JPH0373850B2 - - 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. The present invention relates to a silver halide sensor type polymerizable photosensitive material characterized in that an ethylenically unsaturated compound capable of addition polymerization is polymerized in the presence of exposed silver halide simultaneously with the reduction reaction of silver halide. Various methods have been proposed for forming images by polymerizing ethylenically unsaturated 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) Volume 6 No. 222-226
p. 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 a common developer, the resulting silver image or unreacted silver halide is used as a catalyst to polymerize ethylenically unsaturated compounds. It has also been proposed to generate a polymer compound in an image form (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 an ethylenically unsaturated compound, and causing polymerization of the ethylenically unsaturated compound by the oxidation product or its intermediate product produced in the process. This reaction uses 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. It has been proposed to perform the following (U.S. Pat. No. 3,019,104,
G.Oster.Nature No. 180
Volume No. 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 growth of polymers, or the generation or production of reaction heat was observed. No macromolecule isolation 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, an ethylenically unsaturated compound is polymerized using a resorcinol, naphthol, pyrazolone, or hydrazine compound as a polymerization initiator, as disclosed in Japanese Patent Publication No. 11149/1983.
No. 50-10488, 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, No. 49-1569, No. 49-1570,
This method was proposed in No. 49-48769 and No. 49-10697 (silver halide sensor type polymerizable photosensitive material).
Although these inventions produced polymers of ethylenically unsaturated compounds, the sensitivity was still insufficient. Furthermore, Japanese Patent Applications No. 56-23519 and No. 56-28154 disclose silver halide sensor-type polymerizable photosensitive materials using alkoxyphenol compounds and thioalkylphenol compounds, and Japanese Patent Application No. 56-60265 discloses silver halide sensor type polymerizable photosensitive materials using alkoxyphenol compounds and thioalkylphenol compounds. A method using a hydroxyphenol compound has also been disclosed, but a method with even higher sensitivity has been desired. Furthermore, an invention using hydroquinone or the like as a polymerization initiator is disclosed in JP-A-54-149939.
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 ethylenically unsaturated 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 object of the present invention is to provide a silver halide sensor type polymerizable photosensitive material with a rapid development speed. The present inventors have discovered that when silver halide is cyclized in the presence of an ethylenically unsaturated compound using a suitable polymerization initiator (reducing agent), the ethylenically unsaturated compound is polymerized, and the halogenated When a silver halide photographic emulsion is used as the silver, the reaction occurs more quickly when the silver halide microcrystals have development nuclei, and therefore, if appropriate reaction conditions and reaction time are selected, halogenation with development nuclei can be achieved. A silver halide sensor type polymerizable photosensitive material that can selectively polymerize only in areas where silver particles are present.
It has been found that development can be accelerated by developing in the presence of a primary, secondary or tertiary amine in addition to a reducing agent. The amines of the present invention may be contained in the sensitive material, for example, in the silver halide emulsion layer and/or the adjacent layer,
It may be included in the developer. The amount added is per mole of silver halide contained in the same area,
0.00001 mol to 0.2 mol is good, 0.001 mol to
0.1 mol is preferred. Also, when added to the developer, it is recommended to use 0.00001 mol to 0.1 mol per 1 mol.
0.0001 mol to 0.05 mol is preferred. It is well known to incorporate primary, secondary or tertiary amines into photographic silver halide light-sensitive materials. For example, it is described in Japanese Patent Publication No. 40-23465. However, the silver halide sensor type polymerizable photosensitive material of the present invention uses a reduction reaction of silver halide to polymerize an ethylenically unsaturated compound to obtain a polymer image. Conventionally known photographic silver halide light-sensitive materials obtain silver images using a reduction reaction of silver halide, and are fundamentally different from the present invention. In the method of the present invention, it is necessary to simultaneously carry out the reduction reaction and polymerization reaction of silver halide. Those that promote the reduction reaction of silver halide do not necessarily promote the polymerization reaction, and on the contrary, some substances may suppress the polymerization reaction. Therefore, even with the invention, it could not have been foreseen that the present compound would accelerate development in the silver halide sensor type polymerizable photosensitive material of the invention. Primary, secondary and tertiary used in the present invention
The class amines include amines represented by the following general formula [] and salts thereof. R ¹ , R ² and R ³ may be the same or different, but at least one is not a hydrogen atom. R ¹ , R ² and R ³ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aralkyl group, and R ¹ and R ² may form a ring, and R ¹ and R ² and R ³ may form a ring, and each ring may contain carbon, nitrogen, sulfur, or oxygen, and may be in the form of a salt with an inorganic or organic acid, or may be a polymer. good. Also, R ¹ , R ²
The alkyl group or aralkyl group of R ³ and N may be connected to each other via a divalent linking group. Each substituent of the substituted aryl group and substituted aralkyl group includes a cidroxy group, an alkoxy group, an aryloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfone group,
Sulfonyl group, carbamoyl group, alkylamide group, arylamide group, ureido group, sulfamoyl group, alkylsulfonamide group, arylsulfonamide group, amino group, substituted amino group,
thiocarbamoyl group, acyl group, aldehyde group,
There are cyano groups, halogen atoms, nitro groups, mercapto groups, alkylthio groups, and arylthio groups. Among these, compounds represented by the following general formula [] are preferred. [] Here, R ⁴ and R ⁵ may be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or R ⁴ and R ⁵ may form a ring, with nitrogen in the ring,
Can contain sulfur and oxygen. R ⁶ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
Represents a substituted or unsubstituted alkyl group. A is

【formula】

[Formula] -O-, -S −、

【formula】 【formula】

【formula】

【formula】 【formula】

【formula】

[Formula]-N=N-,

【formula】

【formula】 【formula】

【formula】

【formula】 【formula】

【formula】

【formula】

[Formula] (However, the arylene group is not directly connected to N in the general formula [].)
and divalent heterocyclic groups (e.g. pyrrole, pyrazole, imidazole, triazole, tetrazole, indazole, benzimidazole, benzotriazole, thiadiazole, benzothiazole, oxazole, benzoxazole, oxadiazole, hydantoin, 2,4-oxazolidinedione, urazole, succinimide, and phthalimide (these may form a ring)2
It is a valent group, and N represents a group bonded to a nitrogen, oxygen or sulfur atom. However, R ₂₁ and R ₂₂ are hydrogen atoms, halogen atoms,
represents an alkyl group or an alkoxy group, R ₂₃ and R ₂₄ represent a hydrogen atom, an alkyl group, an acyl group, or a sulfonyl group, and R ₂₅ represents a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, a sulfonyl group,
Represents a halogen atom or a nitro group. q is 1~
Represents an integer of 10 (when q is 2 or more, R ₂₁ ,
R ₂₂ may be the same or different. ). Specific examples of the divalent linking group represented by A are shown below. −OCH ₂ CH ₂ SCH ₂ CONH− −OCH ₂ CONH− −OCH ₂ CH ₂ CONH− −OCH ₂ CH ₂ SO ₂ CH ₂ CONH− −OCH ₂ CH ₂ O− −OCH ₂ CH ₂ SO ₂ NH− −SCH ₂ CH ₂ CONH− −SCH ₂ CH ₂ O− −CH ₂ CH ₂ CH ₂ NHCONH− −CH ₂ CH ₂ NHCONH− −CH ₂ CH ₂ CH ₂ NHCONH− −CH ₂ CH ₂ OCONH− −CH ₂ CH ₂ CH ₂ OCONH− −(CH ₂ ) ₄ NHCO− −(CH ₂ ) ₃ −SO ₂ −

【formula】

[Formula] Furthermore, compounds represented by the following general formula [] are preferred. Here, R ⁷ and R ⁸ may be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or R ⁷ and R ⁸ may form a ring, with nitrogen in the ring,
Can contain sulfur and oxygen. B represents an alkylene group, X represents -NH-, -O-, and Y
represents -CONH-, -CO-, _-SO2- , and ^R9 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. The compounds represented by the above general formula are shown below. 1 H ₂ N−CH ₂ CH ₂ OH 2 N(CH ₂ CH ₂ OH) ₃ 3 (C ₂ H ₅ ) ₂ NCH ₂ CH ₂ OH 4 C ₁₂ H ₂₅ NHCH ₂ CH ₂ COOH 5 C ₁₀ H ₂₁ NHCH ₂ CH ₂ SO ₃ Na 7 (CH ₃ ) ₂ NCH ₂ CH ₂ SCH ₂ CH ₂ N (CH ₃ ) ₂ 8 H ₂ NCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ NH ₂ 10 C ₁₂ H ₂₅ NHC ₂ H ₅ 11 C ₁₂ H ₂₅ N (C ₂ H ₅ ) ₂ 12 C ₁₈ H ₃₅ NH ₂ 13 H ₂ NOH 14 n-C ₁₂ H ₂₅ NH ₂ 15 H ₂ NCH ₂ CH ₂ NH ₂ 16 H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ In the silver halide sensor type polymerizable photosensitive material of the present invention, a non-gaseous ethylenically unsaturated compound (vinyl compound) is contained in the silver halide emulsion layer and/or the adjacent layer, but it is preferably contained in the adjacent layer. . Further, an undercoat layer, a protective layer, and an intermediate layer may be provided. The amount of silver halide contained in the sensitive material of the present invention is 1
0.001g to 5g per ^m2 is suitable, especially 0.05g
1 g is preferred. The combined amount of binder in each layer is suitably between 0.1g and 30g ^per square meter, especially 0.5g.
Preferably, the amount is between 15g and 15g. The vinyl compound is preferably used in an amount of 1/30 to 30 times, particularly 1/4 to 4 times, the amount of the binder in the same layer. When a polymerization initiator, which will be described later, is added to the sensitive material, it is convenient to add it in an amount of 1/10 to 20 moles per mole of silver halide contained in the same area. When adding a polymerization initiator to the treatment solution, the optimum concentration varies somewhat depending on the compound used, but the appropriate concentration is 1/1000 mol to 5 mol, particularly 1/50 mol to 1 mol. preferable. When a vinyl compound is added to the processing solution, the appropriate amount is 0.1 mol to 5 mol, especially 0.3 mol per 1 mol.
mol to 3 mol is preferred. The photographic latent image described in the present invention 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. This is a visual image. In emulsions that produce ordinary 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. (James and Huggins, “Fundamentals of Photographic Theory”)
“Second Edition Morgam & Morgam. Published 1960, 3
(see Chapters and Chapters 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 Chimi Photographique, 2nd edition Photocinema Hall Montel Paris).
(Photocinema Paul Montel Paris) 1957 No.
(See pages 247-301). The Theory of the Photographic Process
See Chapter 5 of the 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., Photography Handbook, Vol. 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
Chapters 6 and 7 of the Photographic Process, Second Edition (MACMILLAN, 1954). To make a direct positive silver halide emulsion using solarization, make a silver halide photographic emulsion of a type that easily undergoes solarization, and either expose the entire surface in advance to light or chemically so that it can be sufficiently developed without image exposure. All you have to do is let the medicine work. 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; Silver halide emulsions containing a large amount of silver chloride are advantageous, and desensitizing dyes such as pinacryptol yellow and phenosafranine are also 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. To obtain a direct positive using the Kleiden effect, it is necessary to give a short image exposure at high illuminance, followed by a full-face exposure at relatively low light; only after this full-face exposure can the high Portions that have not received image exposure of illuminance 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 Kleiden 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. has been done. 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 carboxymethyl cellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid (or poly(methacrylate) ), polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., and a variety of synthetic hydrophilic polymeric substances such as single or copolymers thereof can be used. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolyzate and gelatin oxygen decomposition product may 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 include US Patent Nos. 2,614,982, 3,132,945, and US Pat.
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. In particular, polymers with some degree of compatibility with gelatin, such as acrylic acid,
Graft polymers with polymers such as methacrylic acid, acrylamide, methacrylamide, hydroxyalkylmethacrylate, etc. are preferred. Examples of these are U.S. Pat.
It is described in issues such as No. 2956884. 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 light-sensitive material of the present invention may contain an inorganic or organic hardening agent. In addition, various known surfactants may be included for various purposes such as coating aids, antistatic properties, improving slipperiness, emulsification and dispersion, and preventing adhesion. In the present invention, the vinyl compound (ethylenic unsaturated 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, Nt-butylacrylamide, methacrylic acid, acrylic acid, calcium acrylate, aluminum acrylate, sodium acrylate, and methacrylamide. , methyl methacrylate, methyl acrylate, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid, vinylpyrrolidone, 2-vinylpyrrolidine, 4-vinylpyridine, 2-methyl-N-vinylimidazole, vinylbenzenesulfone Potassium acid, vinyl carbazole, etc. 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,
dipentaerythol hexaacrylate or unsaturated monomers containing urethane groups such as di-
(2'-methacryloxyethyl)-2,4-tolylene diurethane, di-(2'-acryloxyethyl) trimethylene diurethane, and other reaction products of diol mono(meth)acrylate and diisocyanate. . 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. In the present invention, the above vinyl compound can be added to the silver halide emulsion layer. The binder for the polymerizable layer containing the vinyl compound is a natural or synthetic polymer that is soluble or at least swellable in water or an alkaline aqueous solution. Examples of such natural polymers include gelatins such as gelatin, gelatin derivatives and gelatin graft polymers, polysaccharides such as starch and dextran, cellulose derivatives, and silica, as well as binders for silver halide emulsions. Examples of synthetic polymers include mono or copolymers of acrylic acid or methacrylic acid, polymers containing free carboxyl groups such as copolymers of maleic acid, itaconic acid, and vinylbenzoic acid, and sulfonic acids such as sodium styrene sulfonate copolymers. group-containing polymers, carboxylic anhydride group-containing polymers such as maleic anhydride and itaconic anhydride copolymers, novolac resins such as phenol-formalin resins and cresol-formalin resins, hydroxyl group-containing polymers such as polyhydroxystyrene, polyvinyl alcohol, and vinyl alcohol copolymers. group-containing polymers, amide group-containing polymers such as polyacrylamide and acrylamide copolymers, sulfonamide group-containing polymers such as styrene sulfamide copolymers, polyvinylpyrrolidone and vinylpyrrolidone copolymers, copolymerized nylons, methoxymethylated nylons, These include polyalkylene glycols. A coloring material may be added to the above polymerizable layer. Coloring materials include metal oxides such as titanium oxide, zinc oxide, and iron oxide, pigments such as carbon black, phthalocyanine pigments, and azo pigments, xanthene dyes such as rhodamine, triphenylmethane dyes such as crystal violet, and methylene blue. Dyes such as thiazine dyes, azo dyes, and anthraquinone dyes are used. The dye or pigment can be added according to conventional methods such as dissolving, emulsifying, and dispersing. A plasticizer may be added to the polymerizable layer. Plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butylbenzyl phthalate,
Phthalate esters such as diisodecyl phthalate and diaryl phthalate, dimethyl glycol phthalate, ethyl phthalyl ethyl glycol,
Glycol esters such as methyl phthalyl ethyl glycol, butylphthalyl butyl glycol, triethylene glycol dicaprylate, phosphoric esters such as tricresyl phosphate, triphenyl phosphate, diisobutyl adipate, dioctyl adipate, dimethyl seba These include aliphatic dibasic acid esters such as cate, dibutyl sebacate, and diisooctyl azelate, triethyl citrate, glycerin triacetyl ester, and butyl laurate. Various types of known surfactants may be further added to the polymerizable colorant layer for the purpose of improving coating properties. When developing the silver halide sensor type polymerizable photosensitive material (reduction reaction of silver halide and polymerization reaction of vinyl compound), the following polymerization initiator is used. The reducing agent (polymerization initiator) may be contained in the coating film of the sensitive material or may be contained in the developer. However, in order to achieve the purpose of the present invention, it is preferable to include it in the developer. Further, the developing method may be by immersing the sensitive material in a developer or by heating alone. In the present invention, the following polymerization initiators are used. The polymerization initiators may be used alone or in combination of two or more. In the present invention, the polymerization initiators include resorcinol and its derivatives, naphthol and its derivatives, pyrazolone compounds, hydrazine compounds, catechol and its derivatives, p-phenylenediamine, m-phenylenediamine, alkylphenols, etc. Any of those listed can be used. (Special Publication No. 11149, Showa 45-11149, same)
No. 50-10488, 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, No. 49-1569, No. 49-1570,
49-48769 and 49-10697). Furthermore, a phenol compound represented by the following general formula can also be used. 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.

【formula】

【formula】

In the formula, A represents an oxygen atom or a sulfur atom, R ₁ represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or an aralkyl group, and R ₂ and R′ ₂ each represent a hydrogen atom, an alkyl group, or a substituted aralkyl group. Alkyl group, alkoxy group, thioalkyl group,
represents an aryl group, a substituted aryl group or a halogen atom, R ₃ represents an aryl group, a substituted aryl group or an aralkyl group, X represents -CH ₂ -, a substituted aryl group or an aralkyl group, R ₂ and
R′ ₂ each represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, a thioalkyl group, an aryl group, a substituted aryl group, or a halogen atom; R ₃ represents an aryl group, a substituted aryl group, or an aralkyl group; , −CH ₂ −,

【formula】

[Formula] -S- or

[Formula], n represents an integer from 1 to 4. Was.

【formula】

[Formula] In the formula, R ₁ , R ₂ , R ₃ , and R ₄ each represent hydrogen, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a thioalkyl group, or a cyano group, and R At least one of ₁ , R ₂ , R ₃ and R ₄ represents a halogen atom. Specific examples of phenol compounds include the following. 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 aqueous solution to generate sulfite ions, such as adjuncts with aldehydes such as formalde or glyoxal. The appropriate amount of sulfite ions to be added depends on the phenol compound used,
0.002 mol or more per reaction system,
Particularly effective is 0.01 mol or more. Although the mechanism of action of sulfite is not clear, it seems reasonable to think that it prevents the inhibition of polymerization caused by oxygen. The polymerization reaction can be accelerated by the concomitant use of a small amount of a conventional photographic developer or by a prebath with a conventional photographic developer. 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 common photographic developing agents do not have the effect of causing polymerization by themselves, they can promote the polymerization reaction by promoting the developing effect of a reducing agent that has the effect of initiating polymerization. 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
The above is especially convenient. The reaction can be easily stopped by making the system acidic (for example, pH 5 or less), cooling, dissolving the silver halide with a photographic fixer, or adding a polymerization inhibitor to the system. It can also be stopped by immersing the polymerizable layer in a processing solution (etching solution) that can dissolve it and eluting the unpolymerized portion. In the photographic light-sensitive material produced using the present invention, the polymerizable colorant layer containing a vinyl compound and a colorant, the silver halide photographic emulsion layer, and other layers are made of plastic film, paper, etc., which are commonly used in photographic light-sensitive materials.
It is applied to a flexible support such as cloth or a rigid support such as glass, ceramic, or metal. Useful as flexible supports are films, baryta layers or alpha-olefin polymers of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments. It may be painted black for the purpose of blocking light. The surface of these supports is primed to improve adhesion with the polymerizable layer. The support surface is treated with corona discharge,
Ultraviolet irradiation, flame treatment, etc. may also be applied. 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 deposited on paper or plastic film to form a composite support, or may themselves be a support. 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 US Pat. No. 2,714,066, an aluminum plate is grained and then immersed in an aqueous sodium silicate solution, and as described in US Pat. No. 3,181,461, an aluminum plate is anodized. , those treated by immersion in an aqueous solution of an alkali metal silicate are also suitably used. The above-mentioned anodizing treatment may 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 of two or more. Among them, it is particularly preferably carried out by passing an electric current through the aluminum plate in an aqueous solution in phosphoric acid, sulfuric acid or a mixture thereof. Additionally, U.S. Patent No.
Silicate electrodeposition as described in No. 3,658,662 is also effective. Furthermore, 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. 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 light, infrared rays of 1.3 microns or less, X-rays, gamma rays, electron beams, and Alpha rays can be applied. In particular, conventional methods include 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 glow 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. Example 1 0.8 g of benzyl methacrylate-methacrylic acid copolymer (80:20), 0.8 g of pentaerythritol tetraacrylate and 0.01 g of p-methoxyphenol were dissolved in 14 g of methyl ethyl ketone, 14 g of ethylene glycol monomethyl ether acetate and 5 g of cyclohexanone. After adding 0.8g of Lisblack CA (carbon black), it was dispersed with a small dispersion machine and coated on the undercoat polyethylene terephthalate film to a film thickness of 2μ.
A polymerized layer was obtained. Silver halide consisting of 85 mol% silver chloride and 15 mol% silver bromide was prepared using gelatin, and sulfur sensitized and gold sensitized using conventional methods. The average grain size of the silver halide grains was 0.20 μm. As a sensitizing dye
Add a merocyanine dye with maximum sensitivity at 550 mμ, add appropriate stabilizers and surfactants, and then add Table 1
Add the compound shown in , and then add about 0.5 g of trilene 2,4-diisocyanate per 100 g of gelatin as a hardening agent to a photosensitive solution so that it contains 0.2 g of silver and 0.3 g of gelatin per m ² . , and coated on top of the above polymerized layer to prepare a coating sample. This sample was placed in close contact with a step wedge with a step difference of 0.15 (△log E), exposed to 200 lux white tungsten light (2860K) for 1 second, and then exposed to the following developer under red safety light at 40°C. Soaked for 30 seconds. p-methoxyphenol 12g Sodium sulfite 7g Sodium carbonate 5g Potassium bromide 0.1g β-acetylphenylhydrazine 0.3g Adjust the pH to 10.2 with sodium hydroxide, add water 1 After development, apply the following etching solution for 20 seconds Soaked. Ethylene glycol monobutyl ether 30g Sodium dodecylbenzenesulfonate 10g Sodium sulfite 2g Sodium hydroxide 6g Water 1 Wash thoroughly with water to elute the silver halide emulsion layer and the unexposed (unpolymerized) polymer layer to form a black polymer. Got the image.

[Table] Example 2 A 2S aluminum plate mechanically grained using the method disclosed in JP-A No. 48-33911 was immersed in a 2% sodium hydroxide aqueous solution kept at 40°C for 1 minute to remove one part of the surface. The parts were corroded. After washing with water, it was immersed in a sulfuric acid monochromic 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. Next, 0.8g of alcohol-soluble nylon (Torea Milan CM-8000), 0.8g of dipentaerythritol hexaacrylate, and 0.1g of nitrocellulose.
g, p-methoxyphenol 0.01g methanol
20 g of cyclohexanone was dissolved in 5 g of cyclohexanone, and the solution was applied to the above aluminum plate. The dry film thickness was 2μ. 1 m ² of the same photosensitive solution as in Example 1 was placed on the above polymerized layer.
A coating film sample was prepared by applying a coating containing 0.20 g of silver and 0.3 g of gelatin per coat. This sample was exposed, developed and etched in the same manner as in Example 1. After thorough washing with water, the silver halide emulsion layer and the unexposed (unpolymerized) polymer layer were eluted to obtain a polymer surface image. When this treated sample was mounted on a Hamada Star 500CD printing machine and printed using a commercially available dampening solution, 5000
More than one sheet of good printed matter was obtained.

Claims (1)

[Scope of Claims] 1. A silver halide sensor type polymerizable photosensitive material having a silver halide photographic emulsion and an ethylenically unsaturated compound is a primary compound represented by the following general formula [],
A method for forming a polymerized image, characterized by carrying out development treatment in the presence of a secondary or tertiary amine and a reducing agent. General formula [] In the formula, R ¹ , R ² and R ³ may be the same or different, but at least one is not a hydrogen atom. R ¹ , R ² and R ³ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aralkyl group, and R ¹ and R ² may form a ring, and R ¹ and R ² and R ³ may form a ring, and each ring may contain carbon, nitrogen, sulfur, or oxygen, and may be in the form of a salt with an inorganic or organic acid, or may be a polymer. . Further, the alkyl group or aralkyl group of R ¹ , R ² and R ³ may be connected to N by a divalent linking group.