JPS5914737B2 - photography method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic method, particularly a vapor-deposited silver halide photosensitive material (hereinafter referred to as VESH).
The present invention relates to a method of forming an image using the abbreviation "verHalide" (abbreviation of "verHalide").

Compared to ordinary photographic materials using silver halide emulsions, VESH has a much smaller photosensitive layer (several to several tenths of the thickness of the silver halide emulsion layer) and therefore has a high It has the potential to provide high resolution.

In addition, the silver content per unit area required to obtain the same image density is much smaller than that of an emulsion, in other words covering power. has the advantage of being a dog. Furthermore, it has the advantage that the processing time (developing, fixing, etc.) is extremely short. However, VES
H has the following drawbacks.

In other words, VESH is different from a silver halide emulsion. In other words, the silver halide grains are not wrapped in a binder and have a continuous layer of silver halide. As a result, it is known that the resolution is low due to contagious development and fogging is extremely likely. In addition, the development speed is extremely high, and development progresses in a short period of time, and the image area reaches saturation density. If fixing is not carried out promptly before the image area reaches 5 degrees of saturation, blackening of the non-image area will progress and fog will occur. It was difficult to obtain image density. Furthermore, it was difficult to obtain a high transmission image density. Therefore, it is an object of the present invention to provide a method for obtaining fog-free images using VESH.

Another object of the invention is to provide a method for obtaining high resolution images using VESH. 75 Yet another object of the present invention is to provide a method for obtaining images with high image density using VESH.

Yet another object of the present invention is to provide a method using VESH that provides easy-to-handle development speeds. These objects of the present invention are achieved by imagewise exposing a vapor-deposited silver halide photosensitive layer provided on a support, followed by physical development (without chemical development).

Developing a latent image by physical development is called Hello! 5. Although it is well known that a silver genide emulsion photosensitive layer is used, the present inventor discovered that there is a large difference in the physical development effect between an emulsion type photosensitive layer and a VESH, and arrived at the present invention.

That is, in the case of physical development of an emulsion photosensitive layer, the 10(i) sensitivity is reduced to one to several tenths of that in the case of chemical development.

(11) Development time takes several tens of minutes to several hours.

The contrast of the developed image is low (flat).

ゞ5OV) Easy to fog.

(V) It is known that if the latent image is fixed with an acidic fixer before physical development, the latent image disappears, or even if it does not disappear completely, the number of nuclei decreases, resulting in an extremely long development time.

However, physical development for VESH has (1) sensitivity comparable to that of chemical development.

(Ii) The development time may be several minutes. (The contrast of the 110 developed image is extremely high.

0V) Fog can be kept extremely small.

(V) Even if it is fixed with an acidic fixer, it can be physically developed.

Moreover, the developing time only takes a few minutes. It was discovered that favorable results such as the following can be obtained.

It is not clear why this difference occurs between emulsion and VESH, but it is important to note that in VESH the latent image silver is not coated with binder and is therefore very active, and that fluid exchange is difficult. It is conceivable that this will be carried out promptly. The VESH used in the present invention is prepared by depositing silver halide on a support by vacuum evaporation.

As the support, all conventional supports for silver halide emulsions can be used. Paper, paper coated or laminated with polymers of α-olefins having 2 to 10 carbon atoms, such as polyethylene, polypropylene and ethylene-butene copolymers, cellulose nitrate, cellulose acetate, cellulose acetate butyrate, cellulose acetate pro-polymer. Films of plastics such as peonate, polyethylene terephthalate, polycarbonate, nylon, polyacrylonitrile, polymethyl methacrylate, polystyrene, polyvinyl chloride, and vinyl chloride monovinyl acetate copolymer; Films whose surface has been roughened by the method described in No. 119068, and films formed by adding pigments such as titanium oxide and barium sulfate, dyes, carbon black, etc., glass plates, and crystallized glass. These include plates, ceramic plates, ceramic plates, transparent ceramic plates, cermet plates, metal plates, and wooden plates.

Further, silver halides used in the present invention include silver chloride,
These include silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like.

The thickness of the photosensitive layer may range from approximately 2 nm to 3 μm.

If it is smaller than this range, the photosensitivity is too low to be of practical use, and if it is larger than this range, silver is wasted. A more preferable range is 1
The range is from 0 nm to 500 nm. The amount of silver halide deposited on the photosensitive layer is preferably in the range of 0.1y to 6y in terms of metallic silver per m2 of the photosensitive layer.

If the amount of silver halide is less than this range, the density of the image obtained after processing will be too small to be of practical use, and if it is more than this range, the silver will be wasted. Among these, a particularly preferable amount of silver halide is in the range of 0.27 to 37 in terms of metallic silver per 1 m 2 of the photosensitive layer. The photosensitive layer is provided by a known vacuum evaporation method, and the degree of vacuum is 104 to 10-6.
It may be within the range of mmHg, and the object of the present invention can be achieved even outside this range.

The photosensitive layer can also be dye-sensitized and spectral sensitized with dyes.

For example, a dye may be vapor-deposited in parallel with the vapor deposition of silver halide, an already vapor-deposited photosensitive layer may be immersed in a dye solution to adsorb the dye on the surface, or an already vapor-deposited photosensitive layer may be immersed in a dye solution. The dye may be adsorbed onto the surface by applying or spraying a dye solution onto the surface. Suitable dyes used for this purpose include cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes and the like. These color sensitization techniques have been known for a long time, for example, U.S. Pat.
No. 229, No. 3480434, No. 3672897,
No. 3703377, No. 2688545, No. 2912
No. 329, No. 3397060, No. 3615635,
No. 3628964, British Patent Publication No. 1195302,
No. 1242588, No. 1293862, West German Patent Publication No. 2030326, No. 2121780, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 14030-1973, Japanese Patent Publication No. 10773-1973, U.S. Patent No. 3511664, No. 3
No. 522052, No. 3527641, No. 361561
No. 3, No. 3615632, No. 3617295, No. 3
No. 635721, No. 3694217, British Patent No. 113
Dyeing methods described in Japanese Patent No. 7580, No. 1216293, etc. can be used.

The selection depends on the wavelength range to be sensitized, the sensitivity, etc. of the VESH of the present invention.
It can be determined arbitrarily depending on the purpose and use. The VESH of the present invention can be chemically sensitized by exactly the same method. Chemical sensitizers that can be used include, for example, U.S. Pat.
Gold compounds such as chloroauric acid salts and gold trichloride described in U.S. Pat. No. 56 and U.S. Pat. No. 2,597,915;
Salts of noble metals such as platinum, palladium, iridium, rhodium, and ruthenium described in US Pat. No. 6263 and US Pat. No. 2,598,079; US Pat.
No. 10689, No. 3189458, No. 3501313
Sulfur compounds that react with silver salts to form silver sulfide, as described in US Pat. Nos. 2,487,850 and 2,518.
No. 698, No. 2521925, No. 2521926,
No. 2694637, No. 2983610, No. 3201
Examples include stannous salts, amines, and other reducing substances described in No. 254.

Any compound among these chemical sensitizers can be applied to VESH to chemically sensitize it, for example, by the method described in Pelkey Patent No. 800,821. Various compounds can be adsorbed to the VESH of the present invention in a similar manner to prevent a decrease in sensitivity and generation of capri during the manufacturing process, storage, or processing of the photosensitive material. Those compounds are 4-hydroxy-6-methyl-1,3,3
A large number of compounds have been known for a long time, including a-7-tetraazaindene, 3-methylbenzothiazole, 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts. ing. An example of a compound that can be used is K. Mees
Author? TheOryOfthePhOtOgra
phicPrOcess゜゛(3rd edition, 1966) 3
The original documents are listed on pages 44 to 349, and the following patents are also listed. U.S. Patent No. 1758576, U.S. Patent No. 2110178, U.S. Patent No. 2131038, U.S. Patent No. 217
No. 3628, No. 2697040, No. 2304962, No. 2324123, No. 2394198, No. 244
No. 4605-8, No. 2566245, No. 269471
No. 6, No. 2697099, No. 2708162, No. 2
728663-5, 2476536, 2824
No. 001, No. 2843491, No. 3052544,
No. 3137577, No. 3220839, No. 3226
No. 231, No. 3236652, No. 3251691,
No. 3252799, No. 3287135, No. 3326
No. 681, No. 3420668, No. 3622339,
British Patent No. 893428, British Patent No. 403789, British Patent No. 117
No. 3609, No. 1200188.

The VESH photosensitive layer is physically developed after image exposure.

The physical developer used in the present invention may or may not contain a silver halide solvent. Further, the photosensitive layer may or may not be removed by dissolving with a silver halide solvent after imagewise exposure. When the imagewise exposed photosensitive layer is developed with a physical developer containing no silver halide solvent, the silver halide in the unexposed areas is removed after development. Further, if the imagewise exposed photosensitive layer is developed with a physical developer containing a silver halide solvent, it is not necessary to remove the silver halide after development. If the image-exposed photosensitive layer is removed with a silver halide solvent before physical development, no fixing treatment is required after development. The physical developer used in the present invention basically consists of a soluble silver salt and a reducing agent.

It is also possible to use other soluble metal salts (eg mercury nitrate) in place of soluble silver salts. Silver nitrate is a typical soluble silver salt, but silver sulfate, silver acetate, and the like can also be used. Common developing agents as reducing agents, such as hydroquinone, 2-methylhydroquinone, 2
- Polyhydroxybenzenes represented by phenylhydroquinone, 2-chlorohydroquinone, pyrogallol, and catechol, 4-(methylamino)phenol,
Hemisulfate (commonly known as metol), 4-aminophenols represented by 4-(benzylamino)phenol hydrochloride, 4-(diethylamino)phenol hydrochloride and 4-aminophenol sulfate, p-phenylenediamine hydrochloride salts and p-phenylenediamines represented by N-N-diethyl-p-phenylenediamine sulfate, ascorbic acid, N-(p-hydroxyphenyl)glycine, and other C.I. E. K. Mee8 and T
．． H. Co-authored by James “The Ory Of PhO
tOgraphicPrOcess” 3rd edition (Macm
illanCO. , 1966, NewYOrk) No. 1
Chapter 3 and L. F. A. “PhOtOgr” by MasOn
aphicPrOcessingChemistry”
(0xf0rdPress11966) 16-30
The compounds listed as developing agents on the page can be used alone or in combination of two or more.

The physical developer before fixing is desirably acidic in order to suppress reduction of silver halide in unexposed areas.

For this purpose, acids such as acetic acid, citric acid, oxalic acid and malonic acid are preferably added to the physical developer. When the same physical developer was used, it was found that physical development after fixing had better sensitivity than physical development before fixing, but the reason for this is unknown.

Furthermore, when the same physical developer was used, it was found that the pre-fixing physical development resulted in smaller fog than the post-fixing physical development. Therefore, physical development before fixing provides images with higher contrast and no fog. Post-fix physical development, however, gives images without graininess but with lower contrast than pre-fix physical development. In the present invention, by either method, 10
A high resolution of 001p74u or higher and a transmitted image density of 2.0 or higher can be obtained. The resulting silver image can be reinforced by known methods, or other metals can be deposited on top of the silver image by chemical plating.

Further, when the photosensitive layer is composed of silver chloride or silver bromide, physical development may be performed after replacing these with silver iodide.

It has been found that this method provides a silver image with higher sensitivity, less fog, and higher image density. On the other hand, the silver halide fixing agent can be any well-known silver halide solvent,
For example, water-soluble thiosulfates (e.g., potassium thiosulfate,
sodium thiosulfate, ammonium thiosulfate, etc.), water-soluble thiocyanates (e.g., potassium thiocyanate,
sodium thiocyanate, ammonium thiocyanate, etc.), water-soluble organic diols (e.g., 3-thia-1,5
-pentanediol, 3,6-dithia-1,8-octanediol, 3,6,9-trithia-1,11-undecanediol, 3,6,9,12-tetrathia-1,14
-tetradecanediol, etc.), water-soluble sulfur-containing organic dibasic acids (e.g., ethylene bisthioglycolic acid, etc.)
and water-soluble salts thereof, or mixtures thereof.

The solution containing the fixing agent may optionally contain a preservative (for example, a sulfite such as sodium sulfite or potassium sulfite, a bisulfite such as sodium hydrogen sulfite or potassium hydrogen sulfite), a PH buffer (for example, boric acid, sodium borate, borax, etc.). borates, sodium metaborate, acetic acid, acetate salts such as sodium acetate), PH adjusters (e.g. acetic acid), chelating agents (e.g. citric acid, malonic acid, lactic acid, salicylic acid, EDTA, EDTA disodium salt, nitrilotri Acetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid), etc. can be included.

Example 1 Approximately 0.2μ of silver bromide was deposited on a polyethylene terephthalate film whose surface had been flame-treated and then primed with gelatin.
A VESH photographic material was obtained by vacuum deposition to a thickness of m.

A line image illuminated with tungsten light at an illumination intensity of 900 lux was image-exposed for 25 seconds, and then immersed in a physical developer having the following composition for about 3 minutes (20° C.). Mix A liquid and B liquid immediately before using the physical developer.

After washing with water, silver bromide in the unexposed areas was dissolved and removed using a fixing solution (15% aqueous sodium thiosulfate solution).

After washing and drying, the final image was obtained. The silver image before fixing was black and glossy, but the silver image after fixing had metallic luster.

The silver image thus obtained has an extremely high resolution (10001
p/Mm or higher), high contrast and no fog.

The transmitted image density was 2.5 or higher. Example 2 After image exposure in Example 1, processing was performed as follows.

That is, before performing physical development, the photosensitive layer was dissolved and removed using the fixing solution of Example 1. This treatment time was approximately 5 seconds. After washing with water, it was developed with the physical developer of Example 1 for about 2 minutes, washed with water, and dried to obtain a silver image. The obtained silver image was dark brown.

The image density was approximately 3.0. When the development time was further lengthened in an attempt to obtain an optical density of 3.0 or higher, fogging began to occur.

The resolving power was 10001 p/Mm or more as in Example 1. Example 3 The procedure was the same as in Example 2 except that a fixer having the following composition was used instead of the fixer in Example 2.

The resolving power was 10001 p/Mm or more as in Example 1. Fixer Example 4 The fixer was the same as Example 2 except that a fixer having the following composition was used instead of the fixer in Example 2.

The resolving power was 10001 p/Mm or more as in Example 1. Fixer Example 5 Same as Example 1 except that silver chloride was used instead of silver bromide in Example 1.

Similar to Example 1, the resolution was 10001 p/Mu or more. Example 6 It was the same as Example 1 except that the silver bromide film thickness in Example 1 was changed to 0.5 μm.

The results remained virtually unchanged even when the film thickness was increased from 0.2 μm to 0.5 μm. The resolution is 1000 as in Example 1.
It was 1 p/Mm or more. Example 7 The procedure was the same as in Example 2 except that a physical developer having the following composition was used instead of the physical developer in Example 2.

The resolution is 10001p/M7, same as Example 1! It was over L. Immediately before using the physical developer, mix 1 volume of solution A and 5 volumes of solution B.

Example 8 In Example 1, silver bromide in the photosensitive layer after image exposure was immersed in a solution having the following composition for 2 minutes to convert silver bromide into silver iodide.

After washing with water, the film was developed for 2 minutes using the physical developer of Example 1, and a high-density silver image with little fog was obtained.

The sensitivity of this example was about 5 times higher than that of Example 1.
The image density was 4.0 or more, and the fog density was 0.01. Similar to Example 1, the resolution was 10001 p/Mu or more. Preferred embodiments of the present invention are as follows.

1 In the claims, after image exposure to VESH, the V
A photographic method characterized by processing ESH to perform physical development, and then processing the VESH with a fixing solution to dissolve and remove silver halide in unexposed areas.

2. In the scope of claim 2, after imagewise exposing the VESH, the VESH is treated with a solution containing a silver halide-dissolving substance to dissolve and remove the silver halide photosensitive layer, and then the VESH is treated with a physical developer. A photographic method characterized by physical development.

3. In the claims, after image exposure to VESH, the ESH is processed using a physical developer containing a silver halide-dissolving substance.
A photographic method characterized by processing and physically developing and simultaneously dissolving and removing silver halide in unexposed areas.

4. A photographic method according to claims and embodiments 1, 2, and 3, characterized in that the physical developer contains a water-soluble silver compound and a reducing compound.

5 In embodiment 4, the water-soluble silver compound is silver nitrate,
A photographic method characterized by using any one compound selected from silver sulfate and silver acetate, or a combination of two or more compounds.

6. A photographic method according to embodiment 4, characterized in that the water-soluble silver compound is silver nitrate.

7. A photographic method according to claim 7, characterized in that the thickness of the vapor-deposited silver halide photosensitive layer is in the range from 2 nm to 3 μm.

8. Photographic method according to claim 8, characterized in that the thickness of the vapor-deposited silver halide photosensitive layer is in the range from 10 nm to 500 nm.

9 In the claims, the amount of silver in the vapor-deposited silver halide photosensitive layer provided on one surface of the support ranges from 0.17/I to 6y/Rrl in terms of metallic silver. A photographic method characterized by certain things.

10 In the claims, the amount of silver in the vapor-deposited silver halide photosensitive layer provided on one surface of the support ranges from 0.2y/i to 3t/i in terms of metallic silver. A photographic method characterized by certain things.

11 In the scope of claims, the silver halide constituting the vapor-deposited silver halide photosensitive layer is silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiobromide. Photography characterized by being any of silver.

12. A photographic method according to claim 1, characterized in that a sensitizing dye and a spectral sensitizing dye are adsorbed on a vapor-deposited silver halide photosensitive layer.

Claims (1)

[Claims] 1. A photographic method characterized in that an image is obtained by subjecting a photographic light-sensitive material having at least one vapor-deposited silver halide light-sensitive layer provided on a support to image exposure, followed by physical development.