JPH0213289B2 - - Google Patents

Description

Detailed Description of the Invention: Using the physical developer of the present invention, the stability over time of an image forming layer comprising a hydrophilic binder layer containing a metal compound which is reduced to become a metal development nucleus and a compound having a diazo group is determined. It is about improvement.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Below, an image forming material and an image forming method, which are the technical fields to which the present invention pertains, will be explained first, and then the present invention will be explained.

(Image-forming material) The image-forming material to which the present invention pertains is as follows:
As shown in FIG. 1, an image forming layer 2 is formed on a support 1.
will be established.

As the support 1, any solid material such as glass, wood, paper, plastic film, woven fabric, non-woven fabric can be used, and among them, plastic films such as polyester film and triacetate film are particularly preferably used. These supports 1 are provided with the image forming layer 2 after being pretreated 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 compound that is reduced to become metal development nuclei and a development inhibitor.

Examples of binders include natural polymers such as gelatin, casein, glue, gum arabic, and shellac, carboxymethylcellulose, egg albumin, polyvinyl alcohol (partially saponified polyvinyl acetate), polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, and polyvinyl pyrrolidone. Ethylene oxide, maleic anhydride copolymers, 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 2 is formed and brought into contact with a physical developer, the physical developer permeates into the image forming layer 2 to enable physical development.

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. Water-soluble salts such as palladium chloride, silver nitrate, and gold tetrachloride are used. Among these, water-soluble salts of palladium, gold, platinum, and copper, particularly water-soluble salts of palladium, are preferably used.

The image forming layer 2 is preferably made of an aqueous solution of the metal compound mentioned above (a commercially available activator liquid for electroless plating can be used as it is),
By mixing with a binder aqueous solution together with a compound having a diazo group or an azide group, a viscosity of 10
By making a liquid of ~1000 centipoise and coating it on the support 1 and drying it, it is usually 0.1~1000 centipoise.
Obtained as a 30μ coating. 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 may also be used as the solvent.

As the compound having a diazo group, water-soluble zinc chloride double salts, sulfates, phosphates, or diazo resins obtained from these are preferably used. More specifically, p-N,N-diethylaminobenzenediazonium chloride zinc chloride double salt, p-N-ethyl-N-β-hydroxyethylaminobenzenediazonium chloride zinc chloride double salt, p-N,N-dimethylamino Benzenediazonium chloride zinc chloride double salt, 4-morpholinobenzenediazonium chloride zinc chloride double salt, 4-morpholino-2,5-diethoxybenzenediazonium chloride zinc chloride double salt, 4-morpholino-2,5-dibutoxybenzene Diazonium chloride zinc chloride double salt, 4-benzoylamino-2,5-diethoxybenzenediazonium chloride zinc chloride double salt, 4-(4'-methoxybenzoylamino)-2,5-diethoxybenzenediazonium chloride zinc chloride double salt , 4-(p-tolylmercapto)-2,5-dimethoxybenzenediazonium chloride zinc chloride double salt, 4-diazodiphenylamine zinc chloride double salt, 4-diazo-
4'-Methoxydiphenylamine zinc chloride double salt, 4
-Diazo-3-methoxy-diphenylamine zinc chloride double salt, sulfates and phosphates corresponding to the above zinc chloride double salt, and diazo resin which is a reaction product of these diazonium compounds and paraformaldehyde can be suitably used. .

Moreover, as the compound having a diazo group, compounds other than those mentioned above can also be used as long as they are water-soluble and have a diazo group.

The image forming layer 2 contains the binder 100 described above.
part: 0.1 to 100 parts of metal compound, especially 1 to 100 parts
It is preferable to include the compound having a diazo group in an amount of 1 to 100 parts, particularly 20 to 50 parts.

After forming the image forming layer 2, a hardening process is desirably performed in order to suppress elution of the binder into the developer during physical development.

(Image Forming Method) 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, in the exposure section 2A,
A compound having a diazo group is selectively decomposed to a degree depending on the amount of exposure.

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

Then, by pattern exposure, an aqueous reducing agent solution is brought into contact with the image forming layer 2, which has a latent image in which the diazo group-containing compound is broken down in a pattern, by immersion, so that the compound having a diazo group is brought into contact with the image forming layer 2 almost uniformly in the image forming layer 2. 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.

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 2B 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/.

The above image forming technology is applied to industrial applications such as lithium film for adhesion reversal, but the above image forming materials undergo significant changes over time due to the decomposition of the diazo compound after coating. There is a drawback that fog occurs during development after 3 months. Therefore, there is a need to improve the stability over time of the above-mentioned image forming materials after coating.

The present invention relates to improving the stability over time of the above-mentioned image material by adding a stabilizer to the photosensitive material in advance and applying it to the photosensitive material in order to maintain the stability over time after coating.

In general, as stabilizers for diazo compounds, compounds such as organic carboxylic acids such as succinic acid and glutar, organic sulfonic acids such as p-toluenesulfonic acid, and zinc chloride have been commonly used as decomposition inhibitors to suppress the decomposition of diazo compounds. It is used by adding it to diazo-sensitive materials. The present invention has discovered that compounds conventionally used as stabilizers for suppressing the decomposition of diazo compounds, as well as new salts of strong acids and ammonia, are similarly effective as stabilizers, and these compounds are added to the sensitive material in advance. By adding a stabilizer, it was possible to suppress the decomposition of the diazo compound in the image-forming layer after coating, thereby successfully obtaining an image-forming material with improved stability over time of the image-forming layer.

Stabilizers for sensitive materials that can be applied to the present invention include organic carboxylic acids such as citric acid, tartaric acid, succinic acid, and glutaric acid, p-toluenesulfonic acid, and 1- Ethoxybenzene-4-sulfonic acid, 1-methoxynaphthalene-4-sulfonic acid, naphthalenetrisulfonic acid, 1,5-naphthalenedisulfonic acid, sulfosalicylic acid, zinc chloride, tetrafluoroborate In addition, new effects have been added. Ammonium sulfate, ammonium chloride, and ammonium nitrate are used.

Among the conventional products, p-toluenesulfonic acid and zinc chloride, among the newly found effective products, ammonium sulfate and ammonium chloride are effective, but the stabilizing effect of ammonium sulfate is especially effective against other compounds. It's much larger than that.

The amount of the inhibitor to suppress the decomposition of the diazo compound as described above is 10 to 300 parts by weight per 100 parts by weight of the diazo component contained, and specifically, it is added to the sensitive material as a 5 to 20% aqueous solution.

By adding the above-mentioned stabilizer, the film coated with the additive sensitive material has a 40%
In an accelerated aging test in a °C oven, 1.5 to 5 times greater stability over time is obtained.

The present invention will be specifically described below with reference to Examples.

Example 1 A photosensitive material having the following composition and containing ammonium sulfate as a stabilizer was prepared.

PVA (Nippon Gosei Kagaku Gosenal T330)
10% aqueous solution 20 parts pdCl ₂ Hydrochloric acid solution (Nippon Kanigen Retsudo Shumer) 15 parts Diazo monomer (Respe Chemical No. 10) 20%
Aqueous solution 2.0 parts Diazoresin (Shinko Giken D-011) 20%
Aqueous solution 1.0 part N,N'-dimethylolurea 2% aqueous solution
1.5 parts Ammonium sulfate 10% aqueous solution 3.0 parts The above sensitive material was applied to a polyester film (Toray #100) using Miyabur #36 to obtain a coating film with a thickness of 4.5 μm. After leaving the above-mentioned photosensitive film in an oven at 40℃ for 6 days to accelerate aging, the film was heated using an ultra-high pressure mercury lamp (wavelength: 405 nm, 75 W).
It was exposed for a minute with a negative film in close contact.

Next, use Shiba Nickel (manufactured by Okuno Pharmaceutical Co., Ltd.), which is a reducing bath with the following composition at 40°C. [Shibani Tsukel] Boron-based reducing agent...0.5 g Nickel sulfate...3.0 g Sodium citrate...1.0 g Water...95.5 g Then, add TMP Chemical Nickel (manufactured by Okuno Pharmaceutical Co., Ltd.), which is a physical developer with the following composition.
[TMP Chemical Nickel] [Nickel sulfate...9.0g Sodium hypophosphite...7.0g Ammonia saturated solution...6.5g Sodium citrate...10.0g Water...67.5g] Used at 20℃, By dipping for 1 minute, 300 lines/inch 4% halftone dots were reproduced without fogging, equivalent to the photosensitive film immediately after coating, and stability over time at 40°C for 6 days was confirmed.

Comparative Example 1 A photosensitive material having the following composition without adding a stabilizer was prepared.

PVA (Nippon Gohsenal T330)
10% aqueous solution 20 parts pdCl ₂ Hydrochloric acid solution (Nippon Kanigen Red Shumer) 15 parts Diazo monomer (Daito Chemical WH-1300) 20
% aqueous solution 2.0 parts Diazoresin (Shinko Giken D-013) 20%
Aqueous solution 1.0 part N,N'-dimethylolurea 2% aqueous solution
1.5 parts The above photosensitive material was made into a photosensitive film in the same manner as in Example 1, and the film was opened at 40°C to accelerate aging for 2 days. Further, the film was exposed in the same manner as in Example 1, immersed for 30 seconds in Shiba Nikkel (manufactured by Okuno Pharmaceutical Co., Ltd.), a reducing bath having the composition shown in Example 1 at 40°C, and then subjected to physical development with the composition shown in Example 1. By using the liquid TMP Chemical Nickel (manufactured by Okuno Pharmaceutical Co., Ltd.) at 20℃ and immersing it in this solution for 45 seconds, a 300-line 4% halftone dot was reproduced without fogging, equivalent to the photosensitive film immediately after application. However, in a 3-day accelerated aging test in a 40°C oven, similar images after exposure and development showed fogging.

Example 2 A photosensitive material having the following composition was prepared in which p-toluenesulfonic acid was added as a stabilizer.

PVA (Nippon Gohsenal 05) 10%
Aqueous solution 20 parts PdCl _{dihydrochloric} acid solution (Nippon Kanigen Retsudo Schumer) 15 parts Diazo monomer (Respe Chemical No. 2) 20%
Aqueous solution 2.0 parts Diazoresin (Shinko Giken D-012) 20%
Aqueous solution 1.0 part N,N'-dimethylolurea 2% aqueous solution
1.5 parts p-toluenesulfonic acid 20% aqueous solution 2.0 parts The above photosensitive material was made into a sensitive film in the same manner as in Example 1, aged in an oven at 40°C for 4 days, exposed to light, and prepared as shown in Example 1 at 40°C. 20 seconds in Shibanitskel (manufactured by Okuno Pharmaceutical), a reducing bath of the composition.
After dipping, a physical developer having the composition shown in Example 1, TMP Chemical Nickel (manufactured by Okuno Pharmaceutical Co., Ltd.), was added to
By immersing the film in this solution for 1 minute, it was possible to reproduce 300 lines and 4% halftone dots without fogging, equivalent to the photosensitive film immediately after coating, and to confirm its stability over time at 40°C for 4 days.

Example 3 A sensitive material having the following composition was prepared to which zinc chloride was added as a stabilizer.

Gelatin (Nitta Gelatin P-2151) 30% aqueous solution 10 parts PdCl _{dihydrochloric} acid solution (Nippon Kanigen Retsudo Shumer) 10 parts diazo monomer (Respe Chemical No. 2) 20%
Aqueous solution 2.0 parts Diazoresin (Shinko Giken D-011) 20%
Aqueous 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 film in the same manner as in Example 1, and the aging process was accelerated for 4 days in a 40°C oven and exposed to light at 40°C. Immerse for 10 seconds in Shiba Nitsukel (manufactured by Okuno Pharmaceutical), a reducing bath with the composition shown in
Next, a physical developer having the composition shown in Example 1 was prepared.
By using TMP Chemical Nickel (manufactured by Okuno Pharmaceutical Co., Ltd.) at 20℃ and immersing it in it for 60 seconds, halftone dots of 300 lines from 4% to 96% can be obtained without fogging, which is equivalent to that of a sensitive film immediately after application. The product was reproduced and its stability over time was confirmed at 40°C for 4 days.

Example 4 A sensitive material having the following composition and containing ammonium chloride as a stabilizer was prepared. PdCl _{dihydrochloric} acid solution
Prepare by dissolving 2 g of PdCl ₂ in 200 ml of HCl and 1000 ml of water.

PVA (Nippon Gosei T330) 10% aqueous solution
20 parts of the above PdCl ₂ liquid 20 parts Diazoresin (Shinko Giken D-012) 20
% aqueous solution 2.5 parts Glutaraldehyde 0.4% aqueous solution 1.8 parts Ammonium chloride 10% aqueous solution 3.5 parts The above photosensitive material was made into a sensitive film by the same operation as in Example 1, accelerated aging in a 40°C oven for 4 days, and exposed to light at 40°C. Immerse in a reducing bath (sodium borohydride 10 g/) for 5 seconds, then 20°C physical developer (reducing agent: sodium hypophosphite 20 g/,
By immersing the film in nickel sulfate (40g/) for 45 seconds, it reproduces the 300 line 4% to 96% halftone dots without causing fog, equivalent to the photosensitive film immediately after coating.
The stability over time was confirmed at ℃ for 4 days.

[Brief explanation of drawings]

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

Claims (1)

[Claims] 1 An image forming layer consisting of a hydrophilic binder layer is provided on a support, and the hydrophilic binder layer contains a metal compound and a diazo group-containing compound which are reduced to become metal development nuclei, and further contains an organic carboxylic acid, p-toluenesulfonic acid, 1-ethoxybenzene-4-sulfonic acid, 1-methoxynaphthalene-4-sulfonic acid, naphthalenetrisulfonic acid,
An image forming material characterized in that it also contains any one of the following compounds: 1,5-naphthalenedisulfonic acid, sulfosalicylic acid, zinc chloride, tetrafluoroborate, ammonium sulfate, ammonium chloride, or ammonium nitrate.