JPH09251199A - Silver halide photosensitive material for transmission type hologram and image forming method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photosensitive material for transmission type hologram excellent in resolving power, having high efficiency of diffraction, excellent in image preservability and hardly causing image stain due to a residual color, etc. SOLUTION: This photosensitive material has hydrophilic layers on both sides of the transparent org. polymer substrate and has a photosensitive silver halide emulsion layer contg. silver halide particles of <=0.05μm average particle diameter on only one side of the substrate. When this material is exposed, developed, bleached, stabilized, washed and dried, the unexposed part has >=50% light transmissivity at 488nm and an absorbance of >=0.3 at 365nm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photosensitive material for a transmission hologram which records a phase difference of light and reproduces a stereoscopic image, and an image forming method thereof. The present invention relates to a silver halide light-sensitive material for a transmission hologram, which has significantly improved storage stability and image resolving power of an image-formed light-sensitive material after image recording, and improved residual color and processing stains, and an image forming method thereof. is there.

[0002]

2. Description of the Related Art In recent years, in the medical field, with the progress of computer image processing technology and measurement technology, there is a strong demand for stereoscopic visualization of a treatment area. In particular, it is necessary to carefully perform surgery on the eyes and brain, and if preoperative examination can be performed with a stereoscopic image with a clear perspective, surgery will be very easy, and
Be certain. Also, in post-operative check, for example, it is possible to easily and surely verify that the metal bridge used for cranial bone bulging protrudes into the brain and there is no place that may press the brain, and stereoscopic visualization is very useful. Is. In conventional diagnosis using a planar image, CT (Computer X-ray tomography apparatus), MRI (Magnetic resonance tomography apparatus),
You can only see the treatment area two-dimensionally by looking at a number of plane images taken with X-rays, endoscopes, etc.
Although it was time-consuming, it lacked certainty. In order to meet such demands, stereoscopic visualization on a CRT by a stereoscopic television and development of surgery simulation software have been advanced. Similarly, based on CT and MRI information, the industry is demanding the advancement of a stereo hologram image recording system for recording these stereoscopic diagnostic images in a visually recognizable form as a stereoscopic image. Needless to say, advances in stereoscopic image recording materials for advertisement and general use are desired.

As is well known, in the hologram image recording system, image information is recorded as interference fringes due to the phase difference between the image light and the reference light. In the conventional flat image recording method, the light quantity distribution of the image light is recorded as a density distribution, whereas in the hologram image recording method, the interval of interference fringes (hereinafter referred to as the pitch).
Controls the reproduction information (reproduction position, image color) of the reproduced image. The pitch length varies depending on whether it is a reflection hologram or a transmission hologram, but it is determined by the recording light wavelength and the incident light angle, and is usually on the order of submicron. Therefore, the hologram photosensitive material needs to have an extremely high resolution. Further, laser light that is parallel light with a uniform phase is preferable for image recording, and Ar laser light, HeNe laser light, and semiconductor laser light are generally used in terms of accuracy, light source price, running cost, and compactness of equipment. Target. The amount of light emitted from such a laser beam is small, and a photosensitive material for a stereo hologram, which records many images, must be highly sensitive. As a recording material satisfying high sensitivity and high resolution, a silver halide light-sensitive material using Lippmann type AgX particles which are monodisperse and have an extremely small average particle size is the most excellent and has been used conventionally.
For medical use, image diagnosis using a backlight such as Schaukasten is generally used and easy to use, and as a recording format, a transmission hologram using a transparent support is more suitable than a reflection hologram. Further, in order to enhance the diffraction efficiency and form a bright three-dimensional image, it is preferable to use a method in which developed silver is once oxidatively bleached and recorded with a difference in refractive index depending on the presence or absence of AgX particles, rather than a Lippmann hologram in which developed silver is left as it is. Further, even in the latter bleaching method, the method of bleaching and removing the image silver by leaving the silver halide grains contained in the non-image area as it is is more preferable than the method of bleaching the silver image area and leaving it as silver halide. It is well known in the art that the particle size is small and preferable in terms of resolution.

The bleaching method is an excellent recording method, but since silver halide grains are present in the light-sensitive material even after image formation, when the image is observed or stored in a bright place, a so-called print-out phenomenon due to incident light occurs, There is a serious drawback that the non-image area is gradually blackened, and it is strongly desired to solve this problem.

[0005]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a silver halide light-sensitive material for a transmission hologram which is excellent in light resistance during image storage. A second object of the present invention is to provide a silver halide light-sensitive material for transmission holograms which has excellent resolution, high diffraction efficiency and image storability. Further, a third object is a silver halide photosensitive material for transmission holograms, which has excellent resolution and high diffraction efficiency, and has little image contamination such as residual color due to a silver halide photosensitive material for transmission holograms, which has excellent image storability. An object is to provide a method for forming an image of a material.

[0006]

The above objects of the present invention have been attained by the following constitutions.

(1) A transparent organic polymer support has hydrophilic layers on both sides, and only one side of the support contains silver halide grains having an average grain size of 0.05 μm or less. In a silver halide light-sensitive material for a transmission hologram having a light-sensitive silver halide emulsion layer, light-transmission at 488 nm of an unexposed portion of the light-sensitive material after the light-sensitive material is developed / bleached / stabilized / washed / dried as described below. A silver halide light-sensitive material for a transmission hologram, characterized by having a rate of 50% or more and a light absorbance at 365 nm of 0.3 or more.

[0008] (Developer composition) Diethylenetriamine 5 acetic acid (40% aqueous solution) 3.63 g Sodium sulfite 40 g Sodium erythrobinate 10 g Dimezone S 1.2 g Hydroquinone 15 g Sodium carbonate 33 g Potassium carbonate 69 g Potassium bromide 7 g Benzotriazole 0.21 g Boric acid 8 g Diethylene glycol 40 g 2-Mercapto-6-hydroxypurine 60 mg 1-Phenyl-5-mercaptotetrazole 0.025 g Water and sodium hydroxide are added to adjust the pH to 10.4 to 1 liter of the working solution.

(Composition of bleaching solution) After dissolving 30 g of EDTA iron (III) sodium in water, water and sulfuric acid are added to 500 ml.
The pH was adjusted to pH 2.0 at the time of use. When using, add 500 ml of water to make 1 liter.

(Stabilizing solution composition) 2.5 g of potassium iodide
Is dissolved in water by heating to make 1 liter.

(2) The transmission according to the above 1, characterized in that at least one hydrophilic layer on the side opposite to the silver halide emulsion layer of the support contains a dye compound which absorbs exposure light. Type silver halide light-sensitive material for holograms.

(3) The silver halide light-sensitive material for transmission hologram according to the above item 2, wherein the dye compound is contained so that the absorbance at the maximum emission wavelength of the exposure light is 0.1 or more.

(4) It is characterized in that at least one hydrophilic layer coated in the same plane as the silver halide emulsion layer with respect to the support contains a water-soluble dye compound which absorbs exposure light. 2. The silver halide light-sensitive material for transmission hologram as described in 1 above.

(5) The silver halide light-sensitive material for transmission holograms according to the above item 4, wherein the water-soluble dye compound is contained so that the absorbance at the maximum emission wavelength of exposure light is 0.05 or more.

(6) A silver halide sensitizer for a transmission hologram according to the above item 1, which has a non-photosensitive layer containing at least one dye fine particle dispersion between a silver halide emulsion layer and a support. material.

(7) Halogen having a hydrophilic layer on both sides of a transparent organic polymer support and having at least two layers having an average particle size of 0.05 μm or less on only one side of the support. A silver halide light-sensitive material for a transmission hologram comprising a light-sensitive silver halide emulsion layer containing silver halide grains and at least one hydrophilic layer containing a water-soluble dye compound that absorbs exposure light. The light-transmittance at 488 nm of the unexposed area of the photosensitive material after the development / bleaching / stabilization / washing / drying treatment of the above-mentioned item 1 is 50% or more, and the light absorbance at 365 nm is 0.3 or more. And that the sensitivity of the silver halide emulsion coated on the side farther from the support is lower than the sensitivity of the silver halide emulsion coated on the side closer to the support. material.

(8) A silver halide for a transmission hologram according to any one of 1 to 7 above, wherein at least one non-photosensitive layer contains a substantially water-insoluble UV absorber. Photosensitive material.

(9) The above-mentioned 1 characterized in that the support is an organic polymer which absorbs UV light having a wavelength of 365 nm.
9. A silver halide light-sensitive material for a transmission hologram according to any one of items 1 to 7.

(10) The silver halide emulsion for a transmission hologram according to any one of 1 to 9 above, wherein the total dry film thickness of the silver halide emulsion layer is 4 μm or less and 0.5 μm or more. material.

(11) The silver halide light-sensitive material for transmission holograms according to any one of the above items 1 to 10, wherein the silver halide grains contain a Group 8 transition metal salt.

(12) A transparent organic polymer support has hydrophilic layers on both sides, and only one side of the support contains silver halide grains having an average grain size of 0.05 μm or less. A silver halide light-sensitive material for a transmission hologram having a light-sensitive silver halide emulsion layer
A method for forming an image of a silver halide photosensitive material for a transmission hologram, which comprises post-processing so as to contain a UV light absorber that absorbs m of UV light.

(13) For a transmission hologram, which is characterized in that the silver halide photosensitive material for transmission hologram according to any one of 1 to 11 is developed or desilvered in the presence of sulfite ion. Image forming method of silver halide light-sensitive material.

(14) The silver halide light-sensitive material for transmission hologram according to any one of items 1 to 11 is developed in the presence of a mercapto compound represented by the following general formula (1). An image forming method for a silver halide photosensitive material for a transmission hologram.

General formula (1) Z ₁ -SM _{1 In the} formula, Z ₁ is an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxyl group, -SO ₃ M ₂ group, -COO.
M ₂ group (where M ₂ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion),
It represents one substituted with at least one selected from the group consisting of a substituted or unsubstituted amino group and a substituted or unsubstituted quaternary ammonium group, or a substituent having at least one selected from this group. M ₁ represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate).

The higher the resolving power of the silver halide light-sensitive material for a transmission hologram, the more preferable the reproduced image can be obtained.

The average grain size of the silver halide grains used in the silver halide light-sensitive material of the present invention may be 0.05 μm or less. The smaller the average grain size, the shorter the development processing time and the higher the grain size. It is preferable in that a resolution can be obtained and an image without devitrification can be obtained. However, it is not preferable to use silver halide grains having an excessively small average grain size because the sensitivity is lowered, the image and the processing solution are contaminated, and the storage stability of the light-sensitive material is deteriorated. Particularly preferred average particle size is 0.04 μm to 0.01
μm. A so-called Lippmann emulsion can be used as the silver halide emulsion having a thickness of 0.05 μm or less used in the present invention. Lippmann Emulsion is a British patent 1,139,062,
U.S. Pat. No. 3,573,057, Japanese Patent Publication No. 49-8333.
The emulsions described in No. 1 can be used. Particularly preferred emulsions are JP-A-58-160948 and JP-A-60-12.
The emulsion described in No. 540 can be mentioned.

The silver halide composition of the present invention comprises AgI, A
gBrI, AgBr, AgClBrI, AgClBr,
Any of AgCl may be used.

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. You can do it. In addition, as a method for further increasing the fineness of the particle size, the mixing operation is performed in the presence of a silver halide sparingly soluble agent such as azaindenes, mercapto compounds, benztriazoles, benzimidazoles, indazoles, and phthalazines. As a preferable example, a method, in-line mixing of the both aqueous solutions, and then a method of continuously in-line mixing a sparingly soluble agent or a water-miscible organic solvent solution, a method of adding the both aqueous solutions in a water-miscible organic solvent, etc. Can be mentioned.

The average particle size is a term that is commonly used and easily understood by experts in the field of photographic science. The particle size means a particle diameter when the particles are spherical or spherical particles. 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 Mies, James: The Theory of the Photographic Process (CE.
Mees & T. H. By James: The theor
y of the photographicproc
ess), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmilllan")).

In the present invention, the particle size was measured as follows. First, the silver halide emulsion of the present invention is dissolved in ultrapure water at 45 ° C. Polystyrene latex particles of known particle size manufactured by Dow Chemical Co. are mixed with the solution. This solution is dropped on a 200-mesh substrate with a carbon support film and naturally dried. The obtained sample was shadowed with Pt-C at about 30 ° with respect to the substrate surface to prepare a sample for a scanning electron microscope (SEM). The obtained sample for SEM is set in SEM, S-5000H manufactured by Hitachi, and 1K
Scan at V. The obtained data is recorded on the Video bank V built into the S-5000H. The video data thus obtained is used as the image processing device LUZE.
The number of particles was analyzed by X-III (manufactured by NIRECO) to obtain an average particle size.

The shape of the silver halide grains is not limited.
It may have any shape such as a tabular shape, a spherical shape, a cubic shape, a tetradecahedral shape, a regular octahedron shape, and cubic particles are preferable.

The total amount of silver halide in all the coated silver halide emulsion layers is 50 mmol / from the viewpoint of performance and economy.
It is generally set in the range of m ^{2 to} 10 mmol / m ² .

In the present invention, the unexposed portion 488 of the light-sensitive material of the present invention after being processed under the processing conditions described in claim 1.
The light transmittance of nm is 50% or more, preferably 70% or more, and particularly preferably 85% or more.
The transmittance of 488 nm light can be easily measured using a commercially available spectrum meter.

The light absorption of the light-sensitive material of the present invention after processed under the processing conditions described in claim 1 is 365 nm.
It is 3 or more, preferably 0.5 or more, and particularly preferably 1.0 or more. The transmittance of 365 nm light can also be easily measured using a commercially available spectrum meter.

The light-sensitive material of the present invention is generally imagewise exposed by using a laser beam having a visible wavelength having 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 point of view, it is possible to obtain a reproduced image that is so preferable that the unexposed portion of the photosensitive material after processing does not absorb the wavelength of the laser beam used for image formation.

Ar laser is used as the visible laser light,
HeNe lasers, semiconductor lasers, etc. are used,
The Ar laser is most preferably used because of the stability of the emission wavelength, the appropriate copy length, the durability of the light emitting device and the cost. The main emission wavelength of Ar laser is 488 nm, 51
It is 4.5 nm.

The dye compound that absorbs exposure light used in the present invention will be described. The dye compound of the present invention is preferably water-soluble, and particularly preferably a compound that is decolorized during development processing.
As the decoloring mechanism, it is preferable to destroy the conjugated structure by an addition reaction or a redox reaction.

As the water-soluble dye of the present invention, the structure of the preferred dye compound varies depending on the wavelength of exposure light, but dyes generally used in silver halide photographic light-sensitive materials can be used. Dye is Research Disclosure RD-17
643 pages 25-26, classification VIII, RD-18716
649 to 650, RD-308119 1003, class VIII. Particularly preferably, JP-A-1-293342 and JP-A-1-3034 are used.
34, JP-A-1-303433, JP-A-58-83
841, No. 62-103633, No. 62-2916.
36, JP-A-1-44438 and 1-253735.
No. 2, No. 2-201351, No. 2-201352, No. 2-302752. Preferred specific examples are described below.

[0039]

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[0040]

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Preferable results can be obtained by layer-fixing the dye fine particles in at least one non-photosensitive layer between the silver halide emulsion layer and the support of the light-sensitive material of the present invention. 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. Also,
A water-insoluble mordant dyed with a dye and latex fine particles are also one of preferred 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. Preferred specific examples are described below.

[0042]

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[0043]

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[0044]

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As the transparent organic polymer support of the present invention,
Cellulose such as TAC, polyesters such as PET, PEN, polyarylate, polycarbonate, polyvinyls such as syndiotactic polystyrene, polyacrylate, polymethacrylate, polyimides, polyetherimides, PSU, PES, polyaminosulfone, etc. Examples thereof include polysulfones and polyamides.

The transparent organic polymer support of the present invention includes a transparent organic polymer support having a UV light absorbing group in the polymer molecule, or a transparent organic polymer prepared by mixing an organic polymer with an inorganic or organic hydrophobic UV light absorber. A polymer support or a transparent organic polymer support in which a polymer layer that absorbs UV light and a polymer layer that absorbs less UV light are combined into a plurality of layers to improve light resistance during image storage is particularly preferable.

Representative specific examples of the transparent organic polymer support of the present invention will be given.

B-1 Polyethylene-2,6-naphthalate (manufactured by Teijin) B-2 Polyetherimide (UPILEX manufactured by EX.) B-3 Polyimide (Kepler manufactured by EX. DuPont) B-4 Polysulfone (EX. Teijin) B-5 Polyethersulfone (EX. Sumitomo Chemical) B-6 Thermoplastic Polyimide (EX. Mitsui Toatsu Chemicals) B-7 Polyetherimide (EX. Nippon GE Plastics) B- 8 UV light absorbent mixed polycarbonate (Mitsubishi Kasei Diamond Light AR1001) B-9 UV light absorbent mixed acrylic resin (Mitsubishi Chemical Acrylite) B-10 UV light absorbent UV-1 mixed polyethylene terephthalate (UV-1: PET = 1: 100) B-11 UV light absorber UV-1 mixed syndiotactic polystyrene (UV-1 SPS = 1: 100) Specific examples of the hydrophobic UV light absorbers which are preferably used in support of the present invention.

UV-1 p-t-butylphenylsalicylate UV-2 2-hydroxy-4-methoxybenzophenone UV-3 2-hydroxy-4-octoxybenzophenone UV-4 2,2'-dihydroxy-4- Methoxybenzophenone UV-5 2- (2'-hydroxy-5'-methoxyphenyl) benzotriazole UV-6 2- (2'-hydroxy-3'-t-butyl-5'-methyl-phenyl) -5-chloro Benzotriazole UV-7 2- (2'-hydroxy-3 ', 5'-di-
t-Butyl-phenyl) benzotriazole UV-8 2- (2'-hydroxy-3'-undecyl-5'-methyl-phenyl) benzotriazole UV-9 2- (2'-hydroxy-5'-t-butyl) -Phenyl) benzotriazole UV-10 2- (2'-hydroxy-3 ', 5'-di-t-butyl-phenyl) -5-chlorobenzotriazole

[0050]

[Chemical 6]

Specific examples of preferable inorganic UV light absorbers that can be used in the present invention include fine particles of zinc oxide, and zinc oxide fine particles having an average particle diameter of 0.1 μm or less are particularly preferable.

8 used in the silver halide grains of the present invention
Group transition metals will be described. Group 8 transition metal is a conventional expression, and recent expressions include 4th, 5th, and 6th periods.
Means a, 5a, 6a, 7a, 8 group metals. Among them,
Ir, Rh, Co, Os, Ru, Fe, Re, Pt, P
Metal salts such as d and Ni show preferable results, and in consideration of the effect of improving the high illuminance failure characteristic, Ir metal salts show the most preferable results. Further, the metal salt preferably has a complex structure coordinated so as to satisfy d activation, and the ligand is halogen,
Cyano, nitrosyl and H ₂ O are preferred. In particular, preferred specific examples of the transition metal complex of Group 8 which is preferably the transition metal complex having a ligand selected from halogen ion, H ₂ O, nitrosyl, thionitrosyl, and cyan ion are given.

(C-1) Na ₂ [IrCl ₆ ] (C-2) IrCl ₃ .3H ₂ O (C-3) IrBr ₃ 3H ₂ O (C-4) Na ₃ [IrCl ₆ ] (C- 5) K ₃ [IrCl ₆ ] (C-6) [IrCl (NH ₃ ) ₅ ] Cl ₂ (C-7) K ₂ [IrCl ₅ (NO)] (C-8) K ₂ [RuCl ₆ ] (C _{-9) (NH 4) 2 [} RuCl 6] (C-10) RuCl 3 · 3H 2 O (C-11) RuBr 3 · 3H 2 O (C-12) K 2 [RuCl 5 (H 2 O)] (C-13) (NH ₄ ) 2 [RuCl ₅ (H ₂ O)] (C-14) [Ru (NH ₃ ) ₆ ] Cl ₃ (C-15) [Ru (NH ₃ ) ₆ ] Cl ₂ ( C-16) [Ru (NH 3) 6] Br 2 (C-17) K 4 [Ru (CN) 6] (C-18) K 2 [RuCl 5 (NO)] (C-1 _{) [Ru (NH 3) 5} (NO)] Cl 3 (C-20) K 2 [ReCl 6] (C-21) K 2 [ReCl 5 (NO)] (C-22) K 2 [ReCl 4 ( CN) ₂ ] (C-23) Na ₂ [RhCl ₆ ] (C-24) K ₂ [RhBr ₆ ] (C-25) (NH ₄ ) ₂ [RhCl ₆ ] (C-26) (NH ₄ ) ₂ [OsCl ₆ ] (C-27) K ₂ [OsCl ₆ ] For other metals, a portion of the transition metal atom is Os, Pd.
Since it can be represented by substituting it with Pt or Pt, it will be omitted, but the hexadentate transition metal compound is disclosed in JP-A No. 2-2.
082, 2-20853, 2-20854,
No. 2-20855 can be referred to.
As the alkali complex salt, general sodium salt and potassium salt can be selected, but in addition to this, primary, secondary and tertiary amine salts may be used.

The amount of transition metal salt used is preferably such that the sensitivity of the silver halide grains is not significantly lowered, and is preferably 5 × 10 ^-6 mol or less per mol of silver halide.

In the present invention, gelatin is preferably used as the dispersion medium for the protective colloid of silver halide grains, and as the gelatin, ossein gelatin, pigskin gelatin or the like is used. In addition, modified gelatin such as alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 100,000), and phthalated gelatin are used. Other hydrophilic colloids can also be used.

In the production of the silver halide grains of the present invention, unnecessary soluble salts may be removed during the growth of the silver halide grains, or they may remain contained. When removing the salts, see RD Vol. 17643
The method can be carried out based on the method described in section II. Noodle washing with water and ultrafiltration are preferable. A commonly used polymer flocculant (for example, Demol N manufactured by Kao Corporation)
Etc.) may be used.

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used.

The gold sensitization method is a typical one of the noble metal sensitization methods, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

The silver halide emulsion can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

These dyes can be applied to any of the commonly used nuclei. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc. A renin nucleus, a benzindolenin nucleus, an indole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, pyrazoline-containing nuclei having a ketomethine structure are used.
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization.
Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Resea).
rch Disclosure) Volume 176 17643
(Published December 1978), page 23, IV, section J.

In the present invention, a polymer latex generally used in silver halide photographic light-sensitive materials can be used. That is, it is a polymerizable ethylene-based compound or a polymerizable diolefin-based compound and is 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 may be used alone or in combination of two or more kinds, but when a hydrophilic monomer is used, it is preferable to use it in combination with a hydrophobic monomer to obtain a stable latex. In order to obtain it, it is better not to use hydrophilic monomers so much.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azoles, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitro Benzotriazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, azaindenes, tetrazaindenes,
Many compounds known as antifoggants or stabilizers can be added, such as pentazaindenes, benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amides and the like. It is preferable to use a mercapto compound.

Examples of the binder or protective colloid of the photographic emulsion according to the present invention include gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives, sugar derivatives, single or A wide variety of synthetic hydrophilic polymeric materials such as polymers can be used.

In the present invention, as a matting agent, US Pat. Nos. 2,992,101 and 2,701,245 are used.
No. 4,142,894, No. 4,396,70
A homopolymer of polymethylmethacrylate as described in No. 6 or a polymer of methylmethacrylate 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 may be used in combination. it can. The particle size is preferably 0.6 to 10 μm, particularly preferably 1 to 5 μm.

The surface layer of the photographic element of the present invention can be used as a slip agent in US Pat. Nos. 3,489,576 and 4,047.
No. 958, etc .;
In addition to the colloidal silica described in JP-A-3139, paraffin wax, higher fatty acid esters, starch derivatives and the like can be used.

In the present invention, the hardeners include chromium salts, aldehydes, N-methylol compounds, dioxane derivatives, active vinyl compounds, active halogen compounds, mucohalogen acids, isoxazoles, dialdehyde starch, 2-chloro-. 6-Hydroxytriazinylated gelatin, a carboxyl group-activating type hardener and the like can be used alone or in combination.

In the light-sensitive material used in the present invention, various other additives such as surfactants, desensitizers, plasticizers, slip agents, development accelerators and oils are used.

In order to bring out the effect of the present invention more remarkably, at least one hydrophilic colloid layer is provided on the opposite side of the silver halide photographic emulsion layer, but at least one hydrophobic polymer layer is provided on the outer side thereof. It is preferable.

The various photographic additives used in the present invention may be used by dissolving them in an aqueous solution or an organic solvent, but when they are poorly soluble in water, they are made into a fine particle crystal state, and water, gelatin, a hydrophilic or hydrophobic polymer is used. It can be dispersed and used.

A known method is used for packaging the photographic light-sensitive material comprising the photographic element of the present invention.

The silver halide photographic light-sensitive material of the present invention can be post-treated so as to contain a UV light absorber which absorbs UV light of 365 nm after exposure, but it may be subjected to development, bleaching, stabilization treatment and washing with water. And photoprocessing in an automatic processor having at least 5 processes of drying and drying.
The 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.

The silver halide light-sensitive material of the present invention is developed or desilvered in the presence of sulfite ion.

As a developing agent for a developing solution for the light-sensitive material of the present invention, dihydroxybenzenes such as hydroquinone and para-aminophenols such as p-aminophenol and N described in JP-A-4-15641 and JP-A-4-16841 are used. -Methyl-p-aminophenol, 2,4-
Examples of 3-pyrazolidones such as diaminophenol include 1-phenyl-3-pyrazolidones, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and 5,5-
Dimethyl-1-phenyl-3-pyrazolidone and the like, catechol, pyrogallols and ascorbate can be used. It is preferable to use them in combination. More preferably, catechols or ascorbates are used alone.

The silver halide photographic light-sensitive material of the present invention is preferably treated with a developing solution containing a compound represented by the general formula (1). In the general formula (1), Z ₁ is an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxyl group, a —SO ₃ M ₂ group, a —COOM ₂ group (here, M ₂
Represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), at least one selected from the group consisting of a substituted or unsubstituted amino group, a substituted or unsubstituted quaternary ammonium group, or this group Represented by being substituted with a substituent having at least one selected from the group consisting of: M ₁ represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate).

The alkyl group represented by Z ₁ is preferably
It is a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms, and particularly having 2 to 20 carbon atoms, which may have a substituent in addition to the above substituents. The aromatic group represented by Z ₁ is preferably a monocyclic or condensed ring having 6 to 32 carbon atoms and may have a substituent in addition to the above substituents. The heterocyclic group represented by Z ₁ preferably has 1 to 1 carbon atoms.
32 is a monocyclic ring or a condensed ring, which is a 5- or 6-membered ring having 1 to 6 heteroatoms independently selected from nitrogen, oxygen, and sulfur in one ring. You may have. Among the compounds represented by the general formula (1), Z ₁ is preferably a heterocyclic group having one or more nitrogen atoms.

In the formula, Z ₁ is a hydroxyl group, —SO ₃ M ₂
Group, a —COOM ₂ group (wherein M ₂ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, or a substituted or unsubstituted ammonio group. It is substituted with a substituent having at least one selected or at least one selected from this group. The ammonio group preferably has 20 or less carbon atoms and the substituent is a substituted or unsubstituted linear, branched, or cyclic alkyl group (eg, methyl group, ethyl group, benzyl group, ethoxypropyl group, cyclohexyl group). Etc.), a substituted or unsubstituted phenyl group or a naphthyl group.

Further preferred among the compounds represented by the general formula (1) are the compounds represented by the following general formula (1-a).

[0080]

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In the formula, Z is a group necessary for forming an unsaturated 5-membered heterocycle having a nitrogen atom or a 6-membered heterocycle (eg, pyrrole, imidazole, pyrazole, pyrimidine, pyridazine, pyrazine, etc.). is there. Where:
R ¹¹ and R ¹² are a hydrogen atom, a —SM ₃ group, a halogen atom,
Alkyl group (including those having a substituent), alkoxy group (including those having a substituent), hydroxyl group,-
COOM ₃ group, —SO ₃ M ₃ group, alkenyl group (including those having a substituent), amino group (including those having a substituent), carbamoyl group (including those having a substituent), phenyl group ( At least one group selected from (including those having a substituent), and R ¹¹ and R ¹² may form a ring. The ring that can be formed is a 5-membered ring or 6
A ring having at least one member ring, preferably a nitrogen-containing heterocycle. M ₃ is the same as M ₂ defined in the compound represented by the general formula (1). In the formula, the compound represented by the general formula (1-a) is at least one —S
A compound having an M ₃ group or a thione group, which is selected from the group consisting of a hydroxyl group, a —COOM ₃ group, a —SO ₃ M ₃ group, a substituted or unsubstituted amino group, and a substituted or unsubstituted ammonio group. And has at least one substituent. It may have a substituent other than the aforementioned -SM ₁ group or thione group, and the substituent includes a halogen atom (for example, fluorine, chlorine, bromine), a lower alkyl group (having a substituent). A methyl group, an ethyl group or the like having a carbon number of 5 or less is preferable), a lower alkoxy group (including a group having a substituent, methoxy, ethoxy, butoxy or the like having a carbon number of 5 or less is preferable), a lower alkenyl Examples thereof include groups (including those having a substituent, those having 5 or less carbon atoms are preferable), carbamoyl groups, phenyl groups and the like. Further, in the general formula (1-a), compounds represented by the following general formulas A to F are particularly preferable.

[0082]

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In the formula, each of R ₁ , R ₂ , R ₃ and R ₄ is a hydrogen atom, a —SM ₄ group, a halogen atom, a lower alkyl group (including those having a substituent, such as a methyl group and an ethyl group. A group having 5 or less carbon atoms is preferable), a lower alkoxy group (including a group having a substituent, a group having 5 or less carbon atoms is preferable), a hydroxy group, a -COOM ₄ -SO ₃ M ₄ group, a lower alkenyl group. (Including those having a substituent. 5 carbon atoms
The following are preferred. ), An amino group, a carbamoyl group, and a phenyl group, at least one of which is a —SM ₄ group. M ₄ represents a hydrogen atom, an alkali metal atom or an ammonium group. In particular, -SM ₄ except as a substituent hydroxy group, -COOM ₄ -SO ₃ M ₄ groups, it is preferable to have a water-soluble group such as an amino group. The amino group represented by R ₁ , R ₂ and R ₃ represents a substituted or unsubstituted amino group,
A preferred substituent is a lower alkyl group. The ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

Specific examples of the compound represented by the general formula (1) are shown below, but the invention is not limited thereto.

[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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The amount of the compound represented by the general formula (1) used in the present invention is preferably 10 ^-6 to 10 ^-1 mol, and more preferably 10 ^-5 to 10 ^{-2, in} 1 liter of the developing solution. It is preferably molar.

Examples of sulfites and metabisulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, sodium metabisulfite, reductones such as piperidinohexose reductone.

As the alkaline agent, sodium hydroxide,
Potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate, JP-A-61-28
The borate described in No. 708, saccharose, acetoxime, 5-sulfosalicylic acid, phosphate, carbonate and the like described in JP-A-60-93439 may be used.

As the solubilizing agent, polyethylene glycols and their esters can be contained, and as the sensitizing agent, for example, a quaternary ammonium salt can be contained.

As an anti-sludge agent, there is disclosed JP-A-56-
No. 106244, silver stain inhibitor, JP-A-3-518
The sulfides and disulfide compounds described in No. 44, and the cysteine derivatives or triazine compounds described in Japanese Patent Application No. 4-92947 are preferably used.

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

As the chelating agent for masking calcium ions mixed in tap water used in the treatment liquid, there are chelating agents described in JP-A No. 1-193853, sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate salts and the like. .

If necessary, a development accelerator, a surfactant, a defoaming agent, a film hardener and the like can be added to the developing solution. The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5. More preferably, the pH is 8.5 or more and 10.4 or less.

As a preferred bleaching solution, an aqueous solution of a bleaching oxidizer such as EDTA iron (III) sodium, sodium dichromate, parabenzoquinone, ferric nitrate, etc., which is commonly used in the art can be used.

As the bleaching accelerator, for example, Japanese Patent Publication No. 45-
No. 35754, No. 58-122535, No. 58-12
No. 2536, thiourea derivatives, U.S. Pat.
Thioether described in US Pat. No. 6,459.

If desired, the bleaching solution may contain a compound such as a preservative, a pH buffer, a pH adjustor, and a chelating agent capable of softening water.

As the stabilizing solution, an aqueous KI solution is usually used.

The replenishment in the present invention replenishes the amount corresponding to processing fatigue and oxidation fatigue, but 25 to 1 per 1 m ^{2 of} the photographic element.
Perform with a replenishment volume of 70 ml. The replenishment method includes replenishment by width and feed rate described in JP-A-55-126243, area replenishment described in JP-A-60-104946, and area controlled by the number of continuously processed sheets described in JP-A-1-149156. It may be supplemented.

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

As one method for more markedly exhibiting the effects of the present invention, a developer obtained by dissolving a developer comprising a solid processing agent, a bleaching agent and a stabilizer in water,
Preference is given to using bleaching solutions and stabilizing solutions.

The solid processing agent referred to in the present invention is a powder processing agent, a solid processing agent such as tablets, pills, granules, etc., which have been subjected to a moisture-proof treatment if necessary.

[0107]

The present invention will be specifically described below with reference to examples. Note that, needless to say, the present invention is not limited to the embodiments described below.

Example 1 (Preparation of Silver Halide Emulsion A1) Liquid A Pure water 833 cc Gelatin 80 g KBr 0.5 g Liquid B Silver nitrate 60 g Pure water 417 cc Liquid C KBr 42 g KI 2.9 g Pure water 403 cc Ammonia water 14.3 cc Put solution A in the kettle, and mix solution B and solution C for 65 seconds at 50 ° C.
Co-mixed below. 10 seconds after the addition was completed, 6 cc of citric acid (40%) was added to adjust the pH. The obtained emulsion was cooled and set, and then desalted by a noodle washing method. Then 15 mg
Of sodium thiosulfate was added and the mixture was aged at 60 ° C. for 90 minutes. The average grain size of the obtained silver halide emulsion A1 is 0.0
It was 35 μm and σ / r = 0.08.

(Preparation of Comparative Silver Halide Emulsion B1) The same as silver halide emulsion A1 except that the silver potential during mixing was 100%.
Mixing temperature is set to 55 ° C and mixing time is set to 11 while maintaining mv.
A comparative silver halide emulsion B1 was prepared by changing to minutes. The average grain size of the obtained silver halide emulsion was 0.10 μm, σ
/R=0.08.

(Preparation of silver halide photographic light-sensitive material for hologram of Ar laser light source transmission type) Using the above silver halide emulsions A1 and B1, 175 μm having an undercoat layer described in JP-A-3-61945. On one of the biaxially stretched polyethylene terephthalate supports of No. 1, a silver halide emulsion layer of the following Formulation 1 was prepared in a silver amount of 1.4 g / m ² , a gelatin amount of 2.6 g / m ² , and the following Formulation 2 The emulsion protective layer of 1 was simultaneously multilayer coated so that the amount of gelatin was 0.4 g / m ² . On the opposite side, a backing layer having the following formulation 3 was used so that the amount of gelatin was 2.4 g / m ^2, and a backing protective layer having the following formulation 4 was used, so that the amount of gelatin was 1.0 g / m ^2.
A sample was obtained by simultaneous multi-layer coating with the emulsion layer side to obtain m ² . The amount of UV light absorber dispersion added is
The absorbance at 365 nm after bleaching, stabilization, and drying treatment was set so as to satisfy the following Table 1.

Formulation 1 (Silver Halide Emulsion Layer) Silver Halide Emulsion Sensitizing Dye I 634 mg / AgX1 mol Mercaptobenzoxazole 203 mg / AgX1 mol Ethyl gallate 3.38 g / AgX1 mol Polystyrene sulfone so that the silver amount becomes 1.4 g / m ^2. Sodium acid salt 48 mg / m ² Formulation 2 (emulsion protective layer) Gelatin 0.4 g / m ² Activator (SA1) 11.3 mg / m ² Activator (SA2) 9.6 mg / m ² Compound (K1) 2.5 mg / m ² compound (K2) 23 mg / m ² UV light absorber dispersion (1) Sodium polystyrene sulfonate 20 mg / m ² compound (T1) 0.3 mg / m ² glyoxal 30 mg / m ² hardener (H2) 15 mg / m ² formulation 3 (backing layer) Zera Down 2.4 g / m ² Dye (F1) 44.9mg / m ² Dye (F2) 10mg / m ² active agent (SA1) 3.1mg / m ² Saponin 360 mg / m ² Citric acid 20 mg / m ² of polystyrene sulphonic acid sodium 20 mg / m ² glyoxal 27 mg / m ² hardener (H3) 34 mg / m ² formulation 4 (backing protective layer) gelatin 1.0 mg / m ² dye (F1) 18 mg / m ² dye (F2) 4 mg / m ² Activator (SA1) 23 mg / m ² saponin 80 mg / m ² compound (K2) 80 mg / m ² polymethylmethacrylate (average particle size 5 μm) 25 mg / m ² glyoxal 13.6 mg / m ² hardener (H1) 10 mg / m ² .

Preparation of UV Light Absorber Dispersion (1) After mixing the following additives, warm water was added to make 120 g, and then the mixture was dispersed 5 times at 40 ° C. with manton-goulin. The dispersion was cooled and set to prepare a UV light absorber dispersion (1).

3 Dibutyl phthalate 2.46 g Dioctyl phthalate 2.46 g UV-6 0.5 g UV-7 0.5 g UV-8 0.5 g UV-9 0.5 g UV-10 0.5 g UV-11 0.5 g UV-12 2.5g UV-13 1.5g Gelatin 4.2g Activator (SA3) 53.9mg Compound (T1) 1mg

[0114]

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[0115]

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100 images of tomographic image information of the lower half of a person's head by X-ray tomography (image information continuous at equal pitches) are recorded beforehand as digital signals on a hard disk of a computer, and this image information is recorded for each cross section. The images are played back on the CRT in sequence. Using the sample obtained above as a photosensitive material, this CRT screen was positioned as a target object, and master hologram exposure was performed based on the stereo hologram technique.

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 by using a half mirror, and the reference light is incident on the photosensitive surface of the sample at an angle of 45 degrees. The CRT screen placed parallel to the sample was irradiated with the object light so as to expose the CRT screen for master hologram exposure based on the stereo hologram technique. During the exposure, the CRT moved in a position corresponding to the image reproducing section. The exposed sample thus obtained is developed, bleached, stabilized with KI, washed with water under the following processing solution and processing conditions,
It dried and created the master hologram. Subsequently, the obtained master hologram is placed in the place where the photosensitive material is placed at the time of the exposure with the front and back surfaces thereof reversed, and the reference light Ar laser used for the exposure is applied to the master hologram from the same direction. An image was formed, and the same unexposed sample as that used for creating the master hologram was placed at the image forming position, and at the same time, the transmission hologram exposure was performed by irradiating the reference light at 45 degrees. The exposed sample was developed, bleached, stabilized with KI, washed with water and dried under the following treatment liquid and treatment conditions to prepare a transmission hologram.

Evaluation of Lightfastness of Post-Processing Sample The obtained transmission hologram photosensitive material was placed under a 3000 Lux fluorescent lamp with the silver halide coating surface facing the fluorescent lamp surface.
It was stored for a week and the change in density of the unexposed portion was measured with an optical densitometer. The larger the change in density, the poorer the light resistance of the processed sample and the poorer the image storability.

Evaluation of Diffraction Efficiency The obtained transmission hologram sample was irradiated with a constant quantity of iodine quartz lamp light from the reference light irradiation direction. The brightness of the formed three-dimensional image was visually evaluated by 5 ranks and used as the evaluation value of the diffraction efficiency. When the level at which a stereoscopic image is almost unrecognizable is set to 1, the larger the number, the higher the lightness and the excellent diffraction efficiency.

[0120] (Developer composition) Diethylenetriamine 5 acetic acid (40% aqueous solution) 3.63 g Sodium sulfite 40 g Sodium erythrobinate 10 g Dimezone S 1.2 g Hydroquinone 15 g Sodium carbonate 33 g Potassium carbonate 69 g Potassium bromide 7 g Benzotriazole 0.21 g Boric acid 8 g Diethylene glycol 40 g 2-Mercapto-6-hydroxypurine 60 mg 1-Phenyl-5-mercaptotetrazole 0.025 g Water and sodium hydroxide were added to make 1 liter of the working solution so that the pH was 10.4.

(Bleaching solution composition) 30 g of EDTA iron (III) sodium was dissolved in water, water and sulfuric acid were added, and 500 ml was added.
The pH was adjusted to pH 2.0 at the time of use. At the time of use, 500 ml of water was added to make 1 liter.

(Stabilizing solution composition) 2.5 g of potassium iodide
Was dissolved by heating with water to make 1 liter.

The evaluation results are shown in Tables 1 and 2.

[0124]

[Table 1]

[0125]

[Table 2]

Sample No. of the embodiment of the present invention. In Nos. 9 to 12, excellent light resistance and diffraction efficiency are exhibited, and excellent silver halide light-sensitive materials for transmission holograms are provided. In all the samples, the 488 nm light transmittance of the unexposed portion of the photosensitive material after processing was 85% or more.

Example 2 Sample No. 1 of Example 1 using the silver halide emulsion A1. 7
Same as the above but except that the dye (F1) and the dye (F2) added to the backing layer and the backing protective layer were removed, and the UV light absorber dispersion added to the silver halide emulsion protective layer. The liquid was removed, and instead, a water-soluble dye shown in Table 3 and a UV light absorber were combined and changed as shown in Table 3 below to prepare a sample. The UV light absorber was added to the silver halide emulsion protective layer and the backing layer in the same amount per unit m ² .

Using the sample thus obtained, the above evaluation and
The following residual color evaluation was performed and the results are shown in Table 3. In all the samples, the 488 nm light transmittance of the unexposed portion of the photosensitive material after processing was 85% or more.

[0129]

[Table 3]

The sample of the present invention shows excellent light resistance and diffraction efficiency, and it can be seen that it is an excellent silver halide photosensitive material for transmission hologram.

Example 3 Sample No. 2 of Example 2 Same as 103 and 107, but dyes shown in Table 4 were added to the silver halide emulsion layer as shown in Table 4 to prepare samples. The results are shown in Table 4.
In addition, in all samples, 488 nm of the unexposed portion of the photosensitive material after processing
The light transmittance was 85% or more.

[0132]

[Table 4]

It can be seen that the samples of the present invention are superior to the comparison.

Example 4 Sample No. 2 of Example 2 Same as 101 and 105, but based on the following lower layer formulation 5, a fine particle dispersion of the dye shown in Table 5 was added to the lower layer on the support side of the silver halide emulsion layer as shown in Table 5 to prepare a sample. . Table 5 shows the results.
In addition, in all samples, 488 nm of the unexposed portion of the photosensitive material after processing
The light transmittance was 85% or more.

Formulation 5 (lower layer) Gelatin 0.5 g / m ² Solid dispersion of dye (listed in Table 4) (average particle size 0.1 μm) 30 mg / m ² saponin 360 mg / m ² citric acid 20 mg / m ² polystyrene sulfone sodium 20 mg / m ² glyoxal 10 mg / m ² hardener (H1) 10mg / ^{m 2}

[0136]

[Table 5]

It can be seen that the samples of the present invention are superior to the comparison.

Example 5 Sample No. 3 of Example 3 was used. Similar to 32 and 34, but silver halide emulsions A1, A2 and A3 were used and the emulsion layers were multilayer coated in the combinations shown in Table 6. When the emulsion layers are overlaid, the amount of each emulsion layer is 1 unit area per formulation.
It was set so that it would be half of the weight of. Table 7 shows the results of image sharpness in addition to light resistance and diffraction efficiency.

(Preparation of Silver Halide Emulsion A2) The same as silver halide emulsion A1 except that sodium thiosulfate for chemical sensitization is added to the sensitivity of silver halide emulsion A1 at 0.1.
And silver halide emulsions A2 and A3 were prepared by increasing the amount so that the sensitivity was increased by 0.2 LogE. The relative sensitivity is based on a standard method, after wedge exposure using an Ar laser sensitometer, after developing under the developing solution and the developing conditions, it is fixed with a CFL871 fixing solution manufactured by Konica Corp., washed with water, dried, and imaged. The density was measured and determined as the logarithm of the reciprocal of the amount of light to obtain the density of 1.0.

Evaluation of sharpness The obtained hologram reproduction image was visually observed, and the sharpness of the image was visually evaluated as 5 ranks and evaluated as 5 ranks. The higher the number, the sharper and clearer the image.

[0141]

[Table 6]

[0142]

[Table 7]

From Tables 6 and 7, two silver halide emulsion layers were prepared.
In the case of layers, samples 56, 57 corresponding to claim 7 of the present invention
And 58 are excellent in light resistance, diffraction efficiency and sharpness. On the other hand, when the sensitivities of the two layers are the same, it is slightly inferior, and when the sensitivities of the silver halide emulsions in the upper layers are high, they are inferior.

Example 6 Comparative sample No. 4 of Example 4 using the silver halide emulsion A1 and containing no UV light absorber dispersion (1). Same as 3, but a hydrophobic uppermost layer was applied on the upper layer of the backing protective layer using a coating solution of methyl ethyl ketone solvent having the following formulation 6 to prepare each evaluation sample of Table 6.

Table 6 shows the results of the above evaluations using the obtained samples. However, the light resistance was evaluated by using a 3000 Lux fluorescent lamp with the backing layer surface facing upward.
In addition, in all samples, 488 nm of the unexposed portion of the photosensitive material after processing
The light transmittance was 85% or more.

Formulation 6 (hydrophobic layer) Methylmethacrylate: acrylic acid = 97: 3 resin 1.0 g / m ² UV light absorber (described in Table 6) Addition in an amount such that the absorbance at 365 nm after treatment becomes Table 6 Hardener (H3) 6 mg / m ²

[0147]

[Table 8]

It can be seen that the sample of the present invention is superior to the comparison.

Example 7 Comparative sample No. 4 of Example 4 using the silver halide emulsion A1 and containing no UV light absorber dispersion (1). Although the same as No. 43, the type of support used was changed as shown in Table 9 below to prepare each evaluation sample. Table 9 shows the results of the above evaluations using the obtained samples. In all samples, the unexposed area of the photosensitive material after processing had a light transmittance of 85% at 488 nm.
That was all.

[0150]

[Table 9]

It can be seen that the sample of the present invention is superior to the comparison.

Example 8 Sample No. 1 of Example 1 7 and 9, except that the silver halide emulsion used is A4 and the total dry film thickness of the silver halide emulsion layer changes as shown in Table 10 below while adjusting the amount of gelatin contained in the emulsion solution. Each evaluation sample was created. Table 10 shows the results of the above evaluations using the obtained samples. In addition, all samples were treated with 4
The 88 nm light transmittance was 85% or more.

(Preparation of Silver Halide Emulsion A4) Liquid A Pure Water 300 cc Gelatin 8 g Nitric Acid pH 2.0 Liquid B Silver Nitrate 60 g Pure Water 100 cc C Liquid KBr 21 g NaCl 10.4 g Pure Water 100 cc Gelatin 2 g Liquid A in a mixing pot. Then, while controlling EAg to 190 mv, the temperature was kept at 35 ° C., and the liquid B and the liquid C were simultaneously mixed in 4 minutes.
10 seconds after the addition was completed, 200 mg of 1-hydroxy-6-methyltetrazaindene was added. Next, citric acid was added to adjust the pH to 5.9. Precipitated water was washed with a polynaphthalene sulfonic acid derivative and magnesium sulfate by a standard method, and then an aqueous gelatin solution was added and dispersed. Next, sodium thiosulfate was added and the mixture was aged at 50 ° C. for 60 minutes. The obtained silver halide emulsion A4 had an average grain size of 0.035 μm and σ / r = 0.
It was 08.

[0154]

[Table 10]

It can be seen that the samples of the present invention are superior to the comparison.

Example 9 Sample No. 1 of Example 1 Same as 7 and 9, but a silver halide emulsion in which the silver halide grains of silver halide emulsion A3 were doped with a transition metal salt was used. The transition metal salts doped in the silver halide grains are shown in Table 11 below. The transition metal salt was mixed and doped into the liquid C at the time of silver halide grain formation immediately before mixing. The doping amount was 1 × 10 ⁻⁶ mol per mol of AgX. Table 11 shows the results of the above evaluations using the obtained samples. In all the samples, the 488 nm light transmittance of the unexposed portion of the photosensitive material after processing was 85% or more.

[0157]

[Table 11]

The sample of the present invention is excellent in light resistance and sharpness.

Example 10 Sample No. 1 of Example 1 The 7 unexposed samples were divided into 5 parts, one was treated with the same processing liquid as in Example 1 for comparison, and the other 4 samples were each a developing solution containing the following water-soluble UV light absorber (UVV-1). , Bleaching solution, stabilizing solution, washing solution,
Dried to prepare the treated samples of the combinations in Table 12. In addition, for all samples, 488 of the unexposed area of the photosensitive material after processing
The nm light transmittance was 85% or more.

[0160]

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[0161]

[Table 12]

From Table 12, it is understood that the UV light absorber exhibits the effect of the present invention even when it is contained in the developing solution, the bleaching solution, the stabilizing solution or the washing solution instead of the light-sensitive material.

Example 11 Sample No. 1 of Example 1 The 9 unexposed samples were divided into 4 parts, one of which was treated with the same treatment solution as in Example 1 for comparison, and the other 3 samples were each prepared by using 1 of the mercapto compound represented by the general formula (1) shown in Table 13 below. The same treatment was carried out except that the developing solution added to the developing solution was added in an amount corresponding to%, and treated samples of the combinations shown in Table 13 were prepared. In all samples, the unexposed area of the photosensitive material after processing had a light transmittance of 85% at 488 nm.
That was all.

[0164]

[Table 13]

The effect is further excellent when treated with a developer containing the mercapto compound represented by the general formula (1).

[0166]

According to the present invention, a silver halide light-sensitive material for transmission hologram having excellent resolution, high diffraction efficiency, excellent image storability, and little image contamination such as residual color, and an image forming method thereof can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 1/815 G03C 1/815 1/83 1/83 5/26 5/26 5/305 5 / 305 G03H 1/02 G03H 1/02

Claims (14)

[Claims] 1. A photosensitive material having hydrophilic layers on both sides of a transparent organic polymer support and containing silver halide grains having an average grain size of 0.05 μm or less only on one side of the support. In a silver halide light-sensitive material for a transmission hologram having a light-sensitive silver halide emulsion layer, the light-sensitive material is developed and
The unexposed area of the light-sensitive material after bleaching / stabilization / washing / drying has a light transmittance of 50% or more at 488 nm, and 36
A silver halide light-sensitive material for a transmission hologram, which has a light absorbance at 5 nm of 0.3 or more. (Developer composition) Diethylenetriamine 5 acetic acid (40% aqueous solution) 3.63 g Sodium sulfite 40 g Sodium erythrobinate 10 g Dimezone S 1.2 g Hydroquinone 15 g Sodium carbonate 33 g Potassium carbonate 69 g Potassium bromide 7 g Benzotriazole 0.21 g Boric acid 8 g Diethylene glycol 40 g 2-Mercapto-6-hydroxypurine 60 mg 1-Phenyl-5-mercaptotetrazole 0.025 g Water and sodium hydroxide are added to adjust the pH to 10.4 to 1 liter of the working solution. (Bleaching solution composition) After dissolving 30 g of EDTA iron (III) sodium in water, water and sulfuric acid were added to make 500 ml, and the pH was adjusted to pH 2.0 at the time of use. When using, add 500 ml of water to make 1 liter. (Composition of stabilizing solution) 2.5 g of potassium iodide is dissolved by heating with water to make 1 liter. 2. The transmission according to claim 1, wherein at least one hydrophilic layer on the side opposite to the silver halide emulsion layer of the support contains a dye compound which absorbs exposure light. Type silver halide light-sensitive material for holograms. 3. The silver halide photosensitive material for a transmission hologram according to claim 2, wherein the dye compound is contained so that the absorbance at the maximum emission wavelength of the exposure light is 0.1 or more. 4. A water-soluble dye compound which absorbs exposure light is contained in at least one hydrophilic layer coated on the same surface of the support as the silver halide emulsion layer. Item 1. A silver halide light-sensitive material for a transmission hologram according to item 1. 5. The silver halide photosensitive material for a transmission hologram according to claim 4, wherein the water-soluble dye compound is contained so that the absorbance at the maximum emission wavelength of exposure light is 0.05 or more. 6. A silver halide sensitizer for a transmission hologram according to claim 1, which has a non-photosensitive layer containing at least one dye fine particle dispersion between the silver halide emulsion layer and the support. material. 7. A transparent organic polymer support having hydrophilic layers on both sides, and at least two layers having a mean particle size of 0.05 μm or less on at least one side of the support. A silver halide light-sensitive material for a transmission hologram comprising a light-sensitive silver halide emulsion layer containing silver particles and at least one hydrophilic layer containing a water-soluble dye compound that absorbs exposure light. The light transmittance at 488 nm of the unexposed portion of the light-sensitive material after the development / bleaching / stabilization / washing / drying treatment according to claim 1 is 50% or more, and 3
The light absorbance at 65 nm is 0.3 or more, and the sensitivity of the silver halide emulsion coated on the side far from the support is lower than the sensitivity of the silver halide emulsion coated on the side closer to the support. A characteristic silver halide light-sensitive material for transmission holograms. 8. The silver halide for a transmission hologram according to claim 1, wherein at least one non-photosensitive layer contains a substantially water-insoluble UV absorber. Photosensitive material. 9. The support according to claim 1, wherein the support is an organic polymer that absorbs UV light having a wavelength of 365 nm.
13. A silver halide light-sensitive material for a transmission hologram according to any one of 1. 10. The total dry film thickness of the silver halide emulsion layer is 4
10. The silver halide light-sensitive material for a transmission hologram according to claim 1, wherein the silver halide light-sensitive material has a thickness of not more than μm and not less than 0.5 μm. 11. A silver halide light-sensitive material for a transmission hologram according to claim 1, wherein the silver halide grains contain a Group 8 transition metal salt. 12. A photosensitive material having a hydrophilic layer on both sides of a transparent organic polymer support, and containing silver halide grains having an average grain size of 0.05 μm or less only on one side of the support. Of a transmission type hologram-use silver halide light-sensitive material having a light-sensitive silver halide emulsion layer is exposed to U of 365 nm after image exposure.
An image forming method of a silver halide light-sensitive material for a transmission hologram, which comprises post-processing so as to contain a UV light absorber which absorbs V light. 13. A transmission hologram, wherein the silver halide photosensitive material for transmission hologram according to claim 1 is developed or desilvered in the presence of sulfite ion. Image forming method of silver halide light-sensitive material. 14. A silver halide light-sensitive material for a transmission hologram according to claim 1, which is developed in the presence of a mercapto compound represented by the following general formula (1). An image forming method for a silver halide photosensitive material for a transmission hologram. In the general formula ₍₁₎ Z ₁ -SM ₁ formula, Z ₁ represents an alkyl group, an aromatic group or a heterocyclic group, a hydroxyl group, -SO ₃ M ₂ group, -COO
M ₂ group (where M ₂ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion),
It represents one substituted with at least one selected from the group consisting of a substituted or unsubstituted amino group and a substituted or unsubstituted quaternary ammonium group, or a substituent having at least one selected from this group. M ₁ represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate).