JP4500710B2 - Silver halide holography-photosensitive material - Google Patents

Description

The present invention relates to a silver halide holographic photosensitive material (a silver halide photographic photosensitive material for holographic applications; hereinafter referred to as a silver halide photographic material for holography), particularly a high-sensitivity and high-quality silver halide photosensitive material for holography. It is about. Furthermore, the present invention relates to a silver halide photosensitive material for holography that is stable and reproducible.

Various recording systems have been proposed and put to practical use as photosensitive materials for wavefront recording of interference waves, that is, holography. As a typical photosensitive material, a silver halide photosensitive material, a dichromated gelatin photosensitive material, a photoresist photosensitive material, a photopolymer photosensitive material, and a thermoplastic photosensitive material are known. Among them, silver halide photosensitive materials are characterized by high sensitivity, and are widely used in various display fields and research fields. That is, further enhancement of the sensitivity of the silver halide light-sensitive material can be utilized to reduce the amount of laser light used and shorten the exposure time, and can lead to the simplification and facilitation of wavefront recording. Therefore, higher sensitivity of the silver halide photosensitive material for holography is a preferred direction for wavefront recording of interference waves (see, for example, Patent Document 1).
However, the silver halide emulsion grains used in the silver halide photosensitive material for holography are required to be ultrafine grains having an equivalent circle diameter of 100 nm or less. There are cases where the sensitivity enhancement technology cannot be applied as it is.
Conversely, a technique that cannot be applied to ordinary photographic silver halide emulsion grains may be a high-sensitivity technique. Conventional silver halide emulsion grains for photographic use are prohibited from simultaneous use of gold sensitization and reduction sensitization (see, for example, Patent Document 2). That is, although gold sensitization and reduction sensitization each have an effect of increasing sensitivity, if two sensitization methods are used simultaneously, an increase in fogging, deterioration of storage stability, etc. will be caused, and each effect will be sufficiently achieved. Could not be pulled out.
Moreover, since the ultrafine particles with high sensitivity are small in size, they are unstable and easily increase in particle size. Even when the silver halide emulsion grains are prepared, the ripening of the ultrafine particles proceeds due to the change over time until the coating, so that it may be necessary to apply the coating immediately after the preparation of the silver halide emulsion grains. Therefore, a silver halide photosensitive material for holography coated in a multilayer structure in which two or more types of silver halide emulsion grains are coated simultaneously cannot be stably produced with good reproducibility.
Japanese Patent Laid-Open No. 10-123643 JP-A-5-181238

According to the present invention, it is possible to produce a silver halide photosensitive material for holography that has an unprecedented high sensitivity and high image quality. In particular, a silver halide photosensitive material for color holography having good reproducibility and stability can be produced.

The present invention enables simultaneous use of gold-chalcogen sensitization and reduction sensitization, for which simultaneous use in the same period was prohibited. Since gold-chalcogen sensitization and reduction sensitization can be used simultaneously during chemical sensitization, it is possible to achieve both high sensitivity and high image quality. Further, since stable ultrafine silver halide grains can be produced with no change in grain size, the green-sensitive silver halide emulsion layer and the red color in the silver halide photosensitive material for holography, which has not been conventionally coated with a multilayer structure. It has become possible to produce a photosensitive material having a multilayer structure of a photosensitive silver halide emulsion layer.
The object of the present invention is achieved by the following method.

(1) In a silver halide holographic photosensitive material having at least one photosensitive silver halide emulsion layer on a support, the number average equivalent circle diameter of silver halide grains in the silver halide emulsion layer is 10 nm or more. A silver halide holographic light-sensitive material having a thickness of 80 nm or less and subjected to reduction sensitization in addition to gold-chalcogen sensitization during chemical sensitization of silver halide grains.
(2) The silver halide holography-sensitive material as described in (1), wherein the chalcogen sensitization is used in combination with selenium sensitization and sulfur sensitization.
(3) The silver halide holographic photosensitive material as described in (1) or (2), wherein the reduction sensitization is performed by addition of a reduction sensitizer.
(4) The photosensitive silver halide emulsion layer contains a tetrazaindene compound in an amount of 3 × 10 ⁻³ mol to 3 × 10 ⁻² mol per mol of silver in silver halide grains ( The silver halide holography-photosensitive material according to 1), (2) or (3).
(5) The photosensitive silver halide emulsion layer has at least one green photosensitive silver halide emulsion layer having an absorption maximum at 500 nm to 600 nm and a red photosensitive silver halide emulsion having an absorption maximum at 600 nm to 750 nm. The silver halide holography-sensitive material according to any one of (1) to (4), comprising at least one layer.

With the silver halide holographic photosensitive material of the present invention, a high-sensitivity and high-quality silver halide holographic photosensitive material could be obtained. Furthermore, a stable silver halide holographic photosensitive material having good reproducibility could be obtained.

The silver halide holography-sensitive material of the present invention will be described below.
In the present invention, the silver halide holographic photosensitive material is a silver halide photosensitive material capable of recording an interference wave between object light and reference light. By this wavefront recording, both the amplitude and phase of the object light can be recorded, and the object can be reproduced and reproduced three-dimensionally faithfully by the reference light.
The silver halide holographic light-sensitive material of the present invention has at least one silver halide emulsion layer on a support. Particularly preferably, at least one green light-sensitive silver halide emulsion layer having an absorption maximum at 500 nm to 600 nm on the support and 600 nm to 750
It has at least two photosensitive silver halide emulsion layers, at least one red-sensitive silver halide emulsion layer having an absorption maximum at or below nm. At least one blue-sensitive silver halide emulsion layer having an absorption maximum at 350 nm or more and less than 500 nm may be additionally provided.
The blue light-sensitive silver halide emulsion layer can also serve as the green light-sensitive silver halide emulsion layer and / or the red light-sensitive silver halide emulsion layer. Having an absorption maximum at 500 nm or more and 600 nm or less is spectrally sensitized with a spectral sensitizing dye, and at least the absorption wavelength or photosensitive wavelength should have a maximum value at 500 nm or more and 600 nm or less. There may be two or more local maximum values, or additional local maximum values outside the wavelength range. 600nm
Having an absorption maximum at 750 nm or less is spectrally sensitized with a spectral sensitizing dye, and at least the absorption wavelength or photosensitive wavelength only needs to have a maximum value at 600 nm or more and 750 nm or less. There may be two or more local maximum values, or additional local maximum values outside the wavelength range.
The layer sequence of the green light-sensitive silver halide emulsion layer and the red light-sensitive silver halide emulsion layer is arbitrary. That is, the green light-sensitive silver halide emulsion layer may be located far from the support, or the red light-sensitive silver halide emulsion layer may be located far from the support.
As the support, a support usually used for silver halide light-sensitive materials can be used, and glass,
TAC, PET, PEN and the like can be given as representative examples. Preferably, glass or TAC having no optical anisotropy is used. Selection of the thickness of a support body can be suitably selected according to the use and usage method. The above emulsion layer is coated on these supports. In addition to the emulsion layer, protective layer, YF layer, intermediate layer, anti-halation layer, undercoat layer, back layer, etc.
Depending on the purpose, it can be appropriately selected and applied. For a flexible support such as TAC, the application of a back layer is extremely effective in order to keep its curl characteristics good. Further, when there is no protective layer, a matting agent or the like can be introduced into the back layer to improve the adhesion between the samples. In addition, various troubles caused by static electricity, such as dust adhesion, can be positively eliminated by adjusting the chargeability.
The amount of coated silver and coated gelatin in the silver halide emulsion layer and various layers are not particularly limited. The applied silver amount is preferably in the range of 1 g / m ² to 10 g / m ² . The amount of coated gelatin is preferably in the range of 1 g / m ² to 10 g / m ² . The silver / gelatin coating amount ratio can also be selected within an arbitrary range. Preferably it is the range of 0.3-2.0. The coating thickness is usually 3 μm to 12
The range of μm is preferably used. If it is too thin, the interference wave cannot be recorded sufficiently, and if it is too thick, the resolving power decreases due to an increase in light scattering or the like. The swelling film thickness in the treatment step can be arbitrarily selected by adjusting the amount of the hardener used. Preferably, the degree of hardening is strengthened so that the film thickness after processing is not changed, that is, silver halide, gelatin and the like are not lost. The relationship between the amount of coated silver and the amount of coated gelatin in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is basically arbitrary, but preferably the ratio is 1 to 2
The range of is preferable. Although the degree of dura is basically the same, it is preferable to loosen the dura of the lower layer relative to the upper layer in the case of layered dura.

The silver halide grains contained in the silver halide emulsion layer of the present invention are preferably normal crystals, and can be octahedral, cubic, tetradecahedral and rounded. Preferably, it is a rounded cube or a cube with clear corners. It is preferable that twins are not mixed. Particularly preferably, the mixing ratio of twin particles is 3% or less, more preferably 1% or less. Here, twins include single twins, double twins, multiple twins, and parallel twins and non-parallel twins.

The silver halide grains of the present invention are preferably monodispersed. The variation coefficient of equivalent circle diameter in terms of projected area of all silver halide grains is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less. Here, the variation coefficient of the equivalent circle diameter is a value obtained by dividing the standard deviation of the distribution of equivalent circle diameter in each silver halide grain by the average equivalent circle diameter.

The equivalent circle diameter can be obtained, for example, by taking a transmission electron micrograph by a direct method and obtaining the diameter of a circle having an area equal to the projected area of each particle (equivalent circle diameter). In the present invention, since the silver halide grains are ultrafine particles, a clear grain image can be obtained by photographing using a high voltage electron microscope at a low temperature.

In the present invention, the silver halide grains are preferably silver bromide, silver iodobromide, silver chloroiodobromide, or silver chlorobromide. The silver iodide content is particularly preferably 1 mol% or more and 5 mol% or less. The silver chloride content is particularly preferably 5 mol% or less. Further, it is preferable that the silver chloride and silver iodide contents of each grain have no distribution. The variation coefficient of the grain distribution of silver chloride and silver iodide content is preferably 20% or less, particularly preferably 10% or less. The EPMA method (Electron Probe Micro An) is usually used to measure the silver chloride and silver iodide contents of individual grains.
alyzer method) is effective. By preparing a sample in which emulsion grains are dispersed so as not to contact each other and analyzing the X-rays emitted by irradiating with an electron beam, it is possible to perform elemental analysis of a very small region irradiated with the electron beam. . At this time, the measurement is preferably performed by cooling to a low temperature in order to prevent sample damage due to the electron beam.
Since the silver halide grains of the present invention are ultrafine particles, it is not easy to impart a halogen composition structure, but a structure having an internal high silver iodide content, a structure having an external high silver iodide content, and the like are possible. The same applies to the structure of silver chloride. Furthermore, a multilayer structure having a triple structure or more is also possible.

The silver halide grains of the present invention have a number average equivalent circle diameter of 10 nm to 80 nm. More preferably, it is 20 nm or more and 60 nm or less. Especially preferably, they are 30 nm or more and 50 nm or less. In general, when the particle size is too large, the image quality of wavefront reproduction is inferior, and when the particle size is too small, destabilization such as fluctuations in particle size cannot be completely suppressed.
In the present invention, this grain size setting allows reduction sensitization in addition to gold-chalcogen sensitization during chemical sensitization of silver halide grains. If the particle size is too large, the fog increases and high sensitivity cannot be obtained. In addition, storage stability is significantly deteriorated.

The silver halide grains of the present invention can be prepared by a conventionally known method. Preferably, a silver nitrate aqueous solution and a halogen aqueous solution are added to the gelatin aqueous solution by the double jet method. At this time, it is preferable to add at an accelerated flow rate. Moreover, it is preferable to control the pH and pAg of the system at the time of addition. The pH is preferably in the range of 5-8. The pAg is preferably in the range of 5-9. For the preparation of ultrafine particles, the temperature is preferably low, and particularly preferably in the range of 20 ° C to 40 ° C. Various additives described later can be added for particle size adjustment, particle size distribution adjustment, sensitivity / fogging adjustment, gradation / development progress adjustment, and the like.

The silver halide emulsion used in the present invention is chemically sensitized. In particular, gold-chalcogen sensitization and reduction sensitization are performed during chemical sensitization. Here, chemical sensitization means a process corresponding to a chemical sensitization process when the silver halide emulsion production process is divided into three stages of a grain formation process, a water washing process, and a chemical sensitization process according to time. Chemical sensitization is a process in which various chemical sensitizers are added and the temperature is raised and ripened.
Although combined use of gold-chalcogen sensitization and reduction sensitization during chemical sensitization has been conventionally difficult, it has been found that it is possible in the particle size range within the scope of the present invention. With this combination, extremely high sensitivity can be achieved, and the storage stability can be brought to a level that does not cause any practical problems. For chalcogen sensitization and noble metal sensitization, TH James, The Photographic Process, 4th edition, published by Macmillan, 1977, (THJ
ames, The Theory of the Photographic Proc
ess, 4th ed, McCillan, 1977), pages 67-76. Research Disclosure, Volume 120, April 1974, 12008;
Research Disclosure, Volume 34, June 1975, 13452, US Pat. No. 2,
No. 642,361, No. 3,297,446, No. 3,772,031, No. 3,8
57,711, 3,901,714, 4,266,018, and 3,
904,415, as well as British Patent 1,315,755, pAg5
10. Sulfur, selenium, and tellurium chalcogen sensitizers and gold sensitizers at pH 5-8 and temperatures 30-80 ° C, plus platinum, palladium, iridium, or a combination of these sensitizers. . In the case of gold sensitization, chloroauric acid, potassium chloroaurate,
Known compounds such as potassium aurithiocyanate, gold sulfide and gold selenide can be used. The palladium compound means a palladium divalent salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Where R is a hydrogen atom,
Represents an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ Pd
Cl ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferred. Gold compounds and palladium compounds are preferably used in combination with thiocyanate or selenocyanate.

Sulfur sensitizers include hypo, thiourea compounds, rhodanine compounds and US Pat.
, 857,711, 4,266,018, and 4,054,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are described in US Pat. No. 2,131,03.
No. 8, No. 3,411,914, No. 3,554,757, JP-A-58-12552
No. 6 and the aforementioned “Photographic Emulsion Chemistry” by Duffin, pages 138 to 143.

A preferable amount of the gold sensitizer is 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol. A preferred range for the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ mole per mole of silver halide. The preferred range of thiocyanate or selenocyan compound is 1 × 10 ⁻⁴ per mole of silver halide.
To 1 × 10 ⁻² mole.

The preferred amount of sulfur sensitizer used for the silver halide grains used in the present invention is 1 × 10 ⁻⁶ to 1 × 10 ⁻² mole per mole of silver halide, more preferably 1 × 10 ^−5.
~ 5x10 ^-3 mol.

Selenium sensitization is a preferred chalcogen sensitization method for the emulsion of the present invention. In selenium sensitization, a known unstable selenium compound is used. Specifically, colloidal metal selenium and selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea)
Selenium compounds such as selenoketones and selenoamides can be used. Chalcogen sensitization (preferably selenium sensitization) is preferably used as chalcogen sensitization in combination with sulfur sensitization.

In tellurium sensitization, an unstable tellurium compound is used, and JP-A-4-224595, 4
-271341, 4-3333043, 5-303157, 6-27573, 6-175258, 6-180478, 6-208184, 6-208
No. 186, No. 6-317867, No. 7-140579, No. 7-301879, No. 7
Unstable tellurium compounds described in -30880 and the like can be used.

Specifically, phosphine tellurides (eg, normal butyl-diisopropylphosphine telluride, triisobutylphosphine telluride, trinormalbutoxyphosphine telluride, triisopropylphosphine telluride), diacyl (di) tellurides (eg,
Bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (N
-Phenyl-N-benzylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride), telluroureas (for example, N, N'-dimethylethylene tellurourea), telluramides, telluro esters and the like may be used. Preferred are phosphine tellurides and diacyl (di) tellurides.

The silver halide emulsion of the present invention undergoes reduction sensitization in addition to gold-chalcogen sensitization during chemical sensitization.
Here, reduction sensitization means a method of adding a reduction sensitizer to a silver halide emulsion, a method of ripening in a low pAg atmosphere called pAg 1-7 called silver ripening, and a high pH of 8-11 called high pH ripening. pH
Any method of aging in the atmosphere can be selected. Two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method in that the level of reduction sensitization can be finely adjusted.
As reduction sensitizers, for example, stannous salts, ascorbic acid and derivatives thereof, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, and borane compounds are known. In the reduction sensitization used in the present invention, these known reduction sensitizers can be selected and used, and two or more kinds of compounds can be used in combination. As a reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferable compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but a range of 10 ⁻⁷ to 10 ⁻³ mol per mol of silver halide is appropriate.

For example, the reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters, and amides and added during chemical sensitization. The timing of addition may be before or after the addition of the gold sensitizer and chalcogen sensitizer. Preferably, a reduction sensitizer is added and ripened, then a chalcogen sensitizer and a gold sensitizer are added and further ripened to terminate chemical sensitization. It is also preferable to add the reduction sensitizer solution in several portions or continuously for a long time.

In the present invention, the tetrazaindene compound is 3 × per mole of silver halide grains.
It is preferably contained 10 ^-3 mol to 3 × 10 ^-2 mol or less. The tetrazaindene compounds used in the present invention are known as photographic emulsion stabilizers and antifoggants, and are described in Research Disclosure 307, 866. As the tetrazaindene compound used in the present invention, a tetrazaindene compound having a hydroxy group as a substituent,
A hydroxytetrazaindene compound is particularly preferable. The heterocycle of tetrazaindene may have a substituent other than a hydroxy group. Examples of the substituent include an alkyl group,
It may have an amino group, a hydroxyamino group, an alkylamino group, a dialkylamino group, an arylamino group, a carboxy group, an alkoxycarbonyl group, a halogen atom, an acylamino group, a cyano group, or the like. However, those having a substituent containing sulfur (for example, a mercapto group) are not preferable.

Although the specific example of the tetrazaindene compound of this invention is listed below, it is not limited only to these.
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 4-hydroxy-6-tert-butyl-1,3,3a, 7-tetrazaindene 4-hydroxy-6-phenyl-1, 3,3a, 7-tetrazaindene 4-hydroxy-1,3,3a, 7-tetrazaindene 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 2-methylthio-4-hydroxy -6-methyl-1,3,3a, 7-tetrazaindene 4-hydroxy-5-bromo-6-methyl-1,3,3a, 7-tetrazaindene 4-hydroxy-6-methyl-1,2 , 3a, 7-tetrazaindene 4-hydroxy-6-ethyl-1,2,3a, 7-tetrazaindene 10.2,4-dihydroxy-6-phenyl-1,3,3a, 7-triazaindene 11 4-Hydroxy-6-phenyl-1,2,3,3a, 7-pentazaindene

The amount of these tetrazaindene compounds added is preferably 3 × 1 per mole of silver halide.
0 ^-3 mol to 3 x 10 ^-2 mol, preferably 4 x 10 ^-3 mol to 3 x 10 ^-2 mol, more preferably 6 x 10 ^-3 mol to 2 x 10 ^-2 mol. Before start, during chemical sensitization, after chemical sensitization,
It is preferable to add at any time during application. If the amount added is too small, the effect of stabilizing the particle size over time due to the addition of the tetrazaindene compound is not recognized. Here, the time means the time elapsed from the time of preparation of silver halide emulsion grains to the time of coating. Suppressing this change over time makes it possible to achieve stable production and quality. On the contrary, when the amount of the tetrazaindene compound added is too large, the change in the particle size with time is larger than when no addition is made. Therefore, the addition range of the tetrazaindene compound is limited to a narrow addition range in order to obtain the effects of the present invention. Therefore, even in the discovery in preparing silver halide emulsion grains for holography. there were.

In the present invention, it is preferred that 1 × 10 ⁻⁴ or more and 1 × 10 ⁻² mol or less of thiocyanate per 1 mol of silver halide grains. More preferably, 5 × 10 ⁻⁴ or more and 5 × 10 ⁻³ mol or less of thiocyanate is contained per 1 mol of silver in the silver halide grains. If the amount is too small, the effect of increasing the sensitivity is small, and if the amount is too large, the deteriorating effect due to destabilization of the grain size variation of the thiocyanate as a silver halide solvent becomes too large. In the present invention, a silver halide solvent other than thiocyanate is also preferably used. As silver halide solvent,
U.S. Pat.Nos. 3,271,157, 3,531,286, 3,574,628
(A) Organic thioethers described in JP-A Nos. 54-1019 and 54-158717, JP-A Nos. 53-82408, 55-77737, and 55-2982 (B) a thiourea derivative, (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319,
(D) Imidazoles, (e) Sulphite, (f) described in JP-A-54-100717
) Ammonia and the like.

The timing of addition of thiocyanate preferably used in the present invention may be any stage of preparation of silver halide emulsion grains, but preferably after completion of the silver halide grain formation step,
More preferably, it is after the desalting step and before the coating step. Particularly preferred is the chemical sensitization step. As an addition method, it is preferable to add as an aqueous solution. The thiocyanate is preferably KSCN, NaSCN, or NH ₄ SCN.

In the present invention, the J-associative cyanine dye is preferably contained as a sensitizing dye in an amount of 1 × 10 ⁻⁴ mole to 1 × 10 ⁻² mole per mole of silver halide grains. When the J associative cyanine dye is contained in the added amount, the destabilizing effect on the ultrafine silver halide particles due to the use of the above-described silver halide solvent can be remarkably suppressed. Here, J association means that the absorption maximum in the state adsorbed on the silver halide grains is shifted to a long wavelength by 10 nm or more, more preferably 20 nm or more, with respect to the absorption maximum in the dye solution.
Particularly preferably, 5 × 10 ⁻⁴ mol or more and 5 × 10 ⁻³ mol or less of J-associated cyanine dye is contained per 1 mol of silver in the silver halide grains.

In general, sensitizing dyes used in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the aforementioned cyanine dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxador nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole Nuclei, benzimidazole nuclei and quinoline nuclei are applicable. These nuclei may have a substituent on the carbon atom.

These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization. A typical example is US Pat. No. 2,6.
88,545, 2,977,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,617,293, No. 3,628
No. 3,964, No. 3,666,480, No. 3,672,898, No. 3,679,
No. 428, No. 3,703,377, No. 3,769,301, No. 3,814,6
09, 3,837,862, 4,026,707, British Patent 1,344
No. 281, No. 1,507,803, No. 43-4936, No. 53-12375
And JP-A Nos. 52-110618 and 52-109925.

Along with the sensitizing dye, a dye that itself does not have spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization may be added simultaneously or separately. In the present invention, it is particularly preferable to use a stilbene-based supersensitizer.

In the present invention, the sensitizing dye may be added at any stage of the preparation of the silver halide emulsion grains, but preferably before the chemical sensitization process, more preferably after the completion of the silver halide grain formation process and before the desalting process. It is. A conventionally known method can be used as the addition method. Preferably, it is added as an aqueous solution or an aqueous dispersion.

In the present invention, the iridium salt is preferably contained in an amount of 1 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol per mol of silver halide grains. By containing the added amount of iridium salt, the destabilizing effect on the silver halide ultrafine particles due to the use of the silver halide solvent can be remarkably suppressed. Particularly preferably, the iridium salt is contained in an amount of 2 × 10 ⁻⁴ mol or more and 1 × 10 ⁻³ mol or less per mol of silver in the silver halide grains.

In the present invention, the iridium salt may be added at any stage in the preparation of silver halide emulsion grains, but is preferably in the process of forming silver halide grains. As an addition method, it is preferably added as an aqueous solution.

As the iridium salt, a trivalent or tetravalent iridium complex is preferably used. Typical iridium salts include K ₃ IrCl ₆ , K ₂ IrCl ₆ , K ₃ IrCl ₅ (H ₂ O), K ₂
IrCl ₅ (H ₂ O) and the like can be mentioned. In addition to K salt, sodium salt and ammonium salt are also preferably used. As the ligand for Ir, those conventionally known besides Cl and H ₂ O are used. Preferably, an iridium complex containing an organic ligand described in JP-A-7-072569 is used. More preferably, an iridium complex containing a cyano group described in JP-A-2-761027 is used.

In the present invention, it is preferable that 6 cyano metal complex is doped in the silver halide grains in addition to the iridium salt. Among the 6 cyano metal complexes, those containing iron, ruthenium, osmium, cobalt, rhodium, iridium or chromium are preferred. The addition amount of the metal complex is preferably in the range of 10 ^{−6 to} 10 ⁻² mol per mol of silver halide, and more preferably in the range of 10 ^{−5 to} 10 ⁻³ mol per mol of silver halide. preferable. The metal complex can be added by dissolving in water or an organic solvent. The organic solvent is preferably miscible with water. Examples of the organic solvent include alcohols, ethers, glycols, ketones, esters, and amides.

  As the metal complex, a 6-cyano metal complex represented by the following formula (I) is particularly preferable.

(I) [M (CN) ₆ ] ^n-
(Wherein M is iron, ruthenium, osmium, cobalt, rhodium, iridium or chromium, and n is 3 or 4).

Specific examples of 6-cyano metal complexes are shown below.
(I-1) [Fe (CN) ₆ ] ^4-
(I-2) [Fe (CN) ₆ ] ^3-
(I-3) [Ru (CN) ₆ ] ^4-
(I-4) [Os (CN) ₆ ] ^4-
(I-5) [Co (CN) ₆ ] ^3-
(I-6) [Rh (CN) ₆ ] ^3-
(I-7) [Ir (CN) ₆ ] ^3-
(I-8) [Cr (CN) ₆ ] ⁴⁻ .

The counter cation of the hexacyano complex is preferably an ion that is easily miscible with water and is compatible with the precipitation operation of the silver halide emulsion. Examples of counter ions include alkali metal ions (e.g.,
Sodium ion, potassium ion, rubidium ion, cesium ion, lithium ion), ammonium ion and alkylammonium ion.

The holographic silver halide photosensitive material of the present invention preferably contains a low molecular weight gelatin. More preferably, low molecular weight gelatin is contained in the silver halide emulsion. The low molecular weight gelatin in the present invention means that having a number average molecular weight of 3000 to 50000. More preferably, the number average molecular weight is 10,000 to 30,000. The gelatin used in the present invention may be subjected to the following various modification treatments. For example, phthalated gelatin modified with amino group, succinylated gelatin, trimellit gelatin, pyromellitic gelatin, esterified gelatin modified with carboxyl group, amidated gelatin, formylated gelatin modified with imidazole group, methionine group decreased And oxidized reduced gelatin and increased reduced processed gelatin.

On the other hand, other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives Various synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinylpyrazole, or a single or copolymer Substances can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull.
Soc. Sci. Photo. Japan. No. 16. An enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or enzyme-decomposed product of gelatin can also be used.

The silver halide emulsion used in the present invention is usually washed with water. The temperature for washing with water can be selected according to the purpose, but is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can be selected according to the purpose, but is preferably selected between 2 and 10. More preferably, it is the range of 3-8. Washed with water
Although pAg can also be selected according to the purpose, it is preferably selected from 5 to 10. The washing method can be selected from a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like can be selected.

The silver halide emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or processing of the light-sensitive material, or stabilizing the photographic performance. That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; for example, thioketo compounds such as oxadrine thione; azaindenes such as Many compounds known as antifoggants or stabilizers such as triazaindenes, pentaazaindenes can be added. For example, those described in US Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One preferred compound is a compound described in JP-A-63-212932.
Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, water washing process, dispersion after water washing, chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to the original antifogging and stabilizing effect added during emulsion preparation, control the crystal wall of grains, reduce grain size, reduce grain solubility, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

It is preferable depending on the purpose that a metal ion salt is present at the time of preparing the emulsion of the present invention, for example, during grain formation, desalting step, chemical sensitization, and before coating. When the particles are doped, it is preferably added after the formation of the particles, before the completion of the chemical sensitization after the formation of the particles when used as a particle sensitizer or a chemical sensitizer. A method of doping the entire particle and a method of doping only the core portion or the shell portion of the particle can also be selected. For example, Mg, Ca, Sr, Ba, Al, Sc, Y
La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re,
Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, and Bi can be used. These metals can be added in the form of a salt that can be dissolved during particle formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydrate salt, hexacoordinated complex salt, and tetracoordinated complex salt. For example, CdBr ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Pb (CH
₃ COO) ₂ , K ₃ [Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrCl ₆ , (
_{NH 4) 3 RhCl 6, K} 4 Ru (CN) 6 and the like. As ligands for coordination compounds, halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo,
You can choose from carbonyls. These may use only one kind of metal compound, but may be used in combination of two or more kinds.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. To stabilize the solution, an aqueous hydrogen halide solution (eg, HCl, HB
r) or a method of adding an alkali halide (for example, KCl, NaCl, KBr, NaBr) can be used. Moreover, you may add an acid, an alkali, etc. as needed. The metal compound can be added to the reaction vessel before particle formation or can be added during particle formation. In addition, a water-soluble silver salt (for example, AgNO ₃ ) or an alkali halide aqueous solution (for example, Na
Cl, KBr, KI) can also be added continuously during the formation of silver halide grains.
Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

In the emulsion of the present invention, an oxidizing agent for silver is preferably used. The oxidizing agent for silver refers to a compound having an action of acting on metallic silver and converting it into silver ions. Particularly effective are compounds capable of converting extremely fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions. The silver ions generated here may form, for example, a silver salt that is hardly soluble in water such as silver halide, silver sulfide, or silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. May be formed. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and its adducts _{(e.g., NaBO 2 · H 2 O 2} · 3H 2 O, 2NaCO 3 · 3H 2 O 2, Na 4 P 2 O 7 · 2H 2
_{O 2, 2Na 2 SO 4 ·} H 2 O 2 · 2H 2 O), peroxy acid salt _{(e.g., K 2 S 2 O 8,} K 2 C 2
O ₆ , K ₂ P ₂ O ₈ ), peroxy complex compounds (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] · 3H ₂
O, 4K ₂ SO ₄ · Ti (O ₂ ) OH · SO ₄ · 2H ₂ O, Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ ]
6H ₂ O), permanganate (eg KMnO ₄ ), chromate (eg K ₂ Cr ₂ O)
₇ ) Oxygenates, such as iodine and bromine, perhalogenates (eg, potassium periodate), high valent metal salts (eg, potassium hexacyanoferrate) and thio There is a sulfonate.

Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-bromosuccinimide, chloramine T, An example is chloramine B).

Preferred oxidizing agents used in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents, and quinone organic oxidizing agents. It is a preferred embodiment to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver. A method of applying reduction sensitization after using an oxidizing agent, a reverse method thereof, or a method of simultaneously coexisting both can be used. These methods can be selected and used in either the particle formation step or the chemical sensitization step.

The silver halide photosensitive material for holography of the present invention includes a hydrazine compound having an adsorbing group to silver halide described in JP-A-07-134351, JP-A-08-114884,
Contains hydroxamic acid compounds described in JP-A-08-314051, hydroxysemicarbazide compounds described in JP-A-10-090819, and hydroxylamine-based compounds having an adsorbing group to silver halide described in JP-A-2002-323729 It is particularly preferred.
The addition of these compounds can be selected from the formation of emulsion grains until coating, but is preferably selected from the time of chemical sensitization or subsequent coating. Although the addition amount is also arbitrary, as a feature of the ultrafine grain emulsion, it may be preferable to use a large excess amount 10 times or more than the amount described in these patents. The specific addition amount can be easily determined experimentally.

A compound in which a one-electron oxidant produced by one-electron oxidation can emit one electron or more is preferably used in the photosensitive material of the present invention. These compounds are the following types 1, 2
It is a compound chosen from.
(Type 1)
One-electron oxidant produced by one-electron oxidation is further coupled with a subsequent bond cleavage reaction.
A compound that can emit electrons or higher electrons.
(Type 2)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation reaction.

First, the compound of type 1 will be described.
JP-A-9-211769 (specific example: 28-) shows a compound that can be emitted from a one-electron oxidant produced by one-electron oxidation of a type 1 compound, with a subsequent bond cleavage reaction. Compounds PMT-1 to S-37 described in Table E and Table F on page 32), JP-A-9
No. 221774, JP-A No. 11-95355 (specific examples: compounds INV1 to 36), Special Table 2
001-500996 (specific examples: compounds 1-74, 80-87, 92-122), US Pat. No. 5,747,235, US Pat. No. 5,747,236, European Patent 786662A1
(Specific examples: Compounds INV1 to 35), European Patent No. 893732A1, US Pat. No. 6,054
And compounds referred to as “one-photon two-electron sensitizers” or “deprotonated electron-donating sensitizers” described in US Pat. No. 260, US Pat. No. 5,994,051, and the like. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

  Further, as a compound of type 1 that can be emitted by one-electron oxidant formed by one-electron oxidation and further undergoing bond cleavage reaction, one or more electrons can be emitted from the general formula (1) ( General formula (1) described in JP-A-2003-114487), general formula (2) (synonymous with general formula (2) described in JP-A-2003-114487), general formula (3) (JP-A-2003-114487) General formula (1) described in 2003-114488), general formula (4) (synonymous with general formula (2) described in Japanese Patent Application Laid-Open No. 2003-114488), general formula (5) (Japanese Patent Application Laid-Open No. 2003-114488). 114488 (synonymous with general formula (3)), general formula (6) (synonymous with general formula (1) described in Japanese Patent Application Laid-Open No. 2003-75950), and general formula (7) (Japanese Patent Application Laid-Open No. 2003-75950). And general formula (8) (Japanese Patent Application No. 2). The reaction represented by the general formula (1) described in 003-25886 or the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in Japanese Patent Application No. 2003-33446) may occur. Among the compounds, a compound represented by the general formula (9) (synonymous with the general formula (3) described in Japanese Patent Application No. 2003-33446) can be given. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the formula, RED ₁ and RED ₂ represent a reducing group. R ₁ is a non-metallic atomic group capable of forming a cyclic structure corresponding to a tetrahydro form or octahydro form of a 5-membered or 6-membered aromatic ring (including aromatic heterocycle) together with carbon atom (C) and RED ₁ To express. R ₂ represents a hydrogen atom or a substituent. When a plurality of R ₂ are present in the same molecule, these may be the same or different. L ₁ represents a leaving group. ED represents an electron donating group. Z ₁ represents an atomic group that can form a 6-membered ring with a nitrogen atom and two carbon atoms of a benzene ring. X ₁ represents a substituent, and m 1 represents an integer of 0 to 3. Z ₂ represents —CR ₁₁ R ₁₂ —, —NR ₁₃ — or —O—. R ₁₁ and R ₁₂ each independently represents a hydrogen atom or a substituent. R ₁₃ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
X ₁ represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylamino group, an arylamino group, or a heterocyclic amino group. L ₂ represents a carboxy group or a salt thereof, or a hydrogen atom. X ₂ represents a group which forms a 5-membered heterocycle with C═C. Y ₂ represents a group which forms a 5- or 6-membered aryl group or heterocyclic group with C═C. M represents a radical, a radical cation, or a cation.

Next, the type 2 compound will be described.
As a compound in which a one-electron oxidant produced by one-electron oxidation with a type 2 compound can further emit one or more electrons with a subsequent bond formation reaction, a compound represented by the general formula (10) A compound capable of causing a reaction represented by the general formula (1) described in 2003-140287) and the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in Japanese Patent Application No. 2003-33446). And a compound represented by the general formula (11) (synonymous with the general formula (2) described in Japanese Patent Application No. 2003-33446). The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the above formula, X represents a reducing group that is one-electron oxidized. Y reacts with one-electron oxidant produced by one-electron oxidation of X to form a new bond, a carbon-carbon double bond site, a carbon-carbon triple bond site, an aromatic group site, or benzo The reactive group containing the non-aromatic heterocyclic part of a condensed ring is represented. L ₂ represents a linking group for linking X and Y. R ₂ represents a hydrogen atom or a substituent. When a plurality of R ₂ are present in the same molecule, these may be the same or different. X ₂ represents a group which forms a 5-membered heterocycle with C═C. Y ₂ represents a group which forms a 5- or 6-membered aryl group or heterocyclic group with C═C. M represents a radical, a radical cation, or a cation.

  Of the compounds of types 1 and 2, “a compound having an adsorptive group to silver halide in the molecule” or “a compound having a partial structure of a spectral sensitizing dye in the molecule” is preferable. Typical examples of the adsorptive group to silver halide are those described in JP-A No. 2003-156823, page 16, right line 1 to page 17, right line 12. The partial structure of the spectral sensitizing dye is a structure described on page 17, right line 34 to page 18, left line 6 of the same specification.

  More preferably, the compound of type 1 or 2 is “a compound having at least one adsorptive group to silver halide in the molecule”. More preferred is “a compound having two or more adsorptive groups to silver halide in the same molecule”. When two or more adsorptive groups are present in a single molecule, these adsorptive groups may be the same or different.

The adsorptive group is preferably a mercapto-substituted nitrogen-containing heterocyclic group (for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4). -Oxadiazole group, 2-mercaptobenzoxazole group, 2-mercaptobenzthiazole group, 1,5-dimethyl-1,2,4-
A triazolium-3-thiolate group or the like, or imino silver (> NAg)-
A nitrogen-containing heterocyclic group having an NH— group as a heterocyclic partial structure (for example, a benzotriazole group, a benzimidazole group, an indazole group, etc.); Particularly preferred are 5-mercaptotetrazole group, 3-mercapto-1,2,4-triazole group, and benzotriazole group, most preferred are 3-mercapto-1,2,4-triazole group, and 5 -Mercaptotetrazole group.

It is also particularly preferred that the adsorptive group has two or more mercapto groups as a partial structure in the molecule. Here, the mercapto group (—SH) may be a thione group if it can be tautomerized. Preferred examples of the adsorptive group having two or more mercapto groups as a partial structure (such as a dimercapto-substituted nitrogen-containing telocyclic group) include 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3, A 5-dimercapto-1,2,4-triazole group may be mentioned.

A quaternary salt structure of nitrogen or phosphorus is also preferably used as the adsorptive group. Specific examples of the quaternary salt structure of nitrogen include an ammonio group (trialkylammonio group, dialkylaryl (
Or a heteroaryl) ammonio group, an alkyldiaryl (or heteroaryl) ammonio group) or a group containing a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom.
The quaternary salt structure of phosphorus includes a phosphonio group (trialkyl phosphonio group, dialkylaryl (or heteroaryl) phosphonio group, alkyldiaryl (or heteroaryl) phosphonio group, triaryl (or heteroaryl) phosphonio group, etc.) Is mentioned. More preferably, a quaternary salt structure of nitrogen is used, and more preferably, a 5-membered or 6-membered nitrogen-containing aromatic heterocyclic group containing a quaternized nitrogen atom is used. Particularly preferably, a pyridinio group, a quinolinio group, or an isoquinolinio group is used.
These nitrogen-containing heterocyclic groups containing a quaternized nitrogen atom may have an arbitrary substituent.

Examples of counter anions of quaternary salt are a halogen ion, carboxylate ion, sulfonate ion, sulfate ion, perchlorate ion, carbonate ion, nitrate _{^{ion, BF 4 -, PF 6 -}} , Ph
₄ B- ^{and the} like. When a group having a negative charge in the carboxylate group or the like is present in the molecule, an inner salt may be formed together with the group. As a counter anion not in the molecule,
Chlorine ions, bromo ions or methanesulfonate ions are particularly preferred.

A preferred structure of the compound represented by types 1 and 2 having a quaternary salt structure of nitrogen or phosphorus as the adsorptive group is represented by the general formula (X).

In general formula (X), P and R each independently represent a quaternary salt structure of nitrogen or phosphorus that is not a partial structure of a sensitizing dye. Q ₁ and Q ₂ each independently represent a linking group, specifically a single bond,
Alkylene group, arylene group, heterocyclic group, —O—, —S—, —NR _N —, —C (═O)
_{-, - SO 2 -, -} SO -, - it represents the sole of each group, or a combination consisting of these groups, - P (= O). Here, _RN represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. S is a residue obtained by removing one atom from a compound represented by type (1) or (2). i and j are integers of 1 or more, and are selected from a range in which i + j is 2 to 6. Preferably, i is 1 to 3, and j is 1 to 2, more preferably i is 1 or 2, and j is 1, and particularly preferably i is 1 and j is 1. The compound represented by the general formula (X) preferably has a total carbon number in the range of 10 to 100. More preferably 10-70, still more preferably 1.
It is 1-60, Most preferably, it is 12-50.

The type 1 and type 2 compounds of the present invention may be used at any time during the preparation of the emulsion or during the photosensitive material production process. For example, at the time of particle formation, desalting step, chemical sensitization, and before coating. Moreover, it can also add in several steps in these processes. The addition position is preferably from the end of particle formation to before the desalting step, at the time of chemical sensitization (from immediately before the start of chemical sensitization to immediately after the end), and before application, more preferably at the time of chemical sensitization and before application.

The compounds of type 1 and type 2 of the present invention are preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. PH when dissolved in water
For compounds whose solubility is increased by increasing or decreasing the pH, they may be dissolved at a higher or lower pH and added.

The compounds of type 1 and type 2 of the present invention are preferably used in the emulsion layer, but may be added to the protective layer or intermediate layer together with the emulsion layer and diffused during coating. The timing of addition of the compound of the present invention is preferably before or after the sensitizing dye, and preferably 1 × 10 5 per mole of silver halide.
^{-9 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁸ to 2 × 10 ⁻³ mol in the silver halide emulsion layer.

The above-mentioned various additives are used in the light-sensitive material according to the present invention, but various additives can be used depending on the purpose.

These additives are more specifically described in Research Disclosure Item 17643.
(December 1978), Item 18716 (November 1979) and It It
em 308119 (December 1989), and the corresponding parts are shown in the table below.

Additive type RD17643 RD18716 RD308119
1 Chemical sensitizer page 23 page 648 right column page 996
2 Sensitivity increasing agent Same as above
3 Spectral sensitizer, pages 23 to 24, page 648, right column to 996, right to 998 right Supersensitizer, page 649, right column
4 Brightener 24 pages 647 right column 998 right
5 Antifoggant, 24-25 pages 649, right column 998 right-1000 right and stabilizer
6 Light absorber, page 25-26, page 649, right column to 1003, left to 1003 right Filter dye, page 650, left column, UV absorber
7 Stain inhibitor Page 25 Right column 650 Left to right column 1002 Right
8 Dye image stabilizer 25 page 1002 right
9 Hardener page 26 page 651 left column 1004 right to 1005 left
10 Binder page 26 Same as above 1003 right to 1004 right
11 Plasticizer, Lubricant 27 pages 650 right column 1006 left to 1006 right
12 Coating aid, pages 26-27 Same as above 1005 Left to 1006 Left Surfactant
13 Static 27 pages Same as above 1006 Right to 1007 Left Anti-blocking agent
14 Matting agent 1008 left to 1009 left

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It reacts with formaldehyde described in No. 11,987 and No. 4,435,503,
It is preferable to add a compound capable of fixing to the light-sensitive material.

In the light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747, 6
For example, 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4 described in JP-A No. 2-272248 and JP-A-1-809441.
It is preferable to add various preservatives or antifungal agents such as chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole.

For the method of interference wave recording, processing method, reproduction method, and utilization method of silver halide photosensitive material for holography in the present invention, refer to holography technology, the latest knowledge in the scientific field, etc. Can be. Representative reference books include Toshihiro Kubota, Introduction to Holography, Principles and Practice, Asakura Shoten, 1995, and the like. The light-sensitive material of the present invention can naturally be applied as described in these reference books, and the application becomes simple using high sensitivity, high image quality, and stability.

[Example]
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.

The holographic silver halide photosensitive material of the present invention will be described in detail.
(Preparation of emulsion a)
1660 mL of an aqueous solution containing 43.3 g of deionized bone gelatin having a KBr of 0.28 g and an average molecular weight of 100,000 was kept at 33 ° C. and stirred. After adding 0.04 g of thiourea dioxide, p
H was adjusted to 6.0. 800 ml of an aqueous solution of AgNO ₃ (96.0 g) and an aqueous KBr solution containing 1 mol% of KI were added over 15 minutes by the double jet method. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. From the start of addition of aqueous AgNO ₃ solution during particle formation 2
After 5 minutes, 5 × 10 ⁻⁴ mol of K ₃ IrCl ₆ aqueous solution was added to 1 mol of silver halide. After adding 3 × 10 ⁻⁴ mol of supersensitizer I to 1 mol of silver halide, sensitizing dyes I and II were added at a molar ratio of 50:50 to 9 × 10 to 1 mol of silver halide. ^-4 mol was added. In this experiment, the sensitizing dye was used as a solid fine dispersion prepared by the method described in JP-A No. 11-52507. That is, 0.8 parts by mass of sodium nitrate and 3.2 parts by mass of sodium sulfate were dissolved in 43 parts by mass of ion-exchanged water, 13 parts by mass of a sensitizing dye was added, and 20 ° C. at 2000 rpm using a dissolver blade at 60 ° C. By dispersing for a minute, a solid dispersion of a sensitizing dye was obtained.
After the temperature was lowered to 28 ° C., normal water washing was performed. After adding 21 g of deionized bone gelatin having a number average molecular weight of 20000, the pH was adjusted to 6.0 at 40 ° C. Raise the temperature to 60 ° C,
Per mol of silver halide, chloroauric acid (5.5 × 10 ^-4 mol), sodium thiosulfate (
9.9 × 10 ⁻⁴ mol) and N, N-dimethylselenourea (1.7 × 10 ⁻⁴ mol) were added for optimal chemical sensitization. Antifoggants I (1.0 × 10 ⁻³ mol) and II (3.5
× 10 ⁻³ mol) was added to complete the chemical sensitization.
Emulsion a was a clear cubic grain having a number-average equivalent circle diameter of 32 nm and an angle of variation coefficient of 9% of the equivalent circle diameter. This grain is a silver bromide grain containing 1 mol% of silver iodide, and the coefficient of variation of the inter-grain distribution of the silver iodide content is 7%.

(Preparation of emulsions b-1 to 3)
30 minutes before addition of chloroauric acid during chemical sensitization in the preparation of emulsion a, 1 × 10 ⁻⁵ mol, 3 × 10 ⁻⁵ mol, 9 × 10 ⁻⁵ mol of thiourea dioxide with respect to 1 mol of silver halide at 60 ° C. Emulsions b-1 to 3 were prepared in the same manner except that ^x10-5 mol was added. The number average equivalent circle diameter of the fine particles after chemical sensitization was 32 nm, which was the same as that of Emulsion a.

The cellulose triacetate film support having a thickness of 200 μm provided with the undercoat layer is shown in Table 1 below.
A coating sample was prepared by coating the emulsion subjected to the above chemical sensitization under coating conditions as shown in FIG.

  The back layer was coated on the coated sample with the following contents.

<Preparation and application of conductive layer coating solution>
The following compounds were added to the gelatin aqueous solution and coated so that the gelatin coating amount was 0.06 g / m ² .
SnO ₂ / Sb (9/1 mass ratio, average particle size 0.25 μ) 186 mg / m ²
Gelatin (Ca ⁺⁺ content 3000ppm) 60mg / m ²
Sodium p-dodecylbenzenesulfonate 13 mg / m ²
Dihexyl-α-sulfosuccinate sodium 12mg / m ²
Sodium polystyrene sulfonate 10mg / m ²
Compound-A 1 mg / m ²

<Preparation and application of back layer coating solution>
The following compound was added to the gelatin aqueous solution and coated such that the gelatin coating amount was 1.94 g / m ² .
Gelatin (Ca ⁺⁺ content 30 ppm) 1.94 mg / m ²
Polymethylmethacrylate fine particles (average particle size 3.4μ) 15mg / m ²
Sodium p-dodecylbenzenesulfonate 7 mg / m ²
Dihexyl-α-sulfosuccinate sodium 29 mg / m ²
N-perfluorooctanesulfonyl-N-propyl glycine potassium 5 mg / m ²
Sodium sulfate 150mg / m ²
Sodium acetate 40mg / m ²
Compound-E (hardener) 105 mg / m ²
Compound-C 15 mg / m ²

These samples were left under conditions of 40 ° C. and 70% relative humidity for 14 hours. Thereafter, exposure was performed for 10 seconds through a continuous wedge and a green filter.
Development was carried out using a D-19 developer at 20 ° C. for 5 minutes, followed by fixing, washing with water and drying.
Table 2 shows the sensitivity value and the fog value of the sample obtained as described above at the concentration of fog plus 1.5.

As is clear from the results in Table 2, the use of gold-chalcogen sensitization and reduction sensitization during chemical sensitization resulted in almost no increase in fog and extremely high sensitivity was obtained. When the coated sample was stored at room temperature for 3 months and exposed and developed in the same manner, no change in fog or sensitivity was observed. That is, it has been clarified that the photosensitive material for holography of the present invention has low fog and high sensitivity and is excellent in storage stability.

In the emulsion b-2 of the present invention prepared in Example-1, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to 1 mol of silver halide before the start of chemical sensitization. And
Emulsions c-1 to 3 were prepared in the same manner except that 1 × 10 ⁻³ mol, 6 × 10 ⁻³ mol, and 3.6 × 10 ⁻² mol were added. The particle size immediately after preparation and the particle size after storage in a refrigerator for 3 months were measured. The results are shown in Table-3.

As is clear from the results in Table 3, when the tetrazaindene compound was added in an amount of 6 × 10 ⁻³ mol per mol of silver halide, the grain size was not changed at all. 3.6x
When 10 ⁻² mol is added, the particle size changes much more than when it is not added. When these emulsions were applied and exposed and developed in the same manner as in Example 1, it was found that the photographic characteristics changed in accordance with the change in grain size. It has been clarified that by adding an appropriate amount of a tetrazaindene compound, it is possible to prepare an emulsion that is stable against changes over time from preparation of the emulsion to coating.

The effect of the photosensitive material for holography of the present invention under photographing Danish holography is shown.
(Preparation of emulsion d-1)
Emulsion d-1 was prepared in the same manner as in Preparation of Emulsion c-2 of Example-2 except that sensitizing dyes I and II were changed to III and IV, respectively. The number average equivalent circle diameter of the emulsion d-1 was 34 nm, and the variation coefficient of the equivalent circle diameter was 11% rounded cubic grains.

A back layer is coated on one side of a TAC base having a thickness of 200 μm, and emulsion d-
1 and Emulsion c-2 were coated in multiple layers under the coating conditions shown in Table-1. That is, a two-layer structure of a red light-sensitive silver halide emulsion layer and a green light-sensitive silver halide emulsion layer was formed on the base. However, the coating amount of each photosensitive layer was 0.67 times that of Table-1. Together two layers, the coating amount of silver 4g / m ²
The amount of coated gelatin is 5.3 g / m ² .
Helium-neon laser is used for red as a light source, and argon laser is used for green. Toshihiro Kubota, Introduction to Holography-Principle and Practice, 1995 Asakura Shoten Publishing, p. 82 of FIG.
. With reference to the photographing system described in No. 4, a Danish-type holographic photographing was performed.
Ibid, p. 159 was processed according to the formulation of CW-C2 developer + PBQ-2 bleaching solution. Visual evaluation of the reproduced image revealed that a bright and clear color image was obtained. Although blue exposure was not performed in this experiment, it was revealed that a good color reproduction image could be obtained with two colors of red and green. It is predicted that a very clear color image can be obtained if blue exposure is also added.
A simple reproduction device using red and green LEDs corresponding to the reproduction wave wavelength was manufactured. 1 above
A hologram of 0x12 cm can be easily reproduced on a table with a 1.5 V dry cell so that the hologram can be illuminated from above at 45 degrees, which is the same angle as the reference light, and at a distance of 15 cm. It is what. By using the light-sensitive material of the present invention, a good reproduction image could be appreciated in a bright room with a simple reproduction apparatus.

Claims (4)

  In a silver halide holographic photosensitive material having at least one photosensitive silver halide emulsion layer on a support, the number average equivalent circle diameter of silver halide grains in the silver halide emulsion layer is from 10 nm to 80 nm. A silver halide holographic light-sensitive material characterized in that reduction sensitization is performed in addition to gold-chalcogen sensitization during chemical sensitization of silver halide grains.   2. The silver halide holographic photosensitive material according to claim 1, wherein the reduction sensitization is performed by adding a reduction sensitizer. 2. The photosensitive silver halide emulsion layer contains 3 × 10 ⁻³ mol or more and 3 × 10 ⁻² mol or less of a tetrazaindene compound per mol of silver in silver halide grains. 2. A silver halide holography-photosensitive material according to 2.   The photosensitive silver halide emulsion layer has at least one green photosensitive silver halide emulsion layer having an absorption maximum at 500 nm to 600 nm and at least one red photosensitive silver halide emulsion layer having an absorption maximum at 600 nm to 750 nm. The silver halide holography-sensitive material according to claim 1, which contains one layer.