JPH0466016B2 - - 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" refers to a process in which metal development nuclei formed as a latent image are treated with a physical developer containing reducible metal ions and a reducing agent to provide 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⁺
Metals can be developed by reducing noble metal ions with Fe ²⁺ to form metal development nuclei and performing physical development. An example of this is a method in which metal development nuclei are formed from a compound and copper is precipitated by physical development (Proceedings of the 1975 Annual Conference of the Society of Photography). However, 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 hydrophilic binder layer containing a metal compound that becomes a metal phenomenon nucleus when reduced 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,
When performing physical development using a product resulting from the reduction of a metal compound such as iron or copper as a development nucleus, if a compound having a diazo group or an azide group, which itself is photodegradable, is used, the development becomes effective due to these compounds. It is something that is suppressed. 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 needed, and each component can be dissolved. Because it is a system, it has high resolution,
Since this image forming material has various advantages such as being able to reduce 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 base material (for example, using a water-soluble resin such as gelatin, polyvinyl alcohol resin, or carboxymethyl cellulose resin). Because the adhesive strength with the material is insufficient or the water resistance is insufficient, fogging occurs due to binder elution or damage during development. In addition, hardening agents are used to improve water resistance, but the hardening effect is insufficient (posterior hardening, etc.).
Problems arise, such as adversely affecting the stability of other components. Furthermore, there are also problems such as generation of bubbles and thickening during the preparation of the photosensitive liquid used for coating and forming the image forming layer. 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 are 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 the plating metal particles 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.

As a result of research in view of the drawbacks of the above-mentioned conventional techniques, the present inventors have 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 the image forming layer. It is easy to control the degree of hydrophilicity to provide effective penetration, and when using such an image-forming material, a good black image with less fogging can be obtained. It can be formed by diluting it with
It has been found that 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. The gist of the image forming material is an image forming material comprising a resin binder layer containing a development inhibitor and a development inhibitor, wherein the resin binder layer is a lipophilic resin containing a copolymer mainly composed of maleic anhydride. do.

The present invention will be explained in detail below.

The image forming material 1 of the present invention has an image forming layer 3 on the surface of a substrate 2, as shown in FIG.

As the substrate 2, any solid material such as glass, wood, paper, plastic film, woven fabric, or non-woven fabric can be used, among which polyester film,
Plastic films such as triacetate films are particularly preferably used. These supports 1
If necessary, the image forming layer 3 is provided after pretreatment for improving adhesion such as corona discharge treatment and primer treatment.

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

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,
Examples include ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, and maleic acid-modified resin, but methyl vinyl ether-maleic anhydride copolymer is most preferably used because it provides preferable hydrophilicity. It is also preferred that the maleic acid portion of the copolymers is used in anhydrous form, so that these copolymers are
MEK, cyclohexanone, ketones such as acetone, esters such as ethyl acetate, methyl acetate, N
- It can be used by dissolving 5 to 20% by weight in a solvent such as methylpyrrolidone or THF. The proportion of maleic anhydride in the copolymer is 5 to 70%, more preferably 20 to 60%, based on the total weight of the monomers.

The above-mentioned copolymer mainly composed of maleic anhydride may further contain ordinary synthetic resins, such as polyester resins, polyvinyl acetate resins, polyacrylic acid ester resins,
Cellulose resins such as cellulose acetate, ethyl cellulose, cellulose acetate propionate,
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 butyral resin. The blending ratio of ordinary synthetic resins is within a range that allows the developer to penetrate into the binder layer, 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, copolymers mainly composed of maleic anhydride have a weight ratio of 1 to 80% of the total binder.
% is preferable.

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

First, complex compounds of noble 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. Commonly known compounds can be used as complex compounds, such as 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, glycyl, ethylenediaminetetraacetic acid, nitrilotriacetic acid, uraniel diacetic 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.

Metal compounds that are reduced to give metal development nuclei include water-soluble salts such as chlorides and nitrates of noble metals such as palladium, gold, silver, platinum, and copper, such as those contained in the activator solution for electroless plating. Salts such as palladium chloride, silver nitrate, and gold tetrachloride may also be used, and palladium salts are particularly preferably used.

The metal complex compound or metal compound mentioned above is
A compound having a diano group or an azide group, which is a development inhibitor, is mixed with a binder solution dissolved in an appropriate solvent to form a liquid with a viscosity of about 10 to 1000 centipoise suitable for coating, and this is coated on the support 1. By drying, 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-diathylaminobenzenediazonium 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-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, a borofluoride salt can also be used instead of the zinc chloride double salt as described above. Compounds having an azide group include P-azidoacetophenone, 4,4'-diazidechalcone, 2,6-
Bis-(4'-azidobenzal)-acetone, 2,6
-bis-(4'-azitobenzal)-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.

The image forming layer 3 contains the binder 100 described above.
For part: metal compound or metal complex compound
0.1 to 100 parts, especially 1 to 10 parts, 1 to 10.0 parts, especially 20 to 50 parts of a compound having a diazo group or an azide group.
It is preferable to include it in a proportion of 1.5 parts.

To explain the image forming method using the above-mentioned image forming material, first, the image forming layer 3 is subjected to pattern exposure through a transparent original 4 as shown in FIG. 2, for example. As a result, in the exposure section 3A,
A compound having a diazo group or an azide group is selectively decomposed 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 broken down in a pattern by immersion.
Metal development nuclei are generated almost uniformly inside. Examples of reducing agents include stannous chloride, stannous sulfate, sodium borate, dimethylamine borazane, diethylamine borazane, trimethylamine borazane, other borazane derivatives, borane, diborane,
Borane derivatives such as methyldiborane, hydrazine, etc. can be used. Particularly preferably, acidic stannous chloride solution, stannous sulfate solution (Weiss solution)
Alternatively, a commercially available sensitizer solution for electroless plating can be 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 the 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 areas as shown in FIG. 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.

Examples of reducible noble 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.

These reducible heavy metal salts are contained in the physical developer at a rate of, for example, 10 to 100 g/g.

Examples of reducing agents include hypophosphorous acid, sodium hypophosphite, sodium borohydride, hydrazine, formalin, diethylamine borane, dimethylamine borane, trimethylamine borane, borane, diborane, methyldiborane, diborazane,
Borazene, borazine, t-butylamine borazane, pyridine borane, 2,6-lutidine borane,
Ethylenediamineborane, hydrazinediborane,
Dimethylphosphine borane, phenylphosphine borane, dimethylaldineborane, phenylaldineborane, dimethylstibineborane, diethylstivineborane, etc. can be used.

These reducing agents can be added to the physical developer, for example.
It is used at a rate of 0.1 to 50g/.

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 a black image with no Caribbean and excellent contrast through physical development.

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

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

Palladium chloride solution Palladium chloride...1.0g Agricultural hydrochloric acid...50g Ethanol...1 (MEK may be used instead of ethanol) Example 1 Photosensitive liquid Polyvinyl acetate resin (Nippon Gosei Kagaku Kogyo Co., Ltd., Gosenil 50E-8Y)
10 parts diazo monomer (Daito Kagaku DH-300BF ₄ 10% MEK solution) 5.0 parts palladium chloride solution 15 parts methyl vinyl ether maleic anhydride resin (GAF Corporation Gantorets AN-169 10% cyclohexanone solution) 6 parts Photosensitive liquid with the above composition was coated on a 100 μm thick polyester film (Toray, Lumirror, T-100#) using a wire bar No. 32, and dried in an oven 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
405nm, 75W) through negative film.
Close exposure for 2 seconds, then immersion in a 20℃ reduction bath (Okuno Pharmaceutical, Shiba Niktsukel) for 30 seconds, then 20℃
Physical developer (manufactured by Okuno Pharmaceutical, TMP Chemical Nickel)
300 lines/inch,
A black image with 4% halftone dots was reproduced.

Example 2 Photosensitive solution Cellulose acetate propionate (CAP502-0.2 manufactured by Eastman Kodak, 10% MEK solution) 10 parts Diazo monomer (DH-300BF ₄ manufactured by Daito Chemical Co., Ltd. 10% MEK solution) 5.0 parts Palladium chloride solution 15 parts Methyl Vinyl ether maleic anhydride resin (Gantolets AN-139 manufactured by GAF, 10% MEK solution) 10 parts Thickness of photosensitive solution with the above composition subjected to plasma treatment
It was coated on a 100 μm polyester film (Lumirror, T-100#, manufactured by Toray Industries, Ltd.) using a wire bar No. 32, and dried in an oven 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
405nm, 75W) through negative film.
Close exposure for seconds, then immersion in a 20℃ reduction bath (Okuno Pharmaceutical, Shiba Nikkel) for 50 seconds, then 20℃ physical developer (Okuno Pharmaceutical, TMP Chemical Nickel)
The film was developed by immersing it in water for 100 seconds, and a black image with 300 lines/inch and 4% halftone dots was reproduced.

Example 3 Photosensitive liquid Butyral resin (Sekisui Kagaku Eslec BM-1 10%
MEK solution) 9 parts Diazo monomer (Respe Chemical No. 5' 10% MEK solution) 3.0 parts Palladium chloride solution 10 parts Methyl vinyl ether-maleic anhydride resin (Gantolets AN-139 manufactured by GAF 10% MEK solution) 11 parts Above Thickness after plasma treatment of photosensitive liquid with composition
The mixture was coated on a 100 μm polyester film (Lumirror, T-100#, manufactured by Toray Industries, Ltd.) using a wire bar No. 32 and dried in an oven at 80° C. to prepare a photosensitive material having a photosensitive layer with a coating thickness of 4 μm. The prepared photosensitive layer was closely exposed for 30 seconds using an ultra-high pressure mercury lamp (wavelength 405 nm, 75 W) through a negative film, and then heated at 20°C.
30 seconds in a reduction bath (manufactured by Okuno Pharmaceutical, Shiba Niktsukel), then immersed in a physical developer at 20°C (manufactured by Okuno Pharmaceutical, Shiba Niktsukel).
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;
2 and 3 are cross-sectional views showing the process of forming an image using the image forming material shown in FIG. 1. FIG. 1... Image forming material, 2... Base material, 3... Image forming layer (3A... exposed area, 3B... visible area), 4...
...Transparent manuscript.

Claims (1)

[Claims] 1. An image forming material comprising an image forming layer formed on the surface of a substrate, the image forming layer being reduced to become metal development nuclei, and a resin binder layer containing a metal complex or metal compound and a development inhibitor, in which the resin binder layer is An image forming material characterized in that it is a lipophilic resin containing a copolymer mainly composed of maleic anhydride.