquinoline which may also be named 1,4-dihydro-1-methyl-4-( ⁇ ,2,4-trinitrobenzylidene)-quinoline
  • a dry silver composition was first prepared. Under room light a 1000 g dispersion containing 12.5 parts of silver behenate in 87.5 parts of solvent which in turn comprised 75 parts butan-2-one and 25 parts toluene was charged to a mixing vessel maintained at 15°C. 20 g of polyvinyl butyral resin (commercially available from Monsanto under the trade mark Butvar, B-76) and 10 g of 1-methyl-2-pyrrolidinone were added and the mixture stirred for 30 minutes.
  • polyvinyl butyral resin commercially available from Monsanto under the trade mark Butvar, B-76
  • Knife coatings 100 ⁇ m thick on polyester sheets were prepared from each sample and dried 3.5 to 4.0 minutes at 90°C. These dried coatings were overcoated with a solution containing 97 parts butan-2-one and 3 parts vinyl chloride vinyl acetate copolymer available from Union Carbide under the name VYNS with the knife set 50 fl m above the base and dried as before. The performance of these compositions was then evaluated.
  • the strips were then processed by heating for 20 seconds in a fluorochemical bath and examined for flare of the image.
  • the acutance property of the dyes was classified very good, fair by examining the sharpness of the image with the naked eye.
  • the dyes prepared are those having the values of R 11 and one of the substituents R 12 , the remaining substituents R 12 representing hydrogen atoms, as set out in the following Table 2.
  • each candidate acutance dye was weighed into separate vessels with 3 ml of methylethylketone to dissolve or disperse the dye.
  • 50 g portions of the light-sensitive dispersion formed above were combined with the dye solutions and to portions of methylethylketone alone as a control. All materials were stirred for three minutes. The portions were then allowed to stand at room temperature for 30 minutes, then they were knife coated at 85 pm thickness on polyester and dried for four minutes at 85°C.
  • Each sample was top coated with a 50 pm knife coating of a vinylchloride/vinylacetate copolymer as a 5% by weight solution in methylethylketone.
  • the produced film samples were exposed at the wavelengths indicated below through a 0.25 mm aperture mask overlaid with a continuous density wedge in a vacuum frame. This permitted an easy comparison of image flare at equivalent optical densities after development for 15 seconds at 127°C in an inert fluorocarbon chemical bath. All dye samples had markedly less flare than the control samples, particularly at an optical density of 2.0. Except for the Compound No. 51, no samples left significant visible stain after processing. The dye of Compound No. 51 left a magenta stain which faded within an hour under room light.
  • the dyes used in the tests were as follows:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP79302730A 1978-11-29 1979-11-29 Dry silver photo-sensitive compositions, dyes for use therein and preparation of such dyes Expired EP0012020B1 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB4645978 1978-11-29
US05/964,479 US4197131A (en) 1978-11-29 1978-11-29 Dry silver photo-sensitive compositions
GB7846459 1978-11-29
US05/964,480 US4260676A (en) 1978-11-29 1978-11-29 Photothermographic emulsions containing thermolabile acutance dyes
US964480 1978-11-29
US964479 1978-11-29

Publications (2)

Publication Number Publication Date
EP0012020A1 EP0012020A1 (en) 1980-06-11
EP0012020B1 true EP0012020B1 (en) 1983-01-26

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EP79302730A Expired EP0012020B1 (en) 1978-11-29 1979-11-29 Dry silver photo-sensitive compositions, dyes for use therein and preparation of such dyes

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EP (1) EP0012020B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPH0140335B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE2953375C2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB2058116B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1980001213A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR965555A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1950-09-15
GB849741A (en) * 1956-05-15 1960-09-28 Ilford Ltd Improvements in or relating to hemicyanine dyestuffs
USRE29168E (en) * 1968-10-09 1977-04-05 Eastman Kodak Company Photographic elements with light absorbing layers
US3984248A (en) * 1974-02-19 1976-10-05 Eastman Kodak Company Photographic polymeric film supports containing photobleachable o-nitroarylidene dyes
US4033948A (en) * 1976-05-17 1977-07-05 Minnesota Mining And Manufacturing Company Acutance agents for use in thermally-developable photosensitive compositions
JPS53133033A (en) * 1977-04-25 1978-11-20 Fuji Photo Film Co Ltd Silver halide photographic material

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Publication number Publication date
EP0012020A1 (en) 1980-06-11
JPS55501111A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1980-12-11
GB2058116A (en) 1981-04-08
JPH0140335B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1989-08-28
GB2058116B (en) 1983-05-18
WO1980001213A1 (en) 1980-06-12
DE2953375C2 (de) 1996-09-05
DE2953375T1 (de) 1980-12-04

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