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
  • G03F7/027—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
  • G03F7/0285—Silver salts, e.g. a latent silver salt image
• • 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
  • Y10S430/143—Electron beam

Definitions

• This invention relates generally to a process for producing polymer images and, more particularly, to a process for forming a high molecular weight material selectively at the areas corresponding to latent photographic images by the action of a photographic silver halide emulsion and a reducing agent.
• a process in which exposed silver halide grains are developed by a reducing compound in the presence of a vinyl compound and the vinyl compound is polymerized by the oxidation product (or an intermediate product thereof during the development) is very interesting from a theoretical point of view, since, in such a process, the amplification action by both development and by chain polymerization can be utilized.
• a so-called benzenoid compound i.e., a compound having at the ortho or para positions on a benzene ring at least two hydroxyl groups, amino groups, or amino groups substituted by alkyl 3,782,943 Patented Jan. 1, 1974 groups or acyl groups (e.g., US. Pat. N0. 3,019,104, and G. Oster, Nature"; vol. 180, 1275 (1957)).
• an object of the present invention is to provide a process of converting images generated by electromagnetic Waves orparticle rays to the images of high molecular weight material by a simple procedure.
• Another object of this invention is to provide a process for obtaining polymer images having the desired properties by utilizing the aforesaid recording process.
• the inventors have found that the above-mentioned polymerization of vinyl compound can be caused by reducing a silver halide in the presence of the vinyl compound using an alkyl phenol, a halogenated phenol, an acyl phenol or derivatives thereof.
• the reaction occurs more rapidly when the fine crystals of silver halide contain the development nuclei and, accordingly, when the reaction is conducted under suitable conditions and for a suitable period of time, the polymerization can be selectively induced only in the areas where silver halide particles having the development nuclei are present.
• the present invention can be attained by utilizing aforesaid facts. That is, the process of the present invention can be achieved by reacting at least one of the phenols represented by the following formula with a wherein R R R R and R satisfy one of the follow-.
• R represents a methyl group, a hydroxymethyl group, a dialkylaminomethyl group, a bromomethyl group, a carboxymethyl group, a carboxyl group or an acyl group;
• R and R each represents a hydrogen atom or an alkyl group, preferably of from 1 to 4 carbon atoms;
• R represents a hydrogen atom, or an alkyl group, preferably of from 1 to 8 carbon atoms or a halogen atom;
• R represents a hydrogen atom, an alkyl group, preferably methyl, a hydroxymethyl group or a halogen atom; said R and said R may form a naphthalene ring by ring condensation.
• R and R each represents a hydrogen atom or a halogen atoms
• R and R each represents a hydrogen atom or an alkyl group, preferably of from 1 to 4 carbon atoms, and R represents an alkyl group, preferably of from 1 to 8 carbon atoms, an aralkyl group, a substituted alkyl group, or a halogen atom
• said R and K may form an alkylene ring by ring condensation, and when doing so R and R have from 1 to 6 carbon atoms, said R may be an alkylene group to form a bisphenol.
• R represents a tertiary alkyl group, preferably a tertiarybutyl group, and the other Rs represent a hydrogen atom.
• a latent photographic image is formed in a photographic silver halide emulsion layer by light-exposure orbecomes visible when developed.
• an emulsion layer forming a usual negative image
• the formation of a latent image is accomplished by the formation of development centers on the silver halide grains which are irradiated by light or high energy rays.
• the latent image is formed by forming development centers first on every silver halide grain and afterwards destroying the development centers by the irradiation of light or high energy rays (see: James & Huggins; Fundamentals of Photographic Theory, 2nd ed., Morgan & Morgan Co., 1960).
• any silver halide emulsion for forming a negative image by development and any silver halide emulsion for forming direct positive images may be employed effectively.
• silver chloride, silver bromide, silver chlorobromide, silver iodobromide, or silver halide emulsion used in this invention may be subjected to chemical sensitization and optical sensitization usually employed for photographic silver halide emulsions. That is, the photographic silver halide emulsion may be subjeeted to sulphur sensitization and noble metal sensitization as the chemical sensitization, for example see P. Glafkides; Chimie Photographique, 2nd ed., pp.
• the photographic silver halide emulsion used in this invention may contain a stabilizer usually employed in photographic techniques.
• the photographic silver halide emulsion for direct positive images used in the present invention may be prepared by utilizing selarization, a Herschel effect, a Clayden effect, or a Sabattier effect. These effects are described in, for example, C. E. K. Mees; The Theory of Photographic Process, 2nd ed., pars. 6 and 7, McMillan Co. (p. 954).
• a light sensitive layer of a photographic silver halide emulsion susceptible to solarization is prepared, and is light-exposed or treated with a chemical to such extent that the layer can be sufficiently developed without subjecting it to an image exposure.
• the production of such a kind of photographic silver halide emulsion is disclosed, for example, in British Pats. 443,245 and 462,730.
• the Herschel effect is caused by the exposure to long Wave length light of a silver halide which has been provided with developability wholly by overall exposure or chemical treatment. In this case, it is profitable to employ a silver halide emulsion containing a large amount of silver chloride, and also a desensitizing dye such as pinakryptol yellow and phenosafranine is frequently incorporated in the emulsion to promote the occurrence of the Herschel effect.
• the production of the photographic silver halide emulsions for direct positive images by utilizing the Herschel effect is disclosed in, for example, British Pat. 667,206 and U.S. Pat. 2,857,273.
• the Sabattier effect occurs when a silver halide emulsion layer is image-exposed and thereafter uniformly exposed while being immersed in a developer or treated with a chemical, whereby the areas of the emulsion layer which had not been image-exposed become developable.
• the Clayden effect as well as the Sabattier effect, occur easily in practice when using a silver halide emulsion which tends to form development nuclei more in the inner parts of the grains of silver halide than on the surface of the grains by the first exposure.
• the production of a silver halide emulsion capable of easily forming internal development nuclei is described in the specifications of U.S. Pats. 2,592,250 and 2,497,876, British Pat. 1,011,062 and German Pat. 1,207,791.
• the photographic emulsion mentioned above is prepared by dispersing silver halide grains in a solution of a high molecular weight material.
• a high molecular weight material gelatin is most frequently used, but a synthetic high molecular weight compound such as polyvinyl alcohol, polyvinyl pyrrolidone, or polyacrylamide, or a derivative of a natural high molecular weight compound such as carboxymethylcellulose, cellulose oxyethyl ether, or dextran may be used alone or together with gelatin.
• a synthetic high molecular weight compound such as polyvinyl alcohol, polyvinyl pyrrolidone, or polyacrylamide, or a derivative of a natural high molecular weight compound such as carboxymethylcellulose, cellulose oxyethyl ether, or dextran may be used alone or together with gelatin.
• a silver halide is used in the form of a photographic silver halide emulsion as mentioned before increasing the difference of the reactivity between the portions exposed to electromagnetic waves or particle rays and the unexposed portions, that is, the selectivity of reaction.
• the reaction mechanism of initiating the polymerization of a vinyl compound as the result of the reduction of a silver halide by the aforesaid compound, represented by the General Formula 1, has not yet been clarified, but it is generally thought that the polymerization proceeds by a radical mechanism since a compound capable of conducting radical polymerization can generally be utilized, the reaction proceeds in an aqueous solution, and the use of a radical polymerization inhibitor retards the reaction. Furthermore, it has not yet been clear whether the radical is formed directly by the reaction of a silver halide and the compound represented by General Formula 1 or the radical is formed by the interaction of water, oxygen, etc., in the system. However, although the influence of oxygen is not clear from the aforesaid reports, it is considered that following reaction may occur:
• Sulphite ions may be added to the reaction system, either in the form of a compound which originally contained the sulphite ion in the molecule, such as alkali metal sulphites or ammonium sulphite, or in the form of a compound which will give a sulphite ion as the result of hydrolysis, such as pyrosulphites of alkali-metals and ammonium or the adducts of bisulphites with aldehydes such as formaldehyde or glyoxal.
• a compound which originally contained the sulphite ion in the molecule such as alkali metal sulphites or ammonium sulphite
• a compound which will give a sulphite ion as the result of hydrolysis such as pyrosulphites of alkali-metals and ammonium or the adducts of bisulphites with aldehydes such as formaldehyde or glyoxal.
• sulphite ion the appropriate amount depends upon the nature and amount of the reducing agent, and the vinyl monomer being used, the pH of the system, and other factors, more than 0.05, particularly more than 0.2 mol per liter of the system is effective.
• the polymerization promoting effect of sulphite ion is essentially different from the action of removing oxidation products, as in the ordinary developing solutions mentioned above.
• the polymerization would be inhibited rather than promoted if the sulphite simply removes the oxidation products as in conventional developing processes. While the mechanism of the action of sulphite ion in the process of the present invention is not clear, it may be that the sulphite ion prevents the polymerization inhibiting action of free oxygen.
• the vinyl compounds used in the present invention are addition-polymerizable compounds which are liquid or solid at normal temperatures or mixtures thereof.
• Illustrative of such vinyl compounds are acrylamide, acrylonitrile, N-hydroxymethyl, acrylamide, methacrylic acid, acrylic acid, calcium acrylate, methyl methacrylate, sodium acrylate, methacrylamide, methyl acrylate, ethyl acrylate, vinyl pyrrolidone, vinylmethyl ether, vinylbutyl ether, vinylisopropyl ether, vinylisobutyl ether, vinyl butyrate, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-N- vinyl imidazole, potassium vinylbenzene sulfonate, and vinyl carbazole.
• vinyl compounds having more than two vinyl groups are particularly suitable, and such compounds may be used together with the aforesaid vinyl compound having one vinyl group or may be used alone.
• vinyl compounds having a plurality of vinyl groups are N,N-methylene-bis-acrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinyl ether and divinyl benzene.
• water-soluble vinyl compounds are conveniently used but water-insoluble vinyl compounds may also be polymerized by adding them to the reaction system in the form of an emulsion.
• the emulsification of such water-insoluble vinyl compounds may be conducted by means of a suitable stirrer in the presence of a surface active agent and/or a high molecular weight compound according to conventional methods.
• any electromagnetic waves or particle rays to which usual photographic light-sensitive emulsions are sensitive can be utilized. That is, visible rays, ultra-violet rays, infrared rays having wave lengths shorter than 1.3 microns, X-rays, gamma rays, alpha rays, and electron rays all may be used.
• the silver halide grains On irradiation by electromagnetic rays or particle rays, the silver halide grains may be dispersed in an aqueous solution or held in a dry gel.
• a highly viscous or gelled photographic emulsion on a suitable support or substrate may be subjected to the irradiation, either in an undried state or a dried state.
• the reduction should be conducted in the presence of a vinyl compound or compounds. While in the present invention, either the vinyl compound or the compound represented by the General Formula 1 may be incorporated in the photographic emulsion before exposure, but only one of them may be so incorporated, the other being added to the system after the exposure. It is also possible to add both compounds after exposure.
• the reaction is conducted in the presence of a suitable quantity of an alkali, as it proceeds smoothly under alkaline conditions. While the amount of alkali suitable for the reaction depends on the kind of silver halide, reducing agent, and high polymer in the system, their concentrations, and the reaction temperature, it is preferable to use an amount suflicient to make the pH of the system 6 or more preferably higher than 7.
• the reaction can be performed by immersing the thus-produced photosensitive material in an alkaline aqueous solution after it has been exposed to the electromagnetic waves or particle rays.
• the vinyl compounds and/or the reducing agents can conveniently be dissolved in the aqueous alkaline solution.
• reaction is stopped readily by adjusting the pH of the system to, for example, 5 or less, it may also be stopped by cooling, removing the reactants by Washing, dissolving the silver halide by fixation, or adding a polymerization inhibitor to the system.
• the high molecular weight polymer, as the vehicle for the silver halide grains, and the monomerie vinyl compound are mixed and coated together to form a film
• an inhibitor for thermal polymerization it is preferable to add a small amount of an inhibitor for thermal polymerization in order to prevent the spontaneous thermal polymerization of the vinyl monomer.
• a polymerization inhibitor any of the known thermal radical polymerization inhibitors, such as p-methoxyphenol, hydroquinones, 2,6-di-tert.butyl-pcresol, or ,B-naphthol, can be used.
• the vinyl monomer When the vinyl monomer is contained in the system from the first, it is incorporated in an amount by weight of from to 30, and preferably from A to 4 times the amount of the high molecular weight polymer which is originally present in the system.
• the silver halide is conveniently used in an amount by weight of from to 2 and, preferably, to times the amount of the high molecular weight polymer which is originally present in the system.
• the reducing agent When the reducing agent is to be added to the system before the reaction, it is suitable to add it in the amount of from to 20 moles per mole of the silver halide. It is convenient to add the thermal polymerization inhibitor in an amount of from 10 to 20,000 p.p.m. of the weight of the vinyl compound.
• the vinyl monomers are dissolved in the processing solution, it is usually preferable to dissolve them in as high a concentration as possible, and hence the preferable concentration of the monomer is determined mainly by the solubility of the monomer in the solution.
• the pyrazolone reducing agents are dissolved in the processing solution, it is suitable to dissolve them in a concentration between and 5 moles per liter, and preferably between and 1 mol per liter.
• the effect of the exposure may be diminished to some extent and in this case the decrease in effect can be cancelled by increasing the amount of the exposure.
• Relief images of polymeric materials may be formed by dissolving away unpolymerized portions after the irradiation and polymerization, making use of the difference in solubility between the polymerized portions and the unpolymerized portions, so as to leave the thusformed highly polymerized compound, as an image, only the irradiated areas. In this case, it is convenient if the high molecular Weight polymer originally present in the system can be washed away with the unpolymerized vinyl compound.
• the high molecular Weight polymer originally present in the system be a linear, substantially uncrosslinked one, or such a crosslinked one that is susceptible to chain fission or break-up of the crosslinkage, and that the highly polymerized compound formed by the polymerization of the vinyl compound is a crosslinked one of so-called threedimensional structure.
• the highly polymerized compound formed by the polymerization of the vinyl compound is a crosslinked one of so-called threedimensional structure.
• the image which is made by this procedure and consists of highly polymerized substances can be used in various printing processes.
• the process of this invention can be utilized for the formation of color images.
• a vinyl monomer having a group capable of having a charge via an electrolytic dissociation or the addition of hydrogen cations is used as the vinyl compound to form a polymer capable of having a charge by electrolytic dis sociation or addition of hydrogen cation, and then the polymer image is selectively dyed by a dye having the opposite charge to that of the polymer.
• the color images thus formed may be transferred to other supports by various means.
• addition polymerizable vinyl compounds capable of having a charge by electrolytic dissociation or addition of hydrogen cations used in this invention are as follows:
• the monomer capable of providing a negative charge to the high molecular weight compound formed from the monomer there may be employed vinyl compounds having carboxyl groups, such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid; vinyl compounds containing metal or ammonium salts of carboxyl groups, such as ammonium acrylate, sodium acrylate, potassium acrylate, calcium acrylate, magnesium acrylate, zinc acrylate, cadmium acrylate, sodium methacrylate, potassium methacrylate, magnesium methacrylate, calcium methacrylate, zinc methacrylate, cadmium methacrylate, sodium itaconate, and sodium maleate; vinyl compounds having sulphonic acid groups such as vinyl sulphonic acid and p-vinylbenzene sulphonic acid; and vinyl compounds containing metal or ammonium salts of sulphonic acid groups
• vinyl compounds that provide a positive charge to the high molecular weight compound formed from the monomer there are vinyl compounds having basic nitrogen atoms, such as 2-vinylpyridine, 4-vinylpyridine, 5-vinyl-2- methylpyridine, N,N-dimethylaminoethyl acrylate, N,N- dimethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, and vinyl compounds containing quaternary ammonium salts prepared from a base of the aforesaid vinyl compounds and methyl chloride, ethyl bromide, dimethyl sulphate, diethyl sulphate, or methyl p-toluenesulphonate.
• basic nitrogen atoms such as 2-vinylpyridine, 4-vinylpyridine, 5-vinyl-2- methylpyridine, N,N-dimethylaminoeth
• the aforesaid vinyl compounds may be prepared by well known processes, or are easily commercially available. These compounds may be used alone or as mixtures, and may be used together with a water-soluble addition polymerizable vinyl compound having no charge.
• the reactivity and the proportion of the vinyl compound must be selected so that a high molecular weight compound having substantially no electrolytically dissociating group is not formed as the result of the polymerization of only the vinyl polymer having no charge.
• a dye capable of having a charge by electrolytic dissociation there are generally employed conventional acid dyes and basic dyes.
• a basic dye is employed.
• an acid dye is employed.
• a basic dye has a positive charge, it selectively dyes high molecular weight compounds having a negative charge, while since an acid dye has a negative charge, it selectively dyes high molecular weight compounds having a positive charge.
• a color image can be obtained in accordance with the charge of the high molecular weight compound.
• the isoelectric point of the gelatin must be considered for dyeing, since gelatin is an amphoteric electrolyte.
• the pH of the system is lower than the isoelectric point of the gelatin to be used, the gelatin is positively charged, while if the pH is higher than that, the gelatin is negatively charged. Accordingly, when a high molecular weight compound having a negative charge is formed, only the image of the high molecular weight compound can be dyed without dyeing gelatin by dyeing the polymer image with the basic dye at a pH lower than the isoelectric point of the gelatin.
• the photographic emulsion layer after the formation of images of a high molecular weight compound is first uniformly dyed at a pH higher than the isoelectric point of gelatin and thereafter the layer is washed with a washing solution having a pH lower than the isoelectric point of gelatin, whereby the areas having no images of the high molecular weight compound are washed out to leave the colored image areas of the high molecular weight compound. If it is desired to dye an im age of a high molecular weight compound having a positive charge with an acid dye, the process may be conducted at a pH higher than the isoelectric point of gelatin.
• the optimum range of pH depends on the type of the vinyl compound and the dye as well as the kind of binder used, such as gelatin.
• a suitable pH for the system is 2.5 to 4.5 when a high molecular weight compound having a negative charge is dyed by a basic dye and 5.0 to 8.0 when a high molecular weight compound having a positive charge is dyed with an acid dye.
• the examples of the acid dyes used in this invention are, for instance, C.I. Acid Yellow 7 (Color Index 56,- 205), C.I. Acid Yellow 23 (C.I. 19,140), C.I. Acid Red (C.I. 18,050), C.I. Acid Red 52 (C.I. 45,100), C.I. Acid Blue 9 (C.I. 42,090), C.I. Acid Blue 62 (C.I. 62; 045), and C.I. Acid Violet 7 (C.I. 18,055).
• the examples of the basic dyes used in this invention are C.I. Basic Yellow 1 (C.I. 49,005), C.I Basic Yellow 2 (C.I. C.I. Basic Red 1 (C.I.
• Polymer images can be formed by washing away only the unpolymerized portion of the vinyl monomer after exposure, reduction, and polymerization, because the polymer is less soluble than the monomer and can scarcely diffuse through the high polymer such as gelatin which is used as a binder for the silver halide photographic emulsion.
• monomers having at least two vinyl groups in combination, insolubility and non-dissolubility of polymer obtained can be increased.
• Dye images corresponding to the polymer images are obtained by dyeing, as aforementioned, after polymerization.
• the images which are made by this procedure can be utilized as clear dye images by fixing the silver halide to remove it, and then dissolving out the silver image by applying an oxidizing agent and a solvent for silver salts.
• the dye images thus produced can be transferred onto other supports.
• a support to receive dye images must be brought into intimate contact with a layer containing dye image produced as above mentioned, which is wetted with a solvent for the dye such as methanol, water, or an aqueous solution of acid, base or salt.
• the supports onto which the dye image is to be transferred may be of ordinary paper, or paper or film coated with a hydrophilic polymer of gelatin can be used.
• a mordant such as aluminum salt beforehand, in the same way as the usual dye transfer process.
• an image composed of the ionizable polymer is made, it is possible to make a number of copies by dyeing and transferring as above mentioned, since several copies can be made with one dyeing and the polymer image can be dyed repeatedly.
• EXAMPLE 1 A fine grain gelatin silver chlorobromide photographic emulsion which contained silver chlorobromide, corresponding to about 42 g. of elementary silver and containing chlorine and bromine in molar ratio of 7:3, and about 60 g. of gelatin per liter was divided into two portions and was exposed to fluorescent lamps. For the purpose of exposure, 200 cc. of the liquid emulsion at 35 C. was spread in a vat of 20 cm. x 25 cm. and then exposed to light of about 300 luxes for 5 minutes with continuous agitation. Thereafter, 2 ml. each of the exposed emulsion and unexposed emulsion was charged into a test tube of about 1.6 cm. in diameter and after adding 6 ml.
• acrylamide was polymerized to raise the temperature of the system by the heat of polymerization.
• the temperature of the system reached 96 C. at about 82 minutes after the start of reaction, and the content of the test tube became rubbery due to the polyacrylamide formed, and was. not dissolved in a large quantity of methanol.
• the temperature reached to 100 C. after 27 minutes and 21 minutes, respectively, in the case of exposed emulsion, while the temperature of the unexposed emulsion reached only to 50 C. and 53 C., respectively, at the same time.
• EXAMPLE 4 EXAMPLE 2 T d E I d
• Examples 1 through were carried out using using th r a lieri dlz gh y v n T able l iii st eat 'l Zi 1352:4 1 Water 1 1 3 Vinyll onipounds, 1ssilrgbhtly scl luble tetiraethylene co imet acr ate cou e o erize in an pheuylacetlc acid and varying the amount of sodium hyemuliign' y p ym g gfi 1 33 2 'g igj g lgi ig g i j A tetraethylene glycol dimethacrylate emulsion was prethe amouni of 1 N a ueou sodiurn h dro id solution pared by mixing 20 ml: of tet
• yrosine 8 6 30 3,5-diiodotyrosine 433 45 1.0 100 s7 52 24 2,6-b1's-(hydroxymethyl)-p-cresol 168 48 2.0 56 27 61.5 18 Dimethylaminornethylphenol (o.p. mixture) 151 48 2. 0 98.1 30 48. 1 19.. Hordenine sulfate 465 48 2.0 100 18 48 10 5 149 48 2.0 75 57 5s a a 2; as a 91 5-hydroxyhydrindene 134 48 210 70 9 a a a a a a -B.I11l!10n FY10 11.- 3-methyl-4-isopropylphenol 160 48 2.0 54 48 49 27..
• the film had been prepared by applying a subbing coat to both sides of a polyethylene terephthalate film, applying an antihalation layer to one of the surfaces of the so under-coated film, and applying to the other surface a silver halide photographic emulsion.
• the photographic emulsion was prepared by adding a suitable amount of merocyanine dyes with a sensitization maximum of about 550 mm. for the sake of optical sensitization, and 1.5 g.
• a gelatino silver chloroiodobromide emulsion containing, per mole of silver, about 0.7 mole of chlorine, about 0.3 mole of bromine, about 0.001 mole of iodine and about 100 g. of lime processed gelatin.
• the resulting coated film contained 50 mg. of silver per 100 cm.
• a gelatin protective layer of about 0. 8p. thickness was further applied on said emulsion layer.
• the resulting product is suitable for making line and half-tone images .for the graphic arts.
• the emulsion layer was exposed for 2 seconds to light of about 100 luxes and thereafter immersed in a solution having the following composition under a red stable light.
• the sample was immersed in a 0.1% aqueous solution of a red basic dye (Rhodamine 6 G.C.P., C.I. Basic Red I) for minutes at room temperature. Thereafter, when the sample was washed with an aqueous 5% acetic acid solution for 5 minutes, the dye at the areas other than the brown image area was washed out, while the image portions remained colored red. Since the brown image was a silver image, the silver image could be removed by farmers reducer. By removing the silver image, a clear red image was obtained. When the order of dyeing and removal of silver image was changed, that is the silver image was first removed to provide a colorless and transparent image and thereafter the image was dyed, a clear red image was also obtained.
• a red basic dye Rhodamine 6 G.C.P., C.I. Basic Red I
• the dye image thus prepared could be transferred to paper.
• the surface of a usual writing paper was lightly rubbed by a sponge containing methanol to wet the surface with methanol, the color image prepared above was brought into close contact with the wet surface of the paper, and both members were separated after about 30 seconds; the red image was thereby transferred onto the paper.
• EXAMPLE 6 The photographic light-sensitive film as in Example 5 was exposed as in the same example, and then immersed in the solution having the following composition:
• EXAMPLE 8 The photographic light-sensitive film, as in Example 5, was exposed as in the same example and was processed in a solution having the following composition.
• the density increase by dyeing the exposed portion was higher than that of the unexposed portion, and hence the exposed portion was dyed selectively.
• a red acid dye Solar Rhodamine B extra (C.I. Acid Red 52) was employed.
• the film having a polymer image was immersed in the dye solution for minutes, to dye the whole area of the layer, and thereafter immersed for 3 minutes in a Kolthoffs buffer solution, having a pH of 5.0, followed by rinsing to provide the sample in which only the image area was dyed red.
• the dye image could be transferred to a writing paper wetted by ethanol.
• the image could be transferred also to the wet receiving paper described above.
• EXAMPLE 9 The photographic light-sensitive film of Example 5 was exposed as in the same example and then processed in the By using a photographic light-sensitive film having a solution having the following composition to conduct silver iodobromide emulsion, the polymerization of sodevelopment and polymerization. dium methacrylate was conducted.
• Potassium methasulfite 03 with steep gradation 1n photoengravmg processes was pre- 2 N aq. sodium hydroxide The amount necessary to pared y solution. maintain a pH of 11.5.
• a receiving paper prepared by applydium methacrylate 7.5 g. ing a gelatin layer to a baryta-coated paper in a thickness Orthoxylenol 0.54 g. of 10 microns, immersing the paper in an aqueous solu- Potassium metabisulfite 0.3 g. tion of alum, and drying, was wetted by water closely con- Water 7.5 ml, tacted to the aforesaid dye image and allowed to stand 2 N aq. sodium hydroxide The amount necessary to adjust for 1 minute, the dye image was transferred to the receiving paper and after separation a clear blue image having high density was obtained.
• the film was processed in the solution for 50 minutes at 30 C., a faint brown image was obtained.
• the layer was dyed with Rhodamine 6 GCP and a dye image having a high density was obtained only at the exposed portions.
• EXAMPLE 11 The same photographic light-sensitive film as used in Example was irradiated by X-rays and thereafter processed in the same way as in Example 5.
• the X-ray exposure was conducted at 30 kv. and ma., using a cobalt X-ray tube made by Phylips Co. In this case, a part of the sample had been covered by a razor blade of 0.2 mm. in thickness and the sample had been place in front of a window of the X-ray tube at the distance of 1 cm.
• the exposed layer was processed for 18 minutes at 30 C., as in Example 5, fixed, rinsed, and dyed by Rhodamine 6 GOP, whereby a silver image was formed at only the portions directly irradiated by X-rays and these portions were selectively dyed.
• the process of this invention can also be applied to a silver halide emulsion layer exposed to a high energy ray as well as visible rays.
• a process for forming polymer images by develop ment polymerizing at least one addition-polymerizable vinyl monomer without the formation of a dense silver image comprising:
• R R R R R and R is selected from the group (a), (b), and (c), as follows:
• R represents a member selected from the group consisting of methyl, hydroxymethyl, dialkylaminomethyl, bnomomethyl, carboxymethyl, carboxyl, and acyl groups; R and R each represent a member selected from the group consisting of hydrogen and alkyl groups; R represents a member selected from the group consisting of hydrogen, halogen, and alkyl groups; and R represents a member selected from the group consisting of hydrogen, halogen, alkyl and hydroxymethyl group; said R and R may form a naphthalene ring;
• R and R each represent a member selected from the group consisting of hydrogen and halogen atom; R and R each represents a member selected from the group consisting of hydrogen and alkyl groups; and R represents a member selected from the group consisting of halogen, alkyl, aralkyl and substituted alkyl groups; said R and R may form an alkylene ring of l to 6 carbon atoms; and
• R R R and R each represents hydrogen and R represents a tertiary alkyl group.
• said latent image is formed by exposing imagewise the photographic silver halide emulsion layer formed on a support to visible rays or high energy rays and said polymerization is conducted by immersing said layer, after said imagewise exposure in an aqueous alkaline solution containing said monomer and said phenol.
• said latent image is formed by exposing imagewise the photographic silver halide emulsion layer formed on a support to visible rays or high energy rays and said polymerization is conducted by immersing said layer after said imagewise exposure in an aqueous alkaline solution containing said monomer together with said phenol and said sulfite ions.
• said addition polymerizable vinyl monomer contains a group capable of being charged by electrolytic dissociation or by the addition of a hydrogen cation whereby said monomer is selectively polymerized at the portions of the emulsion layer bearing the latent silver image to form an image of said polymer on said emulsion layer, and dyeing said polymer image selectively with a dye having a charge, when dissociated, opposite to the charge of said polymer.
• said latent silver image is formed by exposing imagewise the photographic silver halide emulsion layer formed on a support to visible rays or high energy rays and said polymerization is conducted by immersing said layer after said imagewise exposure in an aqueous alkaline solution containing said monomer and said phenol.
• R and R have from 1 to 4 carbon atoms when alkyl, when R is alkyl there are from 1 to 8 carbon atoms in said alkyl group, and R is methyl when alkyl, and R -R5 are selected from group (a).
• R and R when alkyl have from 1 to 4 carbon atoms; R when alkyl, has from 1 to 8 carbon atoms and said R and R when forming an alkylene ring, have from 1 to 6 carbon atoms and -R R are selected from group (b).
• R is t(er)tiary butyl, and said R R are selected from group 13.
• said sulfite ions are present in an amount of greater than 0.05 mole per liter of the system.
• said vinyl monomer is acrylamide, acrylonitrile, N-hydroxymethylacrylamide, methacrylic acid, acrylic acid, calcium acrylate, methyl methacrylate, sodium acrylate, methacrylamide, methyl acrylate, ethyl acrylate, vinyl pyrrolidone, vinylmethyl ether, vinylbutyl ether, vinylisopropyl ether, vinylisobutyl ether, vinyl butyrate, 2-vinylpyridine, 4-vinylpyridine, Z-methyl-N-vinyl imidazole, potassium vinylbenzene sulfonate, vinyl carbazole, and N,N'-methylenebis-acrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinyl ether or divinyl benzene.
• phenol compound is selected from the group consisting of p cresol, 4-t-butylphenol, 3-t-butylphenol, 4-sec-butylphenol, 4-taminophenol, 4-t-octyl-phenol, p-benzylphenol, orthoxylenol, S-hydroxyhydrindene, 5,6,7,8-tetrahydro-fl-naphthol, 3-methyl-4-isopropylphenol, 3-butyl-4-isopropylphenol, 3, 4,5-trimethylphenol, 2,3,5-trimethylphenol, 2,3,5,6-tetramethylphenol, hexestrol, 2-dimethylaminomethylphenol, dimethylaminomethylphenol (QR-mixture), hordenine, tyramine, tyrosine, 2-dimethylaminomethyl-3,6-xylenol, 2,6-dihydroxymethylphenol, 2,6-dihydroxymethyl-p-cresol,

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• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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• 1969
  • 1969-01-06 BE BE726531D patent/BE726531A/xx unknown
  • 1969-01-06 GB GB811/69A patent/GB1247251A/en not_active Expired
  • 1969-01-09 FR FR6900207A patent/FR2000110A1/fr not_active Withdrawn
  • 1969-01-10 DE DE1901193A patent/DE1901193C3/de not_active Expired
• 1971
  • 1971-08-03 US US00168742A patent/US3782943A/en not_active Expired - Lifetime

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