WO1980001213A1 - 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

Info

Publication number
WO1980001213A1
WO1980001213A1 PCT/GB1979/000203 GB7900203W WO8001213A1 WO 1980001213 A1 WO1980001213 A1 WO 1980001213A1 GB 7900203 W GB7900203 W GB 7900203W WO 8001213 A1 WO8001213 A1 WO 8001213A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
alkyl
hydrogen
light
Prior art date
Application number
PCT/GB1979/000203
Other languages
English (en)
French (fr)
Inventor
B Lea
R Burrows
H Brown
J Reece
Original Assignee
Minnesota Mining & Mfg
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
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 & Mfg filed Critical Minnesota Mining & Mfg
Priority to DE2953375T priority Critical patent/DE2953375C2/de
Publication of WO1980001213A1 publication Critical patent/WO1980001213A1/en

Links

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 behanate or silver sjaccharine, 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. It is because the exposure and development of the layer occur without using water, that these materials are often referred to as dry silver light-sensitive materials.
  • a dye known as an acutance dye is often incorporated into photo-sensitive 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 that 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. It is therefore an object of this invention to provide dry silver compositions containing acutance dyes, which absorb light at at least some of those wavelengths to which the composition is sensitive and which are rendered colourless upon heat development of the dry silver composition.
  • 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, characterised in that the composition contains as an acutance dye, a compound of the general formula:
  • R 1 represents an alkyl group containing 1 to 12 carbon atoms
  • R 2 represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, a phenyl group, a substituted phenyl group of molecular weight less than 350, -COO R 1
  • R 1 is as defined above, C 6 H 5 CO- or R 6 NH.CO in which R 6 represents a hydrogen atom or an alkyl, aryl or aralkyl group, R 3 , R 4 and R 5 independently represent a hydrogen atom or a substituent which can be present in a cyanine dye type heterocyclic nucleus, D represents O, S, Se, or in which R 7 represents an alkyl group containing
  • Y represents -CN or -NO 2 , n is l when k is 0 or k is l when n is O, and m is 0, 1 or 2.
  • the substituents R 3 , R 4 and R 5 independently represent a substituent which , as known in the art , canbe present in a cyanine dye type heterocylic 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 alk ⁇ xy 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 actuance 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:
  • R 11 represents an alkyl group containing 1 to 4 carbon atoms
  • each R 12 independently represents a or alkoxy hydrogen or halogen atom, an alkyl/group containing 1 to
  • R 11 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.
  • X, Y 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 Y is NO 2 and R 3 , R 4 and R 5 independently represent a hydrogen or halogen atom, an alkyl or alkoxy of 1 to
  • R 16 represents an alkyl group of 1 to 8 carbon atoms
  • R 17 represents alkyl, alkoxy, halogen, NO 2 or aryl
  • R 18 represents hydrogen, alkyl of 1 to 8 carbon atoms or alkoxy of 1 to 8 carbon atoms.
  • the acutance dyes can be incorpo'rated into the dry silver compositions of the invention in an amount from 5 ⁇ 10 -4 to 0.1 mole of acutance dye per kilogram of total dry solids in the composition.
  • the. dyes are incorporated in an amount of from 2 ⁇ 10 -3 to 3 ⁇ 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 methadrylate, cellulose acetate, polyvinyl acetate, cellulose acetate-propionate and celluloseacetate 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-hydroxy-naphthalene, methyl gallate, catechol, phenylene diamine, p-amino-phenol and 1-phenyl-3-pyrazolidone.
  • the reducing agent can be incorporated into the light-sensitive composition. Alternatively, the composition can be placed in contact with the reducing agent after exposure to light. For example, 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. 011 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.
  • dye sensitized dry silver compositions of the present invention can contain 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 Application No. 1 6677/77.
  • the compounds of general formula (I) may be prepared by a process which comprises reacting a compoundof the general formula:
  • Z 3 is selected from the group consisting of SR 1 , wherein R 1 is as defined above, and
  • 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 analogo ⁇ s 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
  • R 1 represents an alkyl group containing 1 to 12 carbon atoms
  • R 3 , R 4 and R 5 are cyanine dye compatible substituen
  • D represents a member of the group consisting of - O, S, Se, or in which R 7 is selected from an alkyl group containing 1 to 4 carbon atoms or CH 3 COO- , n is 1 when k is 0 or k is 1 when n is 0, m is 0, 1 or 2, when m is 0 or 2:
  • R 2 represents a member selected from the group consisting of an alkyl group, a phenyl group, a substituted phenyl group of molecular weight less than 350, -COOR wherein R 1 is as defined above, C 6 H 5 CO- or R 6 NH.CO- wherein R 6 is a member of the group consisting of a hydrogen atom or an alkyl, aryl or aralkyl group, and when m is 1:
  • R 2 represents R 6 NH . CO wherein R 6 is as defined above.
  • 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.
  • Knife coatings 100 microns thick on polyester sheet 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 microns 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, good, fair by examining the sharpness of the image, with the naked eye.
  • Example 7 A series of dyes of general formula (II) were prepared according to the method described in J.A.C.S. 73, 3328. The dyes prepared are those having the values of
  • Example 8 The following compounds of general formula (III) reported in Table 5 were prepared .in accordance with reaction scheme (A).
  • Example 9 Four hundred grams of a dispersion containing 13 parts by weight of silver behenate in 87 parts of a solvent composed of 67 parts by weight methylethylketone, 26 parts by weight toluene, and 7 parts by weight methylisobutylketone was charged to a temperature-controlled stirred reaction vessel at 15oC. Dark room conditions were maintained during all subsequent work.
  • 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 methylethyl ⁇ ketone 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 microns thickness on polyester and dried for four minutes at 85°C.
  • Each sample was topcoated with a 50 micron 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 vaccum frame. This permitted an easy comparison of image flare at equivalent optical densities after development for 15 seconds at 127oC in ah 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:

Landscapes

  • 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)
PCT/GB1979/000203 1978-11-29 1979-11-29 Dry silver photo-sensitive compositions,dyes for use therein and preparation of such dyes WO1980001213A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE2953375T DE2953375C2 (de) 1978-11-29 1979-11-29 Thermophotographisches Aufzeichnungsmaterial

Applications Claiming Priority (4)

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

Publications (1)

Publication Number Publication Date
WO1980001213A1 true WO1980001213A1 (en) 1980-06-12

Family

ID=27260633

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1979/000203 WO1980001213A1 (en) 1978-11-29 1979-11-29 Dry silver photo-sensitive compositions,dyes for use therein and preparation of such dyes

Country Status (5)

Country Link
EP (1) EP0012020B1 (enrdf_load_stackoverflow)
JP (1) JPH0140335B2 (enrdf_load_stackoverflow)
DE (1) DE2953375C2 (enrdf_load_stackoverflow)
GB (1) GB2058116B (enrdf_load_stackoverflow)
WO (1) WO1980001213A1 (enrdf_load_stackoverflow)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR965555A (enrdf_load_stackoverflow) * 1950-09-15
GB849741A (en) * 1956-05-15 1960-09-28 Ilford Ltd Improvements in or relating to hemicyanine dyestuffs
US3984248A (en) * 1974-02-19 1976-10-05 Eastman Kodak Company Photographic polymeric film supports containing photobleachable o-nitroarylidene dyes
USRE29168E (en) * 1968-10-09 1977-04-05 Eastman Kodak Company Photographic elements with light absorbing layers
US4033948A (en) * 1976-05-17 1977-07-05 Minnesota Mining And Manufacturing Company Acutance agents for use in thermally-developable photosensitive compositions
FR2389159A1 (fr) * 1977-04-25 1978-11-24 Fuji Photo Film Co Ltd Materiau photographique absorbant les ultraviolets

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR965555A (enrdf_load_stackoverflow) * 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
FR2389159A1 (fr) * 1977-04-25 1978-11-24 Fuji Photo Film Co Ltd Materiau photographique absorbant les ultraviolets

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chemische Berichte, Volume 101, issued 1968 (Verlag Chemie, Weinheim Bergstrasse), T. Severin et al., "Darstellung von Nitromerocyaninen", see pages 2925 to 2930 (cited in the application) *

Also Published As

Publication number Publication date
EP0012020B1 (en) 1983-01-26
GB2058116B (en) 1983-05-18
DE2953375C2 (de) 1996-09-05
JPH0140335B2 (enrdf_load_stackoverflow) 1989-08-28
DE2953375T1 (de) 1980-12-04
EP0012020A1 (en) 1980-06-11
JPS55501111A (enrdf_load_stackoverflow) 1980-12-11
GB2058116A (en) 1981-04-08

Similar Documents

Publication Publication Date Title
US4123274A (en) Heat developable imaging materials and process
US4271263A (en) Thermally developable photosensitive compositions containing acutance agents
US4088497A (en) Acutance agents for use in thermally-developable photosensitive compositions
CA1039553A (en) Photothermographic compositions, element and process
US4138265A (en) Antifoggants in certain photographic and photothermographic materials that include silver salts of 3-amino-1,2,4-mercaptotriazole
EP0119831B1 (en) Heat bleachable dye systems
EP0107093B1 (en) Photothermographic recording material comprising a substituted triazine stabilizer precursor compound
US4081278A (en) Heat sensitive dye layers comprising a benzopinacol
US4283487A (en) Thermolabile acutance dyes for dry silver
EP0350202B1 (en) Photothermographic elements
US4197131A (en) Dry silver photo-sensitive compositions
EP0194026B1 (en) Photothermographic stabilizers for syringaldazine leuco dyes
US3753395A (en) Photo-thermographic recording process with 5-pyrazolane
US4153463A (en) Photothermographic emulsions containing magenta acutance dyes
EP0012020B1 (en) Dry silver photo-sensitive compositions, dyes for use therein and preparation of such dyes
US4030930A (en) Heat-developable light-sensitive material
EP0273590B1 (en) Stabilization of ketazine dyes
US4316984A (en) Thermolabile acutance dyes
US4308379A (en) Acutance agents for use in thermally developable photosensitive compositions
US4260676A (en) Photothermographic emulsions containing thermolabile acutance dyes
JPH10502460A (ja) 光熱写真要素用ブロック化ロイコ染料
CA1139149A (en) Dry silver photo-sensitive composition containing a 1-alkyl-4-nitromethylene-quinolane yellow acutance dye
EP0126595B1 (en) Stabilization of latent images in photothermographic elements
JPH0652387B2 (ja) 熱現像性感光材料
CA1133905A (en) Thermolabile acutance dyes

Legal Events

Date Code Title Description
AK Designated states

Designated state(s): DE GB JP

RET De translation (de og part 6b)

Ref country code: DE

Ref document number: 2953375

Date of ref document: 19801204

Format of ref document f/p: P