JPH0326375B2 - - 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 nuclei are visible particles made of metal particles that are grown by treating metal development nuclei forming a latent image with a developer containing reducible metal ions and a reducing agent (hereinafter often referred to as "physical developer"). It refers to the process of providing an image, and is generally known as a means of forming a silver image. In recent years, non-silver salt image forming materials have been reconsidered due to the limited quality of silver salts and the rise and fluctuation of prices, but printed circuit boards are the only example of materials that use physical development. . A conventional image forming method using physical development utilizes a reaction in which Fe ³⁺ ions become Fe ²⁺ ions, and the generated Fe ²⁺ ions reduce noble metal ions to form metal development nuclei. There is a physical development method using metal development nuclei. In this case, gold, mercury, silver, etc. can be used as the precious metal. Furthermore, a method using an organic compound as a photoreducing agent has also been proposed. For example, one method uses a system consisting of a combination of a diazosulfonate and a water-soluble mercury compound capable of nucleating, upon exposure to which the sulfite ions of the diazosulfonate are liberated and disproportionate the monovalent mercury salt. This produces zero-valent mercury, which is then brought into contact with a silver physical developer to precipitate silver on the mercury nuclei to obtain a visible image. Similarly, instead of diazosulfonate,
It is said that images can be obtained using photosensitive compounds that liberate CN ^- , CNS ^- , NO ^- and S ₂ O ₃ ^2- ions (Japanese Patent Publication No. 37-3319). However, these methods have difficulties in waste liquid treatment and operation due to the use of mercury. Another method is to use a photosensitizer system consisting of a combination of a special diazonium salt, such as a hydroxybenzenediazonium salt, and nucleating silver nitrate, in which exposure to light causes the diazonium salt to decompose into phenols. There is a method in which silver nuclei are formed by the reducing power of the phenol and a visible image is produced by contacting the silver nuclei with a physical silver developer, but this method uses silver. On the other hand, the present inventors have already proposed a new image forming material and an image forming method based on a principle different from the above-mentioned conventional method while utilizing physical development.
This method uses a compound having a diazo group or an azide group, which is itself photodegradable, for physical development using the product of reduction of a metal compound such as gold, platinum, palladium, silver, iron, or copper as a development nucleus. This is based on the discovery that the image forming material can be effectively suppressed by performing a process of forming metal development nuclei by reduction, a pattern exposure process, and a physical development process. It gives a visible image. The image forming material and image forming layer described above have many advantages as follows. In other words, it has a transmission optical density of 4 or higher, and can form a black image with gradations as required. Also, since it uses a development inhibitor dissolution system, it has high resolution, and can be used as an alternative to images produced by silver salt photography. is obtained.
Furthermore, since the image is a metal image, it can be corrected using a reducing fluid such as Firmer reducing fluid made of red blood salt and sodium thiosulfate, Kodak R-4, or the like. 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 the above image forming materials, since the image forming layer is constructed using a hydrophilic binder, a water-soluble diazo compound or a water-soluble diazide compound is used, and a hydrophilic binder, a water-soluble diazo compound or a water-soluble azide compound, and a metal compound are used. A water-based paint is prepared by dissolving it in a solvent mainly composed of water, and is applied onto a substrate using a known coating method. However, when an image forming material having an image forming layer composed of a water-soluble diazo compound or a water-soluble azide compound as a photosensitive agent is used, the development inhibitor tends to be eluted into the developer during physical development. This elution tendency is particularly noticeable when using a developer that has already been used, a so-called fatigued developer.If the development inhibitor is eluted in this way, the effect of suppressing physical development will be poor, resulting in background fog (fog). This is undesirable. It is predicted that the above disadvantages of water-soluble photosensitizers can be avoided by using an oil-soluble development inhibitor, but even if the water-soluble development inhibitor in the water-based paint is simply changed to an oil-soluble one, However, it is difficult to obtain an image forming material because the dispersibility is insufficient in a water-based paint, and it is difficult to form it into a paint itself. As a result of studying various photosensitive agents in view of the above-mentioned conventional drawbacks, the present inventor has developed a new method by first dissolving an oil-soluble development inhibitor in a solvent that is compatible with water, and then adding it to a water-based paint. , can be made into a paint, and the image forming material formed using such a paint has a physical development inhibitory effect equivalent to that of a water-soluble development inhibitor, and also has no effect on the elution of the development inhibitor into the developer and its effects. The present invention was achieved by discovering that such problems do not occur. That is, in the image forming material of the present invention, an image forming layer is formed on the surface of a substrate, and the image forming layer is formed of a hydrophilic binder layer containing a metal compound that is reduced to become metal development nuclei and an oil-soluble development inhibitor. It is characterized by: 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 dispersing, preferably dissolving, in a hydrophilic binder layer, a metal compound that is reduced to become metal development nuclei and an oil-soluble development inhibitor. 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. As the oil-soluble development inhibitor, a diazo resin which is a borofluoride salt having a diazo group or a condensation compound obtained from the borofluoride salt and paraformaldehyde is preferably used. More specifically, P-N,N-diethylaminobenzenediazonium borofluoride salt, P-N-ethyl-N-β-
hydroxyethylaminobenzenediazonium borofluoride salt, P-N,N-dimethylaminobenzenediazonium borofluoride salt, 4-morpholinobenzenediazonium borofluoride salt, 4-morpholino-2,5-diethoxybenzenediazonium borofluoride salt, 4-morpholino-2,5-dibutoxybenzenediazonium borofluoride salt, 4
-Benzoylamino-2,5-diethoxybenzenediazonium borofluoride salt, 4-(4'-methoxybenzoylamino)-2,5-diethoxybenzenediazonium borofluoride salt, 4-(P-tolylcapto)-2,5 -dimethoxybenzenediazonium borofluoride salt, 4-diazodiphenylamine borofluoride salt, 4-diazo-4'-methoxydiphenylamine borofluoride salt, 4-diazo-3-
Methoxy-diphenylamine borofluoride salts and diazo resins which are reaction products of these diazonium compounds and paraformaldehyde can be suitably used. Also, p is an oil-soluble azide compound.
-azidoacetophenone, 4,4'-diazidochalcone, 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 also be used. Further, as the compound having a diazo group or an azide group, compounds other than those mentioned above can also be used as long as they are oil-soluble and have a diazo group or an azide group. Furthermore, in the present invention, in addition to the above-mentioned compounds having an oil-soluble diazo group or azide group, a compound having a water-soluble diazo group or an azide group can also be added. It is preferable to use them together because you can take advantage of the strengths of both. When using only the above-mentioned oil-soluble development inhibitor, for its production, it is first dissolved in an organic solvent, and then
Generally, it is added to an aqueous solution of a hydrophilic binder, but since the development inhibitor precipitates in the form of fine particles when added to the aqueous solution, it has lower resolution and sensitivity than a water-soluble development inhibitor. This is somewhat disadvantageous.
These disadvantages can be overcome by using oil-soluble and water-soluble development inhibitors together, and oil-soluble development inhibitors
1 to 500 parts by weight, preferably 10 to 200 parts by weight of a water-soluble development inhibitor can be added to 100 parts by weight. The image forming layer 3 contains a metal compound that is reduced to give a metal development nucleus, such as palladium, gold, silver,
Water-soluble salts such as halides and nitrates of noble metals such as platinum and copper are mixed with an aqueous binder solution along with the oil-soluble development inhibitor to create a viscosity suitable for coating.
By making a liquid of about 10 to 1000 centipoise and applying it onto the substrate 2 and drying it, it is usually 0.1 to 1000 centipoise.
Obtained as a 30μ coating. As the solvent, 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 can also be used. In the above, as the water-soluble salt, palladium chloride, silver nitrate, gold tetrahydrogen chloride, etc. contained in the activator solution for electroless plating can also be used. The image forming layer 3 contains the binder 100 described above.
0.1 to 100 parts of the metal compound, especially 1 to 100 parts
It is preferably contained in a proportion of 100 parts, particularly 20 to 50 parts. In the present invention, in order to disperse, preferably dissolve, the oil-soluble development inhibitor in the hydrophilic binder layer, the oil-soluble development inhibitor is first dissolved in a solvent that is compatible with water, and then the resulting solution is dissolved. It is recommended to knead it with other ingredients. Solvents that dissolve oil-soluble development inhibitors and are compatible with water include cellosolve acetate, methyl cellosolve acetate, methyl cellosolve, DMF, methyl alcohol, ethyl alcohol, acetonitrile,
Examples include tetrahydrofuran, pyridine, methyl ethyl ketone, isophorone, and the like. Further, it is desirable that the particle size of the oil-soluble development inhibitor be reduced in order to promote dissolution. 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 2.
It is carried out by mixing 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 cyclobentane-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 a phosphorus compound or carbodiimide represented by Cl, n is 1 or 2); 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, dimethylol urea,
Dimethylol compounds such as trimethylolmelamine 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 applied by coating it to a thickness of 1 μm and drying it, 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. 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 is generally carried out for about 10 seconds to 400 seconds at room temperature or under heating using a reducing agent solution containing a reducing agent at a concentration of 0.1 to 50 g, although it varies depending on the strength of the reducing agent. 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, 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; 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/. 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 preferably contains organic carboxylic acids as a complex chloride forming agent, and further contains organic carboxylic acids as a complexing agent. In order to improve storage stability, operability, etc., PH regulators, buffers, preservatives, surfactants, etc. are added to the liquid according to conventional methods. Since the image forming material of the present invention described above uses an oil-soluble development inhibitor, even if developed for a long time using a tired developer, the development inhibitor will not be eluted into the developer. This prevents background fog (fog) from occurring in non-image areas. Example 1 A sensitive material coating liquid having the following composition was mixed and prepared in order from above.
Miyabar #36 on polyester film (Toray, Lumirror Q-82) that has been undercoated in advance.
and dried. [PVA (manufactured by Nippon Gosei Kagaku Kogyo, Gosenal T)
-330) 10% aqueous solution 20 parts PdCl _{dihydrochloric} acid aqueous solution (Nippon Kanigen, Retsudo Shumer) 15 parts Diazo monomer (Respe Chemical, No. 10') 20% methyl cellosolve solution 2.0 parts Diazoresin (Shinko Giken, D-011) 20% aqueous solution 1.0 parts N,N-dimethylolurea 2% aqueous solution
1.5 parts ammonium sulfate 10% aqueous solution 3.0 parts] The above photosensitive film was contact-exposed for 45 seconds with an ultra-high pressure mercury lamp through a negative film. Next, an image was obtained by immersing it in a reduction bath at 40°C (Shibanitsukel, manufactured by Okuno Pharmaceutical Co., Ltd.) for 10 seconds, and then immersing it in a physical developer solution at 20°C (Okuno Pharmaceutical TMP Chemical Nickel) for 60 seconds. In addition, even after processing with a physical developer for 70 seconds, there is no background fog and the result is 300 lines/inch4%.
The halftone dots were reproduced on a par with those processed for 60 seconds. Comparative Example 1 Oil-based diazo monomer (manufactured by Respé Chemical, No.
A film was similarly prepared using a water-soluble diazo monomer (No. 10, manufactured by Respé Chemical Co., Ltd.) in place of 10'), and the same image forming process as in Example 1 was performed.
As a result, there was no background fog when the physical developer treatment time was 60 seconds, but background fog occurred when the physical developer was treated for 65 seconds. Example 2 [PVA (Nippon Gosei Kagaku, Gosenal T-
330) 10% aqueous solution 20 parts PdCl _{dihydrochloric} acid aqueous solution (Nippon Kanigen, Retsudo Shumer) 15 parts Diazo monomer (Daito Kagaku, DH-300BF ₄ ) 10% methyl cellosolve solution 2.0 parts Diazoresin (Shinko Giken D-011) 20% aqueous solution 1.0 parts N,N-dimethylolurea 2% aqueous solution
1.5 parts ammonium sulfate 10% aqueous solution 1.0 parts] The above photosensitive material was coated in the same manner as in Example 1, and imaging was performed in the same manner. The allowable range of physical development bath processing time was 60 seconds to 75 seconds and 15 seconds. It was hot. Example 3 [Gelatin (Nitta Gelatin Co., Ltd., P-2151) 30% aqueous solution 10 parts PdCl _{dihydrochloric} acid aqueous solution (Nippon Kanizen Co., Ltd. Retsudo Schumer) 10 parts Diazo monomer (Respe Chemical Co., Ltd., Diazo No.
11') 10% methyl cellosolve solution 1.0 parts Glyoxal 5% aqueous solution 0.4 parts Zinc chloride 10% aqueous solution 2.0 parts] The above photosensitive material was made into a photosensitive film in the same manner as in Example 1, exposed, and placed in a 40°C reduction bath (Okuno Pharmaceutical Co., Ltd. When the film was immersed for 5 seconds in Nikrad 754R-2 diluted 4 times with water (manufactured by Okuno Pharmaceutical Co., Ltd.) for 5 seconds and then developed for 50 seconds using a physical developer (manufactured by Okuno Pharmaceutical Co., Ltd., TMP Chemical Nickel), fogging occurred. Without, 300
Reproduced lines and halftone dots from 4% to 96%. Furthermore, even after processing with a developer for 60 seconds, images with almost the same reproducibility were obtained.

[Brief explanation of the drawing]

1 to 4 are cross-sectional views showing embodiments of the present invention, and FIGS. 5 and 6 are cross-sectional views showing each step of forming an image using the image forming material of the present invention. 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 characterized in that an image-forming layer is formed on the surface of a substrate, and the image-forming layer is composed of a hydrophilic binder layer containing a metal compound that is reduced to become metal development nuclei and an oil-soluble development inhibitor. .