JPS59214848A - Image forming material - Google Patents

Abstract

PURPOSE:To facilitate control of a hydrophilic degree and to prevent fog by incorporating a solvent-soluble resin made of a copolymer composed essentially of maleic anhydride units in a resin binder. CONSTITUTION:An image forming layer 3 is prepared by dispersing, preferably, dissolving a metal complex compd. or this and a development inhibitor in a binder layer. An oleophilic resin contg. a copolymer composed essentially of maleic anhydride units is used for the binder. The layer 3 is patternwise exposed through a transparent original 4, and immersed into an aq. soln. of reducing agent to form a visible image 3B. As a result, the layer 3 is made properly hydrophilic, requires no hardening treatment, and can form a black image superior in contrast.

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" processes metal development nuclei formed as a latent image with a physical developer containing reducible metal ions and a reducing agent.
Refers to the process of producing a visible image 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, a method in which noble metal ions are reduced by Fe2+ to form metal development nuclei using the reaction in which Fe'+ becomes Fe2+, and physical development is performed, or a method in which quinones, hydrogen donors, and metal compounds capable of forming nuclei are used to perform light exposure. An example of this is a method in which metal development nuclei are formed from a metal compound using the reducing power of the generated hydroquinones, and copper is precipitated by physical development (Proceedings of the 1975 Annual Conference of the Society of Photography). but,
All of these methods are only used for printed circuit boards.

The present inventors have disclosed an image forming material for physical development that has a single layer of a hydrophilic binder 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 1984-1')
s 2661).

In such image-forming materials, when physical development is performed using a product of reduction of a metal compound such as gold, platinum, palladium, silver, iron, or copper as a development nucleus, a diazo group or an azide group that is itself photodegradable is used as a development nucleus. When using a compound having
These compounds effectively inhibit development.

By performing pattern exposure, reduction, and physical development using this image-forming material, a visible image with a transmission optical density of 4.0 or more can be obtained, and a black image with gradation can be formed as necessary, and each component Since it is a dissolved system, it has high resolution,
Since this image forming material has various advantages such as being able to reduce the force, it can be used as a substitute for lithographic film or as a mask material. Although it has various advantages as described above, since the image forming layer forming this image forming material is made of a hydrophilic binder, it is difficult to use a substrate (for example, using a water-soluble resin such as gelatin, polyvinyl alcohol resin, or carboxymethyl cellulose resin). Due to insufficient adhesive strength or insufficient water resistance, capri occurs due to binder elution or damage during development. Further, hardening agents are used for the purpose of improving water resistance, but problems arise such as insufficient hardening effect (posterior hardening, etc.) and adversely affecting the stability of other components. Furthermore, the generation of air bubbles during the preparation of the photosensitive liquid used to coat and form one image forming layer,
It also has problems such as thickening. When forming an image forming layer by diluting a lipophilic binder with a solvent, problems arising from the hydrophilicity of the binder such as water resistance can be improved, but penetration of the plating solution during physical development is insufficient. Therefore, metals tend to precipitate on the surface of the image forming layer, and while an image with metallic luster can be obtained, the surface strength of the image is weak and metal particles of the plating flow out, making it impossible to obtain a good image. ing. Therefore, it has been difficult to simultaneously eliminate the drawbacks of hydrophilic binders and lipophilic binders and obtain good images.

In view of the above-mentioned drawbacks of the prior art, the present inventors conducted research and discovered that a developing solution consisting of an alkaline aqueous solution can be improved by containing a copolymer mainly composed of maleic anhydride in the resin binder constituting one image forming layer. It is easy to control the degree of hydrophilicity to provide effective penetration, and furthermore, using such an imaging material, a good black image with less fogging can be obtained, and the entire resin pad is oleophilic. It has been found that since the resin can be formed by diluting it with a solvent, the above-mentioned drawbacks when using a water-soluble resin can also be improved.

The present invention has been made based on the above-mentioned fact, that is, an image forming layer is formed on the surface of a substrate, and the image forming layer is made of a metal complex or metal compound that becomes metal development nuclei when reduced. An image forming material comprising a single layer of a resin binder containing a development inhibitor and a development inhibitor, the image forming material comprising a solvent soluble resin comprising a copolymer mainly composed of maleic anhydride in the resin binder layer. shall be.

The present invention will be explained in detail below.

The image forming material 1 of the present invention has an image forming layer 6 on the surface of a substrate 2 as shown in Figure @1.

As the substrate 2, any solid material such as glass, wood, paper, plastic film, woven fabric, non-woven fabric, etc. can be used.
Among them, plastic films such as polyester films and triacetate films are particularly preferably used. These supports 1 are provided with the image forming layer 6 after being pretreated to improve adhesion, such as corona discharge treatment and primer treatment, if necessary.

The image forming layer 3 is formed by dispersing, preferably dissolving, a metal complex or metal compound which is reduced to become metal development nuclei and a development inhibitor in a binder layer.

As the binder, a lipophilic resin containing a copolymer mainly composed of maleic anhydride is used. Examples of copolymers mainly composed of maleic anhydride include methyl vinyl ether-maleic anhydride copolymer, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, inbutylene-maleic anhydride copolymer, maleic acid-modified resin, etc. A methyl vinyl ether-maleic anhydride copolymer is most preferably used since it provides favorable hydrophilicity. Furthermore, the maleic acid moiety of the copolymer is preferably used in the anhydride form, and therefore these copolymers can contain MEK, cyclohexanone, ketones such as acetone, esters such as ethyl acetate, methyl acetate, N-methylpyrrolidone, 5~ for solvents such as THF
It can be used by dissolving 20% by weight. The proportion of maleic anhydride in the copolymer is 5 to 70%, more preferably 20 to 6%, based on the total weight of the monomers.
It is 0%.

The above-mentioned maleic anhydride-based copolymer may further contain a common synthetic resin, such as polyester resin, polyvinyl acetate resin, polyacrylate resin, cellulose acetate, ethyl cellulose, A wide range of materials can be used as long as they are not reactive with the maleic acid moiety of a copolymer mainly composed of maleic anhydride, such as cellulose resins such as cellulose acetate propionate and butyral resins. The blending ratio of normal synthetic resins is such that the developer penetrates into one layer of the binder, and if the copolymer mainly composed of maleic anhydride is used alone or in a large amount, the binder may flow out or be damaged during development. Generally, it is preferable that the copolymer mainly composed of maleic anhydride has a weight ratio of 1 to 80 parts based on the total binder.

Next, the metal complex compound or metal compound that is reduced and becomes a metal development nucleus will be explained.

First, complex compounds of responsible metals such as palladium, gold, silver, platinum, and copper are used as metal complex compounds that are reduced and become metal development nuclei, and ligands that serve as electron donors to ions of these metals are used. For example, the following complex compounds can be used: bis(ethylenediamine)palladium(1) salt, dichloroethylenediaminepalladium(I)m, dichloro(
Ethylenediamine) platinum (V) salt, TetracOO diammine platinum (1v) salt, dichlorobis(ethylenediamine) platinum (V) salt, tetraethylammonium M(I) salt, bis(ethylenediamine copper(It) salt.

Furthermore, as a ligand for forming a metal complex compound, it is preferable to use a so-called chelating agent that forms a cyclic structure by coordinating at two or more sites because the stability of the metal complex compound formed is high. be. Examples of the chelating agent include primary, secondary, or tertiary amines, oximes, imines, and ketones, and more specifically, the following: dimethyl Glyoxime, dithizone, oxine, acetylacetone, glycine, ethylenediaminetetraacetic acid, nitrilotriacetic acid, uranyldiacetic acid.

Bis(2,2
'-dopyridine)palladium(x) salt, bis(acetylacetonato)palladium(1), bis(N,N-diethylethylenediamine)copper CI) salt, bis(2,2'-
bipyridine) copper (1) salt, bis(1,10-phenanthroline) m (1) salt, bis(dimethylglyoximate) copper (■), bis(acetylacetonate) copper (■
), bis(acetylacetonato)platinum(II), and the like are preferred.

Examples of metal compounds that are reduced and provide all-area development nuclei include chlorides of responsible metals such as palladium, gold, silver, platinum, and copper;
Water-soluble salts such as nitrates, for example, salts of palladium chloride, silver nitrate, gold tetrahydrogen chloride, etc. contained in the activator solution for electroless plating are also used, and palladium salts are particularly preferably used.

The above-mentioned metal complex or metal compound is mixed with a binder solution dissolved in an appropriate solvent together with a compound having a diazo group or an azide group as a development inhibitor to form a liquid with a viscosity of about 10 to 1000 centipoise suitable for coating. ,
By applying this onto the support 1 and drying it, an image forming layer can be obtained as a coating film having a thickness of usually 0.1 to 30 μm.

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 chloride double salt, 4-morpholino-2,5-dibutoxypenzenediazonium zinc chloride double salt, 4-benzoylamino-2,5-jethoxybenzene Diazonium zinc chloride double salt, 4-(4'-methoxybenzoylamino)-2,5-jethoxybenzenediazonium zinc chloride double salt, 4-(P-)ruylmercab))-2,5-dimethoxybenzenediazonium zinc chloride double salt salt, 4-diazo-4'-methoxydiphenylamine zinc chloride double salt, 4-
Diazo 6-methoxy-diphenylamine zinc chloride double salt or the like, or instead of the above-mentioned zinc chloride double salt, borofluoride salt can also be used. Compounds having an azido group include P-azidoacetophenone, 4,4'-diazidechalcone, and 2°6-bis-C4/-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 the above-mentioned diazo species or more may be used in combination.

In the image forming layer 3, 0.1 to 10 parts of a metal complex or a metal complex compound is contained per 100 parts of the above-mentioned binder.
It is preferable to include 0 parts, especially 1 to 10 parts, and 1 to 10.0 parts, especially 20 to 50 parts of a compound having a diazo group or an azide group.

To explain the image forming method using the image forming material described above, first, the image forming material is subjected to pattern exposure through a transparent original 4 as shown in FIG. 2, for example. As a result, the compound having a diazo group or an azide group is decomposed in the exposed portion 6A selectively and to a degree depending on the amount of exposure.

As the light source, any light source can be used as long as it is capable of decomposing the above-described compound having a diazo group or an azide group.

Then, by pattern exposure, 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 distributed in a pattern by immersion, so that the compound having a diazo group or an azide group is almost uniformly distributed in the image forming layer 3. Similarly, metal development nuclei are generated. As a reducing agent, stannous chloride, stannous sulfate
Tin, sodium borohydride, dimethylamine borazane, diethylamine borazane, trimethylamine borazane, other borazane derivatives, borane derivatives such as borane, diborane, and methyldiborane, hydrazine, and the like 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 generally any strong reducing agent can be used.

Furthermore, a physical developer is brought into contact with the image forming layer having a latent image formed by selective decomposition of the metal development nucleus and the compound having a diazo group obtained in this manner by immersion, so that metal is formed in the exposed area as shown in Figure 3. A visible image 3B is formed in which the metal in the developer is precipitated by reduction around the development nuclei.

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.

As the reducible noble metal salt, for example, water-soluble salts of group VIb metals such as nickel, cobalt, iron and chromium, and group Ib metals such as copper are used alone or in combination.

These reducible heavy metal salts are contained in a physical developer solution, for example, 1
It is contained at a ratio of 0 to 1 DDfl-/i.

Examples of the reducing agent include hypophosphorous acid, sodium hypophosphite, sodium borohydride, hydrazine, formalin, diethylamine borane, dimethylamine borane, trimethylamine borane, borane, diborane, methyldiborane, diborazane, porazine, borazine, t -butylamineborazane, pyridineborane, 2,6-rutisimporane, ethylenediamineborane, hydrazinediborane, dimethylphosphineborane, phenylphosphineborane,
Dimethylarsine borane, phenylarsine borane, dimethylstivine borane, diethylstivine borane, etc. can be used.

These reducing agents may be added in the physical developer, for example, from 0.1 to 5
It is used in the proportion of D5'#.

The image-forming material of the present invention described above contains a copolymer mainly composed of maleic anhydride, which has appropriate permeability to a physical developer consisting of an alkaline aqueous solution, as a lipophilic resin binder, so that the image-forming layer has a hydrophilic property. is suitable, does not require hardening treatment, and provides fog-free black images with excellent contrast through physical development.

Examples for explaining the present invention more specifically are listed below. In the following, "part" and "ch" are based on weight.

In Examples 1 to 3 below, the palladium chloride solution refers to one having the following composition.

Palladium chloride solution (MEK may be used instead of ethanol) Photosensitive solution A photosensitive solution with the above composition was applied to a 100 μm thick polyester film (Toshi Co., Ltd., Lumirror, T-100'll!') using a wire par N0.32. It was coated and dried in an open air at 80°C to produce a photosensitive material having a photosensitive layer with a coating thickness of 4 μm.

An ultra-high pressure mercury lamp (wavelength: 405 nm) was applied to the photosensitive layer of the prepared photosensitive material.
, 75W) through a negative film for 30 seconds, then immersed in a 20°C reduction bath (Okuno Pharmaceutical, Shiba Nickel) for 30 seconds, and then a 20°C physical developer (
The film was developed by immersing it in TMP chemical nickel (manufactured by Okuno Pharmaceutical Co., Ltd.) for 90 seconds to reproduce a black image with 300 lines/inch and 4 dots.

Example 2 Photosensitive liquid A 100 μm thick polyester film (Lumirror, T-100 manufactured by Toshi Co., Ltd.) was prepared by plasma-treating a photosensitive liquid having the above composition.
A photosensitive material having a photosensitive layer with a coating thickness of 4 .mu.m was prepared by coating the film on a paper using wire par N.alpha.32 and drying in an open air at 80.degree.

An ultra-high pressure mercury lamp (wavelength: 405 nm) was applied to the photosensitive layer of the prepared photosensitive material.
, 75W) for 60 seconds through a negative film, then immersed in a 20"C reduction bath (Okuno Pharmaceutical, Shiba Nickel) for 50 seconds, and then immersed in a 20"C physical developer (
The film was developed by immersing it in TMP chemical nickel (manufactured by Okuno Pharmaceutical Co., Ltd.) for 100 seconds to reproduce a black image with 300 lines/inch and 4 halftone dots.

Example B Photosensitive liquid A 100 μm thick polyester film (Lumirror, T-100 manufactured by Toshi Co., Ltd.) prepared by plasma processing a photosensitive liquid having the above composition.
”) using wire par N0.32 and drying in the open at 80°C to produce a photosensitive material having a photosensitive layer with a coating thickness of 4 μm.
5nm, 75W) through a negative film for 30 seconds, then immersed in a 20°C reduction bath (Okuno Pharmaceutical, Shiba Nickel) for 30 seconds, and then a 20°C physical developer (Okuno Pharmaceutical, Shiba Nickel). The film was developed by immersing it in TMP (chemical nickel) for 90 seconds, and a black image with 300 lines/inch and 4% halftone dots was reproduced.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing the image forming material of the present invention, and FIGS. 2 and 6 are sectional views showing the process of forming an image using the image forming material shown in FIG. 1. 1... Image forming material 2...
・・・・・・・・・・・・Base material 6・・・・・・・・・
......Image forming layer (3A...exposed area, 6
B...Visible part) 4...Transparent manuscript Figure 1 Figure 2 Figure 8

Claims (1)

[Claims] In an image forming material consisting of a single layer of a resin binder, in which an image forming layer is formed on the surface of the substrate, and the image forming layer is reduced to become metal development nuclei, the resin binder contains a metal complex or a metal compound and a development inhibitor. An image forming material characterized by containing a solvent-soluble resin made of a copolymer mainly composed of maleic anhydride.