JPH10149083A - Silver halide photosensitive material for hologram - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material capable of quick processing and having a stable property with high diffraction efficiency by providing a silver halide emulsion subjected to ultrafiltration in which the silver halide grain contained in a photosensitive silver halide emulsion layer has a specified average grain size, and setting the silver/gelatin ratio to a specified value. SOLUTION: A silver halide photosensitive material for hologram is of transmission type, and as the resolving force of the photosensitive material is higher, the more preferable reproduced image can be provided. The resolving force of the photosensitive material is significantly influenced by the size of silver halide grain. Therefore, the average grain size of the silver halide grain used for the silver halide photosensitive material is set to 10-50nm. In the silver halide emulsion used for the photosensitive material, unnecessary soluble salts are removed by ultrafiltration after formation of silver halide grains. The resulting silver halide photosensitive material has a silver/gelatin ratio of 0.2-2.0 on the silver halide emulsion side. According to such a structure, the photosensitive material excellent in quick processing adaptability and diffraction efficiency can be provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material for holograms. More specifically, the present invention relates to a silver halide photographic material for holograms which can be rapidly processed and has stable photographic performance.

[0002]

2. Description of the Related Art The application range of holograms has been gradually expanding in recent years for appreciation or medical use. 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 material for a hologram, which has a bright and clear reproduced image, a high diffraction efficiency, and can be processed quickly, is strongly desired, for example, in US Pat. No. 4,720,441. The disclosed method using potassium iodide before bleaching, or 3,695,879
And a method of performing hardening after the development treatment disclosed in Japanese Patent Application Laid-Open No. H11-260, 1988.

[0007] However, these prior arts are not satisfactory, and further improvement is required.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to enable rapid processing and high diffraction efficiency.
It is an object of the present invention to provide a hologram silver halide photographic light-sensitive material capable of obtaining stable photographic light-sensitive material performance.

[0009]

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

That is, the silver halide grains contained in at least one photosensitive silver halide emulsion layer have an average grain size of 1
A silver halide photographic material for holograms, which is a silver halide emulsion having a silver / gelatin ratio of 0 to 50 nm and ultrafiltered, and having a silver / gelatin ratio of 0.2 to 2.0.

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 disadvantageous in that the sensitivity is insufficient, the image and the processing solution are contaminated, and the storage stability of the light-sensitive material is not excellent. 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 refers to 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.

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, a silver nitrate aqueous solution and a water-soluble halide aqueous solution 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 any other shapes. 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 ( (Including a complex salt), and a metal ion can be added to the inside of the particle and / or the surface of the particle to contain these metal elements.

Considering the effect of improving the high illuminance failure characteristics, a 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.

The silver halide emulsion used in the light-sensitive material of the present invention is characterized in that unnecessary soluble salts are removed by ultrafiltration after forming silver halide grains.

Ultrafiltration is a method of purifying colloidal particles larger than the pores of a membrane by pressing a colloidal solution against the membrane under pressure to pass a substance having a smaller particle size than the pores of the membrane. By selecting the size of the pores of the membrane, the size of the colloidal particles to be purified can be selected. By repeatedly passing the colloid solution through the ultrafiltration membrane while adding water and washing, the efficiency of purifying the colloid particles can be improved. Further, if ultrafiltration is performed while applying a voltage to the electrodes on both sides of the membrane, the colloid particles can be purified more efficiently. In the case of ultrafiltration of silver halide as in the present invention, unnecessary inorganic salts are passed through a membrane to obtain a residue composed of silver halide grains and a peptizer (mainly gelatin).

A desalting method using an ultrafiltration unit will be described.

FIG. 1 is a conceptual diagram showing one example of desalting by the ultrafiltration device (ultrafiltration membrane) used in the present invention. In FIG. 1, a silver halide emulsion after completion of physical ripening in a reaction tank 1 is sent to an ultrafiltration device 5 by a pump 3 through a valve 2, and is subjected to an ultrafiltration membrane 6 to remove inorganic ions or the like. The part is separated and removed as waste liquid and desalted. The waste liquid is discharged through a waste liquid outlet 7.

As shown in FIG. 1, a circulation loop is formed by the ultrafiltration device 5 and the conduits 4, 8, and 9, and the flow of the emulsion in the circulation loop is advanced by the pump 3. As the emulsion repeatedly passes through the ultrafiltration apparatus, the degree of desalination increases.

The pressure of the emulsion 3 in contact with the ultrafiltration membrane 6 can be adjusted by adjusting the flow rate of the pump 3, and this pressure can be monitored by the pressure gauges 10 and 11. To terminate the desalting and return the emulsion to the reaction tank, the control valve 13 is a three-way valve, which is adjusted so that the emulsion returns to the reaction tank without passing through the conduit 9. Whether the emulsion returned to the reaction tank has a desired salt concentration can be confirmed by the conductivity meter 12. The stirring device 14 is used during physical ripening of the emulsion or during re-dispersion after desalting.

The ultrafiltration is carried out by circulating the dispersion in the reaction vessel while making contact with the semipermeable ultrafiltration membrane so that a pressure difference is generated across the semipermeable ultrafiltration membrane. Is preferred.

Suitable membranes that are permeable to only molecules of a particular size or less and that contain pores sized to retain the larger molecules and silver halide grains in the dispersion are about 500-500. It can be selected from those exhibiting a permeation cutoff in the molecular weight range of 300,000 or more, preferably about 500 to 50,000.

The membrane used for ultrafiltration typically uses a very thin layer with a very fine porous structure, and the pressure of the dispersion in contact with the ultrafiltration membrane can vary over a wide range. Typically, the pressure of the reaction vessel in contact with the ultrafiltration membrane is about 7.03
kg / cm ² and the outlet pressure of the retentate is about 0.703
kg / cm ² or less. The pressure differential across the membrane is typically about 2.81~4.22kg / cm ^2. Of course, operating at pressures outside these ranges depending on the structure of the reaction vessel and the ultrafiltration membrane, the viscosity of the dispersion, the concentration of the retentate and the desired purity of the retentate are within the skill of a person skilled in the art. . There is an anisotropic film supported and included on a thicker porous structure layer.

These useful membranes include various polymeric substances such as polyvinyl chloride, polyvinyl carboxylate, polyvinyl formate, polyvinyl acetate, polyvinyl alcohol, polysulfone, polyvinyl ether, polyacrylamide,
Polyacrylonitrile, polymethacrylamide, polyimide, polyester, polyfluoroalkylene (polytetrafluoroethylene, polyvinylidene fluoride, etc.), and cellulosic polymers (cellulose and cellulose esters such as cellulose acetate, cellulose butyrate, cellulose acetate butyrate, etc.) And so on.

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 suitability of the 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 between 0.2 and 2.0. 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 optional, but is preferably 1 to 3 g / m ² . More preferably, it is 1.2 to 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 holograms of the present invention can take any value, but is preferably 15 minutes to 120 minutes, more preferably 15 to 90 minutes. .

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

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. Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in RD. 1764
3 (December 1978), page 23, IV, section J.

Gelatin is preferably used as a dispersion medium for the protective colloid of the silver halide grains, and ossein gelatin, pigskin gelatin and the like are used as gelatin. 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 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 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.

The silver halide photographic light-sensitive material for holograms of the present invention contains, as a hardening agent, for example, a chromium salt, an aldehyde, an N-methylol compound, a dioxane derivative, an active vinyl compound, an active halogen compound, a mucohalogen acid,
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).

In the silver halide photographic light-sensitive material used in the present invention, a layer containing an antihalation dye corresponding to the exposure wavelength is provided on the side opposite to the side having the silver halide emulsion layer in order to prevent halation upon exposure. It is preferred to have. 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 photographic light-sensitive material used in the present invention may contain fine particles of solid disperse dye in the 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. 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 silver halide photographic light-sensitive material according to the present invention may contain an ultraviolet light absorber in order to prevent baking out of the processed silver halide. 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.

The hologram silver halide photographic light-sensitive material and the processing method according to the present invention comprise, after exposure, processing steps including at least four processes of development, bleaching, stabilization, 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 para-aminophenols 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.

Examples of chelating agents for concealing calcium ions mixed in tap water used in the treatment liquid include chelating agents described in JP-A-1-193853, sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate and the like.

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

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, the replenishment of the processing solution replenishes the processing fatigue and the oxidative fatigue, but the processing can be performed at a replenishing rate of 25 to 170 ml per 1 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 bleaching solution according to the present invention may contain a bleaching accelerator. 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 such as preservatives, pH buffering agents, pH adjusters, chelating agents capable of softening water and the like. .

The pH of the bleaching solution is from 2.0 to 6.0,
Preferably it is 2.5-5.5. Bleaching time is 15
The time is preferably from 5 seconds to 5 minutes, more preferably from 20 seconds to 3 minutes. The bleaching temperature is preferably from 10 to 45 ° C.

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

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 also 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.

[0070]

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

Example 1 <Preparation of silver halide emulsion Em1> 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 14.3 ml mixed Put the above solution A in a kettle, 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.
m, σ / r = 0.08.

<Preparation of Silver Halide Emulsion Em2> Em1
Was prepared in the same manner except that the desalting method was ultrafiltration by the method of the present invention.

<Preparation of Comparative Silver Halide Emulsion Em3> While maintaining the silver potential of the mixed solution at 100 mV, the mixing temperature was adjusted to 55
C. and a comparative silver halide emulsion Em3 was prepared in the same manner as Em1, except that the mixing time was changed to 11 minutes. The average grain size of the obtained silver halide emulsion Em3 was 0.10 μm,
σ / r = 0.08.

<Preparation of Comparative Silver Halide Emulsion Em4>
Em4 was prepared in the same manner as in the preparation of m3 except that the desalting method was ultrafiltration by the method of the present invention.

<Preparation of silver halide photographic light-sensitive material for transmission type hologram> Using the above-mentioned Em1, Em2, Em3 and Em4, the following coating solutions for the protective layer, backing layer and backing protective layer were prepared. The support is made of 175 μm biaxially stretched polyethylene terephthalate. On one surface, the emulsion layer has a silver content of 1.4 g / m ² , and the protective layer has a gelatin content of 0.4 g / m ² . Coating was performed simultaneously and the coating sample No. 1-16 were obtained. The amount of gelatin in the silver halide emulsion layer is determined by the ratio of silver / Ge on the emulsion layer side of the support.
The ratio was adjusted so that the 1 ratio became the amount 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.
A silver halide photographic light-sensitive material sample was obtained by simultaneous multi-layer coating at 0 g / m ² .

(Silver halide emulsion layer) Spectral sensitizing dye DI (per mole of silver) 0.6 g Compound A (per mole of silver) 0.2 g Compound B (per mole of silver) 3.4 g Gelatin (Table 1) (Amount resulting in the stated silver / Gel ratio) 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- Sulfosuccinate 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 (emulsion layer) Dye 1 45 mg Dye 2 40 mg Sodium-i-amyl-n-decyl-sulfosuccinate 4 mg Potassium nitrate 0mg formalin (4%) 1.0 ml (Backing protective layer) (1 m ² added per) Gelatin 1g dye 1 18 mg Dye 2 16 mg Sodium -i- amyl -n- decyl - sulfosuccinate 30mg polymethylmethacrylate (area Matting agent having an average particle size of 3.5 μm) 30 mg compound (3) 0.1 g formalin (4%) 0.4 ml

[0078]

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[0079]

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<Evaluation of Diffraction Efficiency> 100 images of tomographic image information of the lower half of the human head by X-ray tomography (image information continuous at equal pitches) are recorded in advance as digital signals on a hard disk of a computer, The image information is sequentially reproduced on the CRT for each section.
The sample obtained above was used as a photosensitive material, the CRT screen was positioned as a target object, and exposure for a master hologram was performed based on the technique of tomographic multicolor exposure hologram.

At this time, a light beam having a wavelength of 488 nm oscillated from a single Ar laser light source is split into object light and reference light using a half mirror, and the reference light enters the photosensitive surface of the sample at an angle of 45 degrees. The object light was radiated onto a CRT screen placed parallel to the sample and subjected to master hologram exposure based on the technique of tomographic multicolor exposure hologram.

At the time of exposure, the CRT moved the arrangement corresponding to the image reproducing section. The exposed sample thus obtained was developed, bleached, stabilized with KI, washed with water and dried under the following processing solutions and processing conditions to prepare a master hologram. continue,
The obtained master hologram is placed at the place where the photosensitive material was placed at the time of the exposure, with the front and back arranged upside down, and a reference light Ar laser used for the exposure is irradiated on the master hologram from the same direction to form a three-dimensional image. An image was formed, and the same unexposed sample as that used for forming the master hologram was arranged at the image forming position, and simultaneously, the reference light was irradiated at 45 degrees to perform image hologram exposure. This exposed sample is
Development, bleaching, KI stabilization, washing with water, and drying were performed under the following processing solutions and processing conditions to prepare a transmission hologram.

Processing conditions Current image 30 ° C. for 60 seconds Rinse at room temperature for 30 seconds Bleaching 38 ° C. for 45 seconds Rinse for water at room temperature for 30 seconds Stabilized at room temperature for 30 seconds Drying at 50 ° C. for 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 HOOCH 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 was adjusted to 4.5 with ammonia water or acetic acid. ,
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 is irradiated with a certain amount of iodine quartz lamp light from the reference light irradiation direction, and the brightness of the formed stereoscopic image is 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> a. Processing stability Sensitometry at initial and equilibrium levels was measured to evaluate processing stability. The values in Table 1 are shown as relative sensitivities when the sensitivity value at the initial level is 100.
The sensitivity was determined according to a standard method, after wedge exposure using an Ar laser sensitometer, development with the above-mentioned developer and developing conditions, followed by fixing with Konica Corporation's CFL871 fixer, washing with water, drying, and image density. Was measured as a logarithm of the reciprocal of the amount of light to obtain a density of 1.0. Table 1 shows the obtained results.

B. Bleaching property The obtained coating 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. did.

A: All developed silver has been bleached. B: A small amount of developed silver remains, causing a problem in practical use. C: A considerable amount of developed silver remains, causing a problem in practical use.

C. Residual Color The unexposed sample of each sample was subjected to the above-mentioned development treatment, and residual color contamination was visually evaluated by the following three-stage evaluation.

A: no residual color B: slightly residual color but acceptable level C: residual color too high for practical use

Table 1 shows the above results.

[0093]

[Table 1]

As is evident from Table 1, the sample of the present invention is suitable for rapid processing and excellent in diffraction efficiency and suitable as a silver halide photographic material for holograms.

[0095]

According to the present invention, a silver halide photographic light-sensitive material for hologram having excellent suitability for rapid processing and excellent diffraction efficiency was obtained.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an example of desalination by an ultrafiltration device used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Reaction tank 2 Valve 3 Pump 4 Conduit 5 Ultrafiltration device 6 Ultrafiltration membrane 7 Waste liquid discharge port 8 Conduit 9 Conduit 10 Pressure gauge 11 Pressure gauge 12 Conductivity meter 13 Control valve 14 Stirrer

Claims (1)

[Claims] An average particle diameter of silver halide grains contained in at least one photosensitive silver halide emulsion layer is 10 to 10.
A silver halide photographic light-sensitive material for holograms, which is a silver halide emulsion having a thickness of 50 nm and ultrafiltered, and having a silver / gelatin ratio of 0.2 to 2.0.