JPS6247295B2 - - 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. 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 that sufficient resolution cannot be obtained. 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 titanium oxide is used, 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. 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 have
It has been found that physical development using metal nuclei such as gold, platinum palladium, silver, iron, and copper as development nuclei can be effectively suppressed by a compound having a diazo group or an azide group that is itself photodegradable. 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 findings, and more specifically, the image-forming material is formed by providing an image-forming layer on a support, and the image-forming layer contains a metal compound that is reduced to become a metal development nucleus. It is characterized by comprising a hydrophilic binder layer containing a compound having a diazo group or an azide group. The above image forming material provides a visible image by subjecting the image forming layer to a step of forming metal development nuclei by reduction, a pattern exposure step, and a physical development step. Therefore, exposure is essentially not involved in the formation of metal development nuclei. That is, the reduction treatment for forming metal development nuclei may be performed either before or after the exposure step. Therefore, the first image forming method of the present invention is a first step of exposing the image forming layer of the image forming material in a pattern, and then bringing the image forming layer into contact with a reducing agent to form image forming nuclei. A developing step (metal development nucleus formation step) is performed in which the image forming layer is brought into contact with a physical developer containing reducible metal ions and a reducing agent to form the reducible metal in the exposed area centering around the metal development nuclei. This method is characterized by carrying out a second development step (physical development step) in which an image is formed of metal particles precipitated and grown by reduction of ions.
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 second image forming method of the present invention is to first contact the image forming layer of the image forming material with a reducing agent to form metal development nuclei in the image forming layer, then perform pattern exposure, and then physically It is characterized by forming an image by contacting it with a developer. The pattern exposure step in the image forming method of the present invention has the effect of selectively decomposing a compound having a diazo group or an azide group as a physical development inhibitor in the exposed area of the image forming layer to remove its physical development inhibitory effect. has. Therefore, during the subsequent physical development, metal ions in the physical developer precipitate and grow as metals in the presence of metal development nuclei. On the other hand, in the non-exposed areas, such precipitation and growth of metal does not occur, and as a result, a visible image consisting of metal particles selectively grown in the exposed 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 reduction regardless of exposure,
The most distinctive feature of the image forming method of the present invention is that the physical development inhibitor is decomposed in the exposure step. The physical development inhibiting effect of a compound having a diazo group or an azide group or a compound treated with a physical developer (hereinafter collectively referred to as a "development inhibitor") is clear from the phenomenon described below. B. After the image forming layer of the present invention from which the development inhibitor has been removed is subjected to reduction treatment to form metal development nuclei,
When physical development is performed without exposure, physical development is performed on the entire surface. (b) If the image forming layer of the present invention containing a development inhibitor is subjected to reduction treatment and physical development treatment without being exposed to light, no physical development effect can be obtained. C. First, the image forming layer of the present invention is subjected to a reduction treatment,
A desired image can also be obtained when pattern exposure and physical development are then carried out (that is, when the second image forming method of the present invention is carried out). (d) When the image forming layer of the present invention is sequentially subjected to pattern exposure, reduction treatment, and physical development treatment (that is, when a typical embodiment of the first image forming method of the present invention is carried out), a desired image is formed. is obtained. (e) When pattern exposure and physical development are performed on the image forming layer of the present invention, and reduction treatment for generating metal development nuclei is not separately performed, the physical development treatment simultaneously reduces the metal compound and the metal. A desired image can be obtained only when the reducing agent is strong enough to form development nuclei. The physical development inhibiting effect of a compound having the above-mentioned diazo group or azide group or a compound treated with a developer was discovered for the first time by the present inventors. The metal development nuclei referred to in the present invention are fine metal particles that are stably formed, and although they themselves are invisible to the naked eye, they already act as physical development nuclei. 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, preferably dissolving, in a hydrophilic binder layer, a metal compound that is reduced to become metal development nuclei and a development inhibitor. 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 polyvinyl pyrrolidone. Ethylene oxide, maleic anhydride copolymers, 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 metal 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),
It is mixed with a binder aqueous solution along with a development inhibitor to form a liquid with a viscosity of about 10 to 1000 centipoise suitable for coating, which is coated 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 compounds having a diazo group or an azide group used as development inhibitors include water-soluble zinc chloride double salts, sulfates, and phosphates having a diazo group, or diazo resins obtained from these. is preferably used. More specifically, p-N,N-diethylaminobenzenediazonium chloride zinc chloride 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-toluylmercapto)-2,5-dimethoxy Benzenediazonium 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-azido phthalic anhydride, 4,4'-diazido diphenyl sulfone, p-azido cinnamic acid, 4,
Sodium 4'-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.
part: 0.1 to 100 parts of metal compound, especially 1 to 100 parts
It is preferable to include 1 to 100 parts, particularly 20 to 50 parts of a development inhibitor. 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, cyclopentane-1,2-dione, diketones such as 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,
Resins such as vinyl methyl ether/maleic acid copolymer, ethyleneimine/maleic acid copolymer, methacrylic acid/methacrylonitrile copolymer, polymethacrylamide, and methacrylic acid ester copolymer. 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. Next, the image forming method of the present invention using the image forming material of the present invention formed as described above will be described. According to the first 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 exposure section 2A, the development inhibitor is selectively broken down 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
It is sufficient to expose for 10 to 200 seconds at an intensity of 300w/ ^m2 . Then, by pattern exposure, the reducing agent aqueous solution 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 by dipping or coating, so that the development inhibitor is almost uniformly distributed in the image forming layer 2. Generates metal development nuclei. 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 formed by selective decomposition of the metal development nuclei and the development inhibitor thus obtained is brought into contact with a physical developer 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 is precipitated by reduction at the center. 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; 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, hydrazinediborane,
Dimethylphosphine borane, phenylphosphine borane, dimethylaldine borane, phenylaldine borane, dimethylstibine borane, diethylstivine 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/. 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 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. Next, according to the second image forming method of the present invention, the first
An image forming material as shown in the figure is sequentially subjected to a reduction treatment for generating metal development nuclei, a pattern exposure treatment, and a physical development treatment in this order. The individual processing steps are not particularly different from those in the first image forming method. As mentioned above, performing the reduction treatment to generate metal development nuclei before exposure as in this method was unthinkable in the various conventional methods that required exposure to generate metal development nuclei. be.
Compared to the first image forming method, this method requires washing with water and drying before exposure, so there is a problem that the number of steps is increased, but similar images can be obtained in both cases. In this way, according to the image forming method of the present invention, in both the first method and the second method, it is possible to form a black image with a transmission optical density of 4 or more and a gradation as necessary. Since a solution of a development inhibitor is used, the resolution is high, and images that can be substituted for images obtained by silver salt photography can be obtained. Also, since the image is a metal image, Kodatsu R-
Correction is possible using a reducing fluid such as No. 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
For example, the first development is performed in a nickel plating bath using a boron-based reducing agent, and the second development is performed in a high-temperature nickel plating bath at 65 to 90°C using a reducing agent with sodium hypophosphite, or high-speed copper plating. For example, a metallic image with metallic luster can be formed on the binder surface. Furthermore, by treating the obtained image with, for example, 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 (Shinko Giken D-011) 20%
Aqueous solution 2.5g Glutaric acid 0.12g The temperature of the above sensitive material was adjusted to 30°C to 40°C, applied to a polyester film (Toray Lumirror S, 100#) that had been subjected to plasma treatment in advance, and dried.
A coating film of μ was obtained. Sensitive film (image forming material) obtained above
The negative film was exposed for 2 minutes using a 2 kW ultra-high pressure mercury lamp printer (distance 100 cm from the light source). 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 c.c. 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, immerse it in a reduction bath (30°C), wash and dry it, and then use an ultra-high pressure mercury lamp 2kW printer (distance 100cm from the light source). The negative film was exposed to light for 2 minutes. 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 A similar sensitive film was exposed for 2 minutes using a 2kW ultra-high pressure mercury lamp printer (distance 100cm from the light source) with the negative film in close contact. Then, without performing any special reduction treatment, it was placed in a boron-nickel plating bath (Shibanitsukel stock solution, manufactured by Okuno Pharmaceutical) at 65℃ for 50 minutes.
It was immersed for a second, developed, and dried. The resulting image was black with 300 lines and 4% halftone dots resolved. In this development process, reduction and development are performed simultaneously. Below are two similar examples. Example 2 A sensitive film was prepared in the same manner as in Example 1,
After exposure through a negative film, the film was developed by immersing it in a physical developer having the composition shown below at 30° C. for 2 minutes to obtain a black image. 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 and exposed in the same manner as in Example 1, and a physical developer (Narcuss electroless plating solution) obtained by mixing liquids A and B having the following compositions at a ratio of 1:1 immediately before use was used. The film was developed by immersing it in a bath for 10 minutes at 22°C to obtain a black image. A: Copper sulfate 60g / Nickel sulfate 15g / Hydrazine sulfate 45g / B: Sodium sulfate 45g / Potassium sodium tartrate 180g / Sodium carbonate 15g / Example 4 A sensitive film prepared in the same manner as in Example 1 was diluted with hydrazine hydrochloride (N ₂ The sample was immersed for 1 minute at 40°C in a reduction bath containing 1.0 mol/ _H2HCl ). The sensitive film was washed with water, dried, and exposed using an ultra-high pressure mercury lamp.
Exposure was performed for 2 minutes using a 2kW printer (distance 100cm from the light source). Then, it was treated with an electroless plating solution shown below for 8 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.
Exposure was performed for 2 minutes using a 2kW printer (distance 100cm from the light source). Then N ₂ H ₂ · HCl
It was treated with a 1.0 mol/concentration solution at 40°C for 1 minute, and further treated with an electroless plating solution having the following composition and pH 5.5 at 21°C for 2 minutes. 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 photosensitive 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 photosensitive material. A film was produced. PdCl _{dihydrochloric} acid aqueous solution (Nippon Kanigen) 20g Gelatin (Nitta Gelatin p-2151) 30% aqueous solution 10g Diazoresin (Shinko Giken D-011) 20%
Aqueous solution 2.5g Glutaraldehyde 50% aqueous solution 0.05g This sensitive film was closely exposed to negative film for 2 minutes using an ultra-high pressure mercury lamp 2kW printer (distance 100cm from the light source), and then a 65°C boron-nickel plating bath (shiba nickel stock solution, (manufactured by Okuno Pharmaceutical) for 150 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 300 lines and 4% halftone dots. Example 6 A sensitive material was prepared with the following composition and used in Example 1.
A sensitive film was prepared in the same manner. PdCl _{dihydrochloric} acid aqueous solution (Nippon Kanigen Retschuma) 20g PVA (Nippon Synthetic Gohsenol NH-14) 10%
Aqueous solution 20g Diazoresin (Shinko Giken D-013) 20%
Aqueous solution 2.5g Malic acid 0.08g The above-mentioned sensitive film was exposed for 40 seconds using a diazocopy lamp (Ricoh Hi-Start 4) by superimposing it on a negative film, and was then exposed to a 1% SnCl ₂ hydrochloric acid aqueous solution (Nippon Kanigen Pink Schuma). Physical development nuclei were formed on the entire surface by immersing the sample in a reducing bath at room temperature for 1 minute. Next, as a physical development bath, hypophosphorous acid-based electroless plating solution Blue Shoumer (manufactured by Okuno Pharmaceutical Co., Ltd.) was used.
C. for 2 minutes 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. In addition, after exposing the above-mentioned photosensitive film, without performing reduction bath treatment, use the following developing bath (with NaOH to reduce pH).
Adjusted to 12.5. By processing at a temperature of 40 to 50° C. for 3 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 O 1% 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, reducing bath conditions, and developing bath conditions were all the same as in Example 1. As a result, a black image was 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. Redshumer 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, reduction conditions, and development conditions were the same as in Example 1. As a result, black images were obtained using any of the three methods.

[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. DESCRIPTION OF SYMBOLS 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 hydrophilic and contains a metal compound that becomes a metal development nucleus when reduced, and a compound having a diazo group or an azide group. An image forming material comprising a binder layer. 2. An image-forming material comprising an image-forming layer provided on a support, and a hydrophilic binder layer containing a metal compound that becomes a metal development nucleus when the image-forming layer is reduced and a compound having a diazo group or an azide group. A first development step of exposing the image forming layer to pattern light, and then bringing the image forming layer into contact with a reducing agent to form metal development nuclei in the image forming layer;
The image forming layer is brought into contact with a physical developer containing reducible metal ions and a reducing agent, and the metal particles are deposited and grown around metal development nuclei in the exposed area by reduction of the reducible metal ions. An image forming method characterized by performing a second developing step of forming an image. 3. The method according to item 2 above, wherein after pattern exposure, the first development step and the second development step are sequentially performed in this order. 4. After the pattern exposure, the image forming layer is brought into contact with the physical developer and metal development nuclei are generated by the action of the reducing agent in the physical developer, thereby performing the first development step and the second development step substantially simultaneously. The method described in item 2 above. 5. An image-forming material comprising an image-forming layer provided on a support, and a hydrophilic binder layer containing a metal compound that becomes a metal development nucleus when the image-forming layer is reduced and a compound having a diazo group or an azide group. The image forming layer is brought into contact with a reducing agent to form metal development nuclei in the image forming layer, followed by pattern exposure, and further brought into contact with a developer containing reducible metal ions and a reducing agent. An image forming method comprising the step of forming an image consisting of metal particles deposited and grown by reduction of the reducible metal ions centering on metal development nuclei in an exposed area.