JPH10123643A - Silver halide photographic material for hologram - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a regenerated image having a high refraction efficiency in quick processing by setting the average grain size in a silver halide emulsion layer to a specified value, containing a selenium or tellurium compound, and setting the silver/gelatin ratio on the emulsion layer side and the quantity of applied silver to specified values. SOLUTION: The average grain size of silver halide grain in a silver halide emulsion layer is 5-50nm, particularly preferably, 10-40nm. It also contains a selenium or tellurium compound. The silver/gelatin ration of the silver halide emulsion layer which is the ratio of the total quantity of silver to the total quantity of gelatin on a support body is 0.2-2.0, preferably 1.0-1.8. To attain such a silver/gelatin ratio, the gelatin quantity is regulated in an optical process from the formation of silver halide grain to just before application of the silver halide emulsion. The silver quantity calculated in terms of silver of the total silver halide per m<2> on the support body is 1-3g/m<2> , preferably, 1.2-2.8g/m<2> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material for holograms which can be rapidly processed.

[0002]

2. Description of the Related Art In recent years, the application range of silver halide photographic materials for holograms (hereinafter, also simply referred to as photographic materials) has been gradually expanding for appreciation or medical use.
Above all, phase-type holograms with bright images have attracted attention.

A hologram is a method in which a light wave coming from an object is recorded on a photosensitive material in the form of interference fringes with a reference wave, and the wavefront of the object light is reproduced as diffracted light from the hologram.

As a photosensitive material which can be used for the hologram and has a high resolution and sufficient sensitivity, a silver halide photographic photosensitive material is mentioned.

To obtain a bright hologram reproduction image,
It is necessary to increase the diffraction efficiency, and for that purpose, it is effective to increase the amount of silver applied to the photosensitive material. However, when the amount of coated silver is increased, the rapid processability deteriorates, and it takes time to obtain an image, which is not preferable.

It is conceivable to activate the developing solution in order to increase the development processing speed. However, in this method, the developed silver filament is easily stretched and the gap between the developed silver is increased, and the resolution of the image is reduced. As a result, eventually, the amplitude of the phase modulation does not increase, the diffraction efficiency is reduced, and a bright reproduced image cannot be obtained.

As a prior art for increasing the diffraction efficiency, for example, US Pat.
No. 79 is disclosed but is not sufficient.

Accordingly, there has been a strong demand for a silver halide photographic material for holograms which has excellent diffraction efficiency and can easily obtain a bright and clear reproduced image by rapid processing.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic material for holograms capable of obtaining a reproduced image having high diffraction efficiency by rapid processing.

[0010]

The object of the present invention has been attained by the following.

In a hologram silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, the silver halide emulsion layer has an average grain size of 5 to 50 nm. Containing a selenium or tellurium compound, and having a silver / gelatin ratio of 0.2 to 2.0 on the silver halide emulsion layer side and a coated silver amount of 1 to 3 g / m ^2.
A silver halide photographic material for holograms, characterized in that:

Hereinafter, the present invention will be described in detail.

The silver halide photographic light-sensitive material for a hologram of the present invention is of a transmission type, and the higher the resolution of the light-sensitive material, the better a reproduced image can be obtained.

The resolving power of the light-sensitive material largely depends on the size of the silver halide particles. The average particle diameter of the silver halide particles used in the silver halide light-sensitive material for holograms of the present invention is 5 to 50 nm. In the present invention, the particularly preferred average grain size of the silver halide grains is from 10 to 40 nm.
The smaller the average particle diameter, the more preferable the processing time can be shortened, high resolution can be obtained, and an image without devitrification can be obtained.

However, the use of silver halide grains having an excessively small grain size has disadvantages such as insufficient sensitivity, contamination of images and processing solutions, and poor storage stability of photosensitive materials. Is not preferred.

Here, the average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood, and the term “particle size” means a particle having a spherical shape or a particle that can be approximated to a sphere. Means particle diameter. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see C.I. E. FIG. K. Mees & T.
H. By James: The theory of th
e photographic process, 3rd
Edition, pages 36 to 43 (1966, Macmillan).

As the silver halide grains according to the present invention, so-called Lippmann emulsions having an average grain size of 50 nm or less can be used. Lippmann emulsion is a British patent 1,139,0
No. 62, U.S. Pat. No. 3,573,057, JP-B-49-
Emulsions described in No. 8333 and the like can be used. Particularly preferred emulsions are described, for example, in JP-A-58-16094.
No. 8 and JP-A-60-12540 are preferably used.

Next, the selenium or tellurium compound contained in the photosensitive silver halide emulsion layer of the present invention will be described.

The selenium compound used for chemical sensitization in the present invention includes a wide variety of selenium compounds.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, N, N-dimethylselenourea, triethyl N, N, N'-seleno). Urea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N '
-Trimethyl-N'-4-nitrophenylcarbonylselenourea, etc.), selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids, and seleno Esters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), selenides (eg, triphenylphosphine selenide, diethyl selenate) And diethyl diselenide). Particularly preferred selenium compounds are selenides, selenoureas, selenamides, and selenium ketones.

The amount of the selenium sensitizer used is not uniform depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally 10 ^-8 to 1 mol per mol of silver halide.
It is preferable to use about 10 ^-4 mol. The temperature of chemical ripening using a selenium sensitizer is preferably in the range of 40 to 90C, more preferably 45C or more and 80C or less. The pH of the emulsion is preferably in the range of 4 to 9, and the pAg is preferably in the range of 6.0 to 9.5.

Hereinafter, specific examples of the selenium sensitizer used in the chemical sensitization of the present invention will be listed, but the present invention is not limited to these.

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[0025]

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The tellurium compounds used for chemical sensitization in the present invention include a wide variety of tellurium compounds.

Examples of useful tellurium compounds include telluroureas (eg, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea, N, N'-dimethyl -N'phenyltellurourea), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), and telluroamides (for example, telluro Acetamide, N, N-dimethyltellurobenzamide), telluro ketones, telluro esters, isotellurocyanates and the like.

Hereinafter, specific examples of tellurium compounds used in the present invention will be listed, but the present invention is not limited thereto.

[0029]

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[0030]

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[0031]

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[0032]

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The technique for using the tellurium sensitizer is the same as the technique for using the selenium sensitizer. In the present invention, chemical sensitization may be performed by combining selenium sensitization and tellurium sensitization.

In the present invention, chemical sensitization with a noble metal salt such as a sulfur compound or a gold salt can also be performed, and the chemical sensitization can be performed by combining these sensitization methods with the selenium / tellurium sensitization method described above.

Specific examples of the sulfur sensitizer applicable to the present invention include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea, and rhodanine. Preferred examples include derivatives, dithiacarbamic acids, organic polysulfide compounds, sodium thiosulfate, and sulfur alone. In addition, as the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

As the gold sensitizer, chloroauric acid, gold thiosulfate,
In addition to gold thiocyanate, thioureas, rhodanines,
Other examples include gold complexes of various compounds.

The amounts of the sulfur sensitizer and the gold sensitizer are not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions and the like.
It is preferably from 1 × 10 ^-4 mol to 1 × 10 ^-9 mol per mol. More preferably, 1 × 10 ⁻⁵ mol to 1 × 1
^0-8 mol.

The sulfur sensitizer and the gold sensitizer may be added by dissolving them in water or alcohols or other inorganic or organic solvents and adding them in the form of a solution. It may be added in the form of a dispersion obtained by emulsifying and dispersing using such a medium. Both sulfur sensitization and gold sensitization may be performed simultaneously or separately and stepwise. In the latter case, favorable results may be obtained if gold sensitization is performed after or during sulfur sensitization appropriately.

The light-sensitive silver halide emulsion of the light-sensitive material of the present invention may be any silver halide grains such as silver chloride, silver iodide, silver bromide, silver iodobromide and silver chloroiodobromide. Average grain size of 5 to 50 nm having a silver iodide content of 5.0 mol% or less
Silver iodobromide emulsion.

As a method for producing such ultrafine silver halide grains, an aqueous solution of silver nitrate and an aqueous solution of a water-soluble halide are mixed by a single jet method, a double jet method, a control double jet method, or the like.
Manufactured.

Further, silver halide grains may be further grown, or may be continuously grown from nucleation. Further, as a method of further promoting the reduction of the particle size, the above-mentioned mixing operation is carried out in the presence of a silver halide insolubilizing agent such as azaindenes, mercapto compounds, benzotriazoles, benzimidazoles, indazoles, and phthalazines. Preferred is a method of performing the in-line mixing of the two aqueous solutions, then a method of continuously in-line mixing the insolubilizing agent and the water-miscible organic solvent liquid, and a method of adding the two aqueous solutions to the water-miscible organic solvent. As an example.

The shape of the silver halide grains used in the present invention is not limited, and may be any one of a tabular shape, a spherical shape, a cubic shape, a tetrahedral shape, a regular octahedral shape and the like. Cubic particles are preferred.

In the process of forming and / or growing particles, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt), and iron salt ( Metal ions are added using at least one selected from the group consisting of
Alternatively, these metal elements can be contained on the particle surface.

Considering the effect of improving the high illuminance failure property, the metal salt of iridium shows the most preferable result. Further, the metal salt preferably has a complex structure coordinated so as to satisfy d activation. As the ligand, halogen, cyano, nitrosyl,
H ₂ O is preferred. In particular, the transition metal complex having a ligand selected from a halogen ion, H ₂ O, nitrosyl, thionitrosyl, and cyanide is particularly preferable.

In the silver halide emulsion used in the present invention, unnecessary soluble salts may be removed during the growth of silver halide grains, or they may be kept contained. When removing the salts, use Research Disclosure (R
D) It can be carried out based on the method described in 17643, Section II. Also, salts can be removed by Nudel washing or ultrafiltration.

As an exposure light source for the silver halide photographic light-sensitive material for a hologram of the present invention, image exposure is generally performed using a laser beam having a visible wavelength in a uniform phase. In image reproduction, light having the wavelength of the laser light on which an image is formed plays the most important role. From this viewpoint, the unexposed portion of the processed photosensitive material is
A preferable reproduced image is obtained so as not to absorb the wavelength of the laser light on which the image is formed.

As the laser light having a wavelength in the visible region, an Ar laser, a HeNe laser, a semiconductor laser, or the like is used. An Ar laser is most preferable from the viewpoint of the stability of the emission wavelength, the appropriate coherent wavelength, the durability of the light emitting device, and the cost. Used. The main emission wavelength of Ar laser is 4
88 nm, 514.5 nm.

The silver halide photographic light-sensitive material of the present invention contains silver /
The gelatin ratio is 0.2 to 2.0, and the coated silver amount is 1 to 3 g / m ² . Here, it refers to the silver / gelatin ratio of the silver halide emulsion layer on the support, and is the ratio of the total amount of silver to the total amount of gelatin on the support having the silver halide emulsion layer. In this case, the amount of silver is an amount obtained by converting silver halide into silver.

The silver halide photographic material of the present invention has a silver / gelatin ratio of 0.2 to 2.0 on the silver halide emulsion layer side.
And preferably from 1.0 to 1.8. In order to adjust the gelatin amount such that the silver / gelatin ratio is attained, it may be adjusted in an optional step from the time of forming silver halide grains to immediately before coating of a silver halide emulsion.

The silver content of the silver halide photographic light-sensitive material according to the present invention is 1 to 3 g / m ² . Preferably 1.2-2.
8 g / m ² . The amount of silver here, on the support on the side having the silver halide emulsion layer refers to an amount converted all of the silver halide per 1 m ² of silver.

The melting time of the emulsion layer of the silver halide photographic light-sensitive material for a hologram of the present invention is from 15 minutes to 120 minutes.
Minutes, and particularly preferably 15 minutes to 90 minutes.

The present inventors have conducted intensive studies to enhance the diffraction efficiency of the silver halide photographic light-sensitive material for holograms. As a result, the silver halide photographic light-sensitive material having a specific range of silver / gelatin ratio and silver content was obtained. It has been found that it is effective to include a selenium compound or tellurium compound in the silver halide emulsion layer.

Although the reason is not clear, it is considered that the present invention is based on the fact that after bleaching, a gelatin shell having a higher refractive index than surrounding gelatin is produced.

After exposure, the silver halide photographic light-sensitive material for holograms in the present invention is generally processed in the steps of development, washing with water, bleaching, washing with water, stabilization and drying.

The bleaching step contains at least one of EDTA (iron) III sodium salt, various iron chelate compounds, potassium dichromate, sodium dichromate, parabenzoquinone and the like generally used in the art. Treated with a bleaching solution.

The silver halide emulsion according to the present invention can be spectrally sensitized to a desired wavelength by a spectral sensitizing dye. As sensitizing dyes that can be used, cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine,
Hemicyanine, styryl dyes and hemioxonol dyes are included. These sensitizing dyes may be added at any time from the time when the silver halide grains are formed until immediately before the application of the silver halide emulsion.

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. A useful combination of a dye exhibiting supersensitization and a substance exhibiting supersensitization are (RD) 17
643 (December 1978), page 23, IV, section J.

As a dispersion medium for the protective colloid of the silver halide grains, gelatin is preferably used, and as the gelatin, ossein gelatin, pig skin gelatin and the like can be used. Modified gelatins such as alkali-treated gelatin, acid-treated gelatin, low-molecular-weight gelatin (molecular weight of 20,000 to 100,000), and phthalated gelatin may be used. Other hydrophilic colloids can also be used.

Further, generally used polymer latex can be used. That is, they are a polymerizable ethylene compound and a polymerizable diolefin compound, and are roughly classified into a hydrophobic monomer and a hydrophilic monomer. Examples of the hydrophobic monomer include alkyl acrylates, alkyl methacrylates, glycidyl esters, alkenylbenzenes, vinyl esters, vinyl ethers, vinyl halides, and diene monomers. Examples of the hydrophilic monomer include hydroxyalkyl acrylates, hydroxyalkyl methacrylates, ethylene glycol (meth) acrylates, and ionic monomers. These monomers are
They may be used alone or in combination of two or more.

The photosensitive material may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing, or stabilizing photographic performance. Examples of binders or protective colloids for photographic emulsions include gelatin, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein, cellulose derivatives, sugar derivatives, and various kinds of synthesis such as homo- or copolymers. A hydrophilic polymer substance can be used.

As the matting agent, homopolymers of polymethyl methacrylate or polymers of methyl methacrylate and methacrylic acid, organic compounds such as starch, and fine particles of inorganic compounds such as silica, titanium dioxide, strontium sulfate, and barium sulfate can be used. .

The silver halide photographic light-sensitive material for holograms of the present invention contains, as a hardening agent, for example, chromium salts, aldehydes, N-methylol compounds, dioxane derivatives, active vinyl compounds, active halogen compounds, mucohalogenic acids,
Isoxazoles, dialdehyde starch, 2-chloro-
6-Hydroxytriazinylated gelatin, carboxyl group-activated hardener and the like can be used alone or in combination. For preparing the emulsion layer having a melting time according to the present invention, it can be selected from the above-mentioned hardeners.

The above various additives are described in RD. 17
643 (December, 1978) and 18716 (1979)
(November) and 308119 (Dec. 1989).

Next, the layer constitution of the silver halide photographic light-sensitive material of the present invention will be described.

The silver halide light-sensitive material of the present invention has at least one light-sensitive silver halide emulsion layer according to the present invention on the light-sensitive silver halide emulsion layer side and a protective layer on the emulsion layer side. An anti-irradiation layer containing an anti-irradiation dye corresponding to the exposure wavelength, or an intermediate layer, an undercoat layer, a dye layer, an antistatic layer, etc. may be provided as necessary.

On the side opposite to the side having the photosensitive silver halide emulsion layer, a layer containing an antihalation dye corresponding to the exposure wavelength is preferably provided in order to prevent halation at the time of exposure.

The silver halide light-sensitive material of the present invention includes:
Solid dye fine particles can be contained in the non-light-sensitive layer between the light-sensitive silver halide emulsion layer and the support. In a preferred embodiment of such a dye, the dye is substantially water-insoluble at a pH of 7 or less, and has a water-soluble structure at a pH of 10 or more, and is insoluble in water, but is decolorized by reaction with a processing solution such as development. And a dye having a structure. In addition, water-insoluble mordants dyed with dyes and fine particles of latex are also preferable embodiments. Particularly, a dye having a water-insoluble structure at a pH of 7 or less and a water-soluble structure at a pH of 10 or more is an excellent embodiment in terms of production and cost.

The hydrophilic layer on the side of the light-sensitive silver halide emulsion layer of the silver halide light-sensitive material of the present invention may contain an ultraviolet absorber in order to prevent baking out of the processed silver halide. it can. Examples of the ultraviolet light absorber that can be used include the following.

Pt-Butylphenyl sal
icylate 2-Hydroxy-4-methyoxybenzop
henone 2-Hydroxy-4-octoxybenzoph
eneone 2,2'-Dihydroxy-4-methyoxyb
Enzophenone 2- (2'-Hydroxy-5'-methylph
enyl) benzotriazole 2- (2'-Hydroxy-3'-t-butyl-
5'-methylphenyl) -5-chloro
Benzotriazole 2- (2'-Hydroxy-3 ', 5'-di-t-
butyl-phenyl) benzotriazol
e 2- (2'-Hydroxy-3'-undecyl-
5'-methyl-phenyl) benzotri
azole 2- (2'-Hydroxy-5'-t-butyl-
phenyl) benzotriazole 2- (2'-Hydroxy-3 ', 5'-di-t-
(butyl-phenyl) -5-chloroben
ZOTRIAZOLE Zinc oxide fine particles (When zinc oxide fine particles are used as an ultraviolet absorber, the average particle size is preferably 0.1 μm or less.) The support used for the photosensitive material of the present invention is a transparent or non-transparent support. Can be used. Preferably, a plastic support made of glass, a polyethylene compound (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), a triacetate compound (eg, triacetate cellulose, etc.), a polystyrene compound or the like is used. Preferably, polyethylene terephthalate and polyethylene naphthalate are preferred.

The thickness of the support is preferably 50 to 2
It is 50 μm, particularly preferably 70 to 200 μm. The support may be a colorless and transparent support, or a support colored blue with a dye or the like. Particularly preferred is a support colored blue.

In order to further improve the curl and curl of the support, it is preferable to perform a heat treatment after forming the film.

As the developing agent of the developer used for processing the light-sensitive material of the present invention, JP-A-4-15641 is used.
Dihydroxybenzenes, for example, hydroquinone, paraaminophenols, for example, p-aminophenol, N-methyl-p-
Aminophenol, 2,4-diamiphenol, etc., 3
-As the pyrazolidones, for example, 1-phenyl-3-
Pyrazolidones, 1-phenyl-3-pyrazolidone, 1
-Phenyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone, 5,5-dimethyl-1-phenyl-3-
Pyrazolidone and the like, catechol, pyrogallols, ascorbic acids, methol and the like can be used, and it is preferable to use them in combination. It is also preferable to use catechols or ascorbic acids alone.

Preservatives can be used in the developer. Examples of preservatives include sulfites and metabisulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, sodium metabisulfite, reductones such as piperidino Hexose reductone or the like can be used. Those which can be used as a solvent for silver halide are preferably used in such a range that the silver halide is not excessively dissolved.

An alkaline agent can be used for the developer. Examples of the alkaline agent include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate, potassium tertiary phosphate, borate described in JP-A-61-28708, and saccharide described in JP-A-60-93439. Rose, acetoxime, 5-sulfosalicylic acid, phosphate, carbonate and the like may be used.

As a dissolution aid, polyethylene glycols and esters thereof can be contained, and as a sensitizer, for example, a quaternary ammonium salt can be contained.

As a silver sludge inhibitor, JP-A-56-1
No. 06244, silver stain inhibitor, JP-A-3-5184
Sulfide and disulfide compound described in No. 4
A cysteine derivative or a triazine compound described in JP-A-92947 is preferably used.

As the antifoggant, azole organic antifoggants, sodium bromide, potassium bromide, potassium iodide and the like can be used.

As a chelating agent for concealing calcium ions mixed in tap water used in the treatment liquid, there are chelating agents described in JP-A-1-193853, sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate and the like.

The photographic material of the present invention can be treated with a stabilizing solution containing a desensitizing dye such as potassium iodide or phenosafranine in order to prevent baking after image formation.

If necessary, a developing accelerator, a surfactant, an antifoaming agent, a hardening agent and the like can be added to the developing solution. The pH of the developer is preferably adjusted to 8.0 to 12.0. More preferably, it is 9.0-11.5.

The developing temperature is preferably from 10 to 45 ° C.
More preferably, it is 20 to 35 ° C.

The development processing time is preferably from 15 seconds to 3 minutes, more preferably from 20 seconds to 2 minutes. The replenishment of the processing solution replenishes the amount corresponding to the processing fatigue and the oxidative fatigue, but the processing can be performed with a replenishing amount of 25 to 170 ml per 1 m ^{2 of} the photosensitive material. As the replenishment method, a replenishment method based on a width and a feed rate, an area replenishment method, and an area replenishment method controlled by the number of sheets continuously processed may be used.

The temperature of the stabilization and washing bath is preferably between 10 and 45 ° C., and each may be separately adjusted in temperature.

In the processing, a developer comprising a solid processing agent, a bleaching agent, a stabilizer and a replenisher thereof can be used by dissolving them in water. Here, the solid processing agents refer to solid processing agents such as powder processing agents, tablets, pills, and granules. These may be subjected to a moisture-proof treatment as required.

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EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 <Preparation of Silver Halide Emulsions Em1 to 6> Liquid A Pure water 833 ml Gelatin 80 g KBr 0.5 g Liquid B nitrate 60 g pure water 417 ml Liquid C KBr 42 g KI 2.9 g pure water 403 ml ammonia water Put the above solution A in a 3 ml mixing kettle, and put solution B and solution C over 65 seconds.
The mixture was mixed at 50 ° C. After the addition was completed, the temperature was raised to 60 ° C., and after aging for 10 minutes, the temperature was returned to 50 ° C.
6 ml of citric acid was added to adjust the pH.

After the obtained emulsion was cooled and set, it was desalted by a noodle washing method. Next, the amounts of sodium thiosulfate and selenium compound or tellurium compound shown in Table 1 were added,
For 90 minutes. The average grain size of the obtained silver halide emulsions Em1 to Em6 was 100 nm. The standard deviation of the particle size was σ / r = 0.08.

<Preparation of Silver Halide Emulsions Em7-12>
In the preparation of silver halide emulsions Em1-6, the temperature was not raised to 60 [deg.] C. after completion of the addition, and after 10 seconds 6 ml of 40% citric acid
Em-7 to 12 were prepared in the same manner except that was added. The obtained silver halide emulsions Em7 to Em12 had an average particle size of 35 nm and σ / r = 0.07.

The details of the obtained emulsions Em1 to Em12 are shown in Table 1 below.

[0090]

[Table 1]

<Preparation of silver halide photographic light-sensitive material for transmission type hologram> Using Em1 to Em12 described above, coating solutions for a protective layer, a backing layer and a backing protective layer shown below were prepared. The support was made of biaxially stretched polyethylene terephthalate of 175 μm. On one surface, the emulsion layer was coated so that the amount of silver was as specified in the table, and the protective layer was formed so that the amount of gelatin was 0.4.
g / m ² at the same time. 1
~ 192. The amount of gelatin in the silver halide emulsion layer was adjusted such that the silver / gelatin ratio on the emulsion layer side of the support became the amount shown in the table. On the other side, a backing layer is coated so that the amount of gelatin on the backing layer side is 0.8 times the total amount of gelatin on the emulsion layer side, and a backing protective layer is further formed thereon with a gelatin amount of 1.0 g / g. A film sample was obtained by simultaneous multi-layer coating to obtain m ² .

(Silver halide emulsion layer) Spectral sensitizing dye DI (per mole of silver) 0.6 g A (per mole of silver) 0.2 g B (per mole of silver) 3.4 g gelatin (described in Table 1) Formalin (4%) (Per gram of emulsion gelatin) 0.14 ml (Protective layer) (Addition amount per 1 m ² ) Gelatin 0.4 g Sodium-i-amyl-n-decyl-sulfo Succinate 20 mg Compound (1) 18 mg Compound (2) 5 mg Compound (3) 44 mg Fungicide Z 0.6 mg Formalin (4%) 0.8 ml (backing layer) (addition amount per 1 m ² ) Gelatin (on the emulsion layer side) Dye 1 45 mg Dye 2 40 mg Sodium-i-amyl-n-decyl-sulfosuccinate 4 mg Potassium nitrate 50 mg Phosphorus (4%) 1.0 ml (Backing protective layer) (added amount per 1 m ²⁾ of gelatin 1g dye 1 18 mg Dye 2 16 mg Sodium -i- amyl -n- decyl - sulfosuccinate 30mg polymethylmethacrylate (area average Matting agent having a particle size of 3.5 μm) 30 mg compound (3) 0.1 g formalin (4%) 0.4 ml

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<Evaluation of Diffraction Efficiency> Tomographic image information (continuous image information at an equal pitch) of the lower half of the human head by X-ray tomography is recorded as a digital signal in advance on a hard disk of a computer, and this image is obtained. The information is sequentially reproduced on the CRT for each section.

Using the sample obtained above as a photosensitive material,
The RT screen was positioned as a target object, and master hologram exposure was performed based on the stereo hologram technique.
At the time of exposure, the CRT moved the arrangement corresponding to the image reproducing unit.

The light source used at this time was a light beam having a wavelength of 488 nm emitted from a single argon laser light source. These methods followed development information (M) 3/1983.

A master hologram was prepared by developing, bleaching, stabilizing, washing with water, and drying the obtained exposed sample under the following processing conditions.

Subsequently, the obtained master hologram was placed in a place where the photosensitive material was placed at the time of the above-mentioned exposure, with the front and rear surfaces being reversed, and the argon laser of the reference light used for the exposure was irradiated from the same direction to the master hologram. Then, the same unexposed sample as that used for the creation of the master hologram was arranged at the image forming position, and at the same time, the transmission light hologram exposure was performed by irradiating the reference light at 45 degrees.

<Processing conditions> Current image 30 ° C. for 60 seconds Rinse at room temperature for 30 seconds Bleaching 38 ° C. for 45 seconds Rinse at room temperature for 30 seconds Stabilization Room temperature for 30 seconds Drying at 50 ° C. for 15 seconds Developer L-ascorbic acid 15 g Sodium carbonate 20 g Sodium hydroxide 6 g Sodium bromide 0.8 g Phenidone 0.3 g Make up to 1 liter with water.

Bleaching solution HOOH ₂ CN (CH ₂ CONH ₂ ) ₂ 0.3 mol Ethylenediaminetetraacetic acid 0.03 mol KBr 1.3 mol Glacial acetic acid 50 ml The pH is adjusted to 4.5 with ammonia water or acetic acid. And make up to 1 liter with water.

Stabilizing solution 2.5 g of potassium iodide was dissolved in water to make 1 liter.

The obtained hologram sample was irradiated with a certain amount of iodine quartz lamp light from the reference light irradiation direction, and the brightness of the formed stereoscopic image was visually evaluated on four ranks A, B, C, and D, and diffraction efficiency was evaluated. Was evaluated. The level at which a three-dimensional image could hardly be recognized was D, and the one with high brightness and excellent diffraction efficiency was A.

<Evaluation of suitability for rapid processing> The obtained coated sample was exposed to sunlight on a sunny day for 1 minute, and the same treatment as above was performed. The bleaching property was visually evaluated by the following three ranks. And the evaluation value of suitability for rapid processing.

A: All developed silver is bleached. B: A little developed silver remains, which is a practically problematic level. C: A large amount of developed silver is left, a practically problematic level. 2 to 5.

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

[Table 4]

[0109]

[Table 5]

As is clear from the table, the sample according to the present invention has excellent rapid processing property and diffraction efficiency as compared with the comparative sample, and can be obtained as a silver halide photographic material for holograms. I understand.

[0111]

As demonstrated in the examples, according to the present invention, a silver halide photographic light-sensitive material for a hologram excellent in rapid processing suitability and diffraction efficiency can be obtained.

Claims (1)

[Claims] 1. A hologram silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, wherein the silver halide emulsion layer has an average particle size of 5%. -50 nm, containing a selenium or tellurium compound and containing silver / silver on the silver halide emulsion layer side
The gelatin ratio is 0.2-2.0 and the coated silver amount is 1-3 g / m
^{2. A} silver halide photographic material for holograms, which is ² .