JPS6247294B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an image forming material of the type that obtains a visible image by physical development, and an image forming method using the same. The physical phenomenon is a visible image made of metal particles grown by processing fine metal nuclei forming a latent image with a developer containing reducible metal ions and a reducing agent (hereinafter often referred to as "physical developer"). It is generally known as a means of forming silver images. In recent years, non-silver salt image forming materials have been reconsidered due to the limited resources of silver salts, but the ones that have been put into practical use as image forming methods that utilize physical development are:
There is only a method for forming conductor patterns on printed circuit boards. An image forming method using physical development that has been proposed so far utilizes the reaction of ferric ions to become ferrous ions when irradiated with light.
There is a method of reducing noble metal ions with iron ions to create metal development nuclei and physically developing them. Development nucleation systems used in this method include iron-gold system, iron-mercury system, and iron-silver system (that is, systems that give brown prints). A method using an organic compound as a photoreducing agent has also been proposed. For example, one method uses a photosensitizer system consisting of a combination of a diazosulfonate and a nucleating water-soluble mercury compound; exposure to this system liberates the sulfite ion of the diazosulfonate, which becomes a monovalent Disproportionation of mercury salt produces zero-valent mercury, and when it is brought into contact with a silver physical developer, silver is precipitated on the mercury nuclei and a visible image is obtained. Instead of diazosulfonate, CN ^- , CNS ^- ,
It is said that images can be obtained even by using photosensitive compounds that liberate NO ^- , S ₂ O ₃ 2- ions (Japanese Patent Publication No. 37-3319) However, these methods have problems due to the use of mercury, etc. There are problems with waste liquid treatment and operation. Another method uses a photosensitizer system consisting of a combination of a special diazonium salt, such as a hydroxybenzenediazonium salt, and nucleating silver nitrate; upon exposure to this system, the diazonium salt decomposes and forms a phenol. Then, a silver nucleus is formed by the reducing power of the phenol, and a visible image is obtained by exposing it to a physical silver developer. This is an example using silver. On the other hand, the present inventors have already proposed a method of combining physical development and photosensitive resin. That is, in this method, a coated layer of photosensitive resin is exposed and developed, the resin is selectively eluted to form a relief image, metal nuclei are included in the relief image, and then physical development is performed. In order to form metal nuclei in the relief image, for example, the relief image is first treated with an acidic aqueous solution of palladium chloride and then with an acidic aqueous solution of stannous chloride to form metal palladium nuclei. This method uses the relief pattern forming ability of the photosensitive resin itself to pattern a metal latent image, but since it is a relief image, it has the disadvantage that sufficient resolution cannot be obtained. In addition, as photoreducing substances, titanium oxide (U.S. Patent No. 2738272 and U.S. Patent No. 2929709), anthraquinone (U.S. Patent No. 2504593), tin chloride (Plating 58 786 (1971)), etc. The methods used are also known and have been put into practical use, but all of these methods are used only as methods for forming patterns on printed circuit boards. When titanium oxide is used, it is difficult to obtain a transparent non-image area, and anthraquinone-2,
Products using sodium 6-disulfonate have already been put to practical use in the production of printed circuit boards, but this method is based on the combination of divalent copper salts such as copper formate and copper gluconate with nickel chloride, cobalt chloride, and iron sulfate. limited to combinations. Furthermore, when using tin chloride, there are problems such as the fact that stannous chloride is easily oxidized by oxygen in the atmosphere, has a short lifespan, and the sensitivity wavelength is around 250 nm, making it impossible to use a powerful light source. be. An object of the present invention is to provide a novel image forming method that utilizes physical development and operates on a principle different from the conventional image forming methods described above, and an image forming material used therein. As a result of various studies for the above-mentioned purpose, the present inventors found that
It has been discovered that physical development using metal nuclei such as gold, platinum, palladium, silver, iron, and copper as development nuclei can be effectively suppressed by compounds having diazo or azide groups that are themselves photodegradable. Ta. Although the mechanism of this development is not clear, it can be assumed that the physical development is effectively suppressed by the compounds themselves having diazo groups or azide groups or by the reaction products obtained by treating these compounds with physical developers. . Although the structure of the compound obtained by this physical developer treatment is not clear, it is likely that some chemical change occurs, considering that compounds with diazo or azide groups are not decomposed by light after physical development. It is estimated that there are. The image-forming material of the present invention is based on the above-mentioned knowledge, and more specifically, it comprises an image-forming layer provided on a support, and the image-forming layer has fine metal development nuclei and a diazo group or an azide group. It is characterized by comprising a hydrophilic binder layer containing a compound having the following properties. Further, the image forming method of the present invention includes pattern exposure of the image forming layer of the image forming material, and then contacting the image forming layer with a physical developer, that is, a developer containing a reducing metal ion and a reducing agent. This method is characterized by forming an image made of metal particles that have grown in the exposed area. When pattern exposure is performed as described above, the compound (development inhibitor) having a diazo group or azide group is decomposed in the exposed area of the image forming layer, and the metal in the physical developer is precipitated around metal development nuclei during physical development. In contrast, the metal does not precipitate and grow in the non-exposed areas, and a visible image consisting of metal particles selectively grown in the exposed areas is obtained. The physical development inhibiting effect of a compound having a diazo group or an azide group, or a reaction product (development inhibitor) after treatment with a physical developer is clear from the following phenomena: (a) Consisting of a binder in which only metal development nuclei are dispersed. When the image forming layer is treated with a physical developer, the entire surface of the image forming layer undergoes physical development without the need for exposure treatment. (b) If the image forming layer according to the present invention is treated with a physical developer without being exposed to light, no physical development is performed. Even in this case, when processing with a physical developer for a long time, gradual growth of nuclei and development effects are observed, but this is because the development inhibitor is eluted into the developer or gradually increases in the presence of the developer. This is thought to be due to the decomposition into C. The image forming layer according to the present invention is developed only when exposed to light and in a normal physical development process time. The above-mentioned physical development inhibiting effect of a compound having a diazo group or an azide group was discovered for the first time by the present inventors. Incidentally, the development nuclei referred to in the present invention are stably formed fine metal particles,
Although it is invisible to the naked eye, it already acts as a physical development nucleus. The present invention is fundamentally different from conventional methods in which metal development nuclei are formed in exposed areas using photochemical reactions in that these fine metal development nuclei are already included in the image forming layer before exposure. . The present invention will be explained in more detail below. In the following description, "%" and "part" are based on weight unless otherwise specified. FIG. 1 is a sectional view in the thickness direction conceptually showing one embodiment of the image forming material of the present invention. As an example shown in FIG. 1, the image forming material A of the present invention comprises a support 1 and an image forming layer 2 provided thereon. As the support 1, any solid material such as glass, wood, paper, plastic film, woven fabric, non-woven fabric can be used, and among them, plastic films such as polyester film and triacetate film are particularly preferably used. These supports 1 are provided with the image forming layer 2 after being pretreated to improve adhesion, such as corona discharge treatment and primer treatment, if necessary. The image forming layer 2 is formed by dispersing (including a dissolved state) fine metal development nuclei and a development inhibitor in a hydrophilic binder layer. Examples of binders include natural polymers such as gelatin, casein, glue, gum arabic, and shellac, carboxymethylcellulose, egg albumin, polyvinyl alcohol (partially saponified polyvinyl acetate), polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, and polyethylene oxide. , maleic anhydride copolymer, etc. are used, but other resins than those mentioned above can also be used as long as they are water-soluble or hydrophilic resins. The degree of hydrophilicity required for the binder is such that when the image forming layer 2 is formed and brought into contact with a physical developer, the physical developer permeates into the image forming layer 2 to enable physical development. Metal development nuclei include palladium, silver, iron,
Fine particles of copper, gold, platinum, etc. are used. Among these, fine particles of palladium, iron, copper, gold, and platinum are preferred. The fineness is such that it provides an image forming layer that is colorless at least to the naked eye and can function as physical development nuclei. The coating liquid for forming the image forming layer 2 can be obtained by dispersing metal fine particles of an appropriate size as described above in a hydrophilic resin liquid together with a development inhibitor, but more preferably palladium chloride, palladium chloride, Aqueous solutions of metal salts such as hydrochloric acid aqueous solution, silver nitrate aqueous solution, hydrogen tetrachloride gold hydrochloric acid aqueous solution (commercially available activators for electroless plating can be used), stannous chloride hydrochloric acid aqueous solution, stannous sulfate aqueous solution, etc. An aqueous solution containing fine metal nuclei by mixing with a reducing agent aqueous solution (a commercially available sensitizer for electroless plating can be used) is mixed with a binder resin solution and a development inhibitor to form a solution of 10% suitable for coating. It can be obtained by adjusting the viscosity to about ~1000 centipoise. As the solvent, in addition to water, a mixed solvent of water and a water-miscible solvent such as a lower alcohol, ketone, or ether may also be used. The image forming layer 2 is usually obtained as a coating film with a thickness of 1 to 30 μm by applying the coating solution obtained as described above onto the support 1 and drying it. In addition, for the image forming layer 2, only a hydrophilic binder layer is formed on the support in advance, and this is sequentially treated with an aqueous solution of easily reducible metal ions and an aqueous reducing agent solution as described above. A metal core can also be included. Of course, it is also possible to treat the hydrophilic binder layer containing easily reducible metal ions with an aqueous reducing agent solution. Examples of the compound having a diazo group or an azide group used as a development inhibitor include p-N,N-diethylaminobenzenediazonium chloride zinc chloride double salt, p-N,N-diethylaminobenzenediazonium chloride zinc chloride double salt,
-N-ethyl-N-β-hydroxyethylaminobenzenediazonium chloride zinc chloride double salt, p
-N,N-dimethylaminobenzenediazonium chloride zinc chloride double salt, 4-morpholinobenzenediazonium chloride zinc chloride double salt, 4-morpholino-2,5-diethoxybenzenediazonium chloride zinc chloride double salt, 4-morpholino-
2,5-dibutoxybenzenediazonium chloride zinc chloride double salt, 4-benzoylamino-2,5
-Diethoxybenzenediazonium chloride zinc chloride double salt, 4-(4-methoxybenzoylamino)-2,5-diethoxybenzenediazonium chloride zinc chloride double salt, 4-(p-tolylmercapto)-2,5-dimethoxybenzene Diazonium chloride zinc chloride double salt, 4-diazodiphenylamine zinc chloride double salt, 4-diazo-4'-methoxydiphenylamine zinc chloride double salt, 4-diazo-
3-methoxy-diphenylamine zinc chloride double salt,
Sulfates and phosphates corresponding to the above zinc chloride double salt, and diazo resins which are reaction products of these diazonium compounds and paraformaldehyde can be suitably used. Examples of the azide compounds include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, and p-azidobenzaldehyde.
Azidobenzalacetone, 4,4'-diazidochalcone, 2,6-bis-(4'-azidobenzal)-
Acetone, 4,4'-diazidostilbene-2,
2'-disulfonic acid, p-azidobenzoyl chloride, 3-azidophthalic anhydride, 4,4'-diazidophenylsulfone, p-azidocinnamic acid, 4,4'-
Sodium diazidobenzoylacetone-2,2'-sulfonate and the like are used. Further, as the development inhibitor, compounds other than those mentioned above can also be used as long as they are water-soluble and have a diazo group or an azide group. The image forming layer 2 contains the binder 100 described above.
0.1 to 100 parts, especially 1 to 100 parts of metal development nuclei per part of
It is preferable to include 10 parts and a development inhibitor in an amount of 1 to 100 parts, particularly 20 to 50 parts. After forming the image forming layer 2, a hardening process is desirably performed in order to suppress elution of the binder into the developer during physical development. For hardening, for example, the following compound is mixed in the coating solution for forming the image forming layer 2 at a ratio of 0.1 to 50 parts per 100 parts of the binder, or an aqueous solution thereof is applied onto the image forming layer. It is carried out by: Al compounds such as potash alum and ammonium alum; Cr compounds such as chromium alum and chromium sulfate;
Aldehydes such as formaldehyde, glyoxal, glutaraldehyde, 2-methylglutaraldehyde, succinaldehyde; o-benzoquinone,
Diketones such as p-benzoquinone, cyclohexane-1,2-dione, cyclopentane-1,2-dione, diacetyl, 2,3-pentanedione, 2,5-hexanedione, 2,5-hexenedione; triglycidyl isocyanurate Epoxides such as acid salts; tetraphthaloyl chloride, 4,4'-diphenylmethane disulfonyl chloride, 4,
Acid anhydrides such as 4'-diphenylmethanedisulfonyl chloride; tannic acid, gallic acid, 2,4-
Dichloro-6-hydroxy-s-triazine, as well as general formulas R ₂ NPOX ₂ , (R ₂ N) _o POX _3-o ,

【formula】

[Formula] and R- N=C=N-R' (where R is an alkyl group having 2 to 6 carbon atoms, R' is a (CH ₃ ) ₃ N ⁺ (CH ₃ ) ₃ X ^- group, and X is F
or Cl, n is 1 or 2) Phosphorus compound or carbodiimide; styrene/maleic acid copolymer, vinylpyrrolidone/maleic acid copolymer, vinyl methyl ether/maleic acid copolymer, ethyleneimine/maleic acid copolymer Resins such as polymers, methacrylic acid/methacrylonitrile copolymers, polymethacrylamide, and methacrylic acid ester copolymers. Glutaric acid, succinic acid as dicarboxylic acids, malic acid as hydroxycarboxylic acids,
Organic carboxylic acids such as lactic acid, citric acid, aspartic acid, glycolic acid, and tartaric acid can also be used. The image forming layer 2 of the image forming material A formed as described above is subjected to pattern exposure, for example, through a transparent original 3 as shown in FIG. As a result, the development inhibitor is selectively broken down in the exposure section 2A to a degree corresponding to the amount of exposure. As the light source, any light source can be used as long as it can decompose the diazo compound or azide compound described above.
For example, an ultra-high-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an arc lamp, a chemical lamp, a xenon lamp, an Ar laser, etc. can be used. Depending on the desired image gradation, for example, when using ultraviolet light with a center wavelength of 405 nm, the power output can vary from 1 W/m ² to
It is sufficient to expose for about 10 to 200 seconds at an intensity of 300 W/m ² . Then, by pattern exposure, a physical developer is brought into contact with the image forming layer 2 having a latent image in which the development inhibitor is broken up in a pattern, for example by dipping or coating, to form metal development nuclei in the exposed areas. A visible image 2B as shown in FIG. 3 is formed in which the metal in the developer precipitates and grows by reduction, centering on the area. As the physical developer, an aqueous solution containing a water-soluble reducible heavy metal salt and a reducing agent is used, if necessary, in a heated state. Examples of reducible heavy metal salts include nickel,
Group VIb metals such as cobalt, iron and chromium, copper etc.
Water-soluble salts of Group Ib metals are used alone or in mixtures. As suitable water-soluble reducible heavy metal salts, for example, the following can be used. Heavy metal halides such as cobaltous chloride, cobaltous iodide, ferrous bromide, ferrous chloride, chromic bromide, chromic iodide, cupric chloride; nickel sulfate, ferrous sulfate , heavy metal sulfates such as cobaltous sulfate, chromic sulfate, cupric sulfate; heavy metal nitrates such as nickel nitrate, ferrous nitrate, cobaltous nitrate, chromic nitrate, cupric nitrate; Organic acid salts of heavy metals such as state, cobalt acetate, chromic acetate, and chromic fluorate. These reducible heavy metal salts are contained in the physical developer in an amount of, for example, 10 to 100 g/g. Examples of the reducing agent include hypophosphorous acid, sodium hypophosphite, sodium borohydride, diethylamine borane, dimethylamine borane, trimethylamine borane, borane, diborane, methyldiborane, diborazane, borazane, borazine, t-
Butylamine borazane, pyridine borane, 2,6
-lutidine borane, ethylenediamine borane, hydrazine diborane, dimethylphosphine borane,
Phenylphosphine borane, dimethylarsine borane, phenyl aldine borane, dimethylstibine borane, diethylstibin borane, etc. can be used. These reducing agents can be added to the physical developer, e.g.
It is used at a rate of 0.1 to 50g/. In addition, in order to prevent heavy metal ions generated by dissolving the above-mentioned reducible metal salts from precipitating as hydroxides, the physical developer contains, for example, monocarboxylic acids; dicarboxylic acids; malic acid, lactic acid, etc. Hydroxydicarboxylic acid, succinic acid, citric acid, aspartic acid, glycolic acid, tartaric acid, ethylenediaminetetraacetic acid, gluconic acid, sugar acid,
One or more complexing agents made of organic carboxylic acids such as quinic acid may be included. These complex chloride agents may be contained in the physical developer, for example, from 1 to 100%.
It is used at a rate of g/g/. Furthermore, the physical developer contains PH regulators such as acids and bases, buffers, preservatives, etc. to improve the storage stability and operability of the developer and the quality of the resulting images.
Brighteners, surfactants, etc. are added as necessary according to conventional methods. In this way, according to the method of the present invention, it is possible to form a black image with a transmission optical density of 4 or higher and a gradation as necessary, and the resolution is high because a development inhibitor dissolution system is used. Images that can replace those obtained by salt photography are obtained. Furthermore, since the image is a metal image, it can be corrected using a reducing fluid such as Firmer reducing fluid made of red blood salt and sodium thiosulfate, or Kodak R-4. The image material obtained by the method of the present invention by taking advantage of these characteristics is
It can be used as a substitute for lithium film or as a mask material. In addition, physical development can be carried out, for example, the first development in a nickel plating bath using a boron-based reducing agent, and the second development in a nickel plating bath using sodium hypophosphite as a reducing agent or a copper plating bath at high temperatures of 65 to 90 degrees Celsius. If plating is carried out under high-speed plating conditions, it is possible to form a metal image with metal photoelectrons on the binder surface. Furthermore, by treating the obtained image with an aqueous solution of 5% hydrochloric acid or 5% nitric acid for 5 minutes, the binder in the non-image area can be selectively removed, so that it can also be used as a printed circuit board. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 Activator PdCl ₂ 2g HCl 20ml H ₂ O 1000c.c. Sensitizer SnCl ₂ 1g HCl 40ml H ₂ O 100c.c. Activator (PdCl _{dihydrochloric} acid aqueous solution) and sensitizer (SnCl _{dihydrochloric} acid A sensitive material (coating liquid for forming an image forming layer) having the following composition was prepared using an aqueous hydrochloric acid solution in which the Pd nuclei thus prepared were mixed in a 2:1 weight ratio. Pd nuclear dispersion hydrochloric acid aqueous solution 30g Gelatin (Nitta Gelatin p-2151) 30% aqueous solution 10g Diazoresin (Shinko Giken D-011) 20%
Aqueous solution 2.5g Methyl vinyl ether/maleic anhydride copolymer (Gokyo Sangyo Gauntlets 149) 5% aqueous solution
5.0g The above photosensitive material is coated on a polyester film (Toray Mirror S, 100#) that has been temperature-controlled to 20-23°C and has been subjected to plasma treatment in advance, and is sufficiently dried to form an image forming layer with a thickness of 4μ. An image forming material (sensitive film) of the present invention was produced. A 2KW ultra-high pressure mercury lamp is applied to the coating film of the above-mentioned sensitive film.
The negative film was closely exposed for 2 minutes using a printer (distance 100 cm from the light source). Then 65
It was immersed for 50 seconds in a boron and nickel-based plating bath (Shibanitsukel stock solution, manufactured by Okuno Pharmaceutical Co., Ltd.) at ℃, developed, and dried. The resulting image was black, with 300 lines and 4% halftone dots resolved. Example 2 A sensitive film was prepared and exposed in the same manner as in Example 1, and developed by immersing it in the following physical developer at 30° C. for 2 minutes to obtain a black image. Nickel chloride 0.1 mole / Dimethylamine borane 0.1 mole / Succinic acid 0.5 mole / NaOH: Amount to make the developer pH 7.0 Example 3 A sensitive film was prepared and exposed in the same manner as in Example 1, and the following composition was obtained. A black image was obtained by immersing the film at 22° C. for 10 minutes in a physical developer (Narcus electroless plating bath) prepared by mixing Liquid A and Liquid B at a ratio of 1:1 immediately before use. A: Copper sulfate 60g / Nickel sulfate 15g / Hydrazine sulfate 45g / B: Sodium hydroxide 45g / Potassium sodium tartrate 180g / Sodium carbonate 15g / Example 4 A sensitive film prepared and exposed in the same manner as in Example 1 was prepared as shown below. An image with metallic luster was obtained by immersing it in a developing bath having the composition of 90° C. for 5 minutes. Cobalt chloride 0.05 mol / Sodium citrate 0.4 mol / N ₂ H ₄ · HCl 1.0 mol / Example 5 A Pd nuclear dispersion liquid was prepared in the same manner as in Example 1 to obtain a sensitive material with the following composition, which was used in Example 1. A photosensitive film was prepared by coating the same on a polyester film in the same manner as above. Pd nuclear dispersion hydrochloric acid aqueous solution 30g Gelatin (Nitta Gelatin p-2152B) 30%
Aqueous solution 10g Diazoresin (Shinko Giken D-011) 20%
Aqueous solution 2.5g Glutaraldehyde 50% aqueous solution 0.05g The resulting sensitive film was closely exposed to light for 2 minutes using an ultra-high pressure mercury lamp 2KW printer (distance from the light source 100cm), and then exposed in a boron/nickel plating bath at 65°C. It was developed and dried by immersing Shiba Nickel stock solution in Okuno Pharmaceutical Co., Ltd. solution for 150 seconds.The development time was longer than in Example 1, but the adhesion of the image forming layer was good and the surface of the image forming layer could not be rubbed by hand during development. This did not peel off.The image quality was good, and 300 lines and 4% halftone dots were resolved.Example 6 A Pd nuclear dispersion was prepared in the same manner as in Example 1, and a photosensitive film was prepared using the following composition. Prepared: Pd nucleus dispersion hydrochloric acid aqueous solution 30g Gelatin (Nitta Gelatin p-2152B) 30%
Aqueous solution 10g Diazoresin (p-tolylmercapto-2,
5-Diethoxybenzenediazonium chloride (condensate of zinc chloride double salt and formaldehyde)
20% aqueous solution 2.5g Chromium alum 20% aqueous solution 2.0g Contact exposure was carried out using the printer of Example 1 and development was carried out under the same conditions, and an image was obtained even with an exposure time of 1 minute. Background fog was observed in the 2 minute exposure. Example 7 Commercially available sensitizer (manufactured by Nippon Kanigen, Pink Shyuma) and activator (manufactured by Nippon Kanigen,
Mixed with 1:2 weight ratio,
A Pd nuclear dispersion was prepared and mixed in the same manner as in Example 5 to obtain a photosensitive material, from which a photosensitive film was prepared. When exposure and development were carried out in the same manner as in Example 1, a black image with good halftone dot shape was obtained. Example 8 Using the Pd nucleus dispersion of Example 7, a photosensitive material was prepared with the following composition. Pd nuclear dispersion hydrochloric acid aqueous solution 30g PVA (Nippon Gohsenyl NM-14) 10%
Aqueous solution 20g Diazoresin (Shinko Giken D-013) 20%
Aqueous solution: 2.5 g Malic acid: 0.05 g The above photosensitive solution was applied onto a polyester film which had been subjected to plasma treatment, and dried to produce a photosensitive film having an image forming layer with a thickness of 4 μm. The above sensitive film was closely exposed for 40 seconds using a diazocopy lamp (Ricoh High Start 4), and immersed in a physical developer having the following composition at 40°C for 100 seconds.
It was developed to obtain a black image. Nickel sulfate 20g/ Potassium sodium tartrate 40g/ Sodium borohydride 2.3g/ NaOH Amount to make PH12.5 Example 9 Activator HAuCl ₄・4H ₂ O 1g HCl 2ml H ₂ O 1000c.c. Sensitizer SnCl ₂ 1g HCl 40ml H ₂ O 100 c.c. The activator and sensitizer having the above composition were mixed at a weight ratio of 2:1, and the thus prepared Au nucleus dispersion was used to prepare a photosensitive material having the following composition. Au nuclear dispersion hydrochloric acid aqueous solution 20g Gelatin (Nitta Gelatin p-2222) 30% aqueous solution 6.7g Diazoresin (Shinko Giken D-011) 20%
Aqueous solution: 2.5 g Tartaric acid: 0.05 g Using this photosensitive material, a photosensitive film was prepared, exposed, and developed in the same manner as in Example 1, and a black image was obtained. Example 10 A metal nucleus dispersion liquid was prepared in the same manner as in Example 1, and a sensitive material was prepared with the following composition. Pd nucleic acid aqueous solution 30g Gelatin (Nitta Gelatin p-2152B) 30%
Aqueous solution 10g 4,4'-diazide diphenyl sulfone 20% aqueous solution 2.5g Mucochloric acid 0.06g Using this sensitive material, a sensitive film was prepared, exposed and developed in the same manner as in Example 8. Got the image. Example 11 2 g of PdCl ₂ was dissolved in 1000 c.c. of water together with 20 ml of HCl, and the resulting aqueous PdCl ₂ hydrochloric acid solution was used to prepare a photosensitive material having the following composition. The above PdCl _{dihydrochloric} acid aqueous solution 20g Gelatin (Nitta Gelatin p-2151) 30% aqueous solution 10g Diazoresin (Shinko Giken D-011) 20%
Aqueous solution: 2.5 g Glutaric acid: 0.12 g The temperature of the above-mentioned sensitive material was adjusted to 30 to 40°C, and it was applied to a polyester film that had been previously subjected to plasma treatment, and dried to form a coating film of 5 μm. Further, this coated body was immersed in a reducing bath having the composition shown below at 30° C. for 1 minute, washed with water, and dried to obtain a sensitive film of the present invention. This sensitive film was exposed to negative film for 2 minutes using a 2KW ultra-high pressure mercury lamp printer (distance 100 cm from the light source). Next, a treatment was performed using a physical developer (electroless plating solution) at 90° C. having the composition shown below to deposit metal and obtain a black image. Nickel sulfate 30g Sodium hypophosphite 10g Sodium citrate 10g Water 950g

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view in the thickness direction showing the laminated structure of the image forming material of the present invention, and FIGS. 2 and 3 show intermediate steps of the image forming method of the present invention using the image forming material shown in FIG. FIG. 1...Support, 2...Image forming layer (2A...Exposed area,
2B... visible image), 3... transparent original, A... image forming material.

Claims (1)

[Scope of Claims] 1. An image forming layer is provided on a support, and the image forming layer is composed of a hydrophilic binder layer containing fine metal development nuclei and a compound having a diazo group or an azide group. Image forming material with characteristics. 2. An image forming layer of an image forming material comprising an image forming layer provided on a support, the image forming layer comprising a hydrophilic binder layer containing fine metal development nuclei and a compound having a diazo group or an azide group. pattern exposure is carried out, and then the image forming layer is brought into contact with a developer containing reducible metal ions and a reducing agent to form an image consisting of metal particles grown in the exposed areas. Formation method.