JPS6058466B2 - Method of forming metal patterns - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a metal pattern and a photographic material used therein.
The present invention relates to a method of forming a metal pattern by forming a nucleus for electroless plating by a photographic method and electrolessly plating metal thereon, and a photographic light-sensitive material applied thereto.

Conventionally, there are two known methods for producing printed wiring boards.

The first method is the etching method or subtractive method (
In this method, a metal (for example, copper is common, but nickel, silver, or other metals may be used) on an insulating substrate (for example, epoxy resin, phenol resin, polyester, etc.).

), and after forming a resist pattern in the desired pattern on top of it, the metal in the areas not covered by the resist pattern is removed by chemical etching, and finally The resist is removed to obtain a printed wiring board. A resist pattern can also be obtained by exposing a photoresist provided on a metal layer in a pattern and then developing it, or by printing a pattern with resist ink using a screen printing method. You can get it no matter what. On the other hand, the second method is called a plating method or an additive method, in which the material is deposited in a pattern on an insulating substrate by electroless plating.

In order to electrolessly plate metal in a pattern on a substrate, it is necessary to form electroless plating nuclei in a pattern on the surface of the substrate.One known method is to provide nuclei on the entire surface of the substrate, and then The surface is masked in a pattern with a material that does not contain nuclei (eg, photoresist, printing ink).
The method for obtaining this mask is exactly the same as the method for forming a resist pattern in the subtractive method. Metal is deposited by electroless plating on the substrate surface not covered by the masking material. This method is described, for example, in US Pat. No. 30,068m. This method has the drawback of low photosensitivity when using a photoresist, and the drawback of low resolution (limited to several hundred μm) when using screen printing. Another known method is to form a nucleus by a photographic method, for example, as described in Japanese Patent Publication No. 49-2621, a nucleus is formed on a substrate on which a nucleus for diffusion transfer is provided. A non-hardening silver halide photographic emulsion layer is provided, the photographic emulsion layer is exposed to light in a desired pattern, silver is deposited in a pattern on the substrate surface by diffusion transfer development, and then the emulsion layer is washed with warm water. After dropping, this silver pattern is activated and becomes the nucleus for electroless plating. This method is superior in that the silver halide emulsion layer has high photosensitivity and high resolution (lines of about 10 μm are easily resolved); however, It was found that it had the following drawbacks. A first drawback has been discovered that after diffusion transfer development, trace amounts of silver may remain in the exposed areas after washing off the silver halide emulsion layer with hot water.

In the unexposed areas, silver is deposited on the substrate surface by diffusion transfer, but in the exposed areas, silver is not deposited on the substrate surface.
It has been thought that it forms in the emulsion layer and is washed away by subsequent hot water washing. However, the inventors discovered that the silver in the exposed areas was not completely washed away by this hot water washing.
In a small amount. However, they discovered that it remained on the surface of the substrate. This trace amount of silver may be easily visible to the naked eye, or it may be barely visible. It has been found that the smaller the grain size of the silver halide and the rougher the substrate surface, the larger the amount of residual silver becomes. Ta. If a trace amount of silver is present in the exposed area in this way, when the silver image deposited in the unexposed area is activated, this trace amount of silver will also be activated and become the nucleus of electroless plating. As a result, the entire surface is plated with metal. A second drawback is the diffusion transfer nucleus (e.g. nickel sulfide, colloidal silver, silver sulfide,
(stannic chloride, etc.) tend to become electroless plating nuclei.

Therefore, in order to prevent this, it is necessary to remove the diffusion transfer nuclei after the diffusion transfer development, which complicates the process. The third drawback is that developers for diffusion transfer generally have poor storage stability and cannot be used for long periods of time.

Therefore, the present inventor used a material with high sensitivity, high resolution, and easy processing to form a nucleus for electroless plating using a photographic method, and then formed a metal pattern by electroless plating metal on the nucleus. The researchers have been intensively researching methods and photographic materials suitable for this purpose, and by combining a silver halide photographic emulsion with a processing technique known as intensification or color toning, the previously known technique described above was discovered. The present invention was achieved by discovering that it is possible to overcome all the drawbacks of the above.

An object of the present invention is to provide a method of forming a nucleus for electroless plating on a highly sensitive photosensitive material by a photographic method and then electrolessly plating a metal onto the nucleus to form a metal pattern. Another object of the present invention is to provide a method for forming a high-resolution metal pattern by electroless plating.

Still another object of the present invention is to provide a method for forming a fog-free metal pattern by electroless plating. Still another object of the present invention is to provide a photographic material suitable for achieving the above object.

These objects of the present invention are to imagewise expose, develop, and fix a photographic light-sensitive material in which a non-curable silver halide photographic emulsion layer is provided on a support directly or through at least one subbing layer. After removing the silver halide in the unexposed areas,
This is achieved by washing off the emulsion layer with warm water and activating the trace amount of silver remaining in the exposed areas, and then electrolessly plating a metal onto the support. Alternatively, after imagewise exposure and development of a photographic light-sensitive material in which a non-curable silver halide photographic emulsion layer is provided on a support directly or via at least one undercoat layer, and the emulsion layer is washed off with warm water. This is achieved by electroless plating of the metal onto the support after fixation and activation of trace amounts of silver remaining in the exposed areas. These objects of the present invention provide a photographic material in which a non-curable silver halide photographic emulsion layer is provided on a support directly or through at least one subbing layer, and the emulsion layer is at least set. After washing with hot water and washing off the emulsion layer, image exposure and development are carried out, and after fixation, a trace amount of silver generated in the exposed area is activated, and then metal is electrolessly plated on the support. achieved by.

The above-mentioned last object of the present invention is to coat a non-curable silver halide photographic emulsion on a support with a finely roughened surface directly or through at least one subbing layer so that the thickness after drying is 10n7T1. This can be achieved by using a photographic light-sensitive material which is provided in a range from 1P7TL to 1P7TL.

In addition, the non-curable silver halide photographic emulsion in the present invention is one that does not contain any hardening agent (or hardening agent), is not hardened at all (or is also referred to as hardening agent),
Alternatively, it refers to a photographic emulsion that contains a small amount of a hardening agent, is weakly hardened, and is soluble in hot water in the temperature range of 30°C to 80°C, preferably in the temperature range of 40°C to 60°C.

The support used in the present invention may be a metal, a metalloid, or an insulator, but one that does not react with silver halide is used.

Further, for printed wiring, an insulator or at least one with an insulating surface is used. As a specific example,
Glass, sapphire, quartz, ceramics (e.g. soft porcelain, hard porcelain, alumina porcelain, titanium porcelain, beryllia porcelain, mullite porcelain, talc porcelain, spinel porcelain, zircon porcelain, ferrite porcelain, earthenware, etc.), enamel, ceramics on the surface Coated metals, metals with oxide films on their surfaces, silicon, germanium, metals (e.g. nickel, cobalt, chromium, titanium, molybdenum, silver, gold, platinum, iridium, rhodium, tantalum, beryllium, chromium-iron alloys, Nickel-iron alloy, cobalt-iron alloy, nickel-chromium alloy, nickel-cobalt alloy, chromium-cobalt alloy, Nikkei chromium-iron alloy, chromium-beryllium alloy, etc.), plastics (
Cellulose nitrate, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, polystyrene, polyethylene terephthalate, polycarbonate, heat-resistant polymer substances (e.g.
Poly(pyromellitic acid-p-phenylenediamineimide)
, poly(p-oxybenzoate), poly(ethylene-2,6-naphthalate), polyamideimides described in U.S. Pat. No. 3,554,984, U.S. Pat. No. 3,472
815), etc.). The support is generally plate-shaped or film-shaped, but is not necessarily limited to this shape. In particular, in the case of a plate-shaped or film-shaped support, a laminate in which two or more different types of plate-shaped or film-shaped substances are laminated and fixed can also be used.
In the present invention, finely roughening the surface of the support means fine pores, fine depressions, fine linear depressions, and combinations of these fine structures (hereinafter, these will be collectively referred to simply as ""finestructure") on the surface of the support.

The support whose surface is finely roughened means a support whose surface is provided with the above-mentioned fine structure. It has been found that in a silver halide photographic emulsion layer provided on a support whose surface has been finely roughened, the silver halide grains remain firmly on the surface of the support. As a result, after the silver halide photographic emulsion layer on the support having a fine structure on the surface is set,
Alternatively, a photographic light-sensitive material prepared by washing off the emulsion layer with hot water after the emulsion layer is dried does not have a decrease in sensitivity and maintains a sensitivity that is easy to handle in practical use. After exposing, developing and fixing the photographic light-sensitive material, the silver image is activated and electroless plating with metal proceeds smoothly, and the resulting metal pattern is firmly adhered to the support. It has been found that problems such as pinholes are extremely rare. On the other hand, after imagewise exposure and development of a photosensitive material in which a silver nitride photographic emulsion layer is provided on a support having a fine structure on the surface, the emulsion layer is washed off with warm water and then fixed or fixed. Even when the method of washing off the emulsion layer with hot water after washing is adopted, the process of activating the next obtained silver image and electrolessly plating metal on it progresses smoothly, and the obtained metal pattern is It has been found that it adheres firmly to the support and has very few problems such as pinholes. A necessary condition is that the fine structure be uniformly provided on the surface of the support.

The shape of the fine structure may be regular or irregular. It is desirable that the fine structure has at least a size that allows the silver halide grains to remain firmly therein. It will also be understood that when the size of the fine structure is about three times or more compared to the size of the silver halide grains, the silver halide grains cannot remain firmly in the fine structure. However, if the fine structure is relatively large compared to the size of the silver halide grains, and if the relatively large structure has small microstructures, the silver halide grains may It is understood that this will remain firmly in place. Regarding the fine structure, pores and depressions are the two extremes, and there are shapes in between. There are linear depressions that intersect with each other and those that do not intersect with each other, and among those that intersect, there are various angles at which they intersect. There are structures in which the depression is relatively large and a hole or depression is further present within the depression, and structures in which a linear depression is further present within the depression. In the method and photographic material of the present invention, it has been found that any of the above-mentioned fine structures are equally effective. As mentioned above, the width of the holes and depressions is related to the size of the silver halide grains used, and therefore the width varies from about 10n7 TL to about 3
The range is up to 0pm. The depth of the microstructures similarly ranges from about 5117 TL to about 5 μm. The width and depth of the fine structures preferably range from about 1:1 to about 5:1. The above-mentioned fine structure can be formed by a known method.

Specific examples of such methods include the Gyokuken polishing method, honing method, brushing method, chemical polishing method, and electrolytic polishing method used for polishing the support of lithographic printing plate materials, and the polishing method of the support of printed wiring. The swell and etch method is used as a polishing method.
Adhesive coating method (Adhes)
There are methods using ivecOatingprOcess) and filled laminate. A fine structure can be formed on the surface of the support by any of the methods described above depending on the material of the support and the intended use of the completed metal pattern. The silver halide emulsion used in the present invention is obtained by dispersing silver halide in a water-soluble binder. Examples of such silver halides include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide. A typical silver halide emulsion contains 90 mol% or more silver bromide (preferably 5 mol% or less silver iodide), and has an average silver halide grain size of about 0.1 μm or less (so-called Lippmann emulsion) in which the weight ratio of silver halide to water-soluble binder (excluding water) ranges from about 1:4 to about 8:1. Other examples include 90 mole percent or more silver bromide (preferably 5 mole percent or less silver iodide), a silver halide average grain size of about 1 μm or less, and a water-soluble silver halide. The emulsion has a binder weight ratio (excluding water) ranging from about 1:6 to about 6:1. Yet another example of a silver halide emulsion is 50 mol% (
preferably 70 mol % or more of silver chloride, the average grain size of the silver halide is about 1 μm or less, and the weight ratio of silver halide to water-soluble binder (excluding water) is from about 1:6 to about Emulsions ranging up to 6:1. On the other hand,
Examples of water-soluble binders include gelatin (alkali-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, etc.),
Colloidal albumin, cellulose derivatives such as tin, carboxymethyl cellulose, hydroxyethyl cellulose, agar, sodium alginate, sugar derivatives such as starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, poly N-vinyl pyrrolidone, polyacrylic acid copolymer Examples include polyacrylamide, polyacrylamide, and derivatives thereof.

Compatible mixtures of two or more of these binders are used if desired. The most preferred binder among these is gelatin, but gelatin can be partially or completely replaced with a synthetic polymeric substance, and in addition, gelatin can be substituted with amino groups, imino groups, etc. as functional groups contained in so-called gelatin derivatives, i.e. The hydroxyl group or carboxyl group may be treated with a reagent having one group capable of reacting with them, or a graft polymer to which molecular chains of other polymeric substances are bonded may be used in place of the hydroxyl group or carboxyl group. Reagents for making gelatin derivatives include, for example, isocyanates, acid chlorides, and acid anhydrides described in U.S. Pat. No. 2,614,928, acid anhydrides described in U.S. Pat. No. 3,118,766, and Bromoacetic acids described in Japanese Patent Publication No. 39-5514, phenyl glycidyl ethers described in Japanese Patent Publication No. 42-21845, US Patent No. 313294
5, N-aryl vinyl sulfonamides as described in British Patent No. 861,414, maleimide compounds as described in U.S. Pat. No. 3,186,846, and U.S. Pat. No. 25,942.
Acrylonitrile compounds described in US Pat. No. 93, polyalkylene oxides described in US Pat. No. 3,321,553, epoxy compounds described in Japanese Patent Publication No. 42-26845, and acids described in US Pat. and alkanesultones described in British Patent No. 103318.

Branch polymer grafted onto gelatin is disclosed in US Patent No. 27636.
No. 25, No. 2831767, No. 2966884 or “POlynler?Tters” Vol. 5, p. 595 (
1967), “PhOt.Sci.EngJ Volume 9 14
8 (1965), “J. POlyr Tler Sci.
．． A-1'', Vol. 9, p. 3199 (1971), there are many descriptions of acrylic acid, methacrylic acid or their esters, amides, derivatives such as nitrile, or what is generally called a vinyl monomer such as styrene. A wide range of polymers or copolymers and the like can be used. However, hydrophilic vinyl polymers that are compatible with gelatin to some extent, such as acrylic acid, acrylamide, methacrylamide, hydroxyalkyl acrylate,
Polymers or copolymers such as hydroxyalkyl methacrylates are particularly desirable. These emulsions may contain any known optical sensitizer, such as U.S. Pat. No. 1,346,301;
No. 63; No. 1942854; No. 1990507;
No. 2493747; No. 2739964; No. 2493
No. 748; No. 2503776; No. 2519001,
No. 2666761; No. 273490; No. 27391
Advantageously, optical sensitization is carried out with cyanine and merocyanine dyes as described in No. 49; and British Patent No. 450,968. Electromagnetic waves to which the silver halide emulsion is sensitive, such as visible light (wavelength range from about 400r17n to about 750r1m), ultraviolet light (wavelength range about 290r1m)
m, to about 400r1TT1,), electron beam and
The silver halide emulsion can be suitably exposed using a line or the like.

In a photographic light-sensitive material having an optically sensitized silver halide emulsion layer, it is convenient to select light having a wavelength mainly in the optical sensitization region of the emulsion as the light for exposing the emulsion layer. . Silver halide emulsions can also be chemically sensitized by conventional methods.

Chemical thickeners that can be used include, for example, U.S. Patent No. 2,399,083, U.S. Pat.
Gold compounds such as chlorauric acid salts and gold trichloride described in No. 597856 and No. 2597915, US Pat.
4806@, No. 2540086, No. 256624
Salts of noble metals represented by platinum, palladium, iridium, rhodium, and ruthenium described in US Pat.
No. 574944, No. 241068 Crocodile, No. 31894
Sulfur compounds that react with silver salts to form silver sulfide as described in US Pat. No. 58, US Pat. No. 3,501,313, etc.; US Pat.
No. 1925, No. 2521926, No. 269463
Examples include stannous salts, amines, and other reducing substances described in No. 7, No. 298361, and No. 3201254. Furthermore, various compounds can be added to the silver halide emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of the light-sensitive material. These compounds include 4-hydroxy-6-methyl-1,3,C, 7-tetraazaindene, 3-methylbenzothiazole, 1-phenyl-5-mercaptotetrazole, and many other heterocyclic compounds, mercury-containing compounds, mercapto compounds, A large number of compounds such as metal salts have been known for a long time. An example of a compound that can be used is K. M
ees, “The'111e0ry0fthePh0t
0graphicPr0cess” (3rd edition, 196@
), pages 344 to 349 list the original documents, as well as U.S. Patent No. 1758576 (mercaptothiazoles), U.S. Patent No. 2110178 (glutathione), U.S. Patent No. 2110178 (glutathione),
No. 31038 (benzothiazolium salts), No. 269
No. 4716 (ventia zolium salts), No. 3326
No. 681 (salts of benzoselenazolium compounds), No. 2173
No. 628 (aminohydroxypyrimidines), No. 230
4962 (Mercaptopyrimidines), 269704
Gin (mercaptotetrazoles and 1-phenyl-5
-tetrazoline-5-thi-ones), 2324123
No. (Aminonitrobenzimidazoles, Nitroindazoles and Aminoindazoles), 23941
No. 98 (salts of benzenesulfinic acids, etc.), No. 244
4605 to 2444608 (Hydroxytetraazaindenes, aminotetraazaindenes and pentaazaindenes) British Patent No. 893428 (Mercaptotetraazaindenes), US Patent No. 25662
No. 45 (complexes and salts of noble metals such as platinum and iridium),
2697099 (mercaptothiazoles and benzothiazolin-2-ones), 270816 (urazole, varapanic acid, and hydantoins), 27
No. 28663 to No. 2728665 (Molecular addition compound of mercuric chloride and nitrogen-containing ring compound), No. 24
No. 76536 (Mercaptotriazines) No. 28240
No. 01 (mercaptothiazoles, etc.), 28434
No. 91 (Mercaptooxadiazoles), No. 3052
No. 544 (poly N-vinyl-2-pyrrolidones), No. 3137577 (organic mercury compounds, e.g. 8-(3
-Hydroxymercury 2-methoxypropyl)-2-
Okiri? -1-benzopyran-3-carboxylic acid, etc.)
, No. 322083 (isothiourea derivatives and isothiouronium salt derivatives), No. 3226231 (mercaptobenzoic acids), No. 323665 (sulfocatechols and cyhydroxynaphthalenesulfonic acids),
No. 3251691 (mercaptoimidazole, benzimidazole and nitrobenzimidazole)
, 325279tan (2-mercaptoimidazole)
, British Patent No. 403789 (mercaptoimidazoles), US Patent No. 3287135 (urazoles, etc.),
No. 3420668 (sulfonamides having N-river loading, e.g. (N-phenyl-N-p-toluenesulfonamide)ethylmercury), No. 3622339 (s-
triazine polycondensates), No. 2933388 (4-mercapto 1◆3●C-7-tetraazaindenes),
No. 3567454 (Mercury (■) salt of sulfo- or sulfonato-substituted organic thiols) and No. 359566? (
It is also described as a chelate compound of polyaminopolycarboxylic acid and mercury (■). Silver halide emulsions have surface activity. The agents may be added alone or in combination. Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsifying and dispersing, sensitizing, improving photographic properties, antistatic, antiadhesive, etc.
These surfactants include saponin. Natural surfactants such as alkylene oxide, glycerin, and glycidol, nonionic surfactants such as higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, and cationic surfactants such as phosphonium or sulfonium.・For sex agents, anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric ester groups, and phosphoric ester groups, amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric or phosphoric esters of amino alcohols. It can be divided. Some of the surfactant compounds that can be used include US Pat. No. 2,271,623, US Pat. No. 2,240,472, US Pat.
No. 68101, No. 3158484, No. 32012
No. 53, No. 3210191, No. 3294540, No. 3415649, No. 3441413, No. 3442654, No. 3475174, No. 354
No. 5974, No. 3666478, No. 350766
No. 0, British Patent Publication No. 119845, "Synthesis of Surfactant J and Its Applications" by Ryohei Oda et al. (Shin Shoten 19)
6 detailed edition) and A. W. "Surface Active Agents" by J. Perry (Interscience Publishing Corporation 19th Edition). P. It is described in books such as "Encyclopedia of Surface Active Agents Vol. 2" (Chemical Publishing Company 196 detailed edition) written by Sisley.
The silver halide emulsion layer has a thickness of 10r1m after drying. Although the thickness of the emulsion layer is preferably in the range from 1 .mu.m to 1 .mu.m, the thickness of the emulsion layer can be selected arbitrarily.

The silver halide emulsion layer can be coated on one side of the support or on both sides of the support. On the support or emulsion layer, a back layer, an antihalation layer, and a top layer (
For example, a protective layer), an undercoat layer, etc. can be provided. The undercoat layer that can be used in the present invention is a layer containing a substance that exhibits strong adhesion to both the support and the silver halide emulsion layer.

If the properties of the support and the silver oxide emulsion layer are extremely different, two or more undercoat layers may be used as required. Materials used for the undercoat layer include gelatin (acid-treated gelatin, alkali-treated gelatin, enzyme-treated gelatin, etc.), gelatin derivatives,
Albumin, tin, cellulose derivatives, starch derivatives, sodium alginate, polyvinyl alcohol, poly N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, alcohol-soluble polyamide resin described in Japanese Patent Publication No. 39-55, Tokuko Sho 43-1
Mixtures of cellulose esters and terephthalic acid-glycol polyesters described in Japanese Patent Publication No. 4503, gelatin-cellulose nitrate mixtures described in Japanese Patent Publication No. 44-2597, and compounds described in Japanese Patent Publication No. 11616-1987. , West German patent application (0LS) 200
Homopolymers or copolymers of glycidyl (meth)acrylate described in 1727 can be applied. In addition, a thin layer of polyvinyl acetate (for example, 0.1 to 0.3 μm thick) is provided on the support, and the surface is saponified by contacting with an aqueous alkaline solution such as an aqueous sodium hydroxide solution, which is then used as an undercoat layer. be able to. In the method of the present invention, the developer for forming the silver image generally includes dihydroxybenzenes and polyhydroxybenzenes well known in the art, such as hydroquinone, 2-chlorohydroquinone, 2-bromohydroquinone, 2-isopropylhydroquinone, etc. , toluhydroquinone, 2-phenylhydroquinone, 2,3-dichlorohydroquinone, 2●5-dimethylhydroquinone, pyrogallol, etc.), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-
Pyrazolidone, 1-phenyl-4●4-dimethyl-3-
pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols, (e.g. o-aminophenol, p-aminophenol, o-(methylamino)phenol, p- (methylamino)phenol, p-
(diethylamino)phenol, 2,4-diaminophenol, p-(benzylamihaphenol, etc.), ascorbic acid, 1-aryl-3-aminopyrazolines (
For example, 1-(p-hydroxyphenyl)-3-aminopyrazoline, 1-(p-methylaminophenyl)-3-
Pyrazoline, 1-(p-aminophenyl)-3-pyrazoline, 1-(p-amino-m-methylphenyl)-3-
Aminopyrazoline, N-(p-hydroxyphenyl)glycine, and other C.I. E. K. Mees and T. H. Ja
mes co-author “TheOryOfPhOtOgra
phicPrOcess” 3rd edition (1966, Mac
miIIanCO. , NewYOrk) Chapter 13 and L.
F. ,A. “PhOtOgraphicP” written by MasOn
rOcessingChemistry” (1966, TlleFOcalPresss.LOndOn) 1
The compounds listed as developing agents on pages 6-30 are used alone or in suitable combinations. The developer is PH
8 or more, preferably about PH8.5 to PHL2. If necessary, an alkaline agent (for example, alkali metal or ammonium hydroxide, carbonate, or phosphate) is added to the developer.
, pH adjusting or buffering agents (e.g., weak acids and bases such as acetic acid and boric acid, and their salts), development accelerators (e.g., various pyridium compounds and cationic compounds described in U.S. Pat. No. 2,648,604, No. 3,671,247, etc.) compounds, potassium nitrate and sodium nitrate, U.S. Patent 25
Polyethylene glycol condensates and their derivatives described in British Patent No. 33990, British Patent No. 2577127, British Patent No. 295097, etc., British Patent No. 1020033 and British Patent No. 10200
Nonionic compounds such as polythioethers represented by the compounds listed in 3.Other organic amines such as pyridine and ethanolamine, benzyl alcohol,
hydrazines, etc.), antifoggants (e.g. alkali bromide, alkali iodide, U.S. Pat. No. 2,496,940, 26
Including nitrobenzimidazoles described in No. 56271, mercaptobenzimidazole, 5-methylbenztriazole, 1-phenyl-5-mercaptotetrazole, U.S. Pat.
No. 2596, No. 3295976, No. 36155,
Compounds for rapid treatment liquids described in 359719 Unagi etc., thiosulfonyl compounds described in British Patent No. 972211, phenazine-N-oxides described in Japanese Patent Publication No. 46-41675, and others. ``Science Photograph Handbook'' (195 K., Maruzen, Tokyo) volume 2, page 29, fog suppressants described in the 4th peak), as well as U.S. Patent No. 3161513, U.S. Patent No. 3161514, British Patent No. 1030442, U.S. Patent No. 1144481, 12
51558, stain or sludge inhibitors, preservatives (e.g. sulfites, bisulfites, hydroxylamine hydrochloride, formaldehyde sulfite adducts, ethanolamine sulfite adducts, etc.);
It can contain surfactants and the like. On the other hand, the silver halide fixing agent is generally any well-known silver halide solvent.

For example, water-soluble thiosulfates (e.g., potassium thiosulfate,
sodium thiosulfate, ammonium thiosulfate, etc.), water-soluble thiocyanates (e.g., potassium thiocyanate,
sodium thiocyanate, ammonium thiocyanate, etc.), water-soluble organic diols (e.g., 3-thia-1,
5-pentanediol, 3,6-dithia 1,8-octanediol, 3,6●9-trithia 1●11-undecanediol, 3●6●9●12-tetrathia 1●
14-tetradecanediol, etc.), water-soluble sulfur-containing organic dibasic acids (e.g., ethylene bisthioglycolic acid, etc.), water-soluble salts thereof, etc., or mixtures thereof. Solutions containing fixing agents may optionally contain preservatives (e.g., sulfites, bisulfites), PH buffering agents (e.g., boric acid, borates), PH adjusting agents (e.g., acetic acid), chelating agents, etc. be able to.

According to one embodiment of the method of the invention, once the image has been exposed, developed and fixed by known methods, the emulsion layer is washed off with warm water.

Since the emulsion is non-hardening, it can be dissolved and removed by hot water, but surprisingly, a small amount of silver image remains in the image-exposed area of the support surface even though tanning development has not been performed. However, it was approved. It was found that the rougher the surface of the support, the greater the amount of residual silver. It was also found that even if the surface of the support was not rough, it remained well even when there was a hydrophilic undercoat layer. Even when the support was made of mirror glass, it was observed that a trace amount of silver remained that could be discerned with the naked eye, but it was observed that it was removed by vigorous rubbing with a sponge. The emulsion layer in non-image exposed areas is completely washed away. The residual amount of silver was also found to depend on the dry film thickness of the emulsion.

Curiously, when the film thickness is large, the amount of silver remaining after washing with hot water (
Therefore, the optical density of the silver image decreases, and the smaller the film thickness, the more the amount of silver increases. Of course, if the film thickness becomes very small, the amount of silver will also decrease, but for example, 3prr
Comparing the film thickness of L and the film thickness of 1 μm, the latter. has a higher amount of silver. The preferred film thickness of the emulsion varies depending on the type of emulsion, so it cannot be generalized, but it is preferably 1 μm or less. Furthermore, it was found that the amount of silver remaining was greater when the substrate surface was etched with chemicals. I made it clear.

For example, when using epoxy resin as a substrate, acid (
It was found that when treated with a chromic acid mixture (for example, a chromic acid mixture), the amount of residual silver was greater than when no treatment was performed, provided that other conditions were the same. Not only does the amount of residual silver increase,
It was found that the adhesion between the silver particles and the substrate increased, and that the silver particles remained uniformly. When the trace amount of silver thus obtained is activated, it becomes the core of electroless plating.

Then, when treated with a known electroless plating solution, metal is deposited on these nuclei. Trace amounts of silver left by hot water washing may be invisible to the naked eye or easily visible, but in either case no binder remains in the image area. Surprisingly, it has been discovered that if the surface of the support is roughened or treated to make it hydrophilic, this residual silver cannot be removed by rubbing with a sponge or by applying ultrasonic vibrations. Activation of residual silver refers to replacing part or all of the remaining silver with a noble metal that has a catalytic action, or bleaching part or all of the remaining silver to convert it into a silver compound ( silver oxide, silver complex compounds, etc.).

As the noble metal having a catalytic action, any metal may be selected from gold and Group I noble metals, preferably gold, platinum, and palladium.

In order to replace silver with a noble metal having a catalytic action, the silver image on the support may be treated with a solution containing a noble metal compound (hereinafter referred to as a replacement solution). Most commonly, an aqueous solution containing a noble metal compound is used as the replacement liquid. If necessary, use a mixture of water and other substances (for example, alcohols such as methyl alcohol and ethyl alcohol; ketones such as acetone and cyclohexanone; aldehydes such as acetaldehyde; and ethers such as dimethyl ether and diethyl ether) as a solvent. You can also do that. The most common processing methods include a method in which the silver image on the support is immersed in a replacement solution, and a method in which the replacement solution is allowed to fall onto the silver image on the support. Although not limited to the method, the silver image and the replacement liquid are
Any other known method of contacting the silver for a period of time necessary to replace the precious metal can be used. Through this treatment, part or all of the silver is replaced with a noble metal having a catalytic action, and at the same time, silver ions or silver compounds are generated. The noble metal compound having catalytic action used in the present invention is selected from the above-mentioned noble metal salts, complexes, oxyacids, oxyacid salts, and complex acid salts (hereinafter collectively referred to as noble metal compounds). One compound or a combination of two or more compounds is dissolved in the displacement liquid.

When used as an aqueous solution of a noble metal compound, the solubility of the noble metal compound does not substantially matter. That is, since the concentration of the noble metal compound in the replacement liquid can be used within the range from 0.01 Wt% to reaching saturation, preferably from 0.05 Wt% to reaching saturation, noble metal compounds with low solubility can be used unless they are extremely poorly soluble. can be used. When the substitution process is performed with a saturated solution in which the solubility of the noble metal compound is low and there are insoluble components of the noble metal compound in the substitution solution, as the silver image and the precious metal are replaced, the insoluble components are dissolved and the precious metal is supplied. . Further, when the solubility of the noble metal compound is low, an acid, a base, a salt, and a compound capable of forming a complex can be used together in order to increase the solubility. Noble metal compounds include halides, halogen complex acids and their salts, cyanides, cyano complex acids and their salts, thiocyanate complex acids and their salts, oxygen acids and their salts, sulfates, nitrates, double salts such as alum, and ammine. complex,
Organic ammine complexes, aco complexes, etc. can be used. Specific examples of these compounds are listed below, but the present invention is not limited to the use of these compounds. Note that all those containing water of crystallization and those containing optical isomers are omitted from description. Examples of halides include gold trichloride, gold (1) gold chloride (■), platinum dichloride, palladium dichloride, rhodium trichloride, iridium trichloride, iridium tetrachloride, ruthenium trichloride, gold tribromide, and tribromide. Platinum, platinum tetrabromide, palladium dibromide,
Rhodium tribromide, iridium hydrogen bromide (■), ruthenium tribromide, platinum tetraiodide, iridium triiodide, and other halogen complex acids of these metals include chloroauric (■) acid and chloroplatinic (■) acid. , palladium chloride (■) acid, iridium chloride (
■) acid, gold bromide (■) acid, platinum bromide (■) acid, etc. These noble metal halide complexes include tetrachlorogold (■) acid, etc.
■) Lithium salts, sodium salts, potassium salts, ammonium salts of acids, etc., hexachloroplatinic (■) Lithium salts, sodium salts, potassium salts, ammonium salts of acids, etc.
Sodium salt, potassium salt, ammonium salt, cesium salt, etc. of tetrachloroplatinic (■) acid, potassium salt, magnesium salt, etc. of hexachloropalladium (■) acid, sodium salt, potassium salt, ammonium salt, etc. of tetrachloropalladium (■) acid. salts, magnesium salts, etc. Hexachlororhodic (■) acid, lithium salts, sodium salts, potassium salts, ammonium salts, dimethylammonium salts, etc., pentachlororhodic (■) acid potassium salts, hexachloroiridic (■) acid lithium salts, sodium salts, potassium salts, etc. of hexachlororuthenium (■) acids, such as lithium salts, sodium salts, potassium salts, ammonium salts of hexachlororuthenium (■) acids, sodium salts, potassium salts, ammonia salts of hexachlororuthenium (■) acids, etc. Sodium salts, potassium salts, ammonium salts, etc., sodium salts, potassium salts, ammonium salts, dimethylammonium salts, tetramethylammonium salts, etc. of pentachlororuthenium (■) acids, sodium salts, potassium salts of tetrabromoauric (■) acids, etc. Sodium salts of tetrabromoplatinic (■) acids, such as rubidium salts and ammonium salts, lithium salts, sodium salts, potassium salts, and ammonium salts of hexabromoplatinic (■) acids;
Potassium salts, lithium salts, sodium salts, potassium salts, rubidium salts of hexabromopalladium (■) acids,
Cesium salts, ammonium salts, sodium salts of tetrabromopalladium (■) acids, potassium salts, etc., sodium salts and pyridinium salts of hexapromodium (■) acids, sodium salts of pentabromorodium (■) acids,
Potassium salts, ammonium salts, etc., sodium salts, potassium salts, etc. of hexabromoiridic (■) acids, sodium salts, potassium salts, ammonium salts, etc. of hexabromoiridic (■) acids, hexabromortenium (■)
Sodium salts, potassium salts, ammonia salts of acids, etc., methylammonium of pentabromorthenium (■) acids,
Cyanides of these precious metals, such as trimethylammonium salt, include gold cyanide (1), gold cyanide (■),
Cyano complex acids of these precious metals, such as platinum cyanide (■), palladium cyanide (■), rhodium cyanide (■), iridium cyanide (■), and ruthenium pentacyanide, and their salts include gold dicyano. (1) Acids and their potassium salts, ammonium salts, etc., tetracyanogold (■)
Acids and their sodium salts, potassium salts, ammonium salts, cobalt salts, etc., tetracyanoplatinic (■) acids and their sodium salts, potassium salts, sodium potassium salts, barium salts, etc., tetracyanopalladium (■) acids and their sodium salts , potassium salts, hexacyanorhodic (■) acids and their potassium salts, sodium salts, monohexamethylenetetramine adducts, sodium salts, potassium salts, barium salts of hexacyanoiridic (■) acids, etc., hexacyanoruthenium (■) acids, etc. Thiocyanato complex acids of these metals and their salts, such as sodium salts, potassium salts, barium salts, etc. ■)
Sodium salts, potassium salts, ammonium salts of acids, sodium salts, potassium salts of tetrathiocyanatoplatinic (■) acids, sodium salts, potassium salts, ammonium salts, barium salts of tetrathiocyanatopalladium (■) acids, etc. , hexathiocyanathrodic (■) acid and its potassium salt, hexaammine cobalt (■) salt, etc. These noble metal oxygen acids and their salts include gold acid and its potassium salt, palladium sulfate (■), nitric acid, etc. Ammine complexes of these noble metals include palladium (■), rhodium sulfate (■), rhodium-potassium alum, sodium salt and potassium salt of ruthenic acid, and diammine gold (1).
) Chloride, diamine gold (1) Bromide, tetraamine gold (■) Triperchlorate, tetraamine gold (
■) Trinitrate, tris (tetraammine gold (■)
Perchlorate tetrasulfate, etc., hexammine platinum (■) tetrahydroxide, hexammine platinum (■) tetrachloride, hexammine platinum (■) tetranitrate, tetraammine platinum (■) dichloride, tetraammine platinum (■) dinitrate , triamminehydroxylamine platinum (■) dichloride, etc., tetraamminepalladium (■) dinitrate, tetraamminepalladium (■) dihydroxide, tetraamminepalladium (■) dichloride, tetraamminepalladium (■) disulfate, etc., hexaammineiridium (■) trinitrate. , hexaammineiridium (
■) trichloride, hexaammineiridium (■) tripromide, hexaammineiridium (■) triiodide, etc., hexaammineruthenium (■) trichloride, hexaammineruthenium (■) tripromide, hexaammineruthenium (■) trisulfate, etc.
Organic amine complexes of these noble metals include tetraethylamine platinum (■), hexaammine rhodium (■) trinitrate, hexaammine rhodium (■) trichloride, hexaammine rhodium (■) tripromide, and hexaammine rhodium (■) trisulfate. ) dichloride [Pt(C2H5NH2)4]Cl2, tetraethylamine platinum (■) dinitrate, tetraethylamine platinum (■) disulfate, etc., trisethylenediamine iridium (■) trinitrate, trisethylenediamine platinum (■) tetrachloride, etc., trisethylenediamine platinum (■) Tetrathiocyanate, trisethylenediamine rhodium (■) trichloride, trisethylenediamine rhodium (■) trithiocyanate, trisethylenediamine rhodium (■) trinitrate, etc.
Aco complexes include acotriammine platinum (■) dihydroxide, diacodiammine platinum (■) disulfate, acopentaammine iridium (■) trinitrate, acopentaammine iridium (■) trichloride, acopentaammine rhodium (■), etc. ) trinitrate, acopentaammine rhodium (■) tripromide, etc., acopentaammine ruthenium (■) trinitrate, etc., as well as ethylenediaminepyridineamine platinum (■) dichloride, dithiocyanatoammine platinum (■)
, dithiosulfatoauric acid trisodium salt (Tr
isOdium) (DithiOsulfatOaur
ate(1)). Among compounds containing these precious metals, chlorides, bromides, chlorinated complex acids, sodium salts, potassium salts, and ammonium chlorinated complex acids of gold, platinum, and palladium, and brominated complex acids of gold and platinum. The sodium, potassium, and ammonium salts of brominated complex acids are moderately stable, do not have extremely low solubility in water, and are commercially available or easy to synthesize. It is a particularly preferred compound for the treatment of the present invention because it has the following characteristics.

In the substitution liquid, the noble metal is transferred from a compound containing a noble metal to a noble metal cation or a ligand (11gand) to a noble metal cation.
) is dissolved in the aqueous medium as a coordinated noble metal complex ion.

When both noble metal cations and noble metal complex ions come into contact with metallic silver in an aqueous medium, the metallic silver becomes positively charged and dissolves into the aqueous medium or becomes a water-insoluble silver compound, while the original As a result, metallic noble metals are precipitated from the coarse water medium where metallic silver is present. That is,
The action of the substitution liquid is substantially the same whether the noble metal-containing compound is dissolved in the substitution liquid in the form of a noble metal cation or in the form of a noble metal complex ion. Therefore, when carrying out the method of the present invention, compounds containing noble metals can be selected from a wide range depending on the treatment time and treatment temperature. Further, the replacement liquid may contain a PH regulator, a surfactant, etc., if necessary. When the photosensitive material on which the silver image is formed is brought into contact with the above-mentioned replacement liquid for an appropriate period of time in the range of 0.1 seconds to 60 seconds, the precious metal will precipitate in the silver image area, and at the same time, will the silver be eluted into the replacement liquid? It becomes an insoluble silver compound and remains in the area of the silver image.

Activation is equally achieved in both cases. moreover,
It has been found that the method of the invention can be achieved by activating only the thin layer of silver image near the surface remote from the support. Another example of a specific method of activating a silver image is to bleach the silver image according to known methods.
Bleaching of the silver image is accomplished by contacting the silver image with a bleaching solution containing a known bleaching agent. Many compounds are used in the bleaching agents contained in bleaching solutions, among which are ferricyanates, dichromates, and water-soluble cobalt (■
) salts, water-soluble copper (■) salts, water-soluble quinones, nitrosophenols, iron (■), cobalt (■), copper (■), and other polyvalent metal compounds, especially these polyvalent metal cations, and organic Complex salts of acids such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, metal complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, Peracids such as 2,6-dipicolinate copper complexes, alkyl peracids, persulfates, permanganates, hydrogen peroxide, hypochlorites,
Commonly used are hypobromite, chlorite, chlorate, bromate, such as chlorine, bromine, canola powder, etc. alone or in appropriate combinations. This treatment solution further includes U.S. Pat.
Various additives can also be added, including the bleach accelerators described in Japanese Patent No. 5-8506 and No. 45-8836. The photosensitive material on which the silver image has been formed is added to the above bleaching solution by 0.1
Activation is achieved by suitable contact in the range of seconds to 6@2 to convert the silver into silver compounds.

In this case as well, it has been found that the method of the present invention can be achieved by activating only the surface of the thin silver image on the side far from the support. Furthermore, the metallic silver constituting the remaining silver image has very fine particles, preferably 5n.
It has also been found that when the silver particles are fine particles in the range from 7TL to 100I17TL and have never come into contact with oxygen-containing gas, the silver image itself becomes the nucleus of electroless plating.

Such a silver image can be obtained by exposing, developing and fixing according to the method of the present invention using, for example, a conventional Lippmann emulsion. At this time, the silver halide emulsion layer may be washed away with warm water after the silver image is obtained, or may be washed off with warm water before exposure; in either case, the silver image finally obtained is As long as it is not brought into contact with oxygen-containing gas (for example, air), it can be used as a nucleus for electroless plating. Methods for activating residual silver include the above-mentioned methods, such as those described in "Tech.P.
rOc. Amer. ElectrOplat. SOcJ
E., Vol. 46, pp. 264-276 (1959). B.
SaLlbeSter's "ElectrOIessCO"
pperPIating” and F. A. Lowenh
"MOdemEIectrOplating" by eim
(JOhn-Wiley & SOns.s Inc., Ne
It is possible to apply the method described in WO Orkll 96 tsubo) and the like. The activated silver image is contacted with a known electroless plating solution to deposit metal.

The electroless plating solution used in the present invention contains a metal ion source, an alkali (or acid), a complexing agent, and a reducing agent.
As the metal ion source, metal compounds that are easily ionized in an aqueous solution are used, such as copper, silver, nickel,
Compounds of cobalt and tin are used. There is no particular limit to the amount of metal ion source in the plating solution, but in particular 0.00
A concentration range of 2 to 0.06 m01eIe is preferred. Alkali (or acid) is used to adjust the pH of the plating solution. Examples of alkalis include metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; examples of acids include hydrochloric acid, sulfuric acid, oxalic acid, and There are phosphoric acids, etc. The PH value of the plating solution is not particularly limited, and ranges from PH3 to PHll, preferably from PH4 to PHlO,
Each is used within the optimum pH range of a known formulation. Among these, it is advantageous to use an alkaline plating solution in terms of operation and preparation and management of the plating solution. The complexing agent is added to prevent the metal in the plating solution from precipitating, and examples include Rothsell's salt, ethylenediaminetetraacetic acid, sodium salt of ethylenediaminetetraacetic acid, citric acid, and triethanolamine.

The amount of the complexing agent added is preferably 0.5 to 5 times the amount of the metal salt in terms of moles. As the reducing agent, formalin, paraformaldehyde, glyoxal, etc. are used, and formalin is particularly preferred. The plating solution may contain preservatives (sodium carbonate, potassium carbonate, etc.), plating accelerators (acetates such as sodium acetate, potassium acetate, triethanolamine,
(e.g., ethylenediaminetetraacetic acid), metal antioxidants (e.g., sulfate), and the like. The temperature of the plating solution is
Because it varies depending on the type of components used in the plating solution,
Although it cannot be determined unconditionally, it is generally in the range of 15°C to 99°C. Further, the plating speed is greatly influenced by the liquid temperature, but within the above temperature range, the rate at which the plating layer increases is usually 1 to 10 μ7 n/hour. The composition of the plating solution, plating conditions, etc. are well known to those skilled in the art, and can be appropriately selected depending on the purpose. For more details, see E. above. B. Saubester's paper, F. A. Fat We
It is described in books such as Yu Eim's book and Lu Bochen's ``Plating of Plastics'' (Tankan Kogyo Shinbunsha, 1964, Tokyo). As an embodiment of the method of the present invention, after development and before fixing, the emulsion layer can be washed away by washing with warm water, and then fixing can be carried out.

According to another embodiment of the method of the invention, the silver halide emulsion layer provided on the support is washed off after drying by hot water washing.

Although the binder of the emulsion was dissolved and removed by this treatment, it was found that a small amount of silver halide grains were adsorbed on the surface of the support. After drying, this minute amount of halogen silver particle layer is imagewise exposed, developed and fixed, to obtain a very low density silver image as in the above-mentioned embodiment. After the silver image thus obtained is activated, it is immersed in the above-mentioned known electroless plating solution and plated with metal. In this aspect, the following must be noted. That is, when the silver nodagenide emulsion is dye-sensitized with a water-soluble dye, the dye is washed away by hot water washing, resulting in a decrease in sensitivity. Therefore, in this embodiment, it is desirable to use a water-insoluble colorant as the colorant. Of course, after washing with hot water, it is also possible to bring the dye solution into contact with the dye solution for amplification. In this aspect,
No matter what method the emulsion is applied to (ImmersiOn method, Spra-on method, Airknife method, spin coating method, etc.), it has the advantage that it becomes a uniform thin layer (adsorption layer) by washing with hot water. Furthermore, since no binder is present, there is no fear that the binder will harden and become water-insoluble even after long-term storage. Conventionally, a low-viscosity silver halide emulsion is coated on a support, silver halide grains are allowed to settle on the support surface by gravity, and then the binder is washed away to obtain a single grain silver halide layer. method is known.

Although the method of the present invention is seemingly similar to this method, there are the following differences. That is, in the method of the present invention, it is not necessary to cause the silver halide grains to settle on the surface of the support by gravity, but it is sufficient to simply bring the emulsion into contact with the surface of the support, set it, and dry it. The silver halide grains are adsorbed when the emulsion is brought into contact with the surface of the support, and these silver halide grains are utilized. It has been found that the amount of silver halide grains adsorbed on the support after hot water washing depends on the dry film thickness of the initially coated emulsion.

That is, it was found that the smaller the film thickness, the more the adsorption amount, and the larger the film thickness, the smaller the adsorption amount. The preferred film thickness varies depending on the type of emulsion, but is from 10r1m to 1m
The range is up to μm. It was also found that the more etched the surface of the support, the greater the amount of silver halide particles adsorbed onto the support after washing with hot water.

If the support is epoxy resin or phenolic resin, acid (
For example, it was found that the amount of adsorption increases when treated with a mixture of chromic acid and sulfuric acid. It has been found that not only the amount of adsorption increases, but also the adsorption force increases, and the adsorption is uniform. In the method of the present invention, the thickness of the silver halide emulsion layer may be extremely small, and may be 11,100 to 1 degrees thicker than the thickness of a conventional silver halide emulsion layer.

Therefore, the emulsion can be diluted with water to a very low viscosity and can be coated using spinners commonly used to coat photoresists. The thickness of the emulsion layer in the present invention is a value obtained by dividing the weight of the emulsion layer per unit area of the support by the specific gravity of the emulsion.

The method of the invention can also be applied to the production of printing plates.

The method of the present invention can be applied using, for example, an aluminum plate whose surface is anodized as the support. A lipophilic metal such as copper is used as the metal to be electrolessly plated. Further, in the photographic material of the present invention, a non-curable silver halide photographic emulsion is deposited on the support having the above-mentioned fine structure on the surface, either directly or through at least one undercoat layer. The thickness (if an undercoat layer is provided,
1 μm from 10r17T1 (including the thickness of the undercoat layer)
It is set up so that it is within the range of .

In the emulsion layer of this photographic light-sensitive material, silver halide grains or beaten silver grains and a binder form a single layer or several layers and are firmly adsorbed and retained on the fine structure of the support surface. Conceivable. When the surface of the support is made of silver halide grains or a substance that shows good affinity for the silver halide grains and the binder, it is not necessarily necessary to provide a fine structure on the surface of the support. Further, it is not necessary to provide an undercoat layer on the surface of the support.
However, in general, by providing a fine structure on the surface of the support, the support and silver halide grains or the silver halide grains and the binder can be combined. Regardless of the material of the support, silver halide grains or silver halide particles The binder is firmly adsorbed and retained on the surface of the support, resulting in silver halide photography. The emulsion remains firmly on the surface of the support. As already described, a specific example of the method for preparing the above-mentioned photographic light-sensitive material is to provide a non-curable silver halide photographic emulsion layer on a support directly or through at least one subbing layer. After at least one layer of the emulsion has set, i.e., after the said emulsion layer has set, or even after the said emulsion layer has dried, the said emulsion layer is washed off with warm water. There is a way to dry it.

Another method is to provide a layer of diluted silver halide photographic emulsion with a large amount of solvent on the support directly or through at least one undercoat layer, and then dry the emulsion. When using diluted silver halide photographic emulsions, water is generally used as the solvent for dilution, but in addition to water, solvents that are miscible with water such as alcohols such as methanol and ethanol can also be used. It can also be used with.
The silver halide photographic emulsion used in the photographic light-sensitive material of the present invention may contain all the additives described above, if necessary.

The silver halide photographic emulsion can also be prepared by a known method. The completed photographic material of the present invention may be provided with an emulsion layer having an amount of silver in the range of 0.001y to 2y per y on its surface.

More preferably, the emulsion layer is provided so that the silver content ranges from 0.03f to 1f. All the characteristics and effects of the photographic material of the present invention apply to those already explained in detail in the method of the present invention. Example 1 1400ml using 50y of gelatin and 188y of silver bromide
Silver bromide emulsion (average grain size of silver bromide is approximately 0.06μ
TrL) was prepared.

This emulsion was physically ripened in a conventional manner, and then chemically ripened by adding sodium thiosulfate and chlorauric (■) acid in a conventional manner. ) ethylidene]-3-carboxymethylrhodanine 0
．． 15y and 510nm. After optical sensitization to -560r1TrL, the surface of the phenolic resin substrate is roughened by polishing with a sponge containing chromium oxide powder, and the emulsion layer on it is dried to a thickness of approximately 0.8 μm. A photographic material was obtained by coating and drying as described above. This photographic light-sensitive material was imagewise exposed and developed with a developer having the following composition (24°C, 5 minutes).
A silver image was obtained by fixing with a fixing solution (24° C., 1 minute). Developer 1-phenyl-3-pyrazolidone 0.5y Sodium sulfite (anhydrous salt) 50y Hydroquinone
12f Sodium carbonate (monohydrate) 60y Potassium bromide
2ybenzotriazole 0.2
f1-phenyl-5-mercaptotetrazole
5Tn9 phenazine-2
-Carboxylic acid 1y Add water to make 1f.

Fixer 70% ammonium thiosulfate aqueous solution 200ml Sodium sulfite (anhydrous salt) 15y Boric acid
8f glacial acetic acid 1.6
m1 Aluminum sulfate (1 emulsion salt) 10y Sulfuric acid (98%) 2ml Add water to make 1e After washing with water, wash with warm water at 55°C. The emulsion layer was washed away in both image and non-image areas, but the image In some cases, a trace amount of silver remained on the substrate surface.

The transmission optical density of the residual silver image was approximately 0.1. The transmission optical density of the silver image before washing with hot water was about 0.7. The thus obtained binder-free residual silver image was washed with water and then activated by immersion in the following activating solution for 2 minutes. Activation liquid Palladium chloride (PdCl3) 0.3f Hydrochloric acid (37%) Add 3ml of water to make 1e.

After washing with water, it was immersed in an electroless plating solution having the following composition for 3 hours to obtain a copper pattern with a thickness of about 10 PTrL.

The copper pattern thus obtained has good adhesion to the substrate,
Furthermore, a line of 20 pm was well resolved with high resolution.

Electroless plating solution A solution Copper sulfate (■) (pentahydrate) 309 Sodium carbonate (anhydrous salt) Add 309 water to make 1e Solution B Lotuselle salt 100y Formalin (37% aqueous solution) Add 30ml of water to make 1e .

Add liquid A and liquid B at a volume ratio of 1:1, and adjust the pH to 12.5 by adding sodium hydroxide.

Example 2 The procedure was the same as in Example 1 except that the dry film thickness of the emulsion was 0.2 μm.

Example 3 The procedure was the same as in Example 1 except that the activation treatment was performed using an activation solution (20° C., 1 minute) having the following composition.

Activation liquid potassium dichromate 10f
Hydrochloric acid (37%) Add 10ml of water to make 1f.

Example 4 The procedure was the same as in Example 1 except that after development, washing with hot water was carried out and then fixing.

Example 5 The procedure was the same as in Example 1 except that the following silver halide emulsion was used instead of the silver halide emulsion in Example 1.

That is, silver chloride 70rn01e% and silver bromide 30n10
200y of silver halide consisting of 1e% and 50y of gelatin
A 1500 mt emulsion was prepared using the following. The average grain size of the silver halide was about 0.2 μm. Example 6 The same procedure was carried out except that the silver halide emulsion obtained in Example 1 was diluted five times with water and applied to the substrate of Example 1 with a spinner to a dry thickness of about 0.1 μm. It was the same as Example 1.

Example 7 A nickel pattern with a thickness of approximately 10 μm was obtained in the same manner as in Example 1, except that a nickel plating bath with the following composition was used in place of the copper plating solution, the liquid temperature was 80° C., and the plating time was set to No. 3α. .

Nickel plating solution A Nickel sulfate (heptahydrate) 35y Ammonium citrate 10y Sodium acetate (trihydrate) 10f Magnesium sulfate (heptahydrate) 20g Add water to make 800ml.

Solution B Sodium hyposulfite (monohydrate) Add 15f water to make 200ml.

Mix liquid A and liquid B.

Example 8 On a polyethylene terephthalate film, an undercoating liquid of the following composition was applied by dipping, and after drying at 130°C, the emulsion of Example 1 was applied on top of the undercoating liquid, with a dry thickness of about 0.2
It was coated to a thickness of μm.

The subsequent treatments were carried out in the same manner as in Example 1, and the same results as in Example 1 were obtained. Primer liquid

Claims (1)

[Scope of Claims] 1. A photographic light-sensitive material having a non-curable silver halide photographic emulsion layer provided on a support is imagewise exposed and developed, and the silver halide in the non-exposed areas is removed by fixing. After washing the emulsion layer with warm water or washing the emulsion layer with warm water and fixing to form a silver image with most of the emulsion layer washed away, and then activating the silver in the silver image, A method for forming a metal pattern, which comprises electroless plating a metal onto the pattern. 2. A non-curable silver halide photographic emulsion was coated on a support, and after the formed silver halide photographic emulsion layer was at least set, the emulsion layer was washed with warm water to wash away most of the emulsion layer. image exposure on the surface coated with the emulsion.
A method for forming a metal pattern, which comprises forming a silver image by developing and fixing the image, activating the silver in the silver image, and then electrolessly plating a metal onto the silver image.