Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/30—Hardeners

Definitions

• This invention relates to a process for preparing a silver halide photographic light-sensitive material for photo-mechanical process (which is hereafter referred to as "light-sensitive material for photo-mechanical process”) and particularly it relates to a process for preparing a light-sensitive material for photo-mechanical process which utilizes the selective hardening technique of the coating layers in order to improve aptitude for reduction treatment.
• Light-sensitive materials for photo-mechanical process are light-sensitive materials used in a photo-mechanical process step in the field of graphic art, such as for converting a continuous density image into a dot image or photographing a line drawing, etc.
• a treatment called reduction treatment is frequently conducted.
• This treatment is performed in order to obtain delicate reproduction of tone or satisfy artistic expression of the images adapting to printing characteristics, by which fine correction of images is carried out partially or completely.
• the corrections may include reduction of the area of dots or widening or narrowing of the width of a line drawing.
• reducers When carrying out reduction treatment of light-sensitive materials for photo-mechanical process having dot images or line drawing images formed by exposure and development processing, it has been known to use a method which comprises contacting metal silver forming the dot images or line drawing images with a reducer.
• a reducer Various kinds of reducers are known.
• reducers using a reducing component such as a permanganate, a ferric salt, a cerium (IV) salt, a ferricyanide, a bichromate or a persulfate, etc., are described in Mees, The Theory of the Photographic Process, pages 738-739 (1954, published by Macmillan Co.).
• reduction treatment means a treatment comprising oxidizing silver images by a reducer to dissolve them
• the decrease in area of dots is achieved accompanying with a decrease in black density of dots. Therefore, the extent to which dot images can be corrected by the reduction treatment is restricted by a degree of the decrease in black density of each dot which occurs together with the decrease in area of dots.
• a measure of the extent to which dot image can be corrected can be represented by a reduction of the area of dots while maintaining the black density of each dot at a specified value or more.
• the term “reduction width” means a decrease in the area of dots from the area of dots before the reduction treatment when the black density of the dots is decreased by the reduction treatment to the lowest value necessary for the photo-mechanical process step.
• the term “reduction time” means the time necessary to accomplish the reduction treatment by which the black density of the dots is decreased to the lowest value necessary for the photo-mechanical process step.
• the reduction time is necessary to be a proper length because when it is so much shorter or longer, the reduction operation is hard to carry out, and it is preferred to be several ten seconds to several minutes.
• a method for improving aptitude for reduction treatment is described, for example, in Japanese Patent Application (OPI) No. 68419/77.
• a mercapto compound is used for the reduction treatment.
• the reducer is specific and difficult to use, because its reduction rate is different from that of conventionally used reducers. Further, it is possible to improve the aptitude for reduction treatment while increasing the covering power by softening the emulsion film, but the required film strength cannot be obtained by this method.
• the most effective method for improving the aptitude for reduction treatment due to widening the reduction width is increasing the silver content for forming the images.
• This method is effective because the ability to correct images by the reduction treatment is generally increased when there is a greater amount of silver in the silver images per unit area, where, as described above, the reduction treatment comprises oxidizing silver images by a reducer to dissolve them. Therefore, the reduction width can be increased when a coating amount of silver halide per unit area in light-sensitive material for photo-mechanical process to be used is increased.
• increasing the coating amount of silver is not preferred in view of the cost of the light-sensitive material for photo-mechanical process and economy of resources.
• the present inventors has found a technique for remarkably improving of the aptitude for reduction treatment by controlling the hardness of the light-insensitive upper layer and the hardness of the silver halide emulsion layer independently using a non-diffusion polymeric hardener for the light-insensitive upper layer (i.e., selective hardening technique of coating layers) and widening the reduction width by enlarging the hardness of the light-insensitive upper layer [Japanese Patent Application (OPI) No. 42039/83 (corresponding to British Patent 2,108,695A)].
• OPI Japanese Patent Application
• solution-preparing and solution- supplying system such as in a preparation tank, in a solution-supplying pipe or in an apparatus for supplying and for coating a coating solution for photographic layer on a support (e.g., a hopper) (hereafter referred to as "solution supplying apparatus") during time from preparation of the coating solution for photographic layer to coating the same (hereafter referred to as "dissolution time") and then gradually increasing a viscosity of the coating solution.
• solution time e.g., a hopper
• the occurrence of the increasing of viscosity of coating solution with the lapse of time can be previously prevented by adding the hardener continuously just before the formation step, as described in German Patent Application (OLS) No. 2,648,286, and the increasing of viscosity of coating solution with the lapse of time can also be prevented ii) by changing the pH of the coating solution or iii) by dividing the hardener to coating solutions of the layers other than the proposed layer.
• the above-mentioned first method is difficult to achieve a uniform hardening
• the above-mentioned second method is also ineffective because the change of the hardening rate due to pH is small, and the third method described above cannot be adopted because of its nondiffusibility.
• fine particles which are referred to a matting agent are often added in order to improve slipping or adhesion resistance, but a problem that the opacity (referred to a haze) of the coating layer becomes large by adding the matting agent proved to be caused.
• the first purpose of this invention is to provide a process for preparing a light-sensitive material aptitude for reduction treatment of which is improved without increasing the coating silver amount, rapidly and without causing the increasing of viscosity of coating solultion with the lapse of time.
• the second purpose of this invention is to provide a process for preparing a light-sensitive material for photo-mechanical process having a coating layer with excellent transparency.
• the purposes of this invention can be achieved by coating at least one light-sensitive silver halide emulsion layer on a support and a light-insensitive upper layer consisting of a hydrophilic colloid on an upper portion of the emulsion layer and, simultaneously or after this coating, coating a composite solution in which a nondiffusion polymeric hardener is contained in a gelatin solution in an amount enough to make the melting time of the layer made by this composite solution larger than the melting time of the emulsion layer on the above-mentioned light-insensitive upper layer so that the gelatin coating amount is in the range of from 0.05 g/m 2 to 0 . 5 g /m 2 .
• An important aspect of the present invention involves making a gelatin thin layer by coating a gelatin solution containing a nondiffusion polymeric hardener on a light-insensitive upper layer so that the gelatin coating amount is in the range of from 0.05 g/m 2 to 0 . 5 g/m 2 .
• the presence of this layer can prevent the viscosity from increasing with the lapse of time which takes place conventionally when a polymeric hardener is added to a coating solution for the light-insensitive upper layer containing a large amount of gelatin.
• the aptitude for reduction treatment and film strength can be sufficiently maintained.
• a matting agent is contained in the light-insensitive upper layer, an advantage in which the transparency of all the coating films increases by coating the above-mentioned gelatin thin layer on the upper part of light-insensitive upper layer can be obtained.
• the gelatin of the gelatin thin layer of this invention is not particularly restricted, but, preferably, a so-called inert gelatin which shows little activity with respect to photographic property is used.
• the gelatin coating amount is set in 0.05 to 0.5 g/m 2 , particularly 0.05 to 0. 2 g/m 2 .
• the gelatin concentration of this gelatin solution is desired to be thin, particularly it is desired to be 0.1 to 2 weight %, more particularly 0.5 to 1.5 weight %.
• a coating solvent water or organic solvents (especially, those having a compatibility with water) can be used, but, in general, water is most preferable.
• various surface active agents can be added as coating aid.
• natural surface active agents such as saponin, nonionic surface active agents such as alkyleneoxide type, glycidol type and the like, anionic surface active agents containing an acidic group such as carboxylic acid, sulfonic acid (e.g., those described in U.S. Patent 3,415,649), phosphoric acid, sulfates, phosphates and the like, and amphoteric surface active agents such as amino acids, aminosulfonic acids, sulfates or phosphates of amine alcohol and the like are preferably used.
• anionic surface active agents containing an acidic group such as carboxylic acid, sulfonic acid (e.g., those described in U.S. Patent 3,415,649), phosphoric acid, sulfates, phosphates and the like
• amphoteric surface active agents such as amino acids, aminosulfonic acids, sulfates or phosphates of amine alcohol and the like are preferably used.
• the nondiffusion polymeric hardener used in this invention is a polymeric compound having a reactive group which can react with gelatin and possesses the nondiffusibility because of being a large molecules.
• the specific examples include the polymeric hardeners which are well known by patents such as Japanese Patent Application (OPI) No. 66841/81, British Patent 1,322,971, U.S. Patent 3,671, 256 and the like and books such as D.M. Burness and J . Pouradier, The Theory of the Photographic Process, 4th ed. (T.H. James ed.), Macmillan,- New York, 1977, p. 84, G. A . Campbell, L.R. Hamilton and I.S. Ponticello, Polymeric Amine and Ammonium Salts (E.J. Goethals ed.), Pergamon Press, New York, 1979, pp. 321-322 and the like.
• A represents an ethylenically unsaturated monomer unit copolymerizable with a monomer unit set forth on the right side
• R 1 represents a hydrogen atom or a lower alkyl group having from 1 to 6 carbon atoms
• Q represents -C0 2 -, (wherein R 1 has the same meaning as defined above) or an arylene group having from 6 to 10 carbon atoms
• L represents a divalent group having from 3 to 15 carbon atoms and containing at least one linking group selected from the members consisting of -CO 2 and (wherein R 1 has the same meaning as defined above) or a divalent group having from 1 to 12 carbon atoms and containing at least one linking group selected from the members consisting of -O-, -co-, -SO-, -SO 2 -, -SO 3 -
• Examples of ethylenically unsaturated monomers represented by A of the general formula (I) include ethylene, propylene, 1-butene, isobutene, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N, N ,N-trimethyl-N-vinylbenzyl- ammonium chloride, N ,N-dimethyl-N-benzyl-N-vinylbenzylammo- nium chloride, a-methylstyrene, vinyltoluene, 4-vinylpyridine, 2-vinylpyridine, benzyl vinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone, l-vinyl-2-methylimidazole, a monoethylenically unsaturated ester of an aliphatic acid (e.g., vinyl acetate
• Preferred examples of ethylenically unsaturated monomers represented by A of the general formula (I) include water soluble monomers, for example sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N,N,N-trimethyl-N-vinylbenzylammonium chloride, N , N - dimethyl-N-benzyl-N-vinylbenzylammonium chloride, sodium acrylate, N,N,N-triethyl-N-methacryloyloxyethylammonium-p-toluene sulfonate, N,N-diethyl-N-methyl-N-methacryloyloxy- ethylammonium-p-toluene sulfonate, acrylamide, N,N,N-trimethyl-N-(N-acryloylpropyl)ammonium-p-toluene sulfonate, sodium 2-acrylamido-2
• ethylenically unsaturated monomers represented by A of the general formula (I) include water soluble anionic monomers are water soluble amphoteric monomers, for example sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, sodium acrylate, sodium 2-acrylamido-2-methylpropane sulfonate, N,N-dimethyl-N'-acryloyl propane diamine propionate betaine, N,N-dimethyl-N'-methacryloyl propane diamine acetate betaine, etc. and acrylamide.
• water soluble anionic monomers are water soluble amphoteric monomers, for example sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, sodium acrylate, sodium 2-acrylamido-2-methylpropane sulfonate, N,N-dimethyl-N'-acryloyl propane diamine propionate betaine, N,N-dimethyl-N'-methacryloy
• "A” includes not only the ethylenically unsaturated monomers described above but also monomers having at least two copolymerizable ethylenically unsaturated groups (e.g., divinylbenzene, methylenebisacrylamide, ethylene glycol diacrylate, trimethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylene glycol dimethacrylate and neopentyl glycol dimethacrylate, etc.).
• divinylbenzene methylenebisacrylamide
• ethylene glycol diacrylate trimethylene glycol diacrylate
• ethylene glycol dimethacrylate trimethylene glycol dimethacrylate
• trimethylene glycol dimethacrylate and neopentyl glycol dimethacrylate etc.
• R 1 of the general formula (I) examples include a methyl group, an ethyl group, a butyl group and an n-hexyl group.
• Q of the general formula (I) include the following groups: -CO 2 -, -CONH-,
• L of the general formula (I) examples include the following groups: -CH 2 CO 2 CH 2 -, -CH 2 CO 2 CH 2 CH 2 -, -CH 2 CH 2 CO 2 CH 2 CH 2 -, -(CH 2 ) 5 -CO 2 CH 2 CH 2 -, -(CH 2 ) 10 CO 2 CH 2 CH 2 -, -C H 2 NHCOCH 2 -, -CH 2 NHCOCH 2 CH 2 -, -(CH 2 )- 3 NHCOCH 2 CH 2 -, -(CH 2 ) 5 NHCOCH 2 CH 2 -, -(CH 2 ) 10 NHCOCH 2 -CH 2 -, -CH 2 OCH 2 -, -CH 2 CH 2 OCH 2 CH 2 CH 2 -, -COCH 2 CH 2 -, -CH 2 COCH 2 CH 2 -, -SOCH 2 CH 2 -, -CH 2 SOCH 2 CH 2 -, -SO 2 CH 2 CH 2 -.
• Other preferred examples of the polymeric hardeners are described in U.S.
• Examples of A of the general formula (II) include the same examples of A of the general formula (I), examples of R of the general formula (II) include the same examples of R 1 of the general formula (I) and examples of R' of the general formula (II) include the same examples of R 2 of the general formula (I), all of which are described above.
• A represents an ethylenically unsaturated monomer unit copolymerizable with a monomer unit set forth on the right side
• R represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms
• L represents a divalent linking group having from 1 to 20 carbon atoms (more preferably a divalent group having from 1 to 12 carbon atoms and containing at least one linking group selected from the members consisting of -CONH- and -CO-)
• X represents an active ester group
• x and y each represents molar percent, x being from 0 to 95% and y being from 5 to 100
• m represents 0 or 1.
• Examples of A of the general formula (III) include the same examples of A of the general formula (I) and examples of R of the general formula (III) include the same examples of R 1 of the general formula (I), both of which are described above.
• L of the general formula (III) examples include the following groups: -CONHCH 2 -, -CONHCH2CH2-, -CONHCH 2 CH 2 CH 2 -, -CONHCH 2 CH 2 CH 2 CH 2 CH 2 -, -COCH 2 CH 2 OCOCH 2 CH 2 -, -CONHCH 2 CONHCH 2 -, -CONHCH 2 CONHCH 2 CONHCH 2 -, -COCH 2 -, -CONHCH 2 NHCOCH 2 CH 2 SCH 2 CH 2 - and -CONHCH 2 OCOCH 2 CH 2 -.
• Examples of X of the general formula (I I I) include the following groups: - -
• M represents a hydrogen atom, sodium atom or potassium atom
• x and y each represents the mole percentage of the starting amount in each unit, and is not limited by the above, and x can take a value of 0 to 99 and y a value of 1 to 100.
• Preferred examples of the compounds which can be used in the present invention include compounds having a vinyl sulfone group and the precursor thereof as a functional group capable of reacting with gelatin, for example, P-l, P-2, P-3, P-4, P-6, P-7, P-8 and P-9. Particularly preferred example of the compound includes P-2.
• the molecular weight of compounds which can be used in the present invention is at least about 10,000, and it is preferably 10,000 to several hundred thousands with respect to a non-cross-linked compounds.
• the addition amount is an amount sufficient to make the melting time of the thin layer made by the low molecular gelatin solution longer than the melting time of the light-sensitive silver halide emulsion layer.
• the amount of compounds which can be used in the present invention is preferably 5xlO -4 equivalent to 0.1 equivalent, particularly preferably 2x10 -3 equivalent to 4x10 -2 equivalent per 100 g of gelatin used in the gelatin thin layer coated on the light-insensitive upper layer expressed in terms of the amount of functional group capable of reacting with gelatin.
• the amount of compounds varies corresponding to a melting time of the gelatin thin layer.
• the polymeric hardener is added to a gelatin solution directly or more preferably by dissolving it in water or an organic solvent.
• melting time of the thin layer made by the gelatin solution having a low concentration is longer than the melting time of the emulsion layer means that the layer made by the gelatin solution having a low concentration is hardened more strongly than the emulsion layer.
• the melting time of the thin layer made by the gelatin solution is larger than that of the emulsion layer by 50 seconds or more, particularly 100 seconds or more, according to the above mentioned measuring method.
• the gelatin solution thus prepared (particularly, a dilute solution) is coated on the light-insensitive upper layer established on the light-sensitive silver halide emulsion layer by the coating processes public known in the field of photographic light-sensitive materials such as extrusion coating, curtain coating, air-knife coating processes and the like. As the occasion demands, all of these layers can be coated by multilayer simultaneous coating, for example, by the methods described in U.S. Patent 2,761,791 and British Patent 837,095.
• the coating film thickness of the gelatin solution of this invention is preferably a thin layer having a dry film thickness of less than 0.3 p, particularly 0.2 p or less.
• the light-sensitive silver halide emulsion layer of this invention and the coating solution for this those generally used for light-sensitive materials for photo-mechanical process can be used.
• silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide and etc. can be used. However, it is particularly preferred to use silver chlorobromide or silver chloroiodobromide containing at least 60% by mol (preferably 75% by mol or more) of silver chloride and 0 to 5% by mol of silver iodide.
• Form, crystal habit and distribution of size of the silver halide particles are not especially limited, but it is preferred to have a particle size of 0.7 p or less.
• the sensitivity of the silver halide emulsion can be increased without increasing the particle size of silver halide by using a gold compound such as chloroaurate or gold trichloride, a salt of noble metal such as rhodium or iridium, a sulfur compound capable of forming silver sulfide by reacting with a silver salt, or a reducing substance such as a stannous salt or an amine. Further, it is possible to add a salt of noble metal such as rhodium or iridium, or an iron compound such as ferricyanide at the time of physical ripening or nucleus forming of silver halide particles.
• the photographic emulsion used in the present invention may be subjected to spectral sensitization using a methine dye, etc.
• These sensitizing dyes may be used individually or as a combination thereof.
• a combination of sensitizing dyes is often employed -particularly for the purpose of supersensitization.
• the sensitizing dyes may be present in the emulsion together with dyes which themselves have no spectrally sensitizing effects but exhibit a supersensitizing effect or materials which do not substantially absorb visible light but exhibit a supersensitizing effect.
• any known anti-fogging agents as described, for example, in Japanese Patent application (OPI) Nos. 81024/74, 6306/75 and 19429/75, U.S. Patent 3,850,639 such as numbers of heterocyclic compounds including 4-hydroxy-6-methyl-l,3,3a,7-tetra- azaindene, 3-methylbenzothiazole or 1-phenyl-5-mercaptotetrazole, etc., mercury containing compounds, mercapto compounds, etc.
• OPI Japanese Patent application
• Patent 3,850,639 such as numbers of heterocyclic compounds including 4-hydroxy-6-methyl-l,3,3a,7-tetra- azaindene, 3-methylbenzothiazole or 1-phenyl-5-mercaptotetrazole, etc., mercury containing compounds, mercapto compounds, etc.
• a surface active agent may be added to the light-sensitive silver halide emulsion layer of the present invention as a coating aid or for the purpose of improving photographic properties.
• useful surface active agents include a natural surface active agent such as saponin, a nonionic surface active agent such as alkylene oxide type, glycidol type, etc.; an anionic surface active agent containing an acid group such as a carboxylic acid, a sulfonic acid (for example, surface active agents as described in U.S. Patent 3,415,649), a phosphoric acid, a sulfuric acid ester, a phosphoric acid ester group, etc.; and an ampholytic surface active agent such as an amino acid, an aminosulfonic acid, or a sulfuric acid or phosphoric acid ester of aminoalcohol, etc.
• a natural surface active agent such as saponin
• a nonionic surface active agent such as alkylene oxide type, glycidol type, etc.
• an anionic surface active agent containing an acid group such as a carboxylic acid, a sulfonic acid (for example, surface active agents as described in U.S. Patent 3,415
• Polyalkylene oxide compounds which can be used in the present invention include alkylene oxide having from 2 to 4 carbon atoms, for example, ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, etc.; preferably condensation products of polyalkylene oxide composed of at least 10 ethylene oxide units and a compound having at least one active hydrogen atom such as water, an aliphatic alcohol, an aromatic alcohol, a fatty acid, an organic amine or a hexitol derivative; and block copolymers of two or more polyalkylene oxides.
• examples of the polyalkylene oxide compounds used include polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol alkylaryl esters, polyalkylene glycol esters, polyalkylene glycol fatty acid amides, polyalkylene glycol amines, polyalkylene glycol block copolymers and polyalkylene glycol graft polymers, etc.
• a polymer latex composed of a homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid or cresidyl acrylate, etc., as described in U.S. Patents 3,411,911, 3,411,912, 3,142,568, 3,325,286 and 3,547,650 and Japanese Patent Publication No. 5331/70, etc., to the light-sensitive silver halide emulsion layer in order to improve dimensional stability of the photographic material or improve film properties thereof.
• hydrophilic colloid binder used in the light-sensitive silver halide emulsion layer of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used.
• a protein such as a gelatin derivative, a graft polymer of gelatin and another polymer, albumin or casein, etc.; a saccharide such as a cellulose derivative such as hydroxyethyl cellulose, carboxymethyl cellulose or cellulose sqlfate, etc.,, sodium alginate, etc.; and a'hydrophilic synthetic polymeric substance such as a homo- or copolymer including polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinyl pyrazole, etc.
• gelatin examples include not only lime-processed gelatin but also acid-processed gelatin and enzyme-processed gelatin as described in Bull. Soc. Sci. Phot. Japan, No. 16, page 30 (1966) may be used. Further, a hydrolyzed product and an enzymatic decomposition product of gelatin can be used.
• the ratio by weight of the hydrophilic colloid binder to silver halide in the light-sensitive silver halide emulsion layer in the present invention is 1/2 or less.
• the light-sensitive silver halide emulsion layer is not always composed of one layer but it may be composed of two or more layers.
• the ratio of the total amount of silver halide in the two layers to the hydrophilic colloid binder is 2 or more and that the upper light-sensitive emulsion layer contains a larger amount of hydrophilic colloid binder than the lower light-sensitive emulsion layer.
• the amount of silver halide to be coated is from 1.0 to 6.0 g and, preferably, from 1.3 to 4.0 g calculated as silver per square meter. Particularly excellent effects can be obtained when a small amount of silver is coated.
• the light-insensitive upper layer of this invention essentially consists of a hydrophilic colloid and the layers having the composition which is generally known as protective layers and inter-layers can be used.
• the use of gelatin is preferable as the hydrophilic colloid, but instead of gelatin or together with gelatin, the hydrophilic colloids other than the gelatin as described above may be used.
• gelatin besides the lime-processed gelatin, the acid-processed gelatin and the enzyme-processed gelatin described in Bull. Soc. Sci. Phot. Japan, No. 16, p. 30 (1966) may be used and the hydrolysis products or enzyme decomposed products of gelatin can also be used.
• slipping and adhesion resistance can be improved by adding a matting agent in the light-insensitive upper layer.
• the matting agent described in Research Disclosure, Vol. 176, pp. 22-28 (December, 1978) can be used, and the grains of 0.1 to 10 p (especially 1 to 5 u) of silicon dioxide or particularly polymethyl methacry - late are preferred.
• the amount of the matting agent used is not particularly limited, but, in general, the range in 0.05 g/m 2 to 0 . 2 g/m 2 is preferable.
• the process of this invention can also improve the haze which conventionally occurred when the matting agent was used.
• a polymer latex may be contained in the light-insensitive upper layer for the purpose of preventing the reticulation which is easy to occur when a layer having a different hardness is established.
• the usable polymer latex includes a hydrate of a vinyl polymer containing a monomer unit such as an acrylic. acid ester, a methacrylic acid ester, styrene, etc., as described in U.S. Patents 2,772, 166, 3,325,286, 3,411,911, 3,311,912 and 3,525,620, Research Disclosure, Vol. 195, No. 19551 (July, 1980), etc.
• a preferred average particle size of the polymer latex used in the present invention is a range from 0.005 p to 1 ⁇ and particularly a range from 0.02 u to 0.1 ⁇ .
• polymer latex By the utilization of polymer latex, the occurrence of reticulation can be extremely effectively prevented.
• polymer latexes those having a high glass transition temperature (Tg) are preferred since they also have an ability to improve any antiadhesive property.
• polymer latexes having a glass transition temperature of room temperature or higher are preferred.
• a hydrate of a homopolymer of vinyl monomer such as methyl methacrylate, ethyl methacrylate, styrene, etc.
• a copolymer of such vinyl monomer and other vinyl monomer such as acrylic acid, N-methylolacrylamide, etc.
• the amount of the polymer latex used is preferably from 5% to 200% and more preferably from 10% to 100%, based on the weight of hydrophilic colloid contained in the layer to be added.
• the polymer latex can be added to the emulsion layer.
• the molecular weights of L-1 to L-5 are 10,000 to several hundred thousands, and those of L-6 to L-11 are infinite because those polymer latexes are subjected to gelation by cross-linked.
• the polymerization initiator was added to the above-described mixture while maintaining the temperature in the flask at 60°C. After 2 hours, the same polymerization initiator as described above was added to the reaction mixture and subjected to post polymerization for 2 hours. After cooling, the reaction mixture was filtered using a thin filter paper to obtain a polymer latex of methyl methacrylate of protein color which has 15.9% by weight of concentration, 0.04 p of particle size and 6.13 of pH.
• the light-insensitive upper layer in the present invention may contain a surface active agent, an antistatic agent, a lubricant, colloidal silica, a plasticizer for gelatin, etc., in addition to the above-described hydrophilic colloid binder (for example, gelatin), matting agent and polymer latex.
• the light-insensitive upper layer is coated at a total dry thickness of from 0.3 P to 5 p and particularly from 0.5 ⁇ to 3 ⁇ .
• a diffusion low molecular hardener is preferably used for hardening of the photosensitive silver halide emulsion layer and the light-insensitive upper layer of this invention.
• the low molecular hardener diffuses also to a thin layer made by the aforesaid gelatin solution, hardening the thin layer too, but as the thin layer is hardened by both the low molecular hardener and a non-diffusion polymeric hardener, it can achieve the selective hardening.
• various organic or inorganic hardeners are used, and typical examples include gelatin harders well known in this field such as aldehyde type compounds such as mucochloric acid, formaldehyde, trimethylolmelamine, glyoxal, 2,3-dihydroxy-l,4-dioxane, 2,3-dihydroxy-5-methyl-1,4-dioxane, suc- cinaldehyde and glutalaldehyde; active vinyl type compounds such as divinyl sulfone, methylene bismaleimide, 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3,5-trivinylsulfonyl-hexa- hydro-s-triazine, bis(vinylsulfonylmethyl) ether, 1,3-bis-(vinylsulfonyl)propanol-2, bis( a)
• the diffusion hardener When used, it may be added to either the light-insensitive upper layer or the emulsion layer.
• Examples of the preferable layer structures of the light-sensitive material for photo-mechanical process produced by the process for preparation of this invention include the order of an emulsion layer, a light-sensitive upper layer and a gelatin thin layer containing a non-diffusion polymeric hardener from the support; the order of an emulsion layer, a light-insensitive first upper layer, a light-insensitive second upper layer and a gelatin thin layer containing a polymeric hardener from the support; the order of an emulsion layer, a light-insensitive first upper layer, a gelatin thin layer containing a polymeric hardener and a light-insensitive second upper layer from the support and the like.
• a subbing layer may be established between the emulsion layer and the support.
• polyester films such as polyethylene terephthalate films and cellulose ester films such as cellulose triacetate films are preferably used.
• the development process of the light-sensitive material for photo-mechanical process produced by the process for preparation of this invention is not especially limited, and any processes generally used for processing of light-sensitive materials for photo-mechanical process can be used.
• the processing temperature is usually selected from the range of 18°C to 50°C, but the temperature lower than 18°C or higher than 50°C may be used.
• the developing solution can contain a known developing agent.
• a known developing agent dihydroxy benzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone), aminophenols (e.g., N-methyl-p-aminophenol), l-phenyl-3-pyrazolines, ascorbic acid and heterocyclic compounds such as the compound in which 1,2,3,4-tetrahydroquinoline ring and indolene ring are condensed as described in U.S. Patent 4,067,872 can be used independently or in combination thereof.
• the developing solution generally contains, besides the above, a public known preservative, an alkali agent, a pH buffer, an antifogging agent and the like, and may contain a dissolving aid, a tone agent, a development accelerator, a surface active agent, an defoaming agent, a water softener, a hardener, a viscosity-imparting agent and the like, as the occasion demands.
• a so-called developer for lithographic materials which is preferably used for this invention, is basically composed of ortho- or paradihydroxybenzene, an alkali agent, a small amount of free sulfites and a sulfurous acid ion buffer and the like.
• the ortho- or para-dihydroxybenzene developing agent can be suitably selected from those well known in the field of photograph.
• the specific examples include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone and the like.
• the hydroquinone is especially practicable.
• These developing agents are used independently or by mixing.
• the addition amount of the developing agent is 1 to 100 g, preferably 5 to 80 g, based on 1 t of the developer.
• the sulfurous acid ion buffer is used in an amount effective to keep the sulfite concentration in the developer nearly constant, and the examples include aldehyde hydrogensulfite alkali adducts such as formalin sodium hydrogensulfite adduct, keton-hydrogenesulfite alkali adducts such as acetone sodium hydrogenesulfite adduct, carbonyl bisulfurous acid-amine condensation product such as sodium-bis(2-hydroxyethyl)aminomethanesulfonate and the like.
• the used amount of th sulfurous acid ion buffer is 13 to 130 g based on 1 1 of the developer.
• the developer used in this invention can control the free sulfurous acid ion concentration by adding a sulfurous acid alkali salt such as sodium sulfite and the like.
• a sulfurous acid alkali salt such as sodium sulfite and the like.
• the addition amount of the sulfite is generally 5 g or less based on 1 1 of the developer, particularly, preferable to be 3 g or less, but it may be, of course, larger than 5 g.
• an alkali halide (especially, bromides such as sodium bromide and potassium bromide) is preferably used as a development modifier.
• the alkali halide is preferably added in an amount of 0.01 to 10 g, more preferably, 0.1 to 5 g, based on 1 l of the developer.
• An alkali agent is added so that the pH in the developer is 9 or more (especially, pH 9.7 to 11.5).
• various amounts of sodium carbonate or potassium carbonate are used as an alkali agent.
• those having the composition generally used can be used.
• the fixing agent as well as thiosulfates and thiocyanates, organic sulfur compounds whose effect as fixing agent is known can be used.
• the fixing solution may contain a water-soluble aluminium salt as hardener.
• a water-soluble aluminium salt as hardener.
• the development process may be carried out by hand or an automatic developing machine.
• the method of carrier e.g., roller carrier and belt carrier
• the carrier type automatic developing machine used in the field can be used.
• the descriptions of U.S. Patents 3,025,779, 3,078,024, 3,122,086, 3,149,551, 3,156,173, 3,224,356, 3,573,914 and the like can be referred.
• the reducer used for this invention is not particularly limited and, for example, those described in M ees, The Theory of the Photographic Process mentioned above is effectively used.
• the reduction component such as a permanganate, a persulfate, a ferric salt, a cupric salt, a cerium (IV) salt, a ferricyanide, a bichromate and the like are used independently or together with, and, if necessary, a reducer in which an inorganic acid such as sulfuric acid and alcohols are contained or a reducer in which a reducing component such as hexacyanoferrate (III), ethylenediamine tetraacetic acid ferric salt and the- like and a silver halide solvent such as thiosulfate, rhodan salt, thiourea or its derivative and the like and additionally an inorganic acid such as sulfuric acid, if necessary, are contained is used.
• a reducer in which an inorganic acid such as sulfuric acid and alcohols are contained or a reducer in which a reducing component such as hexacyanoferrate (III), ethylenediamine tetraacetic acid ferric
• a compound having a mercapto group as described in Japanese Patent Application (OPI) No. 68419/77 can be further contained as the occasion demands.
• composition of the reducer and treatment conditions (temperature, time, etc.) used for the reduction treatment of this invention are not particularly limited, and can be suitably decided by those skilled in the art.
• Keiichi Sakamoto, Retouch Technique Notebook, published by Japan Printing Technique Association (1980) can be referred to.
• the coating solutions of the following prescriptions are coated by multilayer -simultaneous coating method according to the instructions of Table 1 to produce Samples 1 to 5.
• a silver halide emulsion consisting of 80 mol% of silver chloride, 19.5 mol% of silver bromide and 0.5 mol% of silver iodide was prepared by gold sensitization and sulfur sensitization according to the general method.
• the obtained dot strips were immersed in the following cerium type reducer (20°C) and washed.
• the haze in this invention means a characteristic value regulated in JIS standard (JIS K 6714) and is shown by the ratio (%) of scattered light/transmission light based on the total light percent transmission, indicating that the lower the value, the higher the transparency of the coating film.
• the coating solution in which a polymeric hardener is added was kept at 40°C and preserved with stirring homogeneously and the change of viscosity with the lapse of time was measured using 'B-type viscosimeter (produced by Tokyo Keiki Co., Ltd.) to obtain the time until the viscosity became 2 times the initial viscosity.
• this value is preferred to be as large as possible.
• an insoluble lump based on the reaction of the hardener with gelatin tends to form at the time of coating and the degree of improvement in the property of viscosity increase of.coating solution with the lapse of time can be judged by the dimensions of this value.
• Table 2 shows that Sample Nos. 2 to 5, as compared with Sample No. 1, are hardened so that the melting time of the light-insensitive upper layer becomes larger than that of the silver halide emulsion layer. Furthermore, in the comparison between Sample Nos. 2 and 4 and between Sample N os. 3 and 5, the reduction ability is excellent in every case and the sample on which the polymeric hardener is coated in the larger amount shows the larger reduction width and reduction time, indicating that the samples have almost equal reduction ability. However, for the property of viscosity increase of coating solution with the lapse of time, as apparent from the comparison between Sample Nos. 2 and 4 and between 3 and 5, the property of viscosity increase of coating solution with the lapse of time of Sample Nos.
• Sample Nos. 4 and 5 of this invention show quite excellent abilities with respect to production, as they have no problems as described above and can be improved with respect to their reduction ability and the property of viscosity increase of coating solution with the lapse of time is also satisfactory.
• Sample Nos. 1 to 5 were subjected to the same development as described above, and the degree of the formation of reticulation after processing was observed for each sample using a microscope, but in every sample, reticulation was not formed.
• Sample 4 is lower than Sample 2 and Sample 5 lower than Sample 3, and it is apparent that the samples of this invention have excellent transmittance as coating films.

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• Engineering & Computer Science (AREA)
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• 1983
  • 1983-02-23 JP JP58028929A patent/JPS59154436A/ja active Granted
• 1984
  • 1984-02-21 EP EP84301104A patent/EP0119761A3/fr not_active Withdrawn

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