Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/008—Azides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F3/00—Colour separation; Correction of tonal value
  • G03F3/10—Checking the colour or tonal value of separation negatives or positives
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
  • G03F7/346—Imagewise removal by selective transfer, e.g. peeling away using photosensitive materials other than non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/144—Hydrogen peroxide treatment

Definitions

• ABSTRACT A colored image or pattern formed of one or more colored hydrophilic colloid layers is produced on a permanent support by transferring onto such support in the presence of an aqueous liquid from a temporary support carrying the same, an unhardened colored hydrophilic colloid layer containing a photosensitive iron (Ill) complex which yields iron ([1) ions on exposure to active electromagnetic radiation, exposing the thus-transferred colloid layer while in a substantially dry state to imagewise modulated active electromagnetic radiation, treating the exposed layer with an aqueous liquid comprising hydrogen peroxide or containing dichromate ions so as to effect hardening of the exposed regions of the colloid layer, and removing the nonexposed regions of such layer from the permanent support by washing with an aqueous liquid, these steps being repeated in sequence for each colored colloid layer transferred to the permanent support to constitute the ultimate colored image or pattern.
• Ill photosensitive iron
• the present invention relates to a recording and reproduction process for producing colored colloid patterns corresponding with informationwise modulated electromagnetic radiation.
• the present invention more particularly relates to a process for producing halftone and linework multicolor images and to materials used therefor.
• halftone color images is of interest in the field of design, e.g., in the production of color decorative patterns, color wiring and circuit diagrams, cartography, color proofing and in the production of transparencies for diaor overhead projection.
• Color proofing materials serve to produce a showing proof for submission to the printer and its client to give an idea of a multicolor halftone reproduction as will be produced by the successive printing in register with the separate standard inks: yellow, magenta, cyan, and black.
• the color proof makes it possible to determine whether corrections have to be made to the separation halftone negatives, with the aid of which the printing plates have to be produced.
• Known color proofing systems may be catalogued according to the way, wherein the multicolor proof is built up and can be inspected.
• multicolor print is built up on one permanent support having the desired opacity.
• multicolor halftone images are produced e.g., by means of silver halide light-sensitive materials incorporating color couplers or dyes that can be bleached or transferred imagewise.
• the processing conditions applied are rather critical and, when color couplers or dyes take part in a chemical processing it is not easy at all to find or to produce compounds, which have an absorption spectrum practically identical to that of the standard printing inks and which at the same time fulfil specific reactivity requirements.
• photochemically hardenable pigment layers are successively applied by wiping on or whirler coating or roller coating on a same permanent support, and each layer successive to its coating is exposed through a proper separation negative and developed by removing the nonexposed portions.
• a same support is colored by means of properly selected dye solutions imagewise penetrating through successively coated imagewise exposed and photohardened colloid coatings, which are removed integrally after the formation of the separation color image in the support.
• the color proof print is formed on an electrophotographic paper by successive exposures and developments.
• the electrophoretic development applied here is very critical and the apparatus employed expensive and to be handled by skilled people.
• the transferred pigment coating is then exposed to a proper halftone separation negative in a vacuum frame. After exposure the proofing is developed with an organic liquid and the unhardened parts removed by light swabbing. After drying the process is repeated for producing in superposition a reproduction of the yellow, magenta, cyan, and black printer prints.
• This transfer material is rather complicated because of the need of a special adhesive layer.
• the said transfer material is less attractive for its development with organic solvents. Further transfer can be difficultly carried out without blisters.
• hardened colloid patterns corresponding with electromagnetic radiation patterns are produced and developed to relief patterns by means of an aqueous liquid using a nonlight-sensitive hydrophilic colloid or polymer, which is insolubilized or crosslinked by means of a compound that is produced by irradiation of a photosensitive compound.
• dichromated hydrophilic colloid layers e.g., layers containing dichromated gelatin or gum arabic (ref. P. Glafkides, Photographic Chemistry, Fountain Press, London, Vol. ll 1960), p. 669-674) are used.
• Colloid layers sensitized with dichromate suffer, however, from variations in sensitivity with age and have an inherent undesirable color. After drying, the sensitivity first rises, then falls over a period of hours. This can be tolerated in monochrome work but will give rise to less accurate color rendering in tricolor work.
• Another know n process operates with an hydrophilic crosslinkable colloid such as gelatin containing a light-sensitive polyazide compound e.g., a water-soluble aromatic polyazide compound such as 4,4-diazido-stilbene-2,2'-disulphonic acid.
• a light-sensitive polyazide compound e.g., a water-soluble aromatic polyazide compound such as 4,4-diazido-stilbene-2,2'-disulphonic acid.
• the azide system invites interest because of the favorable stability of the coating solutions and coated layers.
• Suitable water-soluble diazido aryl compounds are described in the French Pat. specification 886,716 filed Oct. 10, 1942 by Kalle AG. Exposure to light causes the azide group to break down nitrogen is set free and free radicals are generated. These radicals rapidly couple with the molecules of the hydrophilic c olloid forming cross-links and reduce thereby the solubility of die colloid in water.
• a light-sensitive compound which on exposure produces a substance, by means of which in a reaction following the exposure an active hardening species is formed.
• a hardenable hydrophilic colloid is used, which is mixed with a photosensitive iron(lll) complex compound that on exposure to active electromagnetic radiation produces iron(ll) ions, by means of which on oxidation an active species for the reduction in water-solubility of the surrounding hydrophilic colloid is formed.
• the colored colloid relief patterns are formed by means of an aqueous processing.
• multilayer colored colloid relief patterns are formed on a single permanent support starting from colored electromagnetic radiation-sensitive hydrophilic colloid layers, which are transferred in wet state in superposition to said single permanent support by stripping off before exposure from a preferably relatively hydrophobic temporary support.
• colored electromagnetic radiation-sensitive hydrophilic colloid layers are formed on a temporary support from a coating composition which contains diffusion-resistant coloring substances and particularly stable (in comparison with dichromated gelatin) radiation-sensitive substances in a desired amount already in the coating stage.
• a coating composition which contains diffusion-resistant coloring substances and particularly stable (in comparison with dichromated gelatin) radiation-sensitive substances in a desired amount already in the coating stage.
• no coloring or light-sensitive ingredients are introduced by imbibition which is difficult to control and yields less reproducible results.
• the exposure of the colloid layers can proceed in substantially dry state, which excludes chemical attack of the exposure apparatus and offers a real advantage to the operating personnel.
• differently colored electromagnetic radiationsensitive hydrophilic colloid layers are transferred in wet state from a temporary support to a single permanent support, which-when used in color proofing-4s preferably an opaque hydrophilic or hydrophilized support resembling as much as possible the printing stock.
• Each transferred colloid layer is exposed separately in register on the single permanent support through a properly selected separation negative while directing the exposed colloid layer to the radiation source during the exposure.
• the process of the present invention for the production of (a) colored colloid pattern(s), wherein (a) hydrophilic colored colloid layer(s) is (are) used, which is (are) hardened in the irradiated portions by means of an active species formed during or after the informationwise exposure to active electromagnetic radiation of a photosensitive substance, contains the steps of:
• hydrophilic colored colloid layers(s) is (are) used that contain(s) a water-soluble photosensitive aromatic polyazide compound, by means of which on exposure to active electromagnetic radiation an active species is formed that reduces the solubility in water of the hydrophilic colloid at the exposed portions.
• hydrophilic colored colloid layer(s) is (are) used that contain(s) (a) photosensitive iron(lll) complex compound(s), which produce(s) iron(ll) ions on exposure to active electromagnetic radiation, which iron(ll) ions are oxidized by an oxidizing agent yielding an active species for the reduction in solubility in water of the hydrophilic colloid at the exposed portions.
• colored colloid patterns are produced by a process wherein:
• a colored hydrophilic colloid layer containing (A) a lightsensitive iron(lll) complex compound, by means of which on exposure to active electromagnetic radiation iron(ll) ions are produced, and (B) a hydrophilic colloid that undergoes a reduction in water-solubility on oxidizing said iron(ll) ions with a suitable oxidizing agent, is transferred from a temporary support to a permanent support by pressing it in the presence of an aqueous liquid against the said layer and removing the temporary support, thus leaving the said layer on the permanent support,
• the exposed colloid layer is treated with an oxidizing liquid, by means of which the iron(ll) ions are oxidized and the reaction agent(s) is (are) formed that produce(s) a reduction in water-solubility of the colloid layer at the irradiated areas,
• the unhardened or insufficiently hardened portions of the colloid layer are removed by means of an aqueous liquid washing off the said portions, and when superposed color patterns on a same permanent support have to be produced, the steps (1), (2), (3), and (4) are repeated with said hydrophilic colloid layers having a color as desired.
• the informationwise exposure is a contact exposure carried out through a transparency, which can be a halftone or a linework transparency.
• the exposure for producing multicolor reproductions is an exposure in register, which is preferably carried out with appropriately selected separation negatives held in contact with the radiation-sensitive colloid layer.
• the halftone dots of which have a size largely independent of the exposure time can be produced.
• This property, the reproducibility of the results and the fact that halftone dots of high quality (of particularly good sharpness) are produced makes that process especially suitable for high-quality halftone multicolor work.
• the high reproducibility of the results obtained by the application of the said process is particularly due to the fact that the photosensitive ingredient(s) and dyestuffs of the photosensitive colloid layer are already before the coating of the said colloid layer contained in its coating composition in a properly determined amount. Indeed, less reproducible results are obtained when incorporating one of the ingredients of the colloid layer after coating e. g., by imbihition.
• the washoff treatment applied in the present invention is very simple and provides copies having an excellent sharpness.
• the light-sensitive iron(lll) complex compounds which on exposure to active electromagnetic radiation yield iron(ll) ions, are of the type wherein the iron(lll) ion is complexed by means of ligands having an electron-donating character in respect of the iron(III) ion.
• Such iron(III) complexes are preferably derived from a polybasic acid that forms complexes of the formula (Fe A wherein represents: y the valency of iron (in the present case 3), z the valency of the organic acid and x that of the resulting complex ion.
• the relation Fur-y must apply, n being the number of molecules of acid.
• lron(IlI) complexes that are used more preferably according to the present invention are complex oxalates, complex tartrates, and complex citrates of iron(III) ions.
• the sensitivity of the colloid layer increases with rising concentrations of photosensitive compound.
• the incorporable amount of the light-sensitive iron(III) complex compound and water-soluble aromatic polyazide compound is limited by the concentration, at which crystallization of the said compounds in the colloid layer starts. Consequently, preferably the best water-soluble complexes are used or mixtures of these complexes that do not so easily crystallize.
• Preferred in this respect is ammonium iron(III) oxalate.
• the recording layer may contain up to 40 percent by weight of ammonium iron(III) oxalate without crystallization in the colloid.
• the hardenable colored colloid layer contains to percent by weight of the iron(III) complex calculated on the weight of the dry hydrophilic colloid(s) e.g., gelatin.
• the iron(ll) ions are oxidized with a suitable oxidizing agent from which upon reduction the necessary hardening agent(s) is (are) formed for insolubilizing the hydrophilic colloid of the colored recording layer.
• hardenable colloids are hydrophilic watersoluble colloid polymers containing active hydrogen atoms as are present e.g., in hydroxyl groups and carbonamide groups. Both qualitative characterization and quantitative determination of active hydrogen can be carried out by the procedure known as the Zerewitinoff active hydrogen determination.
• Hardenable colloids containing active hydrogen atoms are e.g., polyvinyl alcohol, polyacrylamide or gelatin, and other film or stratum-forming proteinaceous colloids.
• hydrophilic colloids may be used in admixture with proper latent hardening agents, cross-linking agents,
• a catalytically polymerized monomeric compound suitable for use in combination with gelatin is acrylamide, which compound is soluble in water and compatible i.e., homogeneously miscible with gelatin.
• a cross-linking agent can be used to increase the efficiency of the hardening.
• an unsaturated compound containing at least two terminal vinyl groups each linked to a carbon atom in an unbranched chain or in a ring can be used.
• a preferred cross-linking agent is N,N'-methylene-bis-acrylamide.
• any of the known organic or inorganic peroxides of hydroperoxides may be used to induce the polymerization of the vinyl monomers such as e.g.', hydrogen peroxide, ammonium persulphate, methyl hydroperoxide, ethyl hydroperoxide, cumene hydroperoxide, etc.
• Cold color tones are e.g., standardized in the U.S.A. in the GATF-Color Charts and in the German Standards DIN 16508 and 16509.
• Warm color tones are e.g., standardized in the German Standard DIN 16538.
• the cold color standards are characterized by the use of fairly pure magenta pigments, mostly insolubilized Rhodamine and Phloxine-dyes, which have a very low side-absorption in the blue region of the spectrum.
• the warm color standards are characterized by the use of insolubilized azo dyestuffs. Said dyestuffs are more resistant to solvents e.g., alcohol than the Rhodamines and Phloxines, but they possess a much higher side-absorption in the blue region of the spectrum.
• pigments which are very poorly soluble or insoluble in water and organic liquids of the alcohol or polyhydric alcohol type e.g., glycerol are fulfilling the requirements of resistance to diffusion.
• Pigment dyes that are applied from an aqueous dispersion are used preferably, though the use of substantive dyes that are chemically linked to a colloid or polymer is not excluded.
• the hardenable colloid layer contains pigments in a concentration so high that the optical density in the wavelength range of maximum absorption is at least 0.35.
• Nonmigratory pigments suitable for use in the present invention are known by the name PIGMOSOL and COLANYL dyes.
• PIGMOSOL and COLANYL dyes are trade marks of Badische Anilin- & Soda-Fabrik A.G., Ludwigshafen/Rh., W.-Germany, for organic pigment dyes, which are mixed with a dispersing agent for aqueous medium.
• These pigment dyes excel in resistance to light, heat, acids, bases, ox-
• idizing agents and solvents. They are insoluble in hydrophilic colloids such as gelatin.
• the pigments are completely inert in the aqueous processing and washing liquids they may to some extent stain the permanent support at the nonexposed areas as a result of simple adhesion forces.
• the pigment coating on the temporary support is overcoated with a hydrophilic colloid layer (top layer), which does not contain pigments or dyes for forming the image.
• top layer comes into contact with the permanent support and is sandwiched between said support and the pigmented coating.
• the top layer contains the same colloid(s) as the colored layer and is preferably of the same composition as the pigmented coating except for the presence of the visible image-forming pigment(s) or dyes thereon.
• the top layer may contain a small amount of translucent pigments e.g., silica particles protruding from the layer and being a few microns thicker than the top layer. They avoid sticking of rolled up sheet material at relatively high (e.g., 60 percent) relative humidity.
• the top layer contains e.g., 1 to 1.5 g. of gelatin per sq. m.
• relatively thin radiation-sensitive colored colloid coatings are preferred. Preferably they have a thickness in the range of 1p. and p. Good results are obtained with colored colloid layers containing 2 to 10 g. of gelatin per sq. m. Very good results are obtained with colored layers having a thickness of 4 to 5p. and containing 2.5 to 3 g. of gelatin per sq. m.
• the colloid layers preferably contain at least 50 percent by weight ofgelatin.
• the adhering power of the transferable coating to its temporary support has to be adjusted in such a way that an easy stripping off from the temporary support is possible after pressing the pigment coating into contact with the permanent support.
• a relatively hydrophobic temporary support e.g., an unsubbed cellulose triacetate sheet, a polystyrene sheet, or sheet of copoly(vinyl acetate/vinyl chloride) and a permanent support having a hydrophilic surface e.g., a polyethylene terephthalate support subbed for adhering gelatin coatings
• the photosensitive coating is composed in such a way that its adherence to the temporary support in wet state is less than in dry state.
• hygroscopic agents e.g., a water-soluble organic hygroscopic compound e.g., glycerol and the use of wetting agents and plasticizing agents.
• the colloid relief pattern is dehydrated (unswelled) with a water-attracting alkanol/water mixture preferably an ethanol/water mixture in order to provide a sufficient mechanical strength and to prevent damage when transferring a further colloid layer thereon.
• a temporary support having a repelling power for wet gelatin coatings is e.g., the modified paper base used in the Bromolith" material (Bromolith is a registered trademark of Gevaert-Agfa N.V. for a light-sensitive paper offset plate).
• the said paper base is coated with a layer of insolubilized polyvinyl alcohol or a layer of alginic acid insolubilized with an alkali earth metal salt.
• the permanent support may be rigid as well as flexible and only must present by itself or by means of (a) subbing layer(s) a good adherence in wet as well as in dry state for the transferable hydrophilic colloid coating.
• the permanent support is transparent or opaque. So, it is possible to use metal layers or sheets, glass, ceramics, resin supports and paper impermeabilized for the processing and washing liquids.
• Resin supports characterized by a high mechanical strength and very low water absorption and consequently high dimensional stability in dry and wet state can be formed from a linear polyester e.g., a linear polyester e.g., polyethylene terephthalate, Good results as to dimensional stability are obtained with aluminum sheets sandwiched between two high wet-strength paper sheets although this material is rather expensive.
• a linear polyester e.g., a linear polyester e.g., polyethylene terephthalate
• Permanent resin supports can be made opaque by coating them with a matted subbing layer or by matting or coloring them in the mass.
• the matting may be effected by pigments known therefor in the art e.g., titanium dioxide, zinc oxide. and barium sulphate. Matting can also be obtained by producing a blush coat" as described e.g., in Canadian Pat. specification 654,438 of Labelon Tape Co., issued Dec. I8, 1962.
• Hydrophobic resin supports to be used as permanent support according to the present invention are coated with one or more subbing layers for a hydrophilic colloid layer.
• subbing layers for use on a permanent hydrophobic resin support e.g., a polyethylene terephthalate support are described in the Belgian Pat. specification 721,469 filed Sept. 27, 1968 by Gevaert-Agfa N.V.
• a sheet material which successively comprises a hydrophobic film support, a layer (A), which directly adheres to the said hydrophobic film support and comprises a copolymer formed from 45 to 99.5 percent by weight of at least one of the chlorine-containing monomers vinylidene chloride and vinyl chloride, from 0.5 to 10 percent by weight of an ethylenically unsaturated hydrophilic monomer, and from 0 to 54.5 percent by weight of at least one other copolymerizable ethylenically unsaturated monomer; and a layer (B) comprising in a ratio of 1:5 to 1:0.5 by weight a mixture of gelatin and a copolymer of 30 to 70 percent by weight of butadiene with at least one copolymerizable ethylenically unsaturated monomer.
• the layer formed from the copolymer of vinylidene chloride and/or vinyl chloride is hereinafter referred to as the vinylidene chloride copolymer layer
• the layer formed with the mixture of gelatin and butadiene copolymer is hereinafter referred to as the butadiene copolymer layer.
• the vinylidene chloride copolymer comprises from 0.5 to 10 percent by weight of ethylenically unsaturated hydrophilic monomeric units. These units may be derived from ethylenically unsaturated monoor dicarboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid. Other hydrophilic units, e.g., those derived from N-vinyl pyrrolidone, may be present.
• the vinylidene chloride copolymer may be formed from vinylidene chloride and/or vinyl chloride and hydrophilic monomeric units alone in the ratio indicated above. Preferably up to 54.5 percent by weight of other recurring units, for instance acrylamides, methacrylamides, acrylic acid esters, methacrylic acid esters, maleic esters, and/or N-alkylmaleimides, may also be present.
• Suitable vinylidene chloride copolymers are e.g., the copolymer of vinylidene chloride, N-tert.-butyl acryla mide, n-butyl acrylate, and N-vinyl pyrrolidone (70:23:324),
• copolymers are only examples of the combinations, which can be made with the different monomers, and the invention is not limited at all to the copolymers enu merated.
• the different monomers indicated above may be copolymerized according to various methods. For example,
• the copolymerization may be conducted in aqueous dispersion containing a catalyst and an activator.
• polymerization of the monomeric components may occur in bulk without added diluent, or the monomers are allowed to react in appropriate organic solvent reaction media.
• the vinylidene chloride copolymers may be coated on the hydrophobic film base according to any suitable technique, e. g., by immersion of the surfaces of the film into a solution of the coating-material. They may also be applied by spray, brush, roller, doctor blade, air brush, orwiping techniques.
• the thickness of the dried layer may vary between-0.3 and 311.
• aqueous dispersions of vinylidene chloride copolymer may be applied to at least one side of the nonstretched film, but may also be applied to polyethylene terephthalate film, which has been oriented biaxially.
• the vinylidene chloride copolymer layer may also be coated on at least one side of a polyester film, which was stretched in but one direction, e.g., longitudinally, whereafter the subbed polyester film was stretched in a direction perpendicular thereto in this case transversally.
• the biaxially oriented coated polyester film is provided with the second subbing layer of the mixture of gelatin and butadiene copolymer latex.
• the butadiene copolymer comprises 30 to 70 percent by weight of monomeric butadiene units.
• the balance is formed by units deriving from other ethylenically unsaturated.
• hydrophobic monomers e.g., acrylonitrile, styrene, acrylic acid esters, methacrylic acid esters, and acrolein.
• the butadiene copolymer is formed by emulsion polymerization and the primary latex obtained is directly mixed with the aqueous gelatin solution in such a way that the ratio of gelatin to butadiene copolymer in the dried layer varies between 1:3 parts and 1:0.5 parts all parts being by weight.
• plasticizers for gelatin such as polyethylene oxides and glycerol may also be added.
• the mixture of aqueous gelatinsolution and of butadiene copolymer latex is coated onto the vinylidene chloride copolymer layer by known means.
• the thickness of the dried layer generally varies between 0.10 and 2,1,.
• the subbed film support consists of a hydrophobic film support and. the combination of thetwo anchoring subbing layers used according to the invention.
• the hydrophobic film support may be a film of cellulose triacetate, of polyethylene terephthalate, of polycarbonate, of polystyrene, of polymethacrylic acid ester, etc.
• the subbed hydrophobic film support may be provided on only one side or on both sides with the combination of subbing layers.
• a coating composition is prepared containing gelatin dissolved in water wherein (a) selected pigment(s) is or are dispersed in a concentration to yield after. coating and drying a recording layer having an optical density in the wavelength range of maximal absorption of at least 1.
• the coating composition preferably contains at least 50. percent by weight of gelatin in respect of the pigment particles and a proper amount of plasticizing agent and repellent (a water-attracting compound e.g., glycerol) to provide to the coating a sufficient adherence to its temporary support and to enable its easy wet (aqueous) stripping off from the temporary support, preferably an unsubbed cellulose triacetate support.
• the coating composition contains an amount of an iron'(lIl) complex compound, which is sensitive toelectromagnetic radiation, preferably iron(IlI) potassium and/or ammonium oxalate having the formulas K Fe(C O,,) and (NH Fe-(C O respectively.
• iron(IlI) potassium and/or ammonium oxalate having the formulas K Fe(C O,,) and (NH Fe-(C O respectively.
• the amount of said iron(lll) complex is such that the gelification of the gelatin is not substantially affected and optimum sensitivity is attained without reaching the concentration, at which the complex salt(s) start(s) to crystallize from the dry layer.
• a suitable amount of said light-sensitive iron(lll) complex is in the range of 15 to 25 percent by weight in respect of the dry gelatin.
• the coating preferably contains 1 tolO g. of gelatin per sq. m. Optimal results are obtained with 3 g. of gelatin per sq. m.
• the gelatin layer may contain a screening dye.
• the reduction of sensitivity resulting from the presence of said dye may be compensated by the presence of a catalytically polymerizable vinyl monomer or a cross-linking agent for gelatin such as N,N-methylene-bis-acrylamide.
• a second coating the so-called top layer, the composition of which is preferably identical tothe foregoing, except that no pigment(s) are present, is coated on the first one.
• the second coating preferably contains 1 to 5 g. of gelatin per sq. m. It is, however, not strictly necessary to incorporate a radiation-sensitive ion(lll) complex compound in the said second coating, since a sufficient amount of said compound can diffuse during coating and drying therein from the underlying pigmented layer.
• the said second coating forms with the underlying pigmented coating one hardenable double layer firmly bound together, in other words a composite layer which can be transferred as a whole from the temporary support to the permanent support.
• a set of materials containing such a composite layer is preferably used for preparing a multicolor color proofing image."
• a usual set contains yellow, magenta, cyan, and black pigment coatings on separate cellulose triacetate supports.
• the permanent support e.g., a polyethylene terephthalate support is successively coated with a first subbing layer on the basisof acopolymer containing hydrophobic structural units in a proper ratio and a second subbing layer, which is more hydrophilic than the first one and contains gelatin, a hydrophobic latex polymer and for giving the support an opaque aspect a white pigment e.g., titanium dioxide particles.
• a white pigment e.g., titanium dioxide particles.
• the permanent support preferably applied in color proofing is a hydrophobic polyester resin support subbed with a system of subbing layers as described in the Belgian Pat. specification 72l,469 filed Sept. 27, 1968 by Gevaert-Agfa N.V.
• the opaque white support has an opacity and whiteness resembling as much as possible the whiteness and opacity of the printing stock whereon the actual print has to be made.
• the unexposed pigment coating is transferred by pressing the surface of the subbing layer and of the unexposed coating together in the presence of an aqueous liquid and peeling off the temporary cellulose triacetate support.
• the pressure step can be carried out in an apparatus, in which the materials involved are pressed together between rollers.
• a suitable apparatus for that purpose is described in the United Kingdom Pat. application 48,788/68 filed Oct. 15, 1968 by Gevaert-Agfa N.V.
• the said apparatus is particularly suitable for use in transferring in wet or moist state colloid layers from a temporary support to a permanent support and such apparatus comprises a pair of cooperating pressure rollers and means for driving said rollers, a first platform for supporting the permanent support prior to its engagement by said pressure rollers, said platform being formed in such a way as to make interrupted or discontinuous contact with the permanent support when this is placed thereon, a second platform arranged over and separated from the first surface for supporting at least the leading part of the temporary support to keep said temporary support separated from a permanent support when this is located on the first platform, the forward ends of both said platforms being disposed proximate to the nip of the pressure rollers so that the supports as they are advanced are gripped by said rollers and progressively pressed together.
• the photohardenable gelatin layer is exposed through a first halftone separation transparency (in the photohardening systems a halftone negative) of the original.
• a cyan pigment coating is first applied to the permanent support and exposed through the cyan printer halftone separation negative of the original.
• the iron(ll) ions formed are oxidized to iron(lII) ions and hardening takes place in the exposed portions, whereupon the nonexposed portions are washed away selectively with a jet of tap water preferably at 30-50 C.
• the exposure preferably being a vacuum frame contact exposure, is carried out with a light source sufficiently emitting in the ultraviolet range of the spectrum, e.g., with a carbon are, a xenon are, or a high-pressure mercury vapor tube.
• the duration of the exposure does not only depend on the photosensitivity of the iron(lll) complex but also on the type of the pigment, more particularly on its inherent absorption of ultraviolet radiation and blue light.
• the pigment coating is exposed while being in direct contact with the imagecontaining layer of the transparent original. Less sharp dots are obtained when exposing the pigment coating in direct contact with the support of a silver image transparency used as an original.
• the hydroxyl radicals (OI-1) insolubilize the gelatin and other colloids having active hydrogen atoms.
• the dichromate compound is reduced with iron(ll) ions and yields chromium(Ill) ions acting as insolubilizing agent for gelatin.
• the permanent support carrying the first relief image (the cyan relief image) is pressed between the same rollers while in contact with another pigment coating, e.g., the yellow pigment coating, and after a few seconds of contact the temporary support is peeled off, thus leaving the yellow pigment coating on the cyan part image produced already.
• the said yellow pigment coating is dried before contact exposure. Drying proceeds e.g., with a warm air current of 40 C.
• the oxidative treatment and washing off proceeds with or in one liquid.
• the obtained colloid pattern or multilayer colloid pattern can be protected and given a glossy appearance by a transparent resin top coat, which according to a preferred embodiment is applied by spraying.
• a suitable spray cover consists of polyisobutyl methacrylate.
• EXAMPLE 1 A coating composition was prepared containing the following ingredients:
• a top layer without pigment was coated on the gelled coating. Said coating was applied from the following composition:
• the said composition was coated by air knife at a temperature of 27 C. at a rate of 30 sq.m./l., gelled, and dried.
• the ultraviolet-sensitive pigment material thus obtained had to be transferred to a permanent support consisting of an aluminum sheet whereon on both sides a paper sheet of 90 g./sq.m. was adhered, these paper sheets being covered with a formaldehyde-hardened gelatin coating of g./sq.m.
• the temporary support of the pigment coating was soaked for 1 minute at room temperature with a mixture of ethanol and water 70:30 percent by volume and thereupon pressed in wet state between soft rollers in contact with the described permanent support. After a contact period of 30 seconds the temporary support was stripped off, thus leaving the cyan pigment coating fixed on the permanent support.
• the transferred coating was air dried and put in a vacuum frame in contact with the cyan printer separation halftone negative of the original to be printed.
• the pigment coating was exposed for 2 minutes with a carbon are light source 1X40 a.) placed at a distance of 70 cm.
• the exposed pigment coating was dipped for 30 seconds in a tray containing an aqueous 1 percent hydrogen peroxide solution at 20 C.
• a yellow pigment coating being applied to an unsubbed cellulose triacetate temporary support and having the same composition as the cyan pigment coating except for the fact that 4 g. of Pigment Yellow 16 (C.l. 20,040) sold under the name PERMANENT GELB NCG COLANYL TEIG (trade name for a yellow pigment dispersion marketed by Farbwerke l-loechst AG Frankfurt (M), Hochst, W. Germany was substituted for the l g. of HELIOGEN BLAU B COLANYL TElG, was transferred to the cyan relief image by pressing it into contact for 30 seconds with the still wet cyan relief image and stripping off the temporary support.
• Pigment Yellow 16 C.l. 20,040
• PERMANENT GELB NCG COLANYL TEIG trade name for a yellow pigment dispersion marketed by Farbwerke l-loechst AG Frankfurt (M), Hochst, W. Germany was substituted for the l g. of HELIOGEN BLAU
• magenta printer halftone relief image was formed in superposition with the already present cyan and yellow image.
• the exposure in register of the magenta pigment coating lasted 3 minutes.
• the composition of the transferable magenta pigment coating was the same as that of the cyan pigment coating; except for the presence of 1.2 g. of PIGMENT RED 48 (C.l. 15,865) sold under the name LITHOLSCHARLACH BBM PIG- MOSOL (a magenta pigment dispersion marketed by Badische Anilin- & Soda-Fabrik, Ludwigshafen/Rh., W. Germany) instead of 1 g. of HELIOGENBLAU B COLANYL TElG.
• PIGMENT RED 48 C.l. 15,865
• LITHOLSCHARLACH BBM PIG- MOSOL a magenta pigment dispersion marketed by Badische Anilin- & Soda-Fabrik, Ludwigshafen/Rh., W. Germany
• a black-printer halftone relief image was formed on the magenta-printer halftone relief image in superposition therewith.
• the exposure in register of the black pigment coating lasted 8 minutes.
• the composition of the transferable black pigment coating was the same as that of the cyan pigment coating except for the presence of 1.5 ml. of a carbon black dispersion prepared by ball milling and dispersing 20 g. of carbon black in 77 ml. of ULTRAVON-W (a heptadecyl-benzimidazole disodium sulphonate dispersing agent marketed by CIBA AG, Basel, Switzerland) and 23 ml. of water, instead of l g. of HELIOGENBLAU G COLANYL TEIG.
• Example 1 was repeated, with the proviso however, that use was made of a permanent support consisting of a paper sheet made water impermeable by a treatment with a cellulose nitrate lacquer coated successively with a subbing layer for gelatin and with a formaldehyde-hardened gelatin coating of 3 g. per sq. m.
• a permanent support consisting of a paper sheet made water impermeable by a treatment with a cellulose nitrate lacquer coated successively with a subbing layer for gelatin and with a formaldehyde-hardened gelatin coating of 3 g. per sq. m.
• Example 1 was repeated but instead of potassium iron(lll) oxalate a same amount of ammonium iron(lll) oxalate was used. The exposure times were doubled. A residual staining due to iron(lll) ions left in the developed relief was bleached out by dipping the finished multirelief print for 1 minute at 20 C. in a 5 percent aqueous solution of sodium hexametaphosphate and rinsing in running water for 2 minutes.
• Example 1 was repeated but instead of 23 ml. of a 5 percent aqueous solution of potassium iron(lll) oxalate 20 ml. of ammonium iron(lll) oxalate were used.
• a screening dye viz 1 ml. of a 5 percent aqueous solution of tartrazine (C.l. 19,140) was incorporated into the cyan and magenta pigment coating.
• a mixture of acrylamide and N,N-bis-methylene acrylamide in a ratio by weight of 7 to 3 was added to the pigment coating in an amount of 10 percent by weight calculated on the gelatin.
• the resulting composition was coated by air knife at a temperature of 35 C. at a rate of 23 sq.m./l. to a temporary support of unsubbed cellulose triacetate having a thickness of 0.1 mm.
• the solution was gelled at 8 C.
• a protective layer was coated by air knife.
• the coating composition of the protective layer was formed by allowing to swell 27 g. of gelatin in 768 ml. of water, adding a 10 percent by weight dispersion of colloidal silica (average particle size: 23u) in an 8 percent by weight aqueous solution of gelatin, melting at 45-48 C. and adding successively:
• the coating composition was applied at 24 C. at a ratio of 30 sq.m./l. and after coating the protective layer was gelled and dried.
• the resulting light-sensitive layer was transferred as described further on to an opaque permanent support of polyethylene terephthalate, which was subbed at both sides as follows:
• Both sides of a biaxially stretched polyethylene terephthalate film having a thickness of 180; ⁇ . were coated with the following composition at 2530 C. at a ratio of 1.6 g./sq.m.:
• the resulting layer was coated with a mixture prepared as follows:
• the dispersion was stirred rapidly for minutes at a temperature of 5l 5 C. and then heated to 35 C., at which temperature 400 ml. of a 10 percent by weight aqueous solution of gelatin was added, while continuing the rapid stirring. Subsequently the following composition was added by stirring slowly to avoid scumming:
• the coating was carried out at such a rate that upon drying a layer of 5 was obtained.
• the white permanent support was immersed for at least 90 seconds in an aqueous solution of an alcohol, e.g., ethanol (an aqueous solution of isopropanol or n-propanol can be used also).
• an alcohol e.g., ethanol
• the proportion by volume between the alcohol and water may vary between 1/1 and 6/1.
• the proportion of 2/1 is preferred.
• the wetted permanent support was pressed in contact with the light-sensitive layer (the pressure can be effected by means of a hand roller or two rollers driven by a motor). After the transfer the temporary support was stripped off.
• the layer was dried in a hot airstream not exceeding 60 C.
• the light-sensitive layer was contact exposed through the cyan printer halftone separation negative of the multicolor image to be reproduced to an ultraviolet radiation-emitting arc lamp.
• the exposure was carried out with an arc lamp of 1X40 a. placed at a distance of 70 cm.; the exposure time was 3 minutes. If the material was held in adequate contact by the exposure frame it was not liable to overexposure. Such overexposure may attain 10 times the value of a sufficient exposure time, without a worsening of the quality and the reproducibility of the final product.
• the light-sensitive layer was dipped for at least seconds in an oxidizing solution at 2025 C.
• the oxidizing solution was a peroxide bath containing 0.5 to 5 percent of hydrogen peroxide.
• the colloid relief pattern was developed by washing away the nonhardened gelatin without rubbing in running water of 30-50 C., preferably having a temperature of 35-40 C.
• the cyan relief pattern obtained was immersed before the application thereto of a next colloid layer in an alcohol-water bath having the same composition as that used for wetting the permanent support.
• the solution was coated by air knife on an unsubbed cellulose triacetate support having a thickness of 0.1 mm. at a temperature of 35 C. at a ratio of 23 sq.m.Il.
• the solution was gelled at 8 C.
• a protective layer was coated by air knife from a composition prepared as follows:
• the application on the temporary support was performed as described in part C,.
• the light-sensitive yellow layer was transferred to the permanent support onto the already existing cyan printer image.
• the transfer was carried out according to the same technique as described above for the cyan layer.
• the light-sensitive yellow layer was exposed to the halftone separation negative of the yellow printer image and further processed in the same way as the cyan layer.
• EXAMPLE 5-Part C 1 A light-sensitive magenta layer was transferred to thle yellow relief pattern of the wetted permanent support. This layer had the following composition:
• the light-sensitive layer was then finished and processed as described in part C EXAMPLE 5Part C
• the light-sensitive black layer was now transferred to the permanent support carrying three color images already.
• This solution was coated by air knife on an unsubbed cellulose triacetate temporary support at a temperature of 35 C. at a ratio of 23 sq.m./l.
• the solution was gelled at 8 C.
• a protective layer was coated by air knife from a composition prepared as follows:
• the following compounds were added to A: l()% by weight aqueous solution of saponine 20 ml. Tergitol 4 (trade name) l5 ml. 7.5% by weight aqueous solution of ammonium iron (lll) oxalate 120 ml.
• the protective layer was coated at 24 C. at a ratio of 30 sq.m./l. After gelling the layer was dried.
• the resulting light-sensitive layer was transferred and finished as described in part C
• the developed image was dipped in an alcohol/water bath (volume ratio: 70/30), adhering moisture was raked off and finally the image was dried.
• the result was a four color proofing image having the same colors as if it were printed.
• the multicolor image offered a true reproduction of the separation negatives, and contained very sharply reproduced dots, the size of which was a true reproduction of the dots present in the separation negatives serving as originals in the exposure.
• EXAMPLE 6 The colloid recording layers of the Example 5-part C were processed as described in said example except for the treatment in the oxidizing solution which according to the present example was a 2 percent by weight aqueous solution of potassium bichromate.
• the exposed layers were dipped for 30 seconds at 20 C. in said solution. A longer contacting time with the solution had no influence on the quality of the obtained images. Same results were obtained with aqueous solutions containing from 1 to 8 percent by weight of ammonium bichromate.
• Example 5 was repeated except for the fact that in the composition of the colloid recording layers the aqueous 7.5 percent by weight solution of ammonium iron(lll) oxalate was replaced by a same volume of an aqueous 4 percent by weight 4,4'-diazido-stilbene-2,2-disulphonic acid sodium salt solution.
• the transfer of the differently colored colloid layers proceeded as described in Example 5. The exposure times have, however, to be doubled.
• the processing of the exposed colloid layers producing a relief image corresponding with the exposed parts was a simple washoff treatment under running warm water (40 C.
• the result was a four color proofing image having the same colors as if it were printed.
• the photosensitive compound is an iron(lll) complex compound, which on exposure to said radiation yields iron(ll) ions and which is of the type wherein the iron(IlI) ions are complexed with a moiety having an electromdonating character relative to an ironflll) ion.
• the photosensitive compound is an iron(lll) complex derived from a polybasic acid and has the formula (FeA,,) in which n is the number of acid molecules, z is the valency of the organic acid, and x that of the resulting complex ion.
• a process according to claim 4 wherein the photosensitive iron(IlI) complex compound is an iron(lll) complex oxalate, tartrate, or citrate.
• colloid layer contains a water-soluble hydrophilic colloid polymer having active hydrogen atoms.
• colloid layer contains a water-soluble hydrophilic colloid polymer capable of undergoing sol-gel transformation.
• the hardenable colloid layer contains a substance that imparts to the colloid layer the property of a weaker adherence to the temporary support in wet state than in dry state.
• a process according to claim 1 wherein the temporary support is an unsubbed cellulose triacetate film sheet.
• a process according to claim 1 wherein the permanent support is a hydrophobic resin support carrying an external subbing layer having hydrophilic properties.
• said permanent support is a hydrophobic film support having superposed thereon in succession a layer (A) directly adherent to said hydrophilic film support and comprising a copolymer formed from 45 to 99.5 percent by weight of at least one ofthe chlorine-containing monomers vinylidene chloride and vinyl chloride, from 0.5 to percent by weight of an ethylenically unsaturated hydrophilic monomer, and from O to 54.5 percent by weight of at least one other copolymerizable ethylenically unsaturated monomer, and a layer (B) comprising in a ratio of 1:5 to 1:05 by weight a mixture of gelatin and a copolymer of to 70 percent by weight of butadiene with at least one copolymerizable ethylenically unsaturated monomer.
• A directly adherent to said hydrophilic film support and comprising a copolymer formed from 45 to 99.5 percent by weight of at least one ofthe chlorine-containing monomers vinylidene chloride and vinyl
• each such colored hardenable colloid layer on its temporary support is covered with an uncolored top layer containing the same colloid as the colored colloid layer.
• top layer has the same composition as the colored hardenable colloid layer except for the colored substances contained therein.
• each such colored hardenable colloid layer has a thickness in the range Of115[1..
• each such colored hardenable colloid layer contains dyes that are resistant to diffusion.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Citations (3)

• 1968
  • 1968-05-15 GB GB2307768A patent/GB1264313A/en not_active Expired
• 1969
  • 1969-05-08 JP JP44036087A patent/JPS4920536B1/ja active Pending
  • 1969-05-13 SE SE06842/69A patent/SE362506B/xx unknown
  • 1969-05-13 FR FR6915584A patent/FR2008575A1/fr not_active Withdrawn
  • 1969-05-13 CH CH731469A patent/CH528097A/de not_active IP Right Cessation
  • 1969-05-14 AT AT460369A patent/AT297484B/de not_active IP Right Cessation
  • 1969-05-14 NL NL6907436A patent/NL6907436A/xx unknown
  • 1969-05-14 ES ES367265A patent/ES367265A1/es not_active Expired
  • 1969-05-15 US US825056A patent/US3642474A/en not_active Expired - Lifetime
  • 1969-05-15 SU SU1336748A patent/SU519150A3/ru active
  • 1969-05-16 BE BE733123D patent/BE733123A/xx unknown

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