JPS604941A - Image forming material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

TECHNICAL FIELD This invention relates to an imaging material of the type that obtains a visible image by physical development.

(Prior art) 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 give 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, Fe is F
Utilizing the reaction of
An example of this is a method in which metal development nuclei are formed from a metal compound using the reducing power of hydroquinones generated by exposure, and copper is precipitated by physical development (Proceedings of the 1981 Photographic Society Annual Conference). Can be mentioned. 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 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 1982-182)
No. 661).

In such image-forming materials, when physical development is performed using the product of reduction of metal compounds such as gold, platinum, palladium, silver, iron, copper, etc. as development nuclei, diazo groups or aceto groups, which are themselves photodegradable, are removed. When compounds having the following properties are used, development is effectively suppressed by these compounds.

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 can be Since it is a solution type material, it has advantages such as high resolution and ability to reduce power, so this image forming material can be used as a substitute for lithographic film or as a mask material.

Although it has various advantages as described above, it also has some disadvantages because it uses a diazo compound or an azide compound as a development inhibitor in the image forming material. For example, in the case of a diazo compound, a diazonium salt compound is generally used, which has poor water resistance, is unstable against humidity, and has poor storage stability. Therefore, stabilizers are required, but some of them have an adverse effect on the components forming the photosensitive material, causing problems in the stability of the photosensitive material ink.

In addition, diazonium salt compounds and azide compounds decompose during exposure and react with the binder in the image forming layer, causing hardening of the exposed areas, making it difficult for the developer to penetrate during physical development, resulting in poor image resolution, or conversely, during development. If the strength (hardness) of the image forming layer is lowered in order to improve the penetration of the liquid, the coating film may dissolve or be damaged, making it impossible to obtain a good image and making it difficult to control the strength of the image forming layer. Problems such as difficulty arise.

(Object of the Invention) The object of the present invention is to eliminate the drawbacks of the above-mentioned prior art and to provide an image forming material which has excellent water resistance and excellent developer permeability.

(Structure of the Invention) The image-forming material of the present invention has an image-forming layer formed on the surface of a substrate, and the image-forming layer is made of a single layer of a hydrophilic binder containing a metal compound that is reduced to become metal development nuclei and a development inhibitor. The image forming material is characterized by containing quinone diazide as a development inhibitor.

According to research conducted by the present inventors, when a naphthoquinone diazide compound is used as a development inhibitor, it photodecomposes to become an alkali-soluble indenecarboxylic acid compound. It has been found that the disadvantages of the prior art are overcome by immersing the imaging material in an alkaline physical developer to form an image in the exposed areas.

The present invention will be explained in detail below.

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

As the substrate 1, 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. The image forming layer 2 is provided on these substrates 1 after pretreatment to improve adhesion, such as corona discharge treatment and primer treatment, if necessary.

The image forming layer 2 is formed by dispersing, preferably dissolving, in a hydrophilic binder layer, a metal complex compound or a metal compound which is reduced to become metal development nuclei, and a development inhibitor.

Examples of binders include gelatin, casein,
Natural polymers such as glue, gum arabic, and shellac, carboquine methylcellulose, egg albumin, polyvinyl alcohol (partially saponified polyvinyl acetate), 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.

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, copper, etc. are used as metal complex compounds that are reduced and become metal development nuclei. As the child, commonly known compounds can be used, and examples of complex compounds include the following. : Bis(ethylenediamine)palladium (■) salt - dichloroethylenediaminepalladium fU) salt, dichloro(ethylenediamine)platinum (■ salt, tetrachlorodiamine platinum side salt, dichlorobis(ethylenediamine)platinum (closed, tetraethylammonium copper (Ill salt, bis) (Ethylenediamine copper) (II) 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, uramyl diacetic acid.

Bis(2,2
'-bipyridine)palladium (Ill salt, bis(acetylacetonato)palladium(If), bis(N,N-
diethylethylenediamine) copper(n) salt, bis(2,2
'-Bipyridine) copper(If) salt, bis(1,10-phenanthroline) copper(II) m, bis(dimethylglyoximate) copper(■), bis(acetylacetonate)
Copper (n), bis(acetylacetonato)platinum (Ill
etc. are preferable.

Metal compounds that are reduced to give metal development nuclei include chlorides of noble 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.

As development inhibitors, quinonediazide compounds are used, in particular the following O-naphthoquinone compounds: naphthoquinone-1,2-diazido-5-sulfonic acid, naphthoquinone-↓, 2-diazido-4-sulfonic acid, and Salts of these sulfonic acids, as well as ester derivatives of the following formula (1) obtained from naphthoquinone-1,2-diazide-5-sulfonic acid, can be used as long as they have a naphthoquinone-1,2-diazide skeleton.

However, in the above formula (1), the publications are the following (a) to (e).

CH.

(d) Nobora resin (e) Hydroxy resin In the image forming layer 2, 0.1 to 100 parts of a metal compound or a metal complex compound is added to 100 parts of the above-mentioned Nobora resin.
It is preferable to include a compound having a naphthoquinone diazide skeleton in an amount of 0.2 to 50 parts, particularly 1 to 20 parts.

To explain the image forming method using the image forming material described above, first, the image forming layer 2 is subjected to pattern exposure through a transparent original 3 as shown in FIG. 2, for example. As a result, the naphthoquinonediazide compound is selectively decomposed in the two exposure sections to a degree corresponding to the amount of exposure.

Any light source that can decompose the naphthoquinonediazide compound mentioned above can be used as the light source.

Then, by pattern exposure, the image forming layer 2 having a latent image in which the naphthoquinonediazide compound is decomposed in a pattern is brought into contact with an aqueous reducing agent solution by immersion, so that metal development nuclei are almost uniformly formed in the image forming layer 2. to occur.

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 (Wciss solution), or a commercially available sensitizer solution for electroless plating is used, but in general, any strong reducing agent can be used. .

Furthermore, the image forming layer having a latent image formed by selectively decomposing the metal development nuclei and naphthoquinone diazide compound thus obtained is brought into contact with a physical developer by immersion to form metal development nuclei in the exposed areas as shown in FIG. Visible image 2B is formed in which the metal in the developer is precipitated by reduction around .

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 heavy metal salt, for example, water-soluble salts of group Ib 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
0~], contained at a ratio of OO9/l.

Examples of the reducing agent include hypophosphorous acid, sodium hypophosphite, sodium borohydride, hydrazine, formalin, diethylamine borane, dimethylamine borane, trimethylamine borane, borane, diborane, methyldiborane, diborazane, borazane, borazine, t - Phylamineborazane, pyridineborane, 2.5-/retidineborane, ethylenediamineborane, hydrazinediborane, dimethylphosphineborane, phenylarsineborane, dimethylarsineboraneborane, diethylstibinborane and the like can be used.

These reducing agents are used in physical developers. 0, 1~
509/l).

(Effects of the Invention) According to the present invention, an image forming material using a naphthoquinone diazide compound as a development inhibitor (↓The inhibitor has good water resistance and reacts with the inder in the image forming layer) during exposure.
Since the degree of hardness in the exposed area does not increase abnormally, and because the exposed area is alkali-soluble, alkaline physical development can be carried out well and a black image can be obtained.

(Example) The present invention will be described in more detail below with reference to Examples.

Example 1 Photosensitive liquid The above photosensitive material was coated with a polyester film (Lumirror T- manufactured by Toshi Co., Ltd.).
Wire bar A 3 on the plasma-treated surface of 1.00)
6 and dried at 80°C to obtain a coating film with a thickness of 4 μm. An ultra-high pressure mercury lamp (wavelength 4
05 volume, 75W) for 60 seconds through a negative film, and then immersed in a 20°C reduction bath (manufactured by Okuno Pharmaceutical, Knife Lad 754-R2, aminoborane reducing agent, 5 times diluted) for 20 seconds. Then, the film was immersed in a 20° C. physical development bath (manufactured by Okuno Pharmaceutical Co., Ltd., TMP Chemical Nickel) for 120 seconds, and an image with halftone dots of 50 lines/inch was reproduced.

In addition, the photosensitive material prepared above has sufficient water resistance and can be processed at 20°C and 80% RH without damaging the coating during development.
The inhibitor maintained its inhibitory effect for more than 0 days without decomposing.

Comparative Example 1 Photosensitive Solution A photosensitive material was prepared using the above photosensitive solution in the same manner as in Example 1, exposed in the same manner, and immersed in a reducing bath at 20°C (Nyclad 754, manufactured by Okuno Pharmaceutical Co., Ltd. - 25 times diluted) for 15 seconds. , and 2 more
0″G physical development bath (manufactured by Okuno Pharmaceutical, TMP chemical nickel)
An image of 150 lines/inch and 5 halftone dots was reproduced.

When the photosensitive material prepared above was left for 10 days under the conditions of 20"C and 180% RH, the inhibitory effect decreased due to decomposition of the inhibitor, and capri was produced.

Example 2 Photosensitive solution A photosensitive material was prepared using the above photosensitive solution suspension in the same manner as in Example 1, exposed in the same manner, and immersed in a 20"C reduction bath (Nyclad 75442 manufactured by Okuno Pharmaceutical Co., Ltd., 5 times diluted) for 15 seconds. Then, it was immersed in a 20"C physical developing bath (TMP chemical nickel manufactured by Okuno Pharmaceutical Co., Ltd.) for 120 seconds, and an image with 150 lines/inch and 5 halftone dots was reproduced. The photosensitive material prepared above is 20"C.
The inhibitor was stable and maintained its inhibitory effect for more than 10 days under 80% RH.

[Brief explanation of the drawing]

1 to 3 are cross-sectional views showing the step of forming an image of the image forming material of the present invention. 1...Support 2...Image forming layer (2A...exposed area, 2B...visible area) 3...
...Transparent original A... Image forming material

Claims (1)

[Claims] An image forming material comprising a single layer of a hydrophilic 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 and contains a metal compound and a development inhibitor, which contains quinone dialedo as the development inhibitor. An image forming material characterized by: