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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/02—Direct bleach-out processes; Materials therefor; Preparing or processing such materials

Definitions

• This invention relates to radiation-sensitive elements which are capable of recording a positive image upon image-wise exposure to radiation, e.g. visible light, and to their preparation and use.
• the invention relates to radiation-sensitive elements having a bleachable dye and an iodonium salt in reactive association.
• Positive working imaging systems in which an originally coloured species is decolourised in an image-wise manner are known. These systems have the advantage of giving a positive copy of an original.
• One of the earliest forms of positive working imaging systems was developed utilising the properties of photographic silver, e.g. as disclosed in British Patent Specification No. 17773 (1889), Austrian Patent Specification No. OE42478 and B. Gaspar, Zeitschrift Wiss. Phot. 34, 119 (1935). Since then many forms of colour silver halide photography have been developed.
• United States Patent Specification No. 3 595 655 discloses a silverless dye bleach system consisting essentially of a polymethine dye and an activator which is a carbonyl, azo, diazo, organic-sulphur containing or peroxide compound.
• a radiation-sensitive element capable of recording an image upon image-wise exposure to radiation of selected wavelength, the element comprising, as the image-forming components, an effective amount of a bleachable dye in reactive association with an iodonium ion.
• the elements of the invention are capable of recording a positive image simply upon exposure to radiation of selected wavelength; the radiation absorbed by the dye which is in reactive association with an iodonium ion causes the dye to bleach.
• the dyes are believed to sensitise spectrally the reduction of the iodonium ion through the radiation absorbed by the dyes associated with the iodonium ion. Thereafter the element may be stabilised to fix the image by destruction of the iodonium ion or by separation of the dye relative to the iodonium ion.
• the dyes used in the invention may be of any colour and any chemical class which is capable of bleaching upon exposure to radiation of selected wavelength in the presence of an iodonium ion.
• an element of the invention may be prepared which is sensitive to radiation of a selected wavelength band within the general range 300 to 1000 nm, the particular wavelength and the width of the band depending upon the absorption characteristics of the dye.
• a dye has more than one absorption peak it is the wavelength corresponding to the longest wavelength peak at which one would choose to irradiate the element.
• Elements intended for the production of images from radiation in the visible region will contain dyes which will bleach from a coloured to a substantially colourless or very pale state.
• such bleachable dyes will undergo a change such that the transmission optical density at the ⁇ max will drop from 1.0 or more to less than 0.09, preferably less than 0.05.
• the dyes will generally be coated on the support to provide an optical density of about 3.0 or more.
• the dyes will not normally be coloured to the eye and there may be no I visible change upon exposure to ultraviolet radiation and bleaching.
• the image-wise exposed elements may be used as masks for further ultraviolet exposure after fixing.
• Infrared sensitive elements of the invention contain dyes have an absorption peak in the wavelength range 700 to 1100 nm. These dyes may also have absorption peaks in the visible region before and/or after bleaching. Thus, as well as providing a means for obtaining masks for subsequent infrared exposure in a similar manner to the ultraviolet masks, infrared sensitive elements of the invention may record a visible image upon image-wise exposure to infrared radiation.
• Certain of the elements of the invention e.g. those containing oxonol or cyanine dyes, will bleach upon heating and may be used as heat bleachable antihalation layers or to record thermal images.
• the heat bleaching effect of dye/iodonium ion combination may also be utilised as a method of fixing a visual image obtained with a different dye by reacting the excess iodonium ion upon heating.
• the dyes used in the invention may be anionic, cationic or neutral.
• Preferred dyes are anionic since they give very good photosensitisation which is believed to be due to an intimate reactive association between the negatively charged dye and the positively charged iodonium ion.
• anionic dyes may readily be mordanted to cationic polymer binders and it is relatively simple to remove surplus iodonium iona in an aqueous bath in a fixing step if the mordanting polymer is cationic.
• neutral dyes also give good results and are preferred over cationic dyes for overall photosensitivity.
• Cationic dyes are least preferred since it is more difficult to achieve intimate reactive association between the positively charged dye and iodonium ion, and selective removal of iodonium ion after imaging is more difficult.
• the bleachable dyes may be generically referred to as polymethine dyes which term charactsrtses dyes having at least one electron donor and one electron acceptor group linked by methine groups or aza analogues.
• the dyes have an oxidation potential between 0 and +1 volt, preferably between +0.2 and +0.6 volt.
• the bleachable dyes may be selected from a wide range of known classes of dyes including allopolar cyanine dye bases, complex cyanine, hemicyanine, merocyanine, azine, oxonol, streptocyanine and styryl.
• dyes which include within their structure one of the following systems: It will be appreciated that the two structures a) and b) for each system differ only in the way the electrons are disposed, not in the location of atoms. One or more carbon atoms in the chains may be replaced by nitrogen providing the conjugated structure is not disrupted. In actual dye examples the valencies shown unsatisfied in the skeletal formulae are completed as will be described and illustrated hereinafter.
• bleachable dyes for use in the invention will be of the general formula: in which:
• the conjugated chain is preferably composed of carbon atoms but may include one or more nitrogen atoms providing the conjugation is not disrupted.
• the free valencies on the chain may be satisfied by hydrogen or any substituent of the type used in the cyanine dye art including fused ring systems.
• substituents R 1 to R effects the light absorbance properties of the dye which may be varied to provide absorption peaks ranging from the ultraviolet (300 to 400 nm), near visible (400 to 500 nm), far visible (500 to 700 nm) and infrared (700 to 1100 nm).
• the absorption characteristics of the dyes do not significantly effect-the sensitivity of the composition of the invention, which is governed by the particular selection of mesoionic compound.
• Oxonol dyes are similarly well known in the silver halide photographic art and are disclosed in the above mentioned reference, The Theory of the Photographic Process and, for example, United States Patent Specification No. 2 611 696.
• cyanine, merocyanine and oxonol dyes may bear substituents along the polymethine chain composed of C, N, O and S, and that-_these substituents may themselves join to form 5, 6 or 7 membered rings, or may bond with rings A and B to form further rings, possibly with aromatic character. Rings A and B may also be substituted by C, N, H, O and S containing groups.
• dyes useful in the invention which possess an activated methylene chain include bisquinones, bisnaphthoquinones, hemicyanine, streptocyanine, anthraquinone, indamine, indoaniline and indophenol.
• Preferred dyes for use in the invention are merocyanine and oxonol dyes.
• Examples of oxonol dyes include:
• the cation of the oxonol dye need not be the iodonium ion and can be any cation including Li ⁇ , Na and K ⁇ or quaternary ammonium cations, e.g. as represented by the formula: in which R 6 to R 9 may be selected from a wide range of groups including hydrogen, alkyl, preferably of 1 to 4 carbon atoms, aryl, e.g. phenyl, aralkyl of up to 12 carbon atoms. Preferably at least one of R 6 to R 9 is hydrogen and the rest are alkyl or aralkyl since such amines are readily available and allow easy synthesis of the dyes.
• any cationic polyelectrolyte may be used, e.g. those of the formula: in which:
• R 10 and R 11 groups may be desirable to have a selection of R 10 and R 11 groups in the polymer.
• the dye/iodonium system has its greatest sensitivity at the ⁇ max of the longest wavelength absorbance peak. Generally it is necessary to irradiate the system with radiation of wavelength in the vicinity of this ⁇ max for bleaching to occur.
• a combination of coloured dyes may be used, e.g. yellow, magenta and cyan, in the same or different layers in an element and these can be selectively bleached by appropriate visible radiation to form a full colour image.
• Monochromatic or polychromatic images may be produced using the photosensitive materials of this invention with relatively short exposure times in daylight or sunlight or even artificial sources of light (e.g. fluorescent lamps or laser beams).
• the exposure time for adequate results, for example when using a 0.5 kW tungsten lamp at a distance of 0.7 m, may be between 1 second to 10 minutes.
• the iodonium salts used in the invention are compounds consisting of a cation wherein a positively charged iodine atom bears two covalently bonded carbon atoms, and any anion.
• the acid from which the anion is derived has a pKa (5.
• the preferred compounds are diaryl, aryl/heteroaryl or diheteroaryl iodonium salts in which the carbon-to-iodine bonds are from aryl or heteroaryl groups.
• Aliphatic iodonium salts are not normally thermally stable at temperatures above 0°C. However, stabilised alkyl phenyl iodonium salts such as those disclosed in Chem. Lett. 1982, 65-6 are stable at ambient temperatures and may be used in the invention.
• Suitable iodonium salts may be represented by the formula: in which:
• These groups include substituted and unsubstituted aromatic hydrocarbon rings, e.g. phenyl or naphthyl, which may be substituted with alkyl groups, e.g. methyl, alkoxy groups, e.g. methoxy, chlorine, bromine, iodine, fluorine, carboxy, cyano or nitro groups or any combination thereof.
• alkyl groups e.g. methyl
• alkoxy groups e.g. methoxy, chlorine, bromine, iodine, fluorine, carboxy, cyano or nitro groups or any combination thereof.
• hetero-aromatic groups include thienyl, furanyl and pyrazolyl which may be substituted with similar substituents as described above.
• Condensed aromatic/hetero-aromatic groups, e.g. 3-indolinyl may also be present.
• A represents an anion which may be incorporated into Ar or Ar .
• Ar 1 and A r 2 do not have more than two substituents at the ⁇ positions of the aryl groups. Most preferably Ar 1 and A r 2 are both phenyl groups containing no ⁇ substituents.
• the ⁇ positions of the aryl groups may be linked together to include the iodine atom within a ring structure, e.g. in which Z is an oxygen or sulphur atom.
• Z is an oxygen or sulphur atom.
• Suitable iodonium salts include polymers containing the unit: in which Ph represents phenyl.
• Suitable inorganic anions include halide anions, HSO 4 ⁇ , and halogen-containing complex anions, e.g. tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate and hexafluoroantimonate.
• Suitable organic anions include those of the formulae: RCOO ⁇ or RSO 3 ⁇ in which R is an alkyl or aryl group of up to 20 carbon atoms, e.g. a phenyl group, either of which may be substituted. Examples of such anions include CH 3 COO ⁇ and CF 3 COO ⁇ .
• A may be present in Ar or A r 2 , e.g. in which A ⁇ represents COO ⁇ , etc.
• a ⁇ may be present in a molecule containing two or more anions, e.g. dicarboxylates containing more than 4 carbon atoms.
• the most significant contribution of the anion is its effect upon the solubility of the iodonium salt in different solvents or binders. This criterion is also important for systems fixed by removal of the unreacted iodonium ion in an aqueous processing step where good solubility of the iodonium salt in water is essential.
• iodonium salts are known, they may be readily prepared and some are commercially available.
• the synthesis of suitable iodonium salts is disclosed in F .M. Beringer et al, Journal of the American Chemical Society, 80, 4279 (1958). Previously, these salts have been used in cationically induced epoxy polymerization or radically induced monomer polymerization as disclosed, for example, in United States Patent Specification Nos. 3 741 769, 3 729 313, 3 808 006, 4 026 705, 4 228 232 and 4 250 053.
• Such polymerization systems may form the basis of imaging systems of the type utilizing a coloured toner which will selectively adhere only to the tacky unexposed areas which have not undergone polymerization.
• iodonium salts disclosed in the above referenced Patents have been sensitised with a wide range of dyes to increase speed and/or broaden spectral response and have been used as components in image forming systems in the absence of polymerizable monomers.
• a dye-bleach system suitable for image recording employing a bleachable dye and iodonium salt as the image recording medium.
• the bleachable dye and iodonium salt are in reactive association on the support. Reactive association is defined as such physical proximity between the compounds as to enable a chemical reaction to take place between them upon exposure to light.
• the dye and iodonium salt are in the same layer or in adjacent layers on the support.
• the weight ratio of bleachable dye to iodonium salt in the element of the invention is in the range from 1:1 to 1:50, preferably in the range from 1:2 to 1:10.
• the bleachable dye and iodonium salt may be applied to the support in a binder.
• Suitable binders are transparent or translucent, are generally colourless and include natural polymers, e.g. gelatin, gum arabic, synthetic resins, polymers and copolymers, e.g. polyvinyl acetals, cellulose esters, polyamides, polyacrylates, polymethacrylates, polyurethanes, polyepoxides, polycarbonates, polyvinylacetate, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinylidene chloride, poly(4-vinyl- N -alkylpyridinium salt), and other film forming media.
• the binders may range from thermoplastic to highly crosslinked, and may be coated from aqueous or organic solvents or emulsion.
• the binder may form part of the dye molecule as described above with reference to oxonol dyes.
• the binder comprises from 50 to 98% by weight based on the total dry weight of binder, dye and iodonium salt.
• Suitable supports for use in the invention are any stable substrate, including transparent film, e.g. polyester, paper e.g. baryta-coated photographic paper, and metallised film. Opaque vesicular polyester films are also useful.
• a binder e.g. a synthetic polymer, together with the dye and iodonium salts may be cast to form a self-supporting film.
• the fixing of the radiation sensitive elements of the invention may be effected by destruction of the iodonium ion by disrupting at least one of the carbon-to-iodine bonds since the resulting monoaryl iodine compound is no longer sensitive to the dye.
• the conversion of the iodonium salt to its non-radiation sensitive form can be effected in a variety of fashions. Introduction of ammonia and amines in reactive association with the iodonium ion, or a reaction caused on heating, or U V irradiation of a nucleophilic anion such as I ⁇ , Br a , Cl ⁇ , BAr 4 ⁇ (tetra-arylboronide), ArO ⁇ (e.g. phenoxide), or 4-NO 2 C 6 H 4 CO 2 ⁇ , with the iodonium iori, will effect the conversion.
• An alternative method of achieving post imaging stabilisation or fixing is to remove the iodonium ion from reactive association with the dye by washing with an appropriate solvent.
• an appropriate solvent for example, in the case of elements using mordanted oxonols and water soluble iodonium salts formulated in gelatin, after imaging, the iodonium salt is simply removed by an aqueous wash, which leaves the immobilised dye in the binder. The dye stability to light is then equivalent to that of the dye alone.
• An element in which the dye and iodonium salt is formulated in polyvinylpyridine may be treated with aliphatic ketones to remove the iodonium salt and leave the dye in the binder.
• the elements of the invention have excellent ageing properties. Tests over a period of several months have shown that there is a minimal variation of maximum density, D max , and photosensitivity when elements are stored in the dark in a refrigerator (3 to 5°C) and under ambient conditions (18 to 20°C, relative humidity 50 to 70%).
• a variety of conventional additives such as surfactants, antioxidants, stabilisers, plasticisers, ultraviolet absorbers, coating aids, may be used to prepare the elements of the invention to achieve benefit of their known properties.
• the elements of the invention may be used for )transparencies for overhead visuals, making enlarged copies of colour slides and related graphics applications, such as pre-press colour proof materials.
• the thermally bleachable elements of the invention can be used to give transparency copies from a black on white original, e.g. printed or typed-matter and more particularly a photocopy.
• a black on white original e.g. printed or typed-matter and more particularly a photocopy.
• the elements when placed film face down on a photocopy and passed through a 3M Thermofax machine set at the lightest control, are bleached in the areas corresponding to the black areas of the photocopy.
• a negative (clear on colour) of the black on white original is obtained which after fixing is ready for overhead projection.
• this method could be used to assemble colour overlaps rapidly and conveniently.
• a water wash fixing step may be used to stabilise the element.
• the oxidation potentials referred to in the Examples were measured with an Ag/AgCl/saturated KCl reference electrode.
• magenta oxonol dye was coated as a solution in 10 ml of 10% by weight Butvar (B76) in butan-2-one (Butvar is a registered trade mark of Monsanto Company for polyvinylbutyral polymers).
• Butvar is a registered trade mark of Monsanto Company for polyvinylbutyral polymers.
• the dye solution was prepared in yellow light and the iodonium compounds tested were added in their respective proportions in red light.
• the photosensitive solution was then coated in red light at 100 m wet thickness on a polyester base (75 ⁇ m). The sheets were air dried at 20°C for 1 hour.
• a plot of transmission optical density versus time was made and the exposure time (t) for the optical density to fall from D max to (D max -1) was determined.
• This Example illustates the use of ammonia to stabilise the elements of the invention.
• the ammonia reacts with the light-sensitive iodonium salt and thus decreases the photosensitivity of the film.
• Blue dye (3) 0.04 g in ethanol (4 ml) was added to a photographic grade gelatin (1 g) solution in water (6 ml) at 55°C containing aqueous Tergitol TMN10 (Union Carbide Company) non-ionic surfactant (10%, 0.3 ml), poly(4-vinyl-l-methylpyridinium methylsulphate) as in Example 17 (0.2 g) and 0.5 ml acetic acid.
• aqueous Tergitol TMN10 Union Carbide Company
• the coated sheet was dried in air at 20°C for 2 hours.
• the film was exposed through a black and white transparency on an overhead projector (0.5 kW quartz iodine lamp) using an exposure of 60 seconds.
• a blue copy of the original resulted.
• the imaged film was fixed by washing in water at 18°C for 3 to 5 minutes. After drying in air upon subsequent exposure to laboratory light no further bleaching was noticeable.
• the comparative grey scale and resolution of the copy were excellent.
• the dyes in the quantities reported in Table 5 in 4 ml of ethanol were added to a solution of gelatin (1 g) and poly(4-vinyl-l-methylpyridiniummethyl- sulphate) as in Example 17 (0.2 g) in 6 ml of water at 55 0 C.
• 0.5 g of phenyl(4-methoxyphenyl)iodonium trifluoroacetate was added in red light to the solutions of yellow and magenta dyes and the same addition was made to the cyan solution in green light.
• Imaging the samples with the appropriate colour separation positive transparency was achieved by contacting the transparency with coated sheet (coated side up) on a vacuum frame and exposing at 0.5 m to an unfocussed 1 kW tungsten halide source. After imaging, the film was washed with agitation in a water bath at 15°C for 5 minutes. Drying in air and arranging the three samples, yellow/magenta/cyan, one on top of the other gave a colour proof with a very good grey scale (tonal reproduction) and resolution.
• a full-colour single sheet film element imageable by a tungsten visible source was constructed by coating one side of a 100 ⁇ m (subbed on both sides) polyester film with a 7Spm wet thickness cyan layer and on the other side of the film with a mixed magenta and yellow layer of the same wet thickness.
• the coating compositions comprised phenyl(2-thienyl)-iodonium trifluoroacetate and as the film-forming binder a mixture of gelatin and poly(4-vinyl-l-methyl- pyridinium methylsulphate) as in Example 17 (1:0.2 by weight).
• the multicolour film element was placed in contact with a full colour transparency with the magenta/yellow coating next to the transparency and the composite exposed through the transparency in a slide projector having a 240 watt source bulb for 45 to 50 seconds. A full colour reproduction of the original was obtained. The copy was rendered stable to light by a wash in water for 3 to 5 minutes.
• the yellow dye reported in Table 6 is a novel compound.
• Example 18 A solution of the yellow dye in Example 18 (0.02 g) in ethanol (4 ml) was added to a solution of 1 g gelatin and 0.3 g poly(4-vinyl-l-methylpyridinium methylsulphate) as in Example 17 in 10 ml water and 0.5 ml acetic acid at 40°C. 0.3 ml Tergitol-4 (10% aqueous solution) was added to this yellow lacquer. 0.9 g of 4-methoxyphenyl-phenyl-iodonium trifluoroacetate in 1 ml dimethyl-formamide was added in red light.
• I.R. dyes in combination with iodonium salts may be used to form I.R. sensitive elements useful, for example, as I .R. masks, I . R . bleachable antihalation layers, and optical data storage.
• elements comprising suitable UV absorbing dyes and iodonium salts may be used to form UV masks, UV-bleachable antihalation layers, etc.
• Such an element or mixture may be used for heat-bleachable antihalation layers, UV masks, etc., or for a method of fixing a visible image by heat destruction of the excess iodonium ion.
• Oxonol dyes have a peak half-width of 45 nm: thus to achieve neutral densities of 2.0, high dye densities are required.
• This Example illustrates a typical five-dye, single layer element, in which the five dyes are matched in sensitivity to the requirements of the exposure source.
• Table 9 records the ⁇ max of each of the five dyes in the composite coating, measured by a transmission spectrometer.
• the transmission optical density of each dye at or close to its ⁇ max is recorded in Table 9 as D max .
• the energy, E required to reduce the optical density of each dye at its ⁇ max by 1 optical density unit on irradiation with light of a wavelength corresponding to the ⁇ max is also recorded.
• the five dye composite was found to have an optical density of at least 2, balanced to a good neutral, averaged across the spectrum from 430 to 700 nm.
• the film was placed in contact with a 35 mm colour slide in the focussed beam of a tin halide or Xenon source for 30 seconds.
• the resulting copy was fixed by a water wash (5 minutes/20°C) and drying in air. Good separation of yellow, magenta, red and blue were obtained: cyan and green colours were weak.

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• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
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• 1983
  • 1983-02-24 GB GB838305134A patent/GB8305134D0/en active Pending
• 1984
  • 1984-02-23 CA CA000448111A patent/CA1255309A/fr not_active Expired
  • 1984-02-23 DE DE8484301156T patent/DE3474731D1/de not_active Expired
  • 1984-02-23 EP EP19840301156 patent/EP0120601B1/fr not_active Expired
  • 1984-02-24 JP JP3272584A patent/JPS59164549A/ja active Pending

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