JPH037104B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming images using polymers. In particular, the present invention relates to a method of selectively producing a polymer compound in a portion corresponding to a photographic latent image by the action of a silver halide photographic emulsion and a reducing agent. Various methods have been proposed for forming images by polymerizing vinyl compounds to produce polymeric compounds through the action of light. Direct photopolymerization using silver halide as a catalyst has also been proposed (UK Patent No. 866631, S. Levinos et al. Photographic Science and Engineering).
Science & Engineering) Vol. 6, pp. 222-226 (1962)). In this reaction, the products generated by photolysis of silver halide are thought to act as direct catalysts for polymerization, and the sensitivity is not as high as that of reducing silver halide grains by normal development. Not obtained. Furthermore, after the exposed silver halide emulsion grains are developed with an ordinary developer, a vinyl compound is polymerized using the resulting silver image or unreacted silver halide as a catalyst to form a polymer compound. It has also been proposed to generate images in the form of images (Belgium Patent No. 642477, etc.). This reaction has the disadvantage that the development operation and the polymerization operation must be carried out separately. Developing exposed silver halide with a reducing compound in the presence of a vinyl compound and causing polymerization of the vinyl compound by the oxidation product or its intermediate product produced in the process is as follows:
Such a reaction is carried out using a so-called benzenoid compound, which already has two or more hydroxyl groups, amino groups, alkyl, or aryl-substituted amino groups at mutually ortho or para positions on the benzene ring, as a reducing agent. (U.S. Pat. No. 3,019,104, G. Oster. Nature, Vol. 180, p. 1275 (1957)). However, in this example of a reaction using a benzenoid compound, only an increase in the optical density of the silver image of silver halide was observed, and an increase in viscosity that directly supported the formation of polymers, or the generation of reaction heat was confirmed. No isolation of the produced polymer was performed. Furthermore, other researchers have reported that they were not successful in follow-up testing (S. Levinos and
FWH Mueller, Photographic Science & Engineering, Vol. 6, p. 222 (1962)). Then, in the presence of exposed silver halide, a vinyl compound is polymerized using a resorzine, naphthol, pyrazolone, or hydrazine compound as a polymerization initiator, as described in Japanese Patent Publication Nos. 11149-1986 and 50-1999.
No. 10488, No. 45-30338, No. 46-21723, No. 47
−18585, No. 46-6581, No. 47-14667, No. 47
−14668, No. 47-14669, No. 47-12638, No.
47-20741, 49-1569, 49-1570, 49-1569, 49-1570,
No. 49-48769 and No. 49-10697. Although these inventions produced polymers of vinyl compounds, the sensitivity was still not sufficient. Furthermore, an invention using hydroquinone or the like as a polymerization initiator is disclosed in JP-A-55-149939,
This is because a polymerization reaction occurs in the areas where the silver halide has not been reduced, that is, in the non-exposed areas, and a negative image is formed with respect to the silver halide image. This is still not sufficient in terms of sensitivity. It is an object of the present invention to provide a sensitive method for polymerizing vinyl compounds in the presence of exposed silver halide. Another object of the present invention is to provide a highly sensitive silver halide photosensitive material capable of obtaining a positive polymer image relative to a silver halide image. Another purpose is to provide a highly sensitive printing plate by forming a polymer image on a metal plate such as aluminum. The inventors have discovered that reduction of silver halide in the presence of a vinyl compound using the phenolic compounds described below can cause polymerization of the vinyl compound. Moreover, when a silver halide photographic emulsion is used as the silver halide, the reaction occurs more quickly when the silver halide microcrystals contain development nuclei, and therefore, if appropriate reaction conditions and reaction time are selected, the development nuclei can be removed. Polymerization can occur selectively only in the areas where the silver halide grains containing the silver halide grains are present. The present invention is achieved by taking advantage of the above facts. That is, the present invention involves the application of a silver halide photographic emulsion layer having a photographic latent image in the presence of a vinyl compound capable of polymerizing at least one of the phenolic compounds in the area where the latent image is present. Optionally, this is accomplished by causing the polymerization of the vinyl compound to occur on a metal surface with a hydrophilic surface. A photographic latent image is an image-like change that occurs in a silver halide photographic emulsion due to the action of electromagnetic waves or particle beams and is normally invisible to the naked eye, but becomes a visible image when developed. It is something. In emulsions that produce normal negative images, a latent image is created by the formation of development nuclei in silver halide grains that are irradiated with electromagnetic waves or particle beams, whereas in direct positive emulsions, development nuclei that were initially present in all grains are irradiated. to disappear depending on
``Fundamentals of Photographic Theory'' by James and Huggins.
Photographic Theory)” 2nd edition Morgam&
Published by Morgam., 1960, see Chapters 3 and 4). The silver halide photographic emulsion used in the present invention is
Ordinary silver halide photographic emulsions that produce development nuclei in the irradiated areas due to the action of electromagnetic waves or particle beams, that is, produce negative images upon development, can also be used, and they can also be used to create image-like irradiation with light. It is also possible to use a so-called direct positive emulsion in which a greater number of development nuclei exist in halogen silver grains in the other areas than in the exposed areas. In the present invention, silver halide photographic emulsions used for ordinary development processing can be conveniently used as silver halide photographic emulsions capable of producing negative images. That is, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide photographic emulsions can be used. The photographic emulsion used in the present invention can be subjected to chemical sensitization and optical sensitization as applied to ordinary photographic emulsions. That is, as chemical sensitization, sulfur sensitization, noble metal sensitization, and reduction sensitization can be performed (for example, P. Glafkides Chimic Photographique).
2nd edition Photocinema PaulMontel Paris (Photocinema PaulMontel Paris) 1957 No. 247
(See pages 301 to 301). The Theory of the Photographic Process
See Chapter 5 of Photographic Process, 4th edition, Macmillan, 1977. or,
For optical sensitization, optical sensitizing dyes used in ordinary photography such as cyanine dyes and merocyanine dyes (for example, Shinichi Kikuchi et al., Scientific Photography Handbook, Volume 2, Maruzen Publishing, 1959)
2013, pp. 15-24) are valid. The emulsion used in the present invention may also contain stabilizers such as those used in conventional photography. Direct positive silver halide photographic emulsions that can be used in the present invention can be prepared by utilizing solarization, Herschel effect, Kleiden effect, and Sabatier effect. An explanation of these effects is, for example, CEK
The Theory of the Photographic Process by Mees
To make direct positive silver halide emulsions, use solarization as described in Chapters 6 and 7 of The Photographic Process, Second Edition (MACMILLAN, 1954). It is sufficient to prepare a type of silver halide photographic emulsion that is easy to develop, and to expose the entire surface of the emulsion to light in advance or to make it work with chemicals so that it can be sufficiently developed without image exposure. Examples of how to prepare such emulsions can be found, for example, in British Patent Nos. 443,245 and 462,730. The Hersiel effect is caused by exposing silver halide to long-wavelength light that has been exposed to light or made fully developable by chemicals; A silver halide emulsion containing a large amount of silver chloride is advantageous, and a desensitizing dye such as pinacrybutol yellow or phenosafranin may be added to promote the Herschel effect. Methods for producing direct positive emulsions using the Herschel effect are found in, for example, British Patent No. 667,206 and US Pat. No. 2,857,273. In order to obtain a direct positive image using the Kleiden effect, it is necessary to give a short image exposure at high illuminance, followed by a full-surface exposure at a relatively low effective light-intensity, and only after this full-surface exposure, Areas that did not receive high-intensity image exposure become developable. The Sabatier effect is produced by exposing a silver halide emulsion to light in an imagewise manner, and then exposing the entire surface to light while immersed in a developer or by being exposed to chemical agents. This occurs by creating developability in areas that have not been exposed. The Glidden effect and the Sabatier effect can easily occur practically when using a silver halide emulsion in which the initial exposure tends to produce development nuclei inside the grains rather than on the grain surfaces. be able to. Methods for producing emulsions that are likely to generate such internal development nuclei are described, for example, in US Pat. No. 2,592,250, US Pat. ing. Positives can also be made using core shell emulsions. Methods for making core-shell emulsions are described in US Pat. No. 3,761,276 and US Pat. No. 3,206,313. The above photographic emulsion consists of a system in which silver halide grains are dispersed in a solution of a polymeric substance, and gelatin is widely used as the polymeric substance, but other hydrophilic colloids can also be used. can. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethylcellulose and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid (polyacrylic acid, Various synthetic hydrophilic polymeric substances can be used, such as single or copolymers of polymethacrylic acid and glycidyl acrylate or glycidyl methacrylate (ester bonded to each other), polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.
As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. Specific examples are U.S. Patent No. 2614928, U.S. Patent No. 3132945,
3186846, 3312553, British Patent No. 861414,
It is described in No. 1033189, No. 1005784, and Japanese Patent Publication No. 42-26845. The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. . Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like.
Examples of these are U.S. Pat. Nos. 2,763,625, 2,831,767,
It is described in No. 2956884, etc. Typical synthetic hydrophilic polymer substances include West German patent applications (OLS)
No. 2312708, U.S. Patent No. 3620751, U.S. Patent No. 3879205,
This is described in Japanese Patent Publication No. 7561/1973. The phenol compound used in the present invention is represented by the following general formula. general formula In the formula, R ₁ represents an alkyl group or a substituted alkyl group, R ₂ and R′ ₂ each represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a halogen atom, and R ₃ and
R′ ₃ is hydrogen, alkyl group, substituted alkyl group,
Represents an aryl group, substituted aryl group, aralkyl group, alkoxy group, thioalkyl group, or halogen atom. Among these, R ₂ and R' ₂ are each hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or an aralkyl group, and R ₃ and R' ₃ are each hydrogen, an alkyl group, or a substituted alkyl group. , an aryl group, a substituted aryl group, an aralkyl group, an alkoxy group, and a thioalkyl group are more preferred in terms of the effects of the present invention. Examples of the compounds used in the present invention include the following compounds. The phenol compound of the present invention has a higher oxidation potential than the developing agents (hydroquinone, catechol, metol, p-phenylenediamine) of ordinary silver halide emulsions, and is difficult to reduce silver halide. It is rarely used for development. In addition, the phenol compound of the present invention is usually used as a polymerization inhibitor to improve the storage stability of monomers, and as an antioxidant for plastics, rubber, etc. Examples of use as a polymerization initiator as in the present invention include do not have. Although it is stated in the aforementioned Japanese Patent Publication No. 49-10697 that p-methoxyphenol may be added, this is only as a polymerization inhibitor, and p-methoxyphenol etc. accelerate the polymerization reaction. There is nothing written about it. As described above, it is revolutionary to use p-methoxyphenol, which has been conventionally used as a polymerization inhibitor, as a polymerization initiator as in the present invention. Furthermore, the phenol compound of the present invention had a faster development polymerization rate than resorcinol. The reaction mechanism in which polymerization of vinyl compounds occurs as a result of the reduction of silver halide by the phenol compound is still unclear. However, since compounds that undergo radical polymerization are generally available, the reaction proceeds in an aqueous solution, and oxygen delays the polymerization reaction, it is thought that polymerization proceeds by a radical mechanism. It is not yet clear whether radicals are generated directly by the reaction between the phenol compound and silver halide, or whether radicals are generated by further interaction with water, oxygen, etc. in the system. If the irradiated silver halide is reduced with the phenol compound and then the vinyl compound is added to the reaction system, no polymerization is observed, so the polymerization of the vinyl compound occurs at the same time as the silver halide is reduced. It is clear that this will occur. Therefore, it is considered that an intermediate product between silver halide and the phenol compound contributes to the reaction. It is believed that an intermediate product between silver halide and the phenol compound contributes to the reaction. In the so-called tanning development method, which cross-links gelatin using the oxidation product of a developing agent, which is a well-known method for forming images using polymers by utilizing the photosensitivity of silver halide, the resulting image is formed on gelatin. It is limited to products that have been crosslinked. However, the polymer images obtained in the present invention have various properties depending on the vinyl compound used, so it is possible to obtain properties such as printing durability and chemical resistance that cannot be obtained with gelatin crosslinked images. It is characterized by being able to. Furthermore, in the method of the present invention, the presence of sulfite ions in the system promotes polymerization of the vinyl compound. Sulfite ions may be added as compounds that already contain sulfite ions, such as alkali metal or ammonium sulfites or bisulfites, or may be added as alkali metal or ammonium pyrosulfites or bisulfites. It may also be added as a substance that decomposes in an aqueous solution to generate sulfite ions, such as an adjunct with an aldehyde such as formaldehyde or glyoxal. The appropriate amount of sulfite ion to be added depends on the phenol compound used, the type and amount of vinyl monomer, and the system.
It is effective to use 0.002 mol or more, especially 0.01 mol or more per reaction system, which varies depending on pH etc. The addition of sulfites to photographic developers is well known. In this case, the sulfite is thought to prevent auto-oxidation of the developing agent by reacting with oxidation products of the developing agent such as hydroquinone para-aminophenol, and also prevent the development reaction from occurring non-uniformly. (e.g. CEK Mees)
Author, The Theory of the Photographic Process
Photographic Process (2nd edition) published by Macmillan, 1954 (see page 652)). In the present invention, since the intermediate product of the oxidation of the phenol compound by silver halide initiates polymerization, the polymerization promoting effect of the sulfite salt is due to the effect of removing the oxidation product in the ordinary developer as described above. It must be noted that this is fundamentally different. If the sulfite simply scavenges oxidation products, polymerization should rather be inhibited. In addition, sulfite is a well-known compound as a reducing agent in redox reactions, and polymerization using a silver halide-sulfite ion system may be considered, but in the experiments conducted in the present invention, phenolic compounds as described in the present invention were not used. In its absence, the resulting polymerization was almost negligible. Although the mechanism of action of sulfite in the present invention is not clear, it seems reasonable to assume that it prevents the polymerization inhibition effect caused by oxygen. Further, the development and polymerization of the phenolic compound used in the present invention can be accelerated by the combined use of a small amount of a conventional photographic developer or by prebathing with a conventional photographic developer. This means that resorcinols, meta-aminophenols, phenols,
- Just as development and polymerization with pyrazolones, naphthols, hydrazine derivatives, etc. are promoted by the combined use of small amounts of conventional photographic developers. As a normal photographic developer like this,

[Formula] (where A and B are -OH, _-NH2 or -NHR, where n represents an integer of 4 or less, R is an alkyl group having a total carbon number of 4 or less,
It represents a group selected from a hydroalkyl group, an alkoxyalkyl group and an alkylsulfonamidoalkyl group, or an aryl group. ), 1-aryl-3-oxopyrazolidines, and 1-aryl-3-iminopyrazolidines. Although these conventional photographic developers do not have the effect of causing polymerization by themselves, they can accelerate the polymerization reaction by promoting the developing effect of a reducing agent that has the effect of initiating polymerization. In the present invention, the vinyl compound used is a liquid or solid addition-polymerizable compound at room temperature, or a mixture thereof. Such compounds include acrylamide, acrylonitrile, N-hydroxymethylacrylamide, methacrylamide, N-t-
Butylacrylamide, methacrylic acid, acrylic acid, calcium acrylate, aluminum acrylate, sodium acrylate, methacrylamide, methyl methacrylate, methyl acrylate, ethyl acrylate, 2-acrylamide-2
-Methylpropanesulfonic acid, vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine,
Examples include 2-methyl-N-vinylimidazole, potassium vinylbenzenesulfonate, and vinylcarzol. Compounds having two or more vinyl groups are particularly advantageous in the present invention, and can be used in combination with a compound having one vinyl group as described above, or alone as a compound having a plurality of vinyl groups such as this. Use with. Examples of such compounds include N,N'-methylene bisacrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinyl ether, divinylbenzene bisphenol. -A- Dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, bisoxyethylated bisphenol -A-
diacrylate, dipentaerythritol hexaacrylate or unsaturated monomers containing urethane groups such as di-(2'-methacryloxyethyl)
Examples include reaction products of diol mono(meth)acrylates and diisocyanates such as -2,4-tolylene diurethane and di-(2'-acryloxyethyl)trimethylene diurethane. In the present invention, a water-soluble vinyl compound may be used, or a water-insoluble vinyl compound may be added in the form of an emulsion or dissolved in a suitable solvent for polymerization. Emulsification can be carried out according to a conventional method in the presence of a surfactant and/or a polymer compound using a suitable stirring device. This reaction generally proceeds well under alkaline conditions, but the most appropriate pH varies depending on the type and concentration of silver halide, phenol compound, and medium polymer compound, and the reaction temperature, and the reaction is possible at a pH of about 8 or higher.
9 or above is particularly convenient. When using a photographic emulsion by coating it on a support,
This photosensitive material can be irradiated with electromagnetic radiation or particle beams and then immersed in an alkaline aqueous solution to allow the reaction to proceed. The reducing agent or vinyl compound may be contained in this alkaline aqueous solution, or may be contained in the photosensitive material. The reaction can be easily stopped by making the system acidic, for example, pH 5 or less, but it is also possible to remove reactants by cooling, washing, dissolving silver halide with a photographic fixer, or inhibiting polymerization. It can also be stopped by adding agents to the system. When the vinyl compound monomer is added to the photosensitive material from the beginning, the weight of the vinyl compound used is 1/30 to 30 times, especially 1/4 to 4 times, the weight of the polymer compound added in advance. It's convenient. The silver halide used is preferably 1/1000 to 2 times the weight, particularly 4/1000 to 1/2 times the weight of the polymer compound used in advance. In addition, when the phenol compound of the present application is added to the sensitive material in advance, and when the vinyl compound and the phenol compound are contained in the same layer, the weight of the phenol compound is 3/100 or more of the weight of the vinyl compound used, Preferably 4/
100 or more, and when it is contained in a layer different from the vinyl compound, it is conveniently in a range of 1/10 to 20 moles per mole of silver halide used. The phenol compound may be dissolved in water or an organic solvent, or dissolved in water or an organic solvent with the addition of a suitable surfactant, and may be added at the time of preparing the sensitive material. When adding a vinyl compound to a processing solution, it is usually advantageous to have a concentration as high as possible, and the amount added to the solution is rather limited by the solubility of the vinyl compound used in the processing solution. When adding a phenol compound used as a reducing agent to the processing solution, the optimum concentration varies somewhat depending on the compound used, but the concentration is between 1/1000 mol and 5 mol/1.
mole is appropriate, especially 1/50 to 1 mole,
For vinyl compounds, it is convenient to have a weight ratio of 3/100 or more, preferably 4/100 or more. Further, when adding the phenol compound, it may be added as an aqueous solution or an organic solvent, and a surfactant may be further added to solubilize it. The light-sensitive material of the present invention may contain an inorganic or organic hardening agent. . For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), activated vinyl compound (1,3,
5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl) methyl ether, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucochloric acid, enoxychloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, etc. can be used alone or in combination. A specific example is the U.S. patent
No. 1870354, No. 2080019, No. 2726162, No.
No. 2870013, No. 2983611, No. 2992109, No.
No. 3047394, No. 3057723, No. 3103437, No. 3047394, No. 3057723, No. 3103437, No.
No. 3321313, No. 3325287, No. 3362827, No. 3321313, No. 3325287, No. 3362827, No.
No.3539644, No.3543292, British Patent No.676628, No.3543292, British Patent No.676628,
No. 825544, No. 1270578, German Patent No. 872153,
It is described in No. 1090427, Special Publication No. 34-7133, No. 46-1872, etc. The photosensitive material used in the present invention may contain various known surfactants for various purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, and prevention of adhesion. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides) , polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and non-ionic materials such as urethanes or ethers. surfactants; triterpenoid saponins, alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates,
Alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups: amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, amine imides, Amphoteric surfactants such as amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphoniums or sulfoniums containing aliphatic or heterocyclic rings. Cationic surfactants such as salts can be used. Specific examples of these surfactants are listed in the U.S. patent.
No. 2240472, No. 2831766, No. 3158484, No.
No. 3210191, No. 3294540, No. 3507660, British Patent No. 1012495, No. 1022878, No. 1179290, British Patent No.
No. 1198450, Japanese Unexamined Patent Publication No. 117414, US patent
No. 2739891, No. 2823123, No. 3068101, No.
No. 3415649, No. 3666478, No. 3756828, British Patent No. 1397218, US Patent No. 3133816, No. 3441413,
Same No. 3475174, No. 3545974, No. 3726683, Same No.
No. 3843368, Belgian Patent No. 731126, British Patent
No. 1138514, No. 1159825, No. 1374780, Tokko Akira
40-378, 40-379, 43-13822, U.S. Patent No. 2271623, 2288226, 2944900, U.S. Pat.
No. 3253919, No. 3671247, No. 3772021, No.
3589906, 3666478, 3754924, West German patent application OLS 1961638, Japanese Patent Application Laid-Open No. 50-59025, etc. In the present invention, any electromagnetic waves or particle beams to which ordinary photographic emulsions are sensitive can be used as the electromagnetic waves or particle beams that can be used to obtain photographic images. That is, particle beams such as visible light, ultraviolet rays, infrared rays of 1.3 μm or less, X-rays, gamma rays, electron beams, and Alpha rays can be applied. In particular, conventional methods, such as tungsten lamps, fluorescent lamps, mercury lamps, xenon, arc lamps, carbon arc lamps, xenon flash lamps, halogen lamps, light emitting diodes, cathode ray tubes, flying spots, discharge tubes such as clotue tubes, argon lasers, etc. Any of various known light sources such as laser light can be used.
Exposure times range from 1/1000 seconds to 50 seconds, as well as exposures shorter than 1/1000 seconds, such as 1/1000 seconds using xenon flash lamps, cathode ray tubes, and laser light.
Exposures of 10 ⁴ to 1/10 ⁶ seconds can also be used,
Exposures longer than 50 seconds can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. When using the method of the present invention to record images,
Differences in physical and chemical properties such as solubility, adhesiveness, and dyeability between vinyl compounds and their polymers can be utilized in various ways. By taking advantage of the difference in solubility, by dissolving the unpolymerized portion after irradiation and reaction, the image created by the polymer substance remains only in the irradiated area, creating an image. can be formed. In this case, it is more convenient for the initially added polymer compound to be dissolved away together with unreacted monomers. For this reason, the polymer compounds contained in the system from the beginning are either so-called two-dimensional linear forms with almost no crosslinking, or the main chains or crosslinks are easily severed. It is convenient that the polymer compound produced by the one-sided reaction is a so-called three-dimensional crosslinked polymer.
For this purpose, it is convenient to use the aforementioned compound having a plurality of vinyl groups alone or in combination with a compound having one vinyl group. However, even if the generated polymeric substance is a two-dimensional soluble polymeric substance, as a result of interaction with the polymeric compound added in advance, some parts of the polymeric substance are generated by reaction and others are not. It is not essential to use monomers with multiple vinyl groups, since there are often significant differences in solubility between the parts (eg, in the case of polyacrylic acid and gelatin). Metals with hydrophilic surfaces used in the present invention include aluminum (including aluminum alloys);
Metals such as zinc, iron, copper, etc. are suitable, and these metals may be laminated or vapor deposited onto paper or plastic film to form a composite support, or may serve as a support on their own. good. Among these supports, aluminum plates and composite sheets in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 18327/1984 are preferred. These supports are subjected to treatments such as surface treatment or formation of a hydrophilic layer, if necessary, in order to obtain a hydrophilic surface. There are various types of hydrophilic treatment. In the case of a support having a surface of metal, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. It is preferable. Additionally, U.S. Patent No.
As described in the specification of US Pat. No. 2,714,066, an aluminum plate is grained and then immersed in an aqueous sodium silicate solution, and an aluminum plate is anodized as described in US Pat. No. 3,181,461. Furthermore, those treated by immersion in an aqueous solution of an alkali metal silicate are also suitably used. The above-mentioned anodizing treatment can be carried out using, for example, an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, either alone or in combination. Among them, it is particularly preferably carried out by passing an electric current through an aluminum plate in an aqueous solution of phosphoric acid, sulfuric acid or a mixture thereof. Additionally, U.S. Patent No.
Silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. Additionally, British Patent No.
Also preferred is an aluminum plate which is electrolyzed with alternating current in a hydrochloric acid electrolyte and then anodized in a sulfuric acid electrolyte, as described in No. 1208224. Further, it is preferable to provide an undercoat layer of a cellulose resin containing a water-soluble salt of a metal such as zinc on the aluminum plate anodized in the above process in order to prevent scum during printing. Example 1 A 2S aluminum plate mechanically grained by the method disclosed in JP-A-48-33911 was immersed in a 2% sodium hydroxide aqueous solution kept at 40°C for 1 minute to corrode a part of the surface. . After washing with water, it was immersed in a sulfuric acid-chromic acid solution for about 1 minute to expose the pure aluminum surface. It was immersed in 20% sulfuric acid kept at 30°C, anodized for 2 minutes at a DC voltage of 1.5V and a current density of 3A/dm ² , then washed with water and dried. Also, 75 mol% silver chloride under red safety light,
A silver halide emulsion consisting of 24.5 mole percent silver bromide and 0.5 mole percent silver iodide was prepared in methanol solution with poly-N-vinylpyrrolidone (2 g/g silver) as the protective colloid binder. The average grain size of the silver halide was 0.20 μm. To this silver halide emulsion were added 4 g of pentaerythritol tetraacrylate and 0.017 mol (2 g) of Phenol Compound Example 1 per 1 g of silver, and the mixture was coated on the above aluminum plate to obtain a sample. Coated silver amount is 0.8g/
It was ^m2 . This sample was placed in close contact with a step wedge with a step difference of 0.15 (△logE), exposed for 1 second to an ultra-high pressure mercury lamp through a gray filter with an optical density of 1.0, and then exposed to the following developer at 40°C for 30 seconds under red safety light. Soaked. Sodium sulfite 14g Phenol compound Example 1 0.9 mol The pH was adjusted to 10.2 with sodium hydroxide and water was added. 1 Then, unpolymerized parts were removed by washing with warm water to obtain a polymerized image. Example 2 A polymerized image was obtained in the same manner as in Example 1, except that the compounds shown in Table 1 were used in place of Phenol Compound Example 1. Example 3 A polymerized image was obtained in the same manner as in Example 1 except that dipentaerythritol hexaacrylate was used instead of pentaerythritol tetraacrylate. Comparative Example 1 A sample was prepared and processed in the same manner as in Example 1 except that resorcinol was used in place of Phenol Compound Example 1, and a polymerized image was obtained, but the sensitivity was extremely low.

[Table] Example 4 A sample was prepared by the method described in Example 1, and the following
A polymerized image was obtained by processing in the same manner as in Example 1, except that development was performed at 40° C. for 8 minutes. Sodium sulfite 14g Adjust the pH to 10.2 with sodium hydroxide, then add water to bring it to 1. When the polymerized image samples obtained in Examples 1, 2, 3, and 4 were mounted on a Hamadastar 500CD printer and printed using a commercially available dampening solution, more than 5,000 good prints were obtained.

Claims (1)

[Scope of Claims] 1. Silver halide having development nuclei is reduced using a phenol compound represented by the following general formula in the presence of at least one vinyl compound capable of addition polymerization. A method for producing a printing plate, characterized in that a vinyl compound is selectively polymerized in silver on a metal surface having a hydrophilic surface. general formula In the formula, R ₁ represents an alkyl group or a substituted alkyl group, R ₂ and R′ ₂ each represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a halogen atom, and R ₃ and
R′ ₃ is hydrogen, alkyl group, substituted alkyl group,
Represents an aryl group, substituted aryl group, aralkyl group, alkoxy group, thioalkyl group, or halogen atom.