JPH0361937B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an imaging material of the type that obtains a visible image by physical development. Physical development is a process in which metal development nuclei forming a latent image are treated with a developer containing reducible metal ions and a reducing agent to produce a visible image consisting of grown metal particles. In recent years, non-silver salt photosensitive materials have been reconsidered due to the limited resources of silver salts and the rise and fluctuation of prices, but there are still very few examples of materials using non-silver salts. For example, using the reaction in which Fe ³⁺ becomes Fe ²⁺ ,
A method of reducing noble metal ions with Fe ²⁺ to form metal development nuclei and performing physical development, or using quinones, hydrogen donors, and metal compounds capable of forming nuclei, and utilizing the reducing power of hydroquinones generated by exposure to light. An example of this is a method in which metal development nuclei are formed from a metal compound and copper is precipitated by physical development (Proceedings of the 1981 Photographic Society Annual Conference). However, all of these are used for printed circuit boards at best. The present inventors have disclosed an image forming material for physical development that has a hydrophilic binder layer containing a metal compound that is reduced to become metal development nuclei and a compound having a diazo group or an azide group. (Special Application No. 182661, 1982). Such image forming materials include gold, platinum, palladium, silver, iron,
When performing physical development using a product resulting from the reduction of a metal compound such as copper as a development nucleus, if a compound having a diazo group or an azide group, which itself is photodegradable, is used, the development can be effectively suppressed by these compounds. It is something. By performing pattern exposure, reduction and physical development using this image forming material, a visible image with a transmitted optical density of 4.0 or more can be obtained,
Black images with gradations can be formed as needed, and since each component is a dissolved system, it has high resolving power and can be reduced in force. Therefore, this image forming material can be used as a substitute for lithographic film or as a mask. It can be used for materials such as wood. Although it has various advantages as described above, metals tend to precipitate in the paint for the image forming layer used when forming this image forming material, resulting in disadvantages such as discoloration of the paint and increase in viscosity. Furthermore, since the precipitated metal reacts with a compound having a diazo group or an azide group, which is a development inhibitor, the physical development inhibiting effect of the compound in the image forming material decreases, resulting in the inconvenience of fogging. There is. In view of the above-mentioned conventional drawbacks, the present inventors have conducted various studies and found that the above-mentioned gold, platinum, palladium,
As long as water-soluble salts such as chlorides and nitrates of silver, iron, copper, etc. are used, the above-mentioned conventional drawbacks cannot be eliminated. The present invention was developed based on the discovery that the above-mentioned drawbacks can be overcome by suppressing the reaction with the components. That is, in the present invention, an image forming layer is formed on the surface of a substrate, and the image forming layer is reduced to form an image forming material consisting of a hydrophilic binder layer containing a metal complex compound that becomes metal development nuclei and a development inhibitor. This is a summary. Hereinafter, the present invention will be explained in detail. The image forming material of the present invention has an image forming layer 3 on a substrate 2, as shown in FIG. As the substrate 2, any solid material such as glass, wood, paper, metal foil, plastic film, woven fabric, or non-woven fabric can be used, among which polyethylene film, polypropylene film, polyvinyl chloride film, and polyvinylidene chloride film are used. , polyvinyl alcohol film, polyethylene terephthalate film, polycarbonate film, nylon film, polystyrene film,
Plastic films such as ethylene vinyl acetate copolymer film, ethylene vinyl alcohol copolymer film, ionomer, cellulose diacetate, cellulose triacetate, polysulfone film, and polyimide film, particularly polyester film and triacetate film, are preferably used. These substrates 2 are subjected to pretreatment to improve adhesion, such as corona discharge treatment and primer treatment, if necessary, and then the image forming layer 3 is provided thereon. The image forming layer 3 is formed by dissolving a metal complex compound that is reduced to become metal development nuclei and a development inhibitor in a hydrophilic binder layer. Examples of binders include natural polymers such as gelatin, casein, glue, gum arabic, and shellac, carboxymethyl cellulose, egg albumin, polyvinyl alcohol (including partially saponified polyvinyl acetate and carboxylic acid-modified polyvinyl alcohol), polyacrylic acid , polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, maleic anhydride copolymer, etc. are used, but other resins than the above can also be used as long as they are water-soluble or hydrophilic resins. The degree of hydrophilicity required for the binder is such that when the image forming layer 3 is brought into contact with the physical developer, the physical developer permeates into the image forming layer 3 to enable physical development. Complex compounds of noble metals such as palladium, gold, silver, platinum, and copper are used as metal complex compounds that are reduced to become metal development nuclei, and as ligands that serve as electron donors to ions of these metals, Commonly known compounds can be used; examples of complex compounds include the following; bis(ethylenediamine)palladium ()
Salt, dichloroethylenediamine palladium ()
Salt, dichloro(ethylenediamine) platinum ()
salt, tetrachlorodiamine platinum () salt, dichlorobis(ethylenediamine) platinum () salt, tetraethylammonium copper () salt, bis(ethylenediamine) copper () salt. Furthermore, as a ligand that forms a metal complex compound, it is preferable to use a so-called chelating agent that coordinates at two or more places and forms a cyclic structure because the stability of the metal complex compound formed is high. . Examples of the chelating agent include primary, secondary, or tertiary amines, oximes, imines, and ketones, and more specifically, the following: dimethyl glyoxime, dithizone, oxin,
Acetylacetone, glycine, ethylenediaminetetraacetic acid, nitrilotriacetic acid, uramyldiacetic acid. Those using the above chelating agent include bis(2,2'-bipyridine) palladium () salt, bis(acetylacetonato) palladium (),
Bis(N,N-diethylethylenediamine)copper() salt, bis(2,2'-bipyridine)copper()
salt, bis(1,10-phenanthroline)copper()
salt, bis(dimethylglyoximate)copper(),
Bis(acetylacetonato)copper(), bis(acetylacetonato)platinum(), etc. are preferred. As the development inhibitor, a compound having a diazo group or an azide group is used, and the compound having a diazo group is a zinc chloride double salt or a borofluoride salt having a diazo group, or a condensation compound obtained from these compounds and paraformaldehyde. Diazo resin and the like are preferably used. More specifically, p-
N,N-diethylaminobenzenediazonium zinc chloride double salt, p-N-ethyl-N-β-hydroxyethylaminobenzenediazonium zinc chloride double salt, 4-morpholino-2,5-diethoxybenzenediazonium zinc chloride double salt, 4 -morpholino-2,5-dibutoxybenzenediazonium zinc chloride double salt, 4-benzoylamino-2,5-diethoxybenzenediazonium zinc chloride double salt, 4
-(4'-methoxybenzoylamino)-2,5-diethoxybenzenediazonium zinc chloride double salt, 4
-(p-tolylmercapto)-2,5-dimethoxybenzenediazonium zinc chloride double salt, 4-diazo-4'-methoxydiphenylamine zinc chloride double salt, 4-diazo-3-methoxy-diphenylamine zinc chloride double salt, etc. Alternatively, instead of the above-mentioned zinc chloride double salt, Hofutsu salt can also be used. Compounds having an azide group include p-azidoacetophenone, 4,4'-diazidechalcone, 2,6-
Bis-(4'-azidobenzal)-acetone, 2,6
-bis-(4'-azidobenzal)-cyclohexanone, 2,6-bis-(4'-azidobenzal)-4-
Methylcyclohexanone, 2,6-bis-(4'-
(azidostyryl)-acetone, azidopyrene, etc. can be used. Alternatively, compounds other than those mentioned above may be used as long as they have a diazo group or an azide group, and two or more of the above-mentioned compounds having a diazo group or an azide group may be used in combination. To explain the content of the metal complex compound and development inhibitor described above in the image forming layer 3, the content of the metal complex compound is 0.1 to 100 parts by weight per 100 parts by weight of the binder.
parts by weight, especially 1 to 20 parts by weight, and 1 part by weight of the development inhibitor.
~100 parts by weight, especially 20-50 parts by weight. If the amount of the metal complex compound is less than 0.1 part by weight, the concentration will not be sufficiently increased, and if it exceeds 100 parts by weight, background fogging will tend to occur in non-image areas. In addition, the development inhibitor is 1
When the amount is less than 1 part by weight, the effect of suppressing development is small, so background fogging tends to occur, and when it exceeds 100 parts by weight, the development time required to sufficiently increase the density becomes longer. The image forming layer 3 is made by mixing a metal complex compound and a development inhibitor with an aqueous binder solution so as to have the above-mentioned contents to form a coating liquid with a viscosity of about 10 to 1000 c.p. suitable for coating, and applying it to the surface of the substrate 2. It can be formed by applying by a known coating method and drying, and usually has a thickness of 0.1 to 30 μm. In addition to water, the solvent may also be a mixed solvent of water and a water-miscible solvent such as a lower alcohol, ketone, or ether. Furthermore, among the metal complex compounds used in the present invention, complex compounds in which the above-mentioned chelating agent is mixed with noble metals are generally poorly soluble in water, and such complex compounds can be used by simply mixing them into an aqueous binder solution. Since the resulting image forming material has low resolution and the transmission optical density of the image is also low, it is necessary to add a large amount of a complex compound to increase the transmission optical density of the image. The disadvantages of using such a poorly soluble complex compound can be improved by dissolving the poorly soluble complex compound in a water-miscible organic solvent and then mixing it with an aqueous binder solution. , cellosolve acetate, methyl cellosolve acetate, methyl cellosolve, DMF, acetonitrile, THF, pyridine, methyl ethyl ketone, isophorone, and the like. Among the development inhibitors mentioned above, the borofluoride salts of diazonium compounds and azide compounds are oil-soluble, so like the complex compounds mentioned above, they are first dissolved in the same water-miscible organic solvent as above, and then added to the binder aqueous solution. In order to further promote dissolution, it is desirable to reduce the particle size of the development inhibitor. Since the image forming layer 3 is subjected to a physical development treatment or a water washing treatment, a hardening treatment is preferably performed after its formation in order to prevent the dissolution of the binder or the elution of the contained components. The compound is added as a binder to the coating solution for forming the image forming layer 3.
It can be mixed at a ratio of 0.1 to 50 parts per 100 parts, or by coating the aqueous solution on the image forming layer; Al compounds such as potash alum and ammonium alum; chromium alum and sulfuric acid. Cr compounds such as chromium;
Aldehydes such as formaldehyde, glyoxal, glutaraldehyde, 2-methylglutaraldehyde, succinaldehyde; o-benzoquinone, p-benzoquinone, cyclohexane-1,2
-dione, diketones such as cyclopentane-1,2-dione, diacetyl, 2,3-pentanedione, 2,5-hexanedione, 2,5-hexenedione; epoxides such as triglycidyl isocyanurate; tetraphthaloyl Chloride, 4,4'-
Diphenylmethane disulfonyl chloride, 4,
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 a phosphorus compound or carbodiimide represented by 2); styrene/maleic acid copolymer, vinylpyrrolidone/maleic acid copolymer, vinyl methyl ether/maleic acid copolymer, ethyleneimine/
Resins such as maleic acid copolymers, methacrylic acid/methacrylonitrim copolymers, polymethacrylamide, and methacrylic acid ester copolymers. Glutaric acid and succinic acid can be used as dicarboxylic acids, organic carboxylic acids such as malic acid, lactic acid, citric acid, aspartic acid, glycolic acid, and tartaric acid can be used as hydroxycarboxylic acids, and dimethylol compounds such as dimethylol urea and trimethylol melamine can also be used. The above is the first part about typical embodiments of the present invention.
Although the present invention has been described with reference to the drawings, the following modifications may be made to the present invention. First, a protective layer 4 may be provided on the surface of the image forming layer 3 of the image forming material of the present invention as shown in FIG. The protective layer 4 may be formed using the same hydrophilic binder as that forming the image forming layer 3, or may be formed by adding a water-permeable lipophilic binder or an inorganic filler. Further, an antistatic agent may be added to this protective layer 4 to have an antistatic role. The protective layer 4 may be hardened if necessary, and by providing the protective layer 4 as described above, it is possible to prevent scratches, prevent elution of components constituting the image forming layer, or because the image area is made of metal. It is possible to prevent fogging caused by light reflection during close exposure and to prevent the occurrence of Newton rings. Second, an antistatic layer 5 may be provided on the back surface of the substrate 2, and the antistatic layer 5 may be formed by using the above-mentioned hydrophilic binder or a paint formed by adding an antistatic agent to a suitable lipophilic binder. It is best to apply it and form it. Third, as shown in FIG. 4, a primer layer 6 may be provided between the substrate 2 and the image forming layer 3 using an appropriate material and method. Mix rubber and polyisocyanate at a ratio of 25:1,
Dilute with a mixed solvent of MEK: toluene = 1:1,
It can be provided by coating to a thickness of 1 μm and drying, and the above primer layer is suitable for providing an image forming layer using a PVA resin binder. In addition, as a vehicle for primer paint,
Thermosetting resins such as phenol resin, resorcinol resin, urea resin, ethylene urea resin, melamine resin, epoxy resin, unsaturated polyester resin, polyvinyl acetate resin, polycarbonate resin, polymethyl methacrylate resin, polyacetal resin, polystyrene resin, It can be selected from thermoplastic resins such as ethylene vinyl acetate copolymer and polyvinyl butyral resin, rubber adhesives such as natural rubber, SBR, acrylonitrile butadiene rubber, chloroprene rubber, and polyisoprene/isobutylene rubber. Among the above, using thermosetting resins requires heat treatment, and thermoplastic resins also need to be heated above the glass transition temperature during bonding, both of which may lead to thermal deterioration of the photosensitive component. Therefore, a rubber adhesive having a glass transition point lower than room temperature is preferred. To explain the method of forming an image on the image forming material of the present invention, the image forming layer 3 is subjected to pattern exposure through a transparent original 7, for example, as shown in FIG. Thereby, the compound having a diazo group or an azide group is decomposed selectively in the exposed portion 3A to a degree corresponding to the amount of exposure. Any light source that can decompose the diazo group or azide compound described above can be used as the light source. Next, an aqueous reducing agent solution is brought into contact with the image forming layer 3 having a latent image in which a compound having a diazo group or an azide group is decomposed in a pattern by dipping or coating, so that the image forming layer 3 is almost uniformly coated. generates metal development nuclei. As the reducing agent, stannous chloride, stannous sulfate, sodium borohydride, dimethylamine borazane, diethylamine borazane, trimethylamine borazane, other borazane derivatives, borane derivatives such as borane, diborane, methylborane, hydrazine, etc. are used. be able to. 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. Further, the metal development nuclei thus obtained are brought into contact with the image forming layer 3 having a latent image formed by selective decomposition of a compound having a diazo group or an azide group by immersion or coating with a physical developer to form exposed areas. Then, the metal in the developer is reduced and precipitated around the metal development nuclei, forming a visible image 3B as shown in FIG. As the physical developer, a water-soluble one 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,
Water-soluble salts of Group B metals such as cobalt, iron and chromium, and Group B metals such as copper 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; The reducing heavy metal salt is 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, dimethylarsine borane, phenylarsine 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/. The physical developer preferably contains an organic carboxylic acid as a complex chloride agent in order to prevent the heavy metal ions that are generated when dissolving the above-mentioned reducible heavy metal salts from precipitating as mercury. In order to improve storage stability, operability, etc., PH regulators, buffers, preservatives, surfactants, etc. are added to the liquid according to conventional methods. As described above, in the present invention, in order to use a metal complex compound as a substance that is reduced and becomes a metal development nucleus,
The stability of the paint during the preparation of the image forming material is good, therefore the storage stability of the paint is improved, the viscosity of the paint does not change, and metal complex compounds are used as development inhibitors, binders, and other substances in the paint. It is possible to provide an image-forming material that can provide clear images because it does not easily react with the components of Examples are given below to more specifically illustrate the present invention. Example 1 A photosensitive solution having the following composition was mixed and prepared, and a subbing-treated polyester film (Lumirror Q, manufactured by Toray Industries, Ltd.) was prepared.
-82) was coated with a wire bar No. 36 and dried to prepare a photosensitive material. Carboxylic acid-modified polyvinyl alcohol resin (Nippon Gosei Kagaku Kogyo, Gosenal T-330) 10
% aqueous solution 20 parts by weight Pd-EDTA complex hydrochloric acid aqueous solution (1000ppm)
10 〃 Diazo monomer (manufactured by Recipe Chemical, No. 10) 10
% aqueous solution 1 Diazoresin (Shinko Giken, D-011) 20%
Aqueous solution 0.5〃 N,N-dimethylolurea 2% aqueous solution
1.0 〃 Ammonium sulfate 10% aqueous solution 1.0 〃 A negative film was closely attached to the coated side of the obtained sensitive material, and exposure was performed by irradiating it with an ultra-high pressure mercury lamp from a distance of 1 m. Next, it was immersed in a 40℃ reduction bath (Okuno Pharmaceutical Co., Ltd., Shiba Niktsukel) for 10 seconds, and then 20℃ physical developer (Okuno Pharmaceutical Co., Ltd., TMP Chemical Nickel) for 60 seconds.
A positive image with a transmitted optical density of 4.0 or higher is obtained by dipping for seconds, and the transmitted optical density of the non-colored part is
0.1 and no fog was observed. The viscosity of the photosensitive liquid used above is the same immediately after preparation.
120c.ps, even after 24 hours after preparation.
At 150 c.ps, there was no problem in coating, and no discoloration of the photosensitive solution was observed. Comparative Example 1 A PdCl _{dihydrochloric} acid acidic aqueous solution (1000 p.pm) was used instead of the Pd-EDTA complex in the photosensitive solution of Example 1,
The rest was carried out in exactly the same manner as in Example 1. The viscosity of the photosensitive liquid immediately after adjustment was 330c.ps, but 8 hours after adjustment, the viscosity was 690c.ps.
It was necessary to dilute it during application. In addition, after 8 hours, the color of the photosensitive liquid changed from the initial yellow to reddish brown, and when an image was formed using a photosensitive material prepared using this discolored photosensitive liquid, fogging occurred.
The transmission optical density of the ground part was 0.25. Example 2 The polyvinyl alcohol resin of Example 1 was manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., Gosenal NH-26 (saponification degree
Similar results were obtained in the same manner as in Example 1, except that the temperature was 98% or higher. However, we further changed the Pd-EDTA complex.
When using PdCl ₂ as an acidic aqueous solution of hydrochloric acid, precipitation of Pd was observed 30 minutes after preparation. Example 3 A photosensitive solution having the following composition was prepared. Polyvinyl alcohol resin (manufactured by Nippon Gosei Kagaku Kogyo, Gosenal T-330) 10% aqueous solution
20 parts by weight PdEDTA complex hydrochloric acid acidic aqueous solution (1000p.pm)
10 Diazo monomer (Daito Chemical, DA-300BF ₄ )
10% methyl cellosolve solution 2.0 Diazoresin (Shinko Giken, D-011) 20%
Aqueous solution 1.0 〃 Glyoxal 5% aqueous solution 0.5 〃 Ammonium sulfate 10% aqueous solution The viscosity of the above photosensitive liquid immediately after adjustment is 95 c.ps,
The viscosity after 24 hours of adjustment was 110 c.ps. In addition, when each photosensitive material was created using the photosensitive solution immediately after adjustment and after 24 hours had passed after adjustment, and an image was formed, the processing time such as development was the same.
The transmission optical density of the images was also similar, and no fogging occurred in either case.

[Brief explanation of drawings]

Figures 1 to 4 are cross-sectional views showing examples of the image forming material of the present invention, and Figures 5 and 6 are cross-sectional views showing each step of forming an image using the image forming material of the present invention. be. DESCRIPTION OF SYMBOLS 1... Image forming material, 2... Substrate, 3... Image forming layer, 4... Transparent synthetic resin layer, 5... Antistatic layer, 6... Primer layer, 7... Transparent original.

Claims (1)

[Claims] 1. An image forming material comprising an image forming layer formed on the surface of a substrate, the image forming layer comprising a hydrophilic binder layer containing a metal complex compound which is reduced to become metal development nuclei and a development inhibitor.