JPH103250A - Silver halide photographic sensitive material for hologram and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make rapid processing possible and to improve diffraction efficiency by processing a photosensitive material having specific silver halide emulsion layers with a bleaching bath having the ferric complex salt of specific compds. SOLUTION: This photosensitive material has the silver halide emulsion layers of 10 to 50mm in the average grain size of silver halide grains, 0.2 to 2.0 in a silver/gelatin ratio and 1 to 3g/m<2> in the coated amt. of silver. This processing method has a stage of processing this material with the bleaching bath contg. the ferric complex salt selected from the compds. expressed by formulas I to III. In the formula I, A1 to A4 denote -CH2 OH, -PO3 (M)2 , etc., M denotes a hydrogen atom, alkaline metal atom, etc.; X denotes 2 to 6C alkyl group, an org. group forming a ring, etc.; n1 to n4 are integers of >=1 and at least one thereof is >=2. In the formula II, A5 to A8 are synonymous with A1 to A4 ; X denotes 2 to 6C alkyl group, etc. In the formula III, A9 to A12 are hydrogen atoms, hydroxyl groups, -COOM1 , -PO3 (M)2 , etc., and at least one thereof is -COOM1 , -PO3 (M)2 , etc.; M, M1 denote hydrogen atoms, alkaline metal atoms, etc.

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, and more particularly to a silver halide photographic material for holograms which can be rapidly processed and a processing method thereof.

[0002]

2. Description of the Related Art Holograms have been gradually and widely used for appreciation or medical use in recent years. Above all, attention has been paid to bright phase holograms of images.

A hologram is a method in which a wave of light 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 having a high resolution and sufficient sensitivity that can be used for this hologram, a silver halide photosensitive material can be mentioned. Further, in order to obtain a bright reproduced image with a hologram, it is necessary to have a high diffraction efficiency. In order to increase the diffraction efficiency, the silver halide light-sensitive material may be increased in the amount of coated silver. However, when the amount of coated silver is increased, the developing speed decreases, and it takes time to obtain an image.

If the developing solution is activated, for example, to increase the developing speed, the filaments of the developed silver are apt to elongate, so that the gap between the developed silver is increased and the resolution of the image is reduced. As a result, the amplitude of the phase modulation does not increase, the diffraction efficiency decreases, and a bright reproduced image cannot be obtained.

Accordingly, a silver halide photographic light-sensitive material for hologram, which has a bright and clear reproduced image, high diffraction efficiency, and can be processed quickly, is strongly desired, for example, disclosed in US Pat. No. 4,720,441. A method of using potassium iodide before bleaching, or a method of performing hardening after development processing disclosed in JP-A-3,695,879 is known. However, these prior arts cannot be said to be sufficient, and further improvement is required.

[0007] In order to obtain a phase hologram using a silver halide photographic light-sensitive material, it is necessary to perform a bleaching process after the development process. Hitherto, bichromate has been used as a bleaching agent because of its high oxidizing power and great power to enhance the tanning effect. The term “tanning effect” as used herein refers to a phenomenon in which a developing agent oxide crosslinks gelatin molecules during development, and locally hardens gelatin around developed silver particles. When bleaching is performed after development to enhance this tanning effect, when the developed silver is bleached and turned into larger silver salt particles, it forms a gelatin shell with a higher refractive index than the surrounding gelatin. This is the reason why the phase modulation due to the presence or absence of the silver salt caused by bleaching is further enhanced, and the diffraction efficiency is increased.

However, since chromium in bichromate, which is currently used as a bleaching agent, is a heavy metal, it is not preferable from the viewpoint of environmental friendliness in recent years. In addition, a new technique for obtaining a hologram with high diffraction efficiency has been strongly desired.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photosensitive material for holograms which can be rapidly processed and has a high diffraction efficiency, and a processing method therefor.

[0010]

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

(1) The average grain size of silver halide grains is 10
In up to 50 nm, the silver / gelatin ratio is a 0.2 to 2.0, and, the hologram silver halide having at least one silver halide emulsion layer coated amount of silver is 1 to 3 g / m ² In a method for processing a photographic light-sensitive material, a step of processing with a bleaching solution containing at least one ferric complex salt selected from the compounds represented by the following general formulas (A), (B) and (C) A method for processing a silver halide photographic light-sensitive material for holograms, comprising:

[0012]

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Wherein A ₁ , A ₂ , A ₃ , and A ₄ each represent -C
H ₂ OH, —PO ₃ (M) ₂ or —COOM _1, which may be the same or different. M or M ₁ is a hydrogen atom, an alkali metal atom (eg, Na, K, Li, etc.) or another cation (eg, Na ⁺ , K ⁺ , Li ⁺ , N
H ₄ ⁺ , HN (C ₂ H ₅ ) ₃ ⁺ , pyridinium cation, etc.). X is an organic group having a saturated or unsaturated to form an alkylene group or a ring of 2 to 6 carbon atoms - (B ₁ O) n
-B ₂ - represents a. n represents an integer of 1 to 8, and B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. n1, n2, n3, and n4 each represent an integer of 1 or more, and may be the same or different;
At least one is two or more. ]

[0014]

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Wherein A ₅ , A ₆ , A ₇ , and A ₈ each represent -C
H ₂ OH, —PO ₃ (M) ₂ or —COOM _1, which may be the same or different. M and M ₁ represent a hydrogen atom, an alkali metal atom or another cation, and have the same meaning as described above. X is an alkylene group having 2 to 6 carbon atoms _{- (B 1 O) n-} B 2 - represents a. n represents an integer of 1 to 8, and B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. ]

[0016]

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[In the formula, A ₉ , A ₁₀ , A ₁₁ and A ₁₂ may be the same or different, and each represents a hydrogen atom, a hydroxyl group,
_{-COOM 1, -PO 3 (M)} 2, -CH 2 COOM 1, -
Represents CH ₂ OH or a lower alkyl group (for example, a methyl, ethyl, propyl, butypentyl group, etc.), provided that A
₉ at least one of to A ₁₂ are -CH ₂ COOM _1, -CO
An OM ₁ or -PO ₃ (M) _2, M and M ₁ represents a hydrogen atom, an alkali metal atom or an ammonium group, as defined above. (2) The silver halide photographic material for holograms according to (1), further comprising a step of treating with a bleaching solution containing a ferric complex salt of the compound represented by formula (A). Processing method.

(3) The silver halide photograph for hologram according to (1), further comprising a step of treating with a bleaching solution containing a ferric complex salt of the compound represented by the formula (B). Processing method of photosensitive material.

(4) The average grain size of the silver halide grains is 10
The silver / gelatin ratio is 0.2 to 2.0, the coated silver amount is 1 to 3 g / m ² , and the melting time of the silver halide emulsion layer is 15 to 120 minutes. A silver halide photographic light-sensitive material for holograms, comprising at least one silver halide emulsion layer.

Hereinafter, the present invention will be described in detail.

The silver halide photographic light-sensitive material for holograms according to 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 silver halide grain size, but the average particle diameter of the silver halide particles used in the silver halide light-sensitive material of the present invention is 10 to 50 nm. Particularly preferred average grain size of silver halide grains is 1
0 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 is preferred because of the drawbacks such as insufficient sensitivity, contamination of images and processing solutions, and poor storage stability of the photosensitive material. Absent.

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 particle size is defined as a particle having a spherical shape or a particle approximate 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.

The silver halide composition may be any of silver chloride, silver iodide, silver bromide, silver iodobromide, silver chloroiodobromide, etc., and preferably has a silver iodide content of 5.0 mol%. The following silver iodobromide emulsions are shown.

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 grown continuously 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 particularly 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 producing 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 of the silver halide photographic light-sensitive material for holograms 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, but 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 or the cost, and the like. 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 15 minutes or more and 12 minutes or more.
It is preferably 0 minute or less and 15 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 increasing the melting time of the photosensitive layer, that is, increasing the hardness of the silver halide emulsion layer is effective.

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.

The term "melting time" used in the present invention means that a silver halide emulsion layer contains 1.5% of sodium hydroxide at 60 ° C.
It means the time required for dissolution in an aqueous solution.

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

In the bleaching step, a bleaching solution containing at least one ferric complex salt selected from the compounds represented by formulas (A), (B) and (C) is used. .

Hereinafter, specific examples of the compounds represented by formulas (A), (B) and (C) used in the present invention will be shown, but the present invention is not limited thereto.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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Of the above compounds, those represented by formula (B) are described in, for example, JP-A-63-199295 and
No. 173857, THE JOURNAL OF A
NTIBIOTICS, VOL, XXXVII, No.
4, pp 426 (APR. 1984) and the like. The compounds represented by formulas (A) and (C) can also be obtained by a method according to the above method or as a commercial product.

The ferric complex salt of the above compound is preferably used in an amount of 0.15 to 0.8 mol, more preferably 0.18 to 0.6 mol, per liter of the bleaching solution.
The pH of the bleaching solution is from 2.0 to 6.0, preferably from 2.5 to 5.5. The bleaching time is preferably from 15 seconds to 5 minutes, more preferably from 20 seconds to 3 minutes. The bleaching temperature is preferably from 10 to 45 ° C.

A bleaching accelerator may be used in the bleaching solution according to the present invention, for example, Japanese Patent Publication Nos. 45-35754 and 58-58.
And thiourea derivatives described in U.S. Pat. No. 4,126,459.

The bleaching solution according to the present invention may contain, if desired, compounds commonly used in processing agents, for example, preservatives, pH buffering agents, pH adjusters, chelating agents capable of softening water and the like. .

The silver halide emulsion of the silver halide photographic light-sensitive material according to the present invention may or may not be subjected to chemical sensitization by a conventional method.

The silver halide emulsion can be spectrally sensitized to a desired wavelength by using a sensitizing dye. Sensitizing dyes that can be used include cyanines, merocyanines, complex cyanines, complex merocyanines, holopolar cyanines, hemicyanines, styryl dyes and hemioxonol dyes. 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 are used. In addition, alkali-treated gelatin of those gelatins,
Acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 1
0,000) and modified gelatin such as phthalated gelatin. Other hydrophilic colloids can also be used.

Further, a commonly 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 fog 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 a matting agent, a homopolymer of polymethyl methacrylate or a polymer of methyl methacrylate and methacrylic acid, an organic compound such as starch, and fine particles of an inorganic compound such as silica, titanium dioxide, strontium sulfate, and barium sulfate can be used in combination.

In the silver halide photographic light-sensitive material for holograms of the present invention, for example, chromium salts, aldehydes, N-methylol compounds, dioxane derivatives, active vinyl compounds, active halogen compounds, mucohalogen 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).

The silver halide light-sensitive material used in the present invention has a layer containing an antihalation dye corresponding to the exposure wavelength on the side opposite to the side having the silver halide emulsion layer in order to prevent halation upon exposure. Is preferred. In the light-sensitive material, an irradiation preventing dye corresponding to the exposure wavelength can be added to the emulsion layer in order to prevent irradiation of the emulsion layer.

The silver halide light-sensitive material used in the present invention may contain fine solid dye particles in a non-light-sensitive layer between the 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. In particular, it is substantially water-insoluble at pH 7 or lower,
Further, a dye having a water-soluble structure at a pH of 10 or more is an excellent embodiment in terms of production and cost.

The silver halide photosensitive material according to the present invention includes:
An ultraviolet light absorber can be added in order to prevent baking out of the silver halide after processing. Examples of the ultraviolet light absorber that can be used in the present invention 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 a UV absorber, the average particle diameter 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 film formation.

In the silver halide light-sensitive material for hologram and the processing method thereof according to the present invention, after exposure, development, bleaching,
It is composed of treatment steps including at least four processes of stabilization treatment, washing and drying. Of these, washing or stabilizing treatment may be omitted. It is more preferable to perform a water washing treatment between the bleaching treatment and the stabilization treatment.

Examples of the developing agent of the developer used in the present invention include dihydroxybenzenes such as hydroquinone and paraaminophenols such as p-aminophenol and N-type described in JP-A-4-15641 and JP-A-4-16841. Methyl-p-aminophenol, 2,4-
As 3-pyrazolidones such as diamiphenol,
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, ascorbate, and methol can be used. It is preferable to use them in combination. More preferably, catechols or ascorbates are used alone.

A preservative can be used in the developer. As a preservative, sulfites and metabisulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, sodium metabisulfite, and reductones such as piperidinohexose reductone 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 alkali agent can be used for the developer. As the alkaline agent, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate, potassium tertiary phosphate,
Borate described in JP-A-61-28708;
93439, saccharose, acetoxime, 5
-Sulfosalicylic acid, phosphates, carbonates and the like may be used.

As dissolution aids, polyethylene glycols and esters thereof can be contained, and as sensitizers, for example, quaternary ammonium salts 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.

In the silver halide light-sensitive material for holograms and the processing method according to the present invention, in order to prevent baking after image formation, stabilization containing a desensitizing dye such as potassium iodide or phenosafuranine is performed. It can be treated with a liquid.

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, and more preferably from 20 seconds to 2 minutes.

In the processing method of the present invention, replenishment of the processing solution replenishes processing fatigue and oxidative fatigue, but can be performed with a replenishing amount of 25 to 170 ml per m ^{2 of} the photographic material. As the replenishment method, replenishment method by width, feed speed,
The area replenishment method and the 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 present invention, a developer, a bleaching solution and a stabilizing solution obtained by dissolving a developer, a bleaching agent and a stabilizer comprising a solid processing agent in water can be used.
The solid processing agents include powder processing agents, solid processing agents such as tablets, pills, and granules, and have been subjected to moisture proof processing as necessary.

[0082]

The present invention will be described below with reference to examples.

Embodiment 1 Put the above solution A in a mixing pot, and put solution B and solution C for 65 seconds.
The mixture was mixed at 50 ° C. 10 seconds after completion of addition, 40
% 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, 15 mg of sodium thiosulfate was added and subjected to chemical ripening at 60 ° C. for 90 minutes. The average grain size of the obtained silver halide emulsion Em1 was 0.035 μm,
σ / r = 0.08.

<Preparation of a silver halide photographic light-sensitive material for a transmission type hologram>
Each coating solution for the backing layer and the backing protective layer was prepared. The support was made of 175 μm biaxially stretched polyethylene terephthalate. On one surface, the silver content of the emulsion layer was set as shown in Table 1, and the gelatin content of the protective layer was 0.4 g / g.
m ² at the same time. 1-1
To 1-16. The amount of gelatin in the silver halide emulsion layer was adjusted so that the silver / Gel ratio on the emulsion layer side of the support was as shown in Table 1. 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 Marine (4%) 1.0 ml (backing protective layer) (addition amount per 1 m ² ) Gelatin 1 g Dye 1 18 mg Dye 2 16 mg Sodium-i-amyl-n-decyl-sulfosuccinate 30 mg Polymethyl methacrylate (area average) Matting agent having a particle size of 3.5 μm) 30 mg compound (3) 0.1 g formalin (4%) 0.4 ml

[0087]

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[0088]

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<Evaluation of Diffraction Efficiency> Using a holographic camera FUJINON FH-40 (with a He-Ne laser, reference light incident at 45 °, Fujifilm [manufactured by Fujifilm]), the hollow perfect diffusion reflector was beam-balanced. 3 and the exposure amount was changed. 1-1 to 1-16 were recorded. (Note that this exposure method is a method described in Optics. Vol. 16, No. 10, October 1987, p. 445).

The obtained exposed sample was processed under the following processing conditions to obtain a hologram sample no. 1-1 to 1-64 were prepared.

Processing conditions Current image 30 ° C. 60 seconds Rinse at room temperature 30 seconds Bleaching 38 ° C. 45 seconds Rinse at room temperature 30 seconds Stabilized at room temperature 30 seconds Drying 50 ° C. 15 seconds Developing solution 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 Ferric salt of organic acid (bleaching agent described in Tables 1 and 2) 0.3 mol Ethylenediaminetetraacetic acid 0.03 mol KBr 1.3 mol Glacial acetic acid 50 ml Aqueous ammonia or acetic acid is used to adjust the pH to 4 Adjust to 5 and make up to 1 liter with water.

HOOCH ₂ C was used as a comparative bleaching agent.
-N Using (CH ₂ CONH) _2.

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

The obtained hologram sample was irradiated with a fixed amount of iodine quartz lamp light from the reference light irradiation direction, and the brightness of the formed stereoscopic image was visually evaluated in three ranks A, B, and C to evaluate the diffraction efficiency. Value. The level at which a three-dimensional image could hardly be recognized was C, and the level at which the brightness was high and the diffraction efficiency was excellent 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 the developed silver is bleached. B: A little developed silver remains, which is a practically problematic level. C: A considerable amount of developed silver is left, a practically problematic level. 1 and 2.

[0098]

[Table 1]

[0099]

[Table 2]

As is clear from Tables 1 and 2, when the sample according to the present invention was processed using the bleaching agent of the present invention, all of them were excellent in rapid processing suitability and diffraction efficiency, and were used as silver halide photographic materials for holograms. It can be seen that it has the suitability of

Example 2 The hardening degree was changed by changing the amount of formalin added to the emulsion layer in Example 1 as shown in Tables 3 and 4 below. The hologram sample No. 1 was prepared in the same manner as in Example 1 except that only the comparative bleaching agent was used as the bleaching agent. 2-1 to 2-6
4 was obtained. The obtained samples were evaluated for diffraction efficiency and suitability for rapid processing in the same manner as in Example 1. The melting time of the emulsion layer was measured by the method described above. Tables 3 and 4 show the obtained results.

[0102]

[Table 3]

[0103]

[Table 4]

As is clear from the results in Tables 3 and 4, the silver halide light-sensitive material for holograms according to the present invention, in which the melting time of the emulsion layer was increased, was treated with a bleaching agent, which was outside the scope of the present invention. However, it can be seen that they are excellent in rapid processing suitability and diffraction efficiency.

[0105]

As demonstrated in the examples, according to the present invention, a silver halide photographic light-sensitive material for holograms having excellent suitability for rapid processing and excellent diffraction efficiency and a processing method therefor were obtained.

Claims (4)

[Claims] An average particle diameter of silver halide grains is from 10 to 5.
0 nm, the silver / gelatin ratio is 0.2-2.0,
In a method for processing a hologram silver halide photographic material having at least one silver halide emulsion layer having a coated silver amount of 1 to 3 g / m ² , the following general formulas (A) and (B) And a process of processing with a bleaching solution containing at least one ferric complex salt selected from the compounds represented by (C). Embedded image [Wherein A ₁ , A ₂ , A ₃ , and A ₄ are each —CH ₂ OH,
PO ₃ (M) ₂ or —COOM _1, which may be the same or different. M and M ₁ represent a hydrogen atom, an alkali metal atom or another cation. X is an organic group of a saturated or unsaturated or form an alkylene group or a ring of 2 to 6 carbon atoms - represents a _{- (B 1 O) n-} B 2. n represents an integer of 1 to 8, and B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms.
n1, n2, n3, and n4 each represent an integer of 1 or more, and may be the same or different, and at least one is 2 or more. [Chemical formula 2] [Wherein A ₅ , A ₆ , A ₇ , and A ₈ are each —CH ₂ OH, −
PO ₃ (M) ₂ or —COOM _1, which may be the same or different. M and M ₁ represent a hydrogen atom, an alkali metal atom or another cation. X is an alkylene group having 2 to 6 carbon atoms _{- (B 1 O) n-} B 2 - represents a. n represents an integer of 1 to 8, and B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. [Chemical formula 3] [Wherein A ₉ , A ₁₀ , A ₁₁ , and A ₁₂ may be the same or different, and each represents a hydrogen atom, a hydroxyl group, -COO
M ₁ , —PO ₃ (M) ₂ , —CH ₂ COOM ₁ , —CH ₂ OH
Or a lower alkyl group, provided that at least one of A _{9 to} A ₁₂ is —CH ₂ COOM ₁ , —COOM ₁ or —PO ₃
(M) ₂ , wherein M and M ₁ represent a hydrogen atom, an alkali metal atom or an ammonium group. ] 2. A holographic silver halide photographic material according to claim 1, further comprising a step of treating with a bleaching solution containing a ferric complex salt of the compound represented by the general formula (A). Processing method. 3. The silver halide photographic light-sensitive material for holograms according to claim 1, further comprising a step of treating with a bleaching solution containing a ferric complex salt of the compound represented by the general formula (B). Processing method. 4. The silver halide grains having an average particle size of 10 to 5
0 nm, the silver / gelatin ratio is 0.2-2.0,
And a silver halide emulsion layer having at least one silver halide emulsion layer having a coating silver amount of 1 to 3 g / m ² and a melting time of the silver halide emulsion layer of 15 to 120 minutes. Silver photographic photosensitive material.