JPH0213290B2 - - 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 most.

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 resolution and can be reduced in force.This image forming material can be used as a substitute for lithographic film or as a mask material. It can be used for etc. 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 has disadvantages such as insufficient adhesive strength with the surface of the substrate and insufficient moisture resistance. There is. Furthermore, if hardening treatment is performed to improve moisture resistance, problems arise such as progression of hardening over time and reduction in image forming ability. Furthermore, there are also problems such as generation of bubbles and thickening when a coating material for forming an image forming layer is prepared using a hydrophilic binder.

The present inventors conducted research in view of the above-mentioned drawbacks of the prior art, and found that the above-mentioned drawbacks of the prior art can be overcome by using a lipophilic binder as the binder, and have thus arrived at the present invention. That is, the present invention comprises a polyvinyl acetate resin binder in which an image forming layer is formed on the surface of a substrate, and the image forming layer is reduced to become a metal complex compound or metal compound, a development inhibitor, and a wetting agent. The gist thereof is an image forming material consisting of layers.

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, 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 lipophilic binder layer, a metal complex compound or a metal compound which is reduced to become metal development nuclei, and a development inhibitor.

As a binder, polyvinyl acetate resin, vinyl acetate/acrylic acid ester copolymer resin, acrylic acid/vinyl acetate copolymer resin, ethylene/vinyl acetate copolymer resin, modified vinyl acetate resin containing carboxylic acid group or sulfonic acid group, etc. Oil-soluble polyvinyl acetate resins are preferably used.

In order to maintain the wettability of the binder layer, 0.1 to 10 parts by weight of a wetting agent such as glycerin, polyethylene glycol, polyethylene oxide, etc. is added to the above binder per 100 parts by weight of the binder. and developer bath temperature.

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 (), 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-diethyldiethyleneamine) copper () salt, bis(2,2'bipyridine) copper () salt,
Bis(1,10-phenanthroline) copper() salt,
Bis(dimethylglyoximate)copper(), bis(acetylacetonato)copper(), bis(acetylacetonato)platinum(), and the like 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.

In addition, when using a metal compound, the above-mentioned metal compound (a commercially available activator solution for electroless plating can be used as it is) is mixed with a compound having a diazo group or an azide group as a development inhibitor in an appropriate solvent. The mixture is mixed with a binder solution dissolved in the solution to form a liquid with a viscosity of about 10 to 1000 centipoise suitable for coating, and this is coated onto the support 1 and dried to obtain a coating film of usually 0.1 to 30 μm. Any suitable solvent can be used to dissolve the binder, including lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and n-butyl acetate, and polar solvents such as methyl cellosolve. Solvents with a high pH are preferably used.

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., or instead of the above-mentioned zinc chloride double salt, borofluoride 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.

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 100 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.

When using a compound having a diazo group, it is recommended to use a stabilizer to stabilize the compound, and specific examples include organic carboxylic acids and organic sulfonic acids, and more practically, p-toluenesulfonic acid and the like. It is recommended to use

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 borohydride, 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 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.

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, dimethylaldine borane, phenylaldine 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/.

Since the image forming material of the present invention has a polyvinyl acetate resin binder layer, it has excellent moisture resistance and water resistance without being hardened.
No decrease in image forming ability is observed, and
When producing such an image forming material, since a non-aqueous solution of the binder can be used, the stability of the coating material is good and problems such as thickening and generation of bubbles do not occur.

Examples for explaining the present invention more specifically are listed below.

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

Palladium chloride solution (Palladium chloride...1.0g Concentrated hydrochloric acid...50g Ethanol...1) Example 1 Photosensitive solution (Polyvinyl acetate resin (manufactured by Nippon Gosho Chemical Industry Co., Ltd.)
Gosenil A50-Z5)...20 parts by weight diazo monomer (Daito Chemical, DH-
300BF ₄ , 10% MEK solution) ...5.0 parts by weight Palladium chloride solution ...10 parts by weight polyethylene glycol (MW = 1500) 5
%MEK solution...1 part by weight P-toluenesulfonic acid (stabilizer) 5% ethanol solution...1 part by weight) A photosensitive solution with the above composition was applied to a 100 μm thick polyester film (Toray, Lumirror, #100) using a wire. It was coated using Par No. 36 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 a negative film for 30 seconds, and then apply TMP Chemical Nickel (manufactured by Okuno Pharmaceutical), a physical developer with the following composition, to [TMP Chemical Nickel] (nickel sulfate...9.0g). Sodium hypophosphite 7.0g Ammonium saturated solution 6.5g Sodium citrate 10.0g Water 67.5g % halftone image was reproduced.

Furthermore, even when the photosensitive material prepared above was left at 25°C and 80% RH for more than one week, there was no decrease in image forming ability, no change in resolution, and therefore it had excellent moisture resistance. .

Example 2 Photosensitive liquid (acrylic acid/vinyl acetate copolymer resin (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., Coponil PC-50M)
(H) 20% ethanol solution...20 parts by weight diazo monomer (manufactured by Respé Chemical, No.
11'BF ₄ ) 10% MEK solution) ...3.0 parts by weight Palladium chloride solution ...10 parts by weight Polyethylene oxide (Steel Chemical Co., Ltd., PEO
-3) 1% methanol solution...2.0 parts by weight P-toluenesulfonic acid 5% ethanol solution
...1.0 parts by weight) The viscosity of the photosensitive liquid with the above composition immediately after preparation is 50C.PS.
The viscosity 8 hours after preparation was 60 C.PS, and there was virtually no improvement in viscosity.

A photosensitive material was prepared in the same manner as in Example 1 using the photosensitive solution obtained above, and then the photosensitive material was exposed in the same manner as in Example 1, and then a physical developer having the composition shown in Example 1 was used. Using a certain TMP chemical nickel (manufactured by Okuno Pharmaceutical Co., Ltd.) at 35°C, the image was developed by immersing it in it for 60 seconds, and an image with 300 lines/inch and 4% halftone dots was reproduced.

Example 3 Photosensitive liquid (modified polyvinyl acetate resin (manufactured by Nippon Gosei Chemical Co., Ltd.)
PH-50M) 20% methyl ethyl ketone solution
...20 parts by weight of diazo monomer (manufactured by Daito Chemical Co., Ltd., DH-
300BF ₄ ,) 10% methyl ethyl ketone solution
...5.0 parts by weight palladium solution ...10 parts by weight polyethylene glycol (MW=1500) 5
% methyl ethyl ketone solution...1.5 parts by weight P-toluenesulfonic acid...1.0 parts by weight) Using the above photosensitive solution, a photosensitive material was prepared in the same manner as in Example 1, and an image was formed with a developing time of 90 seconds. A 300 lines/inch, 4% halftone image was produced.

[Brief explanation of drawings]

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 layer is formed on the surface of the substrate, and the image forming layer is composed of a polyvinyl acetate resin binder layer containing a metal complex compound or metal compound that is reduced to become metal development nuclei, a development inhibitor, and a wetting agent. Imaging materials.