JPH0360111B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an image forming method using an image forming material of the type that obtains a visible image by physical development. Physical development is a visible image made of metal particles grown by treating 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 systems, iron-mercury systems, and iron-silver systems (that is, systems that give brown prints). Furthermore, 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;
When exposed to this system, the sulfite ion of the diazosulfonate is liberated, which disproportionates the monovalent mercury salt to form O-valent mercury, and when exposed to a physical silver developer, silver precipitates from the mercury nucleus. and obtain a visible image. Instead of diazosulfonate, CN ^- ,
It is said that images can also be obtained using photosensitive compounds that liberate CNS ^- , NO ^- , and S ₂ O ₃ ^2- ions. (Japanese Patent Publication No. 37-3319) However, since these methods use mercury, there are problems in waste liquid treatment and operation. Another method is to use a photosensitive 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 to form a phenol. A silver nucleus is formed by the reducing power of phenol, and a visible image is obtained by contacting it with a physical silver developer. This is an example using silver. On the other hand, the 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 of not being able to obtain sufficient resolution and the film strength. has a weak disadvantage. In addition, as photoreducing substances, titanium oxide (U.S. Patent Nos. 2738272 and 2929709), anthraquinone (U.S. Patent No. 2504593), tin chloride (Plating 58 , 786 (1971)), etc. Methods using the above are also known and have been put into practical use, but all of these methods are only used as methods for forming patterns on printed circuit boards. When using titanium oxide, it is difficult to obtain a transparent non-image area, and anthraquinone-2,
Sodium 6-disulfonate has already been put to practical use in the production of printed circuit boards, but this is limited to combinations of divalent copper salts such as copper formate and copper gluconate with nickel chloride, cobalt chloride, and iron sulfate. It is being Also, when using tin chloride, stannous chloride
Problems include that tin is easily oxidized by oxygen in the atmosphere, has a short lifespan, and that a powerful light source cannot be used because the photosensitive wavelength is around 250 nm. The inventors further discovered that gold, platinum palladium, silver,
It has also been proposed that physical development using a metal nucleus such as iron or copper as a development nucleus is inhibited by a compound having a diazo group or an azide group, but the mechanism of such inhibition is not clear, but It can be presumed that physical development is effectively suppressed by the compounds themselves having , or the reaction products obtained by treating these compounds with a physical developer, and the structure of the compound obtained by this physical developer treatment. Although it is not clear, it is presumed that some kind of chemical change has occurred since the compound having a diazo group or azodo group does not decompose by light after physical development, and while this can be effectively suppressed, This causes fatigue of the physical developer due to the reaction with the physical developer, and if physical development is performed repeatedly using the same physical developer, the time required for physical development will gradually increase, or physical development may not be completed. This method has drawbacks such as the density of the visible image not being completely increased and the formation of pinholes in the visible image area. The present invention eliminates the drawbacks of the above-mentioned suppression by photocrosslinking agents, and specifically, after pattern exposure, the image forming layer is impregnated with water, and then the entire surface of the image forming layer is exposed to light. Physical development is performed, and the image forming layer of the image forming material is
Performing pattern exposure to react the crosslinking agent in the exposed area to crosslink the hydrophilic binder layer in the exposed area, then impregnating the image forming layer with water, and then exposing the entire surface of the image forming layer, Thereafter, the image forming layer is brought into contact with a reducing agent to form metal development nuclei in the image forming layer, and the image forming layer is subjected to physical development containing reducible metal ions and a reducing agent. A second developing step is performed in which an image is formed in the unexposed area by bringing the metal particles into contact with a liquid, and the metal particles are precipitated and grown by reduction of the reducible metal ions in the unexposed area. It is something to do. In this case, the first development step and the second development step are considered to proceed sequentially in terms of reaction mechanism, but operationally, they may be carried out sequentially in this order, or they may be carried out in a physical developer. It is also possible to carry out substantially simultaneously by using a relatively strong reducing agent. The pattern exposure step in the image forming method of the present invention has the effect of increasing the degree of crosslinking of the hydrophilic binder layer in the exposed portion of the image forming layer and reducing its physical development effect. Therefore, during subsequent physical development, due to the presence of metal development nuclei, the rate at which the metal ions in the physical developer precipitate and grow as metal is lower than in the unexposed area, and the precipitation of such metals is reduced. Growth is difficult to occur, and as a result, a visible image consisting of metal particles selectively grown in unexposed areas is obtained. In this way, conventionally, metal development nuclei were generated during the exposure process, but in the present invention, metal development nuclei are generated by a reduction process independent of exposure, and the penetration rate of the physical developer is controlled in the exposure process. The greatest feature of the image forming method of the present invention is that it makes a difference. The present invention will be explained below with reference to the drawings. 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, preferably dissolving, in a hydrophilic binder layer, a metal compound that is reduced to become metal development nuclei and a photocrosslinking agent. Examples of the binder include natural polymers such as gelatin, casein, glue, gum arabic, and shellac, carboxymethyl cellulose, egg albumin, polyvinyl alcohol (partially saponified polyvinyl acetate), polyacrylic acid, polyacrylamide, and polypynylated vinyl. Polyethylene oxide, polyethylene oxide, maleic anhydride copolymer, etc. are used, but other resins than the 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 compounds that are reduced to give physical development nuclei include water-soluble salts such as chlorides and nitrates of noble metals such as palladium, gold, silver, platinum, and copper, such as those contained in the activator solution for electroless plating. Water-soluble salts such as palladium chloride, silver nitrate, and gold tetrachloride are used. Among these, water-soluble salts of palladium, gold, platinum, and copper, particularly water-soluble salts of palladium, are preferably used. The image forming layer 2 is preferably made of an aqueous solution of the metal compound mentioned above (a commercially available activator liquid for electroless plating can be used as it is),
Mixing with a binder aqueous solution together with a photocrosslinking agent,
A liquid having a viscosity of about 10 to 1000 centivoise suitable for coating is prepared, and this is applied onto the support 1 and dried to obtain a coating film of usually 0.1 to 30 μm. In addition to the water mentioned above, a mixed solvent of water and a water-miscible solvent such as a lower alcohol, ketone, or ether may also be used as the solvent. Examples of the photocrosslinking agent include water-soluble zinc chloride double salts, sulfates, and phosphates having a diazo group, or diazo resins obtained therefrom, more specifically, P-N,N-diethylaminobenzenediazonium chloride. Zinc double salt, P-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-
dimethoxybenzenediazonium 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 zinc chloride double salts, diazo resins which are the reaction products of these diazonium compounds and paraformaldehyde, and azide compounds such as P-azidobenzaldehyde and P-azidoacetate. Phenone, P-azidobenzoic acid, P-azidobenzalacetophenone, P-
Azidobenzalacetone, 4,4'-diazidochalcone, 2,6-bis-(4'-azidobenzal)-acetone, 4,4'-diazidostilbene-2,2'-
Disulfonic acid, P-azidobenzoyl chloride,
3-azido phthalic anhydride, 4,4'-diazido diphenyl sulfone, P-azido cinnamic acid, sodium 4,4'-diazidobenzoylacetone-2,2'-sulfonate, etc. are used. The image forming layer 2 contains the binder 100 described above.
part: 0.1 to 100 parts of metal compound, especially 1 to 100 parts
It is preferable to include the photocrosslinking agent in an amount of 1 to 100 parts, particularly 20 to 60 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 potassium alum and ammonium alum; Cr compounds such as chromium alum and chromium sulfate;
Aldehydes such as formaldehyde, glyoxal, glutaraldehyde, 2-methylglutaraldehyde, succinaldehyde; O-benzoquinone, P-benzoquinone, cyclohexane-1,2
-dione, diketones such as cyclopentane-1,2-dione, diacetyl, 2,3-pentanedione, 2,5-hexanedione, 2,5-hexenedione; epoxides such as triglycidyl isocyanurate; 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 methacrylic acid/methacrylonitrile copolymers, polymethacrylamide, and methacrylic acid ester copolymers. Glutaric acid, succinic acid as dicarboxylic acids, malic acid, lactic acid, citric acid, aspartic acid, glycolic acid, as hydroxycarboxylic acids.
Organic carboxylic acids such as tartaric acid can also be used. According to the image forming method of the present invention, the image forming layer 2 is first subjected to pattern exposure through a transparent original 3 as shown in FIG. Thereby, in the exposed portion 2A, the photocrosslinking agent is selectively decomposed and crosslinked to a degree corresponding to the amount of exposure. As a light source,
Any light source can be used as long as it can destroy the photocrosslinking agent 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,
It is sufficient to expose for 10 to 200 seconds at an intensity of 1w/m ² to 300w/m ² . Due to the pattern exposure described above, the photocrosslinking agent is decomposed in the exposed area 2A, and the hydrophilic binder is crosslinked in the exposed area 2A and is imparted with hydrophobicity. Since the photocrosslinking agent remains unchanged in the unexposed area 2B, which is the area not exposed by the above pattern exposure, subsequent development is performed with the photocrosslinking agent in the unexposed area 2B unchanged. The image forming layer is impregnated with water, and then the entire surface of the image forming layer is exposed to light.
Decomposes the photocrosslinking agent. The image forming layer can be impregnated with water by methods such as spraying with water, immersing in water, applying water using a roller or brush impregnated with water, or impregnating the image forming layer with water. The light source used to expose the entire surface of the image forming layer can be the same as the light source used in the pattern exposure described above, and the exposure conditions include, for example, ultraviolet light with a center wavelength of 405 nm. When used, the intensity of 1w/ ^m2 to 300w/ ^m2 is 10~
All you need to do is expose for 200 seconds. Further, the degree of water impregnation varies depending on the type of hydrophilic binder constituting the image forming layer, but it is 1% to the weight of the image forming layer.
-100%, preferably 5-30%. In the above, when the image forming layer is impregnated with water and then the entire surface of the image forming layer is exposed to light, the photocrosslinking agent causes a chemical reaction and is decomposed without crosslinking the hydrophilic binder layer. An aqueous reducing agent solution is brought into contact with the image forming layer 2 having a latent image imparted with hydrophobicity in a pattern by dipping or coating to generate metal development nuclei almost uniformly in the image forming layer 2. Examples of reducing agents include stannous chloride, stannous sulfate, sodium borohydride, dimethylamine borazane, diethylamine borazane, trimethylamine borazane, other borazane derivatives, borane derivatives such as borane, diborane, and methyldiborane, hydrazine, etc. can be used. Particularly preferably, an acidic stannous chloride solution, a stannous sulfate solution (Weiss solution), or a commercially available sensitizer solution for electroless plating is used, but in general, any strong reducing agent can be used. This reduction treatment generally uses a reducing agent solution containing a reducing agent at a concentration of 0.1 to 50 g/kg, and is carried out at room temperature or under heating, although it varies depending on the strength of the reducing agent.
It takes about 10 seconds to 400 seconds. Furthermore, the image forming layer 2 having a latent image with high crosslinking density and hydrophobicity due to the selective decomposition of the metal development nuclei and photocrosslinking agent obtained in this manner is contacted by dipping or coating with a physical developer. Then, a visible image 2 as shown in Fig. 3 in which the metal in the developer was precipitated by reduction centering on metal development nuclei in the unexposed area.
Form B. 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,
Vib group 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; ferras Organic acid salts of heavy metals such as acetate, cobalt acetate, chromic acetate, and chromic fluorate. These reducible heavy metal salts are contained in the physical developer at a rate of, for example, 10 to 100 g/g. Examples of reducing agents include hypophosphorous acid, sodium hypophosphite, sodium borohydride, hydrazine, formalin, diethylamine borane, dimethylamine borane, trimethylamine borane, borane, diborane, methyldiborane, diborazane,
Borazene, borazine, t-butylamine borazane, pyridine borane, 2,6-lutidine borane,
Ethylenediamineborane, hydrazineborane, dimethylphosphineborane, phenylphosphineborane, dimethylaldineborane, phenylaldineborane, dimethylstibineborane, diethylstivineborane, and the like 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/. Some of the reducing agents available in the physical developer are those for the generation of metal development nuclei. Therefore, when using a physical developer containing a relatively strong reducing agent, the reduction treatment for generating metal development nuclei is not performed after exposure, and the process is directly performed with the physical developer to prevent the generation of metal development nuclei. Physical development can also be performed substantially simultaneously. However, if the reaction is carried out in two stages, there is an advantage that the reduction reaction and the metal precipitation reaction can be controlled accurately by adjusting the temperature and reaction time, respectively. In particular, in the image forming method of the present invention, if the development time is prolonged, the physical developer will penetrate not only the unexposed areas but also the exposed areas, causing so-called fog, so a two-step process is preferable. In order to prevent the heavy metal ions generated by dissolving the above-mentioned reducible heavy metal salts from precipitating as hydroxides, the physical developer contains, for example, monocarboxylic acids; dicarboxylic acids; hydroxyl acids such as malic acid and lactic acid. Carboxylic acid; may contain one or more complexing agents consisting of organic carboxylic acids such as succinic acid, citric acid, aspartic acid, glycolic acid, tartaric acid, ethylenediaminetetraacetic acid, gluconic acid, sugar acid, and quinic acid. can. For example, 1 to 100 g of these complex chloride agents may be added to the physical developer.
used at a rate of 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. According to the present invention, since fatigue of the physical developer is small, it has the advantage that it is possible to extend the predetermined time of physical development, reduce the density of a visible image, and prevent the occurrence of pinholes. With a density of 4 or more, it is possible to form a black image with gradations as required, and because it uses a photocrosslinking agent dissolution system, the resolution is high.
Images that can replace images obtained by silver salt photography are obtained. In addition, since the image is a metal image, Furmar reduction liquid consisting of red blood salt and sodium thiosulfate,
Corrections can be made using a reducing fluid such as Kodak R-4. Taking advantage of these characteristics, the image material obtained by the method of the present invention can be used as a substitute for lithographic film or as a mask material. In addition, physical development is performed, for example, the first development is performed using a nickel plating bath using a boron reducing agent, and the second development is performed using a high-temperature nickel plating bath at 65 to 90°C using a reducing agent containing sodium hypophosphite, or high-speed plating using copper plating. If the conditions are met, a metallic image with metallic luster can be formed on the binder surface. Moreover, the obtained image,
For example, by treating with a 5% aqueous solution of 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 _{2 g of PdCl 2} was dissolved in 1000 c.c. of water together with 20 ml of HCl, and 20 g of the resulting _two PdCl solutions were used to prepare a sensitive material (coating solution for forming an image forming layer) having the following composition. PdCl ₂ liquid with the above composition 20g Gelatin (Nitta Gelatin P-2151) 30% aqueous solution 10g Diazoresin 20% aqueous solution 2.5g Glutaric acid 0.12g The temperature of the above sensitive material was adjusted to 30°C to 40°C, and plasma treatment was performed in advance. Apply to Natsuta polyester film (Toray Lumirror S, 100μm) and dry.
A coating film with a thickness of 5 μm was obtained. Sensitive film (image forming material) obtained above
The negative film was closely exposed for 2 minutes using an ultra-high pressure mercury lamp 2KW printer (distance 100cm from the light source), and then the exposed film was placed in water at 20℃ for 1 hour.
After being immersed for a minute, the entire surface of the film was exposed to light using the same light source used in the above-mentioned negative film contact exposure while immersed in water. At this time, the thickness of water through which ultraviolet rays should pass was 1.0 cm. Next, it was immersed in the following reduction bath at 30°C for 1 minute for reduction treatment. SnCl ₂ 1 g HCl 40 ml H ₂ O 100 ml Next, the sample was treated with a physical developer having the following composition at 90° C. to precipitate metal and form a black image. Nickel chloride 30g Sodium hypophosphite 10g Sodium oxyacetate 50g Water 900g Using the same sensitive film, contact exposure, water impregnation, and full exposure in water were carried out in the same manner as above, followed by special reduction treatment. Boron-nickel plating bath (shiba nickel stock solution,
(manufactured by Okuno Pharmaceutical) for 50 seconds, developed, and dried. The resulting image was black with 150 lines and 4% halftone dots resolved. In this development process, reduction and development are performed simultaneously. Example 2 A sensitive film was prepared in the same manner as in Example 1,
2 in water at 20℃ after exposure through negative film.
After soaking for a minute, take it out of the water and lightly drain the surface with a rubber squeegee. After exposing the entire surface with a 2KW printer using an ultra-high pressure mercury lamp, immerse it in a physical developer with the following composition at 30℃ for 1 minute and 30 seconds. Develop it,
A black image was obtained. Nickel chloride 0.1 mol Dimethylamine borane 0.1 mol Succinic acid 0.5 mol The pH was adjusted to 7.0 with NaOH. Example 3 A sensitive film was prepared in the same manner as in Example 1, subjected to pattern exposure and full-surface exposure by immersion, and a physical developer was obtained by mixing liquids A and B having the following composition at a ratio of 1:1 immediately before use. (Narcuss electroless plating bath) 22℃
The film was immersed in water for 7 minutes and developed to obtain a black image. Solution A Copper sulfate 60g/Nickel sulfate 15g/Hydrazine sulfate 45g/B solution Sodium hydroxide 45g/Potassium sodium tartrate 180g/Sodium carbonate 15g/Example 4 A sensitive film prepared in the same manner as Example 1 was washed with water and dried. After exposure for 2 minutes using a high-pressure mercury lamp 2KW printer (distance 100 cm from the light source) and 3 minutes while immersed in water, a reduction bath containing hydrazine hydrochloride (N ₂ H ₂ HCl) at a ratio of 1.0 mol/ for 1 minute at 40°C. Then, it was treated with an electroless plating solution shown below for 6 minutes to obtain an image with metallic luster. Nickel chloride 50g / Sodium hypophosphite 10g / Sodium citrate 10g / Similarly, the sensitive film of Example 1 was heated using an ultra-high pressure mercury lamp.
Using a 2KW printer (distance 100cm from the light source), the entire surface was exposed for 2 minutes, and after applying sufficient water with a brush, the entire surface was exposed again for 3 minutes using a 2KW printer using an ultra-high pressure mercury lamp, and 1.0 of N ₂ H ₂ HCl was applied. mol/
Treated at 40℃ for 1 minute with a bath solution with a concentration of
Processed for 1 minute and 30 seconds. Nickel hypophosphite 26g/boric acid 12g/ammonium sulfate 2.6g/sodium acetate 20g/A uniform black image was obtained by the above operations. Example 5 A sensitive material was prepared with the following composition using a PdCl _{dihydrochloric} acid aqueous solution prepared in the same manner as in Example 1, and then coated on a polyester film in the same manner as in Example 1, and dried to form a sensitive material. A film was produced. PdCl _{dihydrochloric} acid aqueous solution (Nippon Kanigen) 20g Gelatin (Nitta Gelatin P-2151) 30% aqueous solution 10g Diazoresin 20% aqueous solution 2.5g Glutaraldehyde 0.05g This sensitive film was printed on an ultra-high pressure mercury lamp 2KW printer (distance from the light source 100cm) The negative film was closely exposed for 2 minutes using a roller, and after sufficiently impregnated with water using a roller, the entire surface was exposed for 3 minutes at 65℃.
The film was immersed in a boron-nickel bath (Shibanitsukel stock solution, manufactured by Okuno Pharmaceutical Co., Ltd.) for 100 seconds, developed, and dried. Although the development time is longer than in Example 1, the film has good adhesion and does not peel off even if the film surface is rubbed by hand during development. The image quality was good, resolving 150 lines and 4% halftone dots. Example 6 A sensitive material was prepared with the following composition and used in Example 1.
A sensitive film similar to the above was prepared. PdCl _{dihydrochloric} acid aqueous solution (Nippon Kanigen Retschuma) 20g PVA (Nippon Gosei Cozenol NH-14) 10% aqueous solution 20g Diazoresin 20% aqueous solution 2.5g Malic acid 0.08g The above photosensitive film was heated using a diazocopy lamp (Ricoh Hi-Start 4). The film was superimposed on a negative film and exposed for 40 seconds, and subjected to water-retaining exposure treatment in the same manner as in Example 5. The film was immersed in a reducing bath consisting of a 1% SnCl ₂ aqueous solution of hydrochloric acid (Nippon Kanigen Pink Shuma) for 1 minute at room temperature. Physical development nuclei were formed on the entire surface. Next, as a physical development bath, hypophosphorous acid-based electroless plating solution Blue Syumer (manufactured by Okuno Pharmaceutical Co., Ltd.) was used.
It was processed at ℃ for 1 minute and 30 seconds to obtain a black image in the exposed area. Similarly, even if the above-mentioned sensitive film is pre-treated in the above-mentioned reducing bath, washed with water, dried, pattern-exposed using a diazocopy lamp, and then developed using a blue chemist, there will be no black color in the exposed areas. Got the image. After exposure to light, the above-mentioned photosensitive film was subjected to hydrous treatment and exposure treatment in the same manner as in Example 5, but without reduction bath treatment, the following developing bath (pH was reduced to 12.5 with NaOH).
Adjust to. By processing at a temperature of 40 to 50°C for 2 minutes, reduction and physical development were performed in one bath, and a good black image was obtained. Nickel sulfate 20g Potassium sodium tartrate 40g Sodium borohydride 2.3g Water 1000g Example 7 A photosensitive film was prepared in the same manner as in Example 1 using the photosensitive material having the composition shown below. HAuCl ₄・4H ₂ O1% hydrochloric acid aqueous solution 20g Gelatin (Nitta gelatin p-2222) 30% aqueous solution
6.7g Diazoresin (Shinko Giken D-011) 20% aqueous solution 2.5g Tartaric acid 0.05g The exposure conditions, water-containing exposure conditions, reducing bath conditions, and developing bath conditions were all the same as in Example 1. As a result,
A black image is obtained using any of the three methods. Example 8 A photosensitive material was prepared with the following composition, and a photosensitive film was prepared in the same manner as in Example 1. Redshumar 20g Gelatin (P-2152B Nitta Gelatin) 20% aqueous solution 10g 4,4'-Diazidodiphenylsulfone 20% aqueous solution 2.0g Mucochloric acid 0.06g All exposure conditions, water content, exposure conditions, reduction conditions, and development conditions were carried out. As a result of carrying out the same procedure as in Example 1, a black image was obtained using any of the three methods.

[Brief explanation of drawings]

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 Image formation comprising an image forming layer provided on a support, and a hydrophilic binder layer containing a photocrosslinking agent and a metal salt that becomes metal development nuclei when the image forming layer is reduced. The imaging layer of the material is subjected to pattern exposure to react the crosslinking agent in the exposed areas to crosslink the hydrophilic binder layer in the exposed areas, and then the imaging layer is impregnated with water, and then the image formation A first development step in which the entire surface of the layer is exposed to light, and then the image-forming layer is brought into contact with a reducing agent to form metal development nuclei in the image-forming layer; and a reducing agent to form an image in the unexposed area of metal particles that are precipitated and grown by reduction of the reducible metal ions centering on metal development nuclei in the unexposed area. An image forming method characterized by carrying out the following. 2. The image forming method according to claim 1, wherein the photocrosslinking agent is composed of a single compound or a mixture of compounds having a diazo group or an azide group.