JPH083605B2 - Silver halide photographic material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material. Particularly, it relates to a silver halide photographic light-sensitive material having high sensitivity and excellent reciprocity law failure characteristics.

[Conventional technology]

Higher sensitivity of film is inevitably high because the market demands high sensitivity and high gradation, and the high silver price necessitates reduction of the amount of silver used in the film. Sensitization is strongly demanded and has become an important issue. In addition, for example, in X-ray film, it is important for reducing exposure dose.

In order to increase the sensitivity of the film, there is a method of decreasing the hardness of the film layer made of gelatin or the like.
However, this method is not preferable because the graininess of the developed image deteriorates and the physical properties of the film deteriorate.

JP-A-57-89749 discloses thioethers (for example, C
₆ H ₁₃ OCOCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OCOC ₆ H ₁₃ ) or a nitrogen-containing cyclic compound having a thioketone group, etc. is added to the silver halide emulsion or the developing solution. It is disclosed. However, if the sensitivity is increased by this method, the graininess is deteriorated and, when added to the silver halide emulsion, fog is increased during storage, which is not preferable.

High sensitivity can be achieved by increasing the grain size of the silver halide emulsion, but in order to obtain both high sensitivity and required maximum image density, more silver salt must be contained per unit area of the film, In addition, the graininess is deteriorated and the covering power is lowered, which is not preferable (JP-A-59-1480).
No. 51).

As one of the attempts to improve the covering power while maintaining the high sensitivity, the technology of adding various polymers to the high-sensitivity coarse-grain silver halide emulsion is British Patent No. 1,048,057.
No. 1,039,471, U.S. Pat.No. 3,043,697, No. 3,
No. 446,618 is described in each specification. All of these have some effect of increasing the covering power, but they are not sufficient, and further weaken the strength of the coating film, which is not preferable. Furthermore, this method causes a large change in fog over time,
Development unevenness is likely to occur depending on the development processing method, which is not preferable.

On the other hand, today's high-sensitivity films are used in various ways, and the exposure time reaches from a few seconds to the flash exposure range.
Under the exposure conditions of 1/100 to 1/10 second, the sensitivity is usually the highest, and the sensitivity decreases remarkably when the exposure time is longer than that or extremely short. There is a problem called a phenomenon called.

For example, it is well known that medical X-ray films are often photographed with a relatively long exposure time, and industrial X-ray films are prone to high-illuminance reciprocity law failure. Also, in general photography, since the level of so-called amateur photographers has risen and the photography conditions have become quite wide, a photosensitive material with less reciprocity law failure characteristics that can cope with various photography conditions is desired. .

As a means for further increasing the sensitivity, grains containing a high concentration of silver iodide inside the silver halide grains (hereinafter abbreviated as grains having a high internal AgI content) can be used. Internal high AgI
Regarding the content particles, see, for example, JP-A-59-17753 and 59-1.
78447 and Japanese Patent Application No. 59-254581. However, it was found that the internal high AgI content particles have a sensitizing effect, but desensitize when exposed for a long time at low illuminance, that is, the deterioration of low illuminance failure characteristics occurs.

Regarding the improvement of the reciprocity law failure characteristic, in particular, regarding the high illuminance reciprocity law failure characteristic, for example, Japanese Patent Publication Nos. 43-4935 and 45-3273.
Although it is described in the specification such as No. 8, it is not intended to improve the low-illuminance reciprocity law failure at the same time.

[Object of the Invention]

Therefore, the present invention is to provide a silver halide photographic light-sensitive material which has high sensitivity and is excellent in reciprocity law failure characteristics particularly in low illuminance.

[Structure and Action of Invention]

The silver halide photographic light-sensitive material of the present invention is a multilayered silver halide grain containing at least silver iodide as silver halide, wherein at least one pair of iodide grains adjacent to each other is iodide-containing. A silver halide grain having a silver content difference of 5 mol% or more and a polyhydric alcohol having at least two hydroxyl groups having a melting point of 40 ° C. or more are used.

The silver halide grains contained in the above silver halide photographic light-sensitive material contain at least silver iodide and may be any of silver iodochloride, silver iodobromide and silver chloroiodobromide. In particular, silver iodobromide is preferred from the viewpoint that high sensitivity can be obtained.

The silver halide grains have a multilayer structure.
The multi-layer structure means a structure including at least two layers (core portion and shell portion) or more, such as a core-shell structure.

Further, in the above-mentioned silver halide grains, one of two adjacent layers in the grain has a difference in interlayer silver iodide content of 5 mol% or more. For example, in the case of a core-shell structure, the silver iodide content is high in the entire core, and there is a difference in the content of 5 mol% or more compared to the shell portion.
In the case where the inside of the grain is divided into two or more layers, one of the two adjacent layers has a difference in inter-layer silver iodide content of 5 mol% or more.

To increase the sensitivity of silver halide photographic light-sensitive materials, the average silver iodide content in silver halide grains is 0.5 to 10 mol%.
And more preferably 1 to 8 mol%, and a portion having a high silver iodide concentration due to the presence of a plurality of layers having a difference in silver iodide content of 5 mol% or more in the layer in the grain,
The lower part can be formed. In the case of increasing the sensitivity, it is preferable that the inside of the grain has a layer having a high silver iodide concentration as much as possible from the outer surface of the grain, especially from the outer surface.
It is preferable that a high-concentration portion exists in a portion separated by 01 μm or more.

The silver halide photographic light-sensitive material of the present invention contains the above-mentioned silver halide grains and a compound composed of a polyhydric alcohol having a melting point of 40 ° C. or higher and having at least two hydroxyl groups.

This compound has 2 to 12 hydroxyl groups and 2 to 12 carbon atoms.
An alcohol which has 20 hydroxyl groups and in which hydroxyl groups are not conjugated with a conjugated chain, that is, an oxidized form cannot be written, is preferable. Furthermore, the melting point is 50 ° C or higher and 300
It is preferably below ℃.

Hereinafter, one example of preferable specific examples of the alcohol will be described, but the compound is not limited to the following examples.

Compound example Melting point 1.2,3,3,4-Tetramethyl-2,4-pentanediol 76 ° C 2.2,2-Dimethyl-1,3-propanediol 126-128 ° C 3.2,2-Dimethyl-1,3-pentanediol 60-63 ° C 4.2,2,4-Trimethyl-1,3-pentanediol 52 ° C 5.2,5-Hexanediol 43-44 ° C 6.2,5-Dimemel-2,5-hexanediol 92-93 ° C 7.1,6- Hexanediol 42 ° C 8.1,8-Octanediol 60 ° C 9.1,9-Nonanediol 45 ° C 10.1,10-Decanediol 72 to 74 ° C 11.1,11-Undecanediol 62 to 62.5 ° C 12.1,12-Dodecanediol 79 to 79.5 ° C 13.1,13-Tridecanediol 76.4-76.6 ° C 14.1,14-Tetradecanediol 83-85 ° C 15.1,12-Octadecanediol 66-67 ° C 16.1,18-Octadecanediol 96-98 ° C 17.cis-2,5-Dimethyl -Hexene-2,5-diol 69
℃ 18.Trans-2,5-dimethyl-3-hexene-2,5-diol 77 ℃ 19.2-Butyne-1,4-diol 55 ℃ 20.2,5-Dimethyl-3-hexyne-2,5-diol 95 ℃ 21.2,4-Hexadiyne-1,6-diol 111-112 ° C 22.2,6-Octadiyne-1,8-diol 88.5-89.5 ° C 23.2-Methyl-2,3,4-butanetriol 49 ° C 24.2,3,4- Hexanetriol About 47 ° C 25.2,4-Dimethyl-2,3,4-pentanetriol 99 ° C 26.2,4-Dimethyl-2,3,4-hexanetriol 75 ° C 27.Pentamethylglycerin 116-117 ° C 28.2-Methyl- 2-Oxymethyl-1,3-propanediol 199 ° C 29.2-Isopropyl-2-oxymethyl-1,3-propanediol 83 ° C 30.2,2-Dihydroxymethyl-1-butanol 58 ° C 31.Erythritol 126 ° C 32.D -Tray 88 ° C 33.L-Tray 88 to 89 ° C 34.rac-Tray 72 ° C 35.penta Risuritoru 260~265 ℃ 36.1,2,3,4- pen Thante trawl 106 ℃ 37.2,3,4,5- hexane tetrol 162 ℃ 38.2,5- dimethyl-2,3,4,5-hexane tetrol 153～
154 ℃ 39.1,2,5,6-hexanetetrol 95 ℃ 40.1,3,4,5-hexanetetrol 88 ℃ 41.1,6- (erythro-3,4) -hexanetetrol 121〜
122 ° C 42.3-hexene-1,2,5,6-tetrol 80-82 ° C 43.3-hexyne-1,2,5,6-tetrol 113-114.5 ° C 44.Adonitol 102 ° C 45.D-arabitol 102 ° C 46. L-arabitol 102 ° C 47.rac-arabitol 105 ° C 48.xylitol 93-94.5 ° C 49.L-mannitol 164 ° C 50. dulcitol 188.5-189 ° C Also, as a comparative compound having a melting point of less than 40 ° C, 51 Diethylene glycol-7 ° C 52.1,4-butanediol 16 ° C 53.2,2-dimethyl-1,3 propanediol 10 ° C 54.1,2,6-hexanetriol-20 ° C 55.glycerin 18.2 ° C 56.2,4-dimethyl-2, 4-pentanediol 7 ° C 57. Ethylene glycol -12.6 ° C.

The addition amount of alcohol in the present invention is preferably 1 g to 100 g, and more preferably 1 mol per mol of silver halide.
It is 5g to 50g. If it is less than the above range, the effect is small, and the fog may spread due to spreading of fog during coating and drying. On the other hand, if the amount of addition is too large, so-called scratches may occur in which the emulsion surfaces of the films stick to each other at high humidity, or scratches easily occur between the films or between the films and the side paper. Regarding kutsuki, it can be prevented by dispersing particles such as polymethylmethacrylate or colloidal silica in the layer, that is, by using a so-called matting agent, but if the amount of the polyhydric alcohol added is too large, the matting agent is used. Care should be taken because even if dispersed, it may cause a crackling.

In the present invention, the above alcohol is preferably added to the silver halide emulsion layer or a layer adjacent thereto.

The addition time is optional, but it is added after the chemical sensitization and during the coating.

In addition, as a method of addition, it may be dispersed directly in the hydrophilic colloid, or may be added after being dissolved in an organic solvent such as methanol or acetone.

Thus, the addition of the alcohol in the present invention,
By containing one of the two adjacent layers in the silver halide grain having a difference in inter-layer silver iodide content of 5 mol% or more, the sensitivity is improved and the reciprocity law failure characteristic is improved.

It has been known from the past that using a silver halide grain having a layer with a high silver iodide concentration has a sensitizing effect, but the so-called low-illuminance reciprocity failure characteristic is desensitized when exposed for a long time at low illuminance. Deterioration was a problem. Then, the present inventor has conducted a study to improve the low illuminance reciprocity law failure property, and found that the reciprocity law failure property changes depending on the kind of a polyhydric alcohol having at least two hydroxyl groups, which is called a wetting agent. It was Therefore, as a result of further study, the reciprocity law failure characteristic is improved by adding a polyhydric alcohol having a melting point of 40 ° C or higher and having at least two hydroxyl groups, but a polyhydric alcohol having a melting point of lower than 40 ° C is It turned out that the effect could not be obtained. Thus, by using the above silver halide grains and the above alcohol in combination, a silver halide photographic light-sensitive material having high sensitivity and good photographic performance with less reciprocity law failure characteristics can be obtained. It came to.

As a patent for polyhydric alcohol, Japanese Patent Application Laid-Open No. 49-6632
No. 9, Japanese Patent Publication No. 47-8745, No. 57-80451, No. 52-31737
Although there are specifications such as No., there is no description about reciprocity law failure characteristics, and they are described regardless of melting point.

Next, the adjacent two in the silver halide grain of the present invention
One of the layers has a difference in inter-layer silver iodide content of 5 mol%
The preferred embodiments of the above silver halide grains will be described in more detail.

In the case of the core-shell structure, the silver iodide content is higher than the shell portion by 5 mol% or more in a part or all of the grain core portion excluding the shell portion having a thickness of 0.01 μm or more from the outer surface. It is preferable.

The concentration of silver iodide is higher than that of the adjacent layer.
It is preferably in the range of 30 to 40 mol%.

The outside of such a high silver iodide concentration area is usually
Coated with silver halide formed using a halogen salt solution containing no iodine. That is, in a preferred embodiment, it is 0.01 μm or more from the outer surface, particularly 0.01 to 1.
The 5 μm thick shell portion is formed of silver halide (usually silver bromide) formed using a halogen salt solution containing no iodine.

However, in the present invention, silver iodide may be contained on the surface of the silver halide grain, in the vicinity thereof, or on the outermost layer of the core-shell structure.

In the present invention, in the particles (preferably from the outer wall of the particles 0.
As a method of forming a portion having a silver iodide concentration of 5 mol% or more higher than that of the adjacent layer on the inner side of the grains separated by 01 μm or more), it is preferable to use seed crystals, but not to use seed crystals. It may be.

When seed crystals are not used, the reaction liquid phase containing the protected gelatin (hereinafter referred to as the mother liquor) does not have silver halide that serves as a growth nucleus before ripening. Halide ions are supplied to form growth nuclei. Then, the additive supply is further continued to grow particles from the growth nuclei. Finally, a halide layer containing no iodine ion is supplied to form a shell layer having a thickness of 0.01 μm or more with silver halide.

When using seed crystals, silver iodide is formed only in the seed crystals,
After this, it may be covered with a shell layer. Alternatively, the amount of silver iodide in the seed crystal is set to 0 or within the range of 10 mol% or less, and silver iodide inside the grain is formed in the step of growing the seed crystal,
After that, you may coat with a shell layer.

In the silver halide photographic light-sensitive material according to the present invention, at least 50 silver halide grains present in the emulsion layer are contained.
% Is preferably a grain having an adjacent layer having a difference in silver iodide content of 5 mol% or more as described above.

In the silver halide photographic light-sensitive material of the present invention, it is preferable to use silver halide grains having a regular structure or morphology having a high silver iodide concentration portion in the silver halide grains as described above.

The term "structured or morphologically ordered silver halide grain" as used herein means a grain that does not include anisotropic growth such as twin planes and grows isotropically. For example, a cube, a tetrahedron, a regular octahedron, It has a spherical shape. There are various methods for producing such regular silver halide grains. Journal of Photographic Science (J.Phot.Sci.),
5 , 332 (1961), Berichte der Bunsenges Gesellschaft der Physik Chemie (Ber.Bunsenges.
Phys.Chem.) 67, 949 (1963 ), International Congress of Photographic Science of Tokyo (Intern.Congress Phot.Sci.Tokyo)
(1967) etc.

Such regular silver halide grains can be obtained by controlling reaction conditions when growing silver halide grains by using a double jet method. In such a simultaneous mixing method, silver halide grains are prepared by adding a silver nitrate solution and a silver halide solution in approximately equal amounts to an aqueous solution of a protective colloid with vigorous stirring.

Then, the supply of silver ions and halide ions is not necessary and sufficient for growing only existing particles, which does not dissolve existing crystal particles along with the growth of crystal particles, and conversely does not allow generation and growth of new particles. It is preferable to gradually or continuously increase the growth rate at the critical growth rate at which silver halide is supplied or at the allowable range thereof. This increasing method is described in Japanese Patent Publication Nos. 48-36890, 52-16364 and JP-A 55-142329.

This limiting growth rate varies depending on temperature pH, pAg, degree of stirring, composition of silver halide grains, solubility, grain size, inter-grain distance, crystal habit, or type and concentration of protective colloid. It can be easily determined experimentally by a method such as microscopic observation of emulsion particles suspended in a liquid phase and measurement of turbidity.

It is desirable that at least 50% by weight of the silver halide grains contained in the silver halide emulsion layer are regular grains as described above.

Further, it is desirable to use a monodisperse emulsion having silver halide grains having a partially high silver iodide concentration as described above.

The monodisperse emulsion referred to here is, for example, the
The Photographic J
ournal), 79 , 330-338 (1939), by the method reported by Trivelly, Smith, the average particle diameter was measured to be at least 95 by number of particles or weight.
% Particles are within ± 40% of the average particle size, preferably ± 30
A silver halide emulsion having a silver halide content within 100%.

Such monodisperse emulsion grains are made using the double jet method, as is the case for regular silver halide grains. The various conditions at the time of simultaneous mixing are the same as in the method for producing regular silver halide grains.

As a method for producing such a monodisperse emulsion, for example, Journal of Photographic Science (J.Phot.Sc
i.), 12 , 242 to 251 (1963) JP-A-48-36890, 52-
16364, JP-A-55-142329, and JP-A-58-49938.

In order to obtain the above monodisperse emulsion, it is particularly preferable to use a seed crystal and grow grains by supplying silver ions and halide ions with the seed crystal as a growth nucleus.

The wider the grain size distribution of this seed crystal, the wider the grain size distribution of the grain growth nuclei. Therefore, in order to obtain a monodisperse emulsion, it is preferable to use one having a narrow grain size distribution at the seed crystal stage.

The above-described silver halide grains used in the silver halide photographic light-sensitive material of the present invention are described in, for example, "The Theory of the." By TH James.
Photographic Process "(The Theory of the
Photographic Process) 4th edition, published by Macmillan (Macm
illan) (1977), pages 38-104, etc., neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, controlled-double jet method, conversion method, core shell method. And the like can be applied to manufacture.

Further, various heavy metal salts such as iridium salt and rhodium salt may be contained in these silver halide grains or a silver halide emulsion containing the grains in order to improve their photographic characteristics.

Furthermore, these silver halide grains have a pAg of the mother liquor containing a protective colloid temporarily increased to at least 10.5, particularly preferably 11.5 or more during the growth process, so that (111) on the outer surface of the grain Face 5
The effect of the present invention can be further enhanced by rounding the particles by increasing the amount by at least%.

In this case, the rate of increase of the (111) plane is p
It is for before passing Ag atmosphere, especially the increase rate of (111) plane is 10% or more, more preferably 10 to 2
It is preferably 0%.

Outer surface of silver halide grain is (111) face or (100) face
Akira Hirata's report, "Bretin of the Society of Scientific Photographic of Japan," No. on whether one of the faces is covered or how to measure the ratio .1
3, 5 to 15 (1963).

In the present invention, during grain growth before chemical sensitization, an atmosphere in which the pAg of a mother liquor containing a protective colloid is at least 10.5 or more is once passed to increase the (111) plane by 5% or more by the Hirata measurement method. Whether or not it can be easily confirmed.

In this case, the above-mentioned pAg time is before the chemical sensitization, but is preferably before the desalting step from the time when the silver ions are added for the growth of silver halide grains, especially after the addition of the silver ions. Therefore, it is desirable that it is before the so-called desalting step which is usually performed before the chemical sensitization. This is because it is easy to obtain a monodisperse emulsion having a narrow grain size distribution.

The aging in an atmosphere having a pAg of 10.5 or more is preferably performed for 2 minutes or more.

By such pAg control, the (111) plane increases by 5% or more, and the shape becomes rounded.

When the average grain size of the silver halide grains used in the present invention is larger than 3.0 μ, the graininess is significantly deteriorated,
Furthermore, the sensitizing effect is not always obtained, and the object of the present invention cannot be achieved. On the other hand, when the average particle size is smaller than 0.2 μ, the sensitivity is remarkably lowered, and the sensitivity and the characteristic curve which meet the purpose cannot be obtained. The average grain size of the silver halide grains in the present invention is preferably in the range of 0.4 to 1.7μ.

Next, the emulsion used in the present invention is usually free from soluble salts after the formation of a precipitate or after physical ripening. As a means therefor, it is possible to use the Nudel water washing method in which gelatin, which has been known since old times, is gelled. Well, also inorganic salts consisting of polyvalent anions such as sodium sulfate, anionic surfactants, anionic polymers (eg polystyrene sulfonic acid), or gelatin derivatives (eg aliphatic acylated gelatin, aromatic acylated gelatin, aromatics). A precipitation method (flocculation) using carbamoylated gelatin or the like may be used. The process of removing soluble salts may be omitted.

In the present invention, the emulsions may be used alone, or two or more kinds of silver halide emulsions having different average grain sizes may be used in combination. In this case, the composition of silver halide in each emulsion may be different or the same.

The light-sensitive silver halide emulsion may be used as it is as a so-called unripened (Primitive) emulsion without chemical sensitization, but it is usually chemically sensitized. For chemical sensitization, the above-mentioned works by Glafkides or Zelikman or edited by H. Frieser, edited by D. Grundlagen der Photography Shen Protese Mitt Gilberhalogeny. Den (Academiche Fairlarks Gezelshaft) (Die Grundlargen der Photographischen P
rozesse mit Silberhalogeniden, Akademische Verlagsg
esellschaft.) 1968, can be used.

That is, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or another noble metal compound, or the like is used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are U.S. Pat.No. 1,574,944, 2,41.
0,689, 2,278,947, 2,728,668, 3,656,955. As the reduction sensitizer, primary tin salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and the like can be used, and specific examples thereof are U.S. Patents 2,487,850, 2,419,974, 2,518,698.
No. 2,2,983,609, 2,983,610, 2,694,637. For sensitizing precious metals, in addition to gold complex salts, platinum,
Complex salts of metals of Group VIII of the Periodic Table such as iridium and palladium can be used, and specific examples thereof include US Pat.
083, 2,448,060, British Patent 618,061 and the like.

Various hydrophilic colloids can be used as a binder in the photographic light-sensitive material of the present invention.

Examples of colloids used for this purpose include hydrophilic colloids generally used in the field of photography, such as gelatin, colloidal albumin, polysaccharides, cellulose derivatives, synthetic resins, polyvinyl compounds including polyvinyl alcohol derivatives, acrylamide polymers, and the like. I can name it. Hydrophobic colloids such as dispersed polymeric vinyl compounds, especially those which increase the dimensional stability of the photographic material, can be included together with hydrophilic colloids. Suitable compounds of this type include alkyl acrylates or alkyl methacrylates, acrylic acid,
Water-insoluble polymers made by polymerizing vinyl-based monomers such as sulfoalkyl acrylate or sulfoalkyl methacrylate are included.

Various compounds can be added to the above photographic emulsion in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process of the light-sensitive material, during storage or during processing.

That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds): heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercapto Benzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyridines: the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group: a thioketo compound, for example Oxazoline thione: Azaindenes, for example, tetraazaindenes: (especially 4-hydroxy-substituted (1,3,3a, 7) taylazaindenes): benzenethiosulfonic acids: benzenesulnes Fin acid: may be added a number of compounds such known as stabilizers like.

An example of a compound that can be used is K. Mees
By The Theory of the Photographic Process
(3rd edition, 1966) with reference to the original literature.

For more detailed specific examples of these and methods for using the same, for example, U.S. Pat.Nos. 3,954,474 and 3,982,947,
Reference can be made to the respective specifications of No. 4,021,248 or Japanese Patent Publication No. 52-28660.

In the light-sensitive material of the present invention, the photographic silver halide emulsion layer and the other hydrophilic colloid layer can be hardened with any appropriate hardener. These hardeners include mucochloric acid, mucobromic acid, mucophenoxycycloric acid, mucophenoxybromic acid, formaldehyde, dimethylolurea, trimethylolmelamine, glyoxal, monomethylglyoxal, 2,3-dihydroxy-1,4-dioxane, 2 Aldehyde compounds such as 3,3-dihydroxy-5-methyl-1,4-dioxane, succinaldehyde, 2,5-dimethoxytetrahydrofuran and glutaraldehyde: divinyl sulfone, methylene bismaleimide, 5
-Acetyl-1,3-diacryloyl-hexahydro-s
-Triazine, 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3,5-trivinylsulfonyl-
Active vinyl compounds such as hexahydro-s-triazine bis (vinylsulfonylmethyl) ether, 1,3-bis (vinylsulfonylmethyl) propanol-2, bis (α-vinylsulfonylacetamido) ethane: 2,4-dichloro-6 -Hydroxy-s-triazine sodium salt, 2,4-dichloro-6-methoxy-s-triazine,
2,4-Dichloro-6- (4-sulfoanilino) -s-triazine sodium salt, 2,4-dichloro-6- (2-
Active halogen compounds such as sulfoethylamine) -s-triazine, N, N'-bis (2-chloroethylcarbamyl) piperazine: bis (2,3-epoxypropyl) methylpropylammonium p-toluenesulfonate, 1,4-bis (2 ', 3'-epoxypropyloxy)
Butane, 1,3,5-triglycidyl isocyanurate, 1,3
-Epoxy compounds such as diglycidyl-5- (γ-acetoxy-β-oxypropyl) isocyanurate: 2,
Ethyleneimine compounds such as 4,6-triethyleneimino-s-triazine, 1,6-hexamethylene-N, N'-bisethyleneurea, and bis-β-ethyleneiminoethylthioether: 1,2-di (methane Sulfoneoxy) ethane, 1,
Methanesulfonic acid ester-based compounds such as 4-di (methanesulfonoxy) butane and 1,5-di (methanesulfonoxy) bentane: Further, carbodiimide-based compounds: isoxazole-based compounds: and inorganic-based compounds such as Krommeiban Can be mentioned.

For the photographic emulsion layer or other constituent layers of the light-sensitive material of the present invention, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization).
For various purposes, a surfactant other than the present invention may be included.

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Alkyl amides or amides, polyethylene oxide adducts of silicones) glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols,
Nonionic surfactants such as sugar alkyl esters:
Alkyl carboxylates, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurates, sulfosuccinates, sulfoalkyl polysulfates Anionic surfactants containing carboxy groups such as oxyethylene alkyl phenyl ethers and polyoxyethylene alkyl phosphates, sulfo groups, phospho groups, sulfuric acid ester groups, phosphoric acid ester groups and sugar acidic groups: amino acids, amino Amphoteric surfactants such as alkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides: alkyl amine salts,
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation, prevention of halation, and the like. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful.

In the light-sensitive material of the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like.

Further, the photographic light-sensitive material of the present invention can contain an alkyl acrylate latex described in U.S. Pat. Nos. 3,411,911, 3,411,912 and JP-B-45-5331 in a photographic constituent layer.

Other additives in the photographic silver halide emulsion layer, especially those useful in photographic emulsions, such as lubricants, sensitizers, light absorbing dyes,
Plasticity and the like can be added.

In the light-sensitive material of the present invention, the photographic emulsion may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength with a sensitizing dye.

Dyes used 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 cyanine dyes, merocyaninine dyes and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. 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 nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and these Nuclei of aromatic hydrocarbon rings fused to the nuclei of: indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benzimidazoles A nucleus, a quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-
A 5- or 6-membered heterocyclic nucleus such as 2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, or thiobarbituric acid nucleus can be applied.

The sensitizing dye used in the present invention is used in the same concentration as that used in a normal negative type silver halide emulsion. In particular, it is advantageous to use a dye concentration that does not substantially reduce the intrinsic sensitivity of the silver halide emulsion. Silver halide 1
About 1.0 × 10 ⁻⁵ to about 5 × 10 ⁻⁴ moles of sensitizing dye per mole,
Especially about 4 × 10 ^{-5 of} sensitizing dye per mol of silver halide
It is preferably used at a concentration of ˜2 × 10 ⁻⁴ molar.

The photographic emulsion of the present invention may contain a color image-forming coupler, that is, a compound (hereinafter abbreviated as coupler) which reacts with an oxidation product of an aromatic amine (usually a primary amine) developing agent to form a dye. The coupler is preferably a non-diffusible type having a hydrophobic group called a ballast group in the molecule.
The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion. Further, a colored coupler having a color correcting effect or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be contained. The coupler may be such that the product of the coupling reaction is colorless.

As the yellow color coupler, a known open chain ketomethylene type coupler can be used. Among them, benzoylacetoanilide compounds and pivaloylacetoanilide compounds are advantageous.

A pyrazolone compound, an indazolone compound, a cyanoacetyl compound or the like can be used as the azenta coupler, and the pyrazolone compound is particularly advantageous.

As the cyan coupler, a phenol compound, a naphthol compound or the like can be used.

The protective layer of the silver halide photographic light-sensitive material of the present invention is a layer composed of a hydrophilic colloid, and the above-mentioned hydrophilic colloid is used. Further, the protective layer may be a single layer or multiple layers.

A matting agent and / or a leveling agent may be added to the emulsion layer or protective layer of the silver halide photographic light-sensitive material of the present invention, preferably in the protective layer. Examples of the matting agent are water-dispersible materials such as polymethylmethacrylate having an appropriate particle size (particle size of 0.3 to 5 μm, or preferably 2 times or more, especially 4 times or more the thickness of the protective layer). Organic compounds such as vinyl polymers or inorganic compounds such as silver halide and barium strontium sulfate are preferably used. The smoothing agent is useful for preventing adhesion failure similar to the matting agent, and is particularly effective for improving the frictional characteristics related to the camera suitability during shooting or projection of motion picture film. Specific examples include liquid paraffin, Waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or their derivatives, polyalkylpolysiloxanes, polyarylpolysiloxanes, polyalkylarylpolysiloxanes, or silicones such as their alkylene oxide addition derivatives It is preferably used.

The silver halide photographic light-sensitive material of the present invention may further include an antihalation layer, an intermediate layer, a filter layer, and the like, if necessary.

Specific examples of the silver halide photographic light-sensitive material using the silver halide photographic emulsion of the present invention include Xray light-sensitive material, lith light-sensitive material, black photographic light-sensitive material, color negative light-sensitive material, color reversal light-sensitive material, color photographic paper, etc. Can be mentioned.

Various additives may be added to the photographic light-sensitive material of the present invention, if necessary. For example, dyes, development accelerators, fluorescent whitening agents, color fogging inhibitors, ultraviolet absorbers, and the like. Specifically, Research Disclosure No. 176, pp. 28-30 (RD-17643,
1978) can be used.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for photographic light-sensitive materials. Useful as the flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, a baryter layer or an α-olefin polymer. Examples include paper coated or laminated with (eg, polyethylene, polypropylene, ethylene / butane copolymer). The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally subbed to improve adhesion with photographic emulsion layers and the like. JP-A-52-104913, 59
Those subjected to the undercoating treatment described in Nos. -18949, 59-19940 and 59-19941 are preferable. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various known coating methods. For the coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, or the like can be used.

The present invention can be used for any photographic light-sensitive material that requires high sensitivity or high contrast. For example, it is used for an X-ray photographic light-sensitive material, a lith type photographic light-sensitive material, a black and white negative photographic light-sensitive material, a color negative light-sensitive material, a color paper light-sensitive material.

Further, it can also be used for a diffusion transfer light-sensitive material, a color diffusion transfer light-sensitive material, etc., which forms a positive image by dissolving undeveloped silver halide and precipitating it on the image receiving layer adjacent to the silver halide emulsion layer.

For photographic processing of the light-sensitive material of the present invention, for example, research
Disclosure (Research Disclosure) 176 No. 28
It is possible to apply any of various methods and various processing solutions as described on pages 30 to 30 (RD-17643). This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose.
The treatment temperature is usually selected between 18 ° C and 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C.

For example, the developing solution used for black and white photographic processing can contain a known developing agent. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-3-).
Pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol) and the like can be used alone or in combination. For the photographic processing of the light-sensitive material of the present invention, it is also possible to carry out processing with a developing solution containing imidazoles as a silver halide solvent described in Japanese Patent Application No. 55-155489. Further, it can be processed with a developing solution containing a silver halide solvent described in Japanese Patent Application No. 56-136267 and an additive such as indazole or triazole. The developer generally contains various other preservatives, alkali agents, pH buffers, antifoggants, and the like, and if necessary, dissolution aids, color tones, development accelerators, surfactants, defoamers, Water softener,
A hardener, a viscosity imparting agent, etc. may be included.

A so-called "lith type" development process can be applied to the photographic emulsion of the present invention. What is "lith type" development processing? For the photographic reproduction of line images or photographic reproduction of halftone images with halftone images, dihydroxybenzenes are usually used as the developing agent and the development process is carried out under a low sulfite ion temperature. It means a contagious development process (for details, see Mason's "Photographic Processing Chemistry" (1966), pages 163-165).

As a special form of development processing, a method may be used in which a developing agent is contained in a light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is processed in an alkaline aqueous solution for development. Hydrophobic developing agents are research disclosure
169 (RD-16928) U.S. Patent No. 2,739,890, UK Patent 8
It can be incorporated in the emulsion layer by various methods described in 13,253 or West German Patent 1,547,763. Such a development treatment may be combined with a silver salt stabilization treatment with thiocyanate.

As the stabilizing solution, one having a generally used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

When color photographic development processing is performed, for example, a negative / positive method, a color reversal method, a silver dye bleaching method or the like is used.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are primary aromatic amine developers such as phenylenediamines (eg 4-
Amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amine-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Methanesulfamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylaniline, etc.) and LFA Mason (LFAMaso
n) Photographic Processing Chemistry, published by Focal Press (Photographic Processin
Chemistry. Focal Press), 1966, pp. 226-229, U.S. Patent Nos. 2,193,015 and 2,592,364, JP-A-48-6493.
Those described in No. 3 may be used.

The color developer may further contain a pH buffering agent, a development inhibitor or an antifoggant. If necessary, a water softener, a preservative, an organic solvent, a development accelerator, a dye-forming coupler, a competitive coupler, a fogging agent, an auxiliary developing solution, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant. May be included.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. As a bleaching agent, Fe ⁺³ , Co ⁺⁴ , Cr ⁺⁶ , Cu ⁺²
Compounds of polyvalent metals such as, peracids, quinones, and nitroso compounds are used.

For bleaching or bleach-fixing solution, U.S. Patent 3,042,520,
In addition to the bleaching accelerators described in JP-B No. 3,241,966, JP-B-45-8506 and JP-B-45-8836, and the thioether compound described in JP-A-53-65732, various additives can be added.

The exposure to the photographic emulsion used in the present invention depends on the state of optical sensitization, purpose of use, etc., but it is different from tungsten, fluorescent lamp, mercury lamp, arc lamp, xenon, sunlight, xenon flash, cathode ray tube flying spot, laser beam, electron. Various light sources such as X-rays, X-rays, and fluorescent screens for X-ray imaging can be used as appropriate.

The exposure time is 1/100 to 100 seconds, and 1/10 ⁴ to 1/1 for xenon flash, cathode ray tube, and laser light.
A short exposure of ⁰⁹ seconds can be applied.

Example of Invention

Hereinafter, the present invention will be further described with reference to examples. Needless to say, the present invention is not limited to the examples.

Example 1 A monodispersed cubic emulsion of silver iodobromide emulsion containing 2.0 mol% of silver iodide having an average grain size of 0.3 μm was obtained by the double jet method while controlling at 60 ° C., pAg = 8 and pH = 2.0. It was From the electron micrograph of this emulsion, the generation rate of twin grains was 1% or less in number.

After desalting these particles, add a silver nitrate solution,
Silver ripening was carried out at pAg = 3 and pH = 6 for 70 minutes.

Of this emulsion, the amount corresponding to 2 mol% of the total silver halide used for growth was used as a seed crystal and grown as follows.

That is, the seed crystal was dissolved in 8.5 l of a solution containing protected gelatin and ammonia kept at 40 ° C, and the pH was adjusted with glacial acetic acid.

Using this solution as a mother liquor, an aqueous 3.2 N ammoniacal silver ion solution and an aqueous halide solution were added by the double jet method, followed by stirring and mixing.

At this time, two kinds of emulsions were prepared under the following conditions.

At this time, as shown in Table 1, two kinds of emulsions were prepared by changing the ammonia concentration, pH, pAg, iodide amount in the halide aqueous solution, etc. of this mother liquor. Both emulsions have a total silver iodide to total silver halide ratio of about 2 mole percent.

The pAg was then kept constant at 9.0 and the pH was changed from 9.0 to 8.0 in proportion to the amount of ammoniacal silver ion added to form a silver bromide shell. In this way, two kinds of monodisperse emulsions shown in Table 1 were prepared.

For E-2, pA at 40 ° C for 3 minutes at the end of grain growth
Aging was carried out with g of 11.5. At this time, the particles are (100)
A cube with a face was sharpened and rounded.
JPX-10RA manufactured by JEOL Ltd. was used for the obtained sample based on “Bretin of the Society of Scientific Photography of Japan” No.135, page 15 (1963) by Akira Hirata. X-ray diffraction was performed. According to this, it has about 30% of (111) planes, (10
It was found that the particles are rich in 0) planes. Here, such monodisperse particles with abundant (100) planes and close to spheres (1
00) Named pseudosphere-type monodisperse particles with many faces. As described above, a pseudospherical monodisperse emulsion having many (100) faces was obtained. The total ratio of silver iodide to total silver halide is 2 mol%
Met. Silver bromide shell thickness is 0.58μm, average particle size is 1.
It was 21 μm. S / was 0.12 monodisperse particles.

Excess water-soluble salts were removed from each emulsion obtained by the coagulation-precipitation method, and then ammonium thiocyanate, chloroauric acid and hypo were added to perform gold-sulfur sensitization. Then, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and then general photographic additives such as a spreader, a thickener and a hardener were added.

Polyhydric alcohols shown in the table were added to each emulsion as shown in Table-2. The time of addition was before the addition of the hardener. Furthermore, polymethylmethacrylate was added at 1.5 × 10 ^-2 g / Ge.
It was added per 1 g to prevent film cracking.

A polyethylene terephthalate film base which was subjected to an undercoating treatment by the method described in Example 3 of JP-A-59-19941 was coated and dried by a conventional method so that the amount of silver was 60 mg / 100 cm ^2, and sensitometry was performed. A sample for use was obtained.

The obtained sample was used for 10 ⁻³ seconds (exposure method I) using tungsten light for 10 ⁻² seconds (exposure condition).
II), 0.08 seconds (exposure condition III), 10 seconds (exposure condition IV), 5
0 seconds (exposure condition V) was performed using an optical wedge.

Konishi Rokusha Kogyo Co., Ltd. XD-90 developer and Konishi Rokusha Kogyo Co., Ltd. QX-1200 automatic processor at 35 ℃, 30
After the second development treatment, ordinary fixing, washing with water and drying were carried out to obtain a sample for sensitometry. The blackening density was measured using a PDA-65 densitometer manufactured by Konishi Rokusha Kogyo Co., Ltd., and the sensitivity was calculated by the reciprocal of the exposure required to give a density of fog density +0.5, and the relative value (E- 1
Table 2 shows the sensitivities of the emulsion (1) without adding polyhydric alcohols (when the sample No. 1 is 100).

As can be seen from Table-2, for E-1 in which no silver iodide content layer having a silver iodide content higher than that of the adjacent layer by 5 mol% or more was present inside the silver halide grain, the reciprocal relationship was observed regardless of the melting point of the polyhydric alcohol. Rule failure has not occurred (Sample No. 1 ~
4).

However, with respect to the silver halide grain E-2 having a layer having a high silver iodide content, the sensitivity can be increased, but the reciprocity law failure characteristic is large (Sample Nos. 13 to 16). So E-
By adding the compounds of the present invention to 2, the silver halide photographic light-sensitive material having improved reciprocity failure characteristics, high sensitivity and excellent reciprocity failure characteristics was obtained (Sample Nos. 6 to 1).
2).

Example-2 With respect to the emulsion (E-2) used in Example-1, the compound No. 30 was subjected to the same amount change as shown in Table-3, and the same exposure as in Example-1 was performed to obtain the sensitivity. The sensitivity when the amount of compound added is 0 g is 100. Furthermore, the coated sample is cut into 15 cm x 15 cm, and the humidity of the film is adjusted at 23 ° C and 56% RH for 2 hours. Then, the emulsion sides of the film are put together and sealed in a light-shielding bag (barrier).
After 72 hours of processing, the emulsion surface was examined for scratches. or,
After controlling the humidity of the applied sample to 23 ° C. and 60% RH, 0 to 50 g is obtained using a scratch meter (in this example, an electric pencil scratch coating hardness tester manufactured by Yoshimitsu Seiki Co., Ltd. was used).
Scratching was performed using a steel needle in a dry state with a variable load, the same treatment as in Example-1 was performed, and the number of grams at which a blackened line began to appear was summarized.

As is clear from Table 3, fog due to drying increases when the amount of the compound added is small (Sample Nos. 17 and 18). If the amount of the compound of the present invention added exceeds the range (1 to 100 g per mol of silver halide), the amount of the compound (Sample No. 2) is increased.
3), the reciprocity law failure characteristic remains good, but rather 5
It can be seen that at a high humidity of 5% RH or more, the scratches between the emulsion surfaces and the scratch resistance due to dry scratch are deteriorated, which is not preferable. When the compound addition amount of the present invention is used and the compound addition amount is within the range of the present invention (Sample No. 19 to No. 2
In 3), fog was low, good reciprocity law failure characteristics were exhibited, and scratch resistance was also good due to scratches between emulsion surfaces and dry scratching.

Example-3 In the same manner as in E-1 of Example-1, monodispersed grains having a grain size of 0.69 µm and a silver iodide content of 2 mol were produced (E-3).

Similarly, a monodisperse grain having a silver iodide content of 30 mol% and having a grain size of 0.69 µ was prepared and compared in the same manner as E-2 (E-4). E-4 has a silver iodide content of the inner layer of any of the two adjacent layers of silver halide grains.
It satisfies the condition of 10 mol% or more.

Both had a total silver iodide content of 2 mol%.
To each emulsion, 100 mg of the following compound [a] was added per mol of silver halide, and chemical ripening was performed under optimum conditions using ammonium thiocyanate, chloroauric acid and hypo to perform color sensitization. After adding a stabilizer, coating aid, and hardener, dilute the copolymer consisting of three monomers of glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%, and butyl methacrylate 40 wt% to 10 wt%. The copolymer aqueous dispersion thus obtained was applied as an undercoat liquid. A sample was obtained by uniformly coating and drying this emulsion on both sides on a polyethylene terephthalate film base colored in blue. The coated silver amount was set to 50 mg / dm ² on both sides.

The obtained sample was used with an aluminum wedge and the tube voltage was 70 KV.
At, the irradiation time was changed. The distance and tube current were adjusted to match the light intensity. Samples irradiated with lightning were used in Examples 1-2.
In the same manner as described above, development processing was performed with the above XD-90. The sensitivity of E-3, in which the high silver iodide portion is not localized, to which polyhydric alcohol is not added (Sample No. 25) is 100. (Fog +0.5
Sensitivity to obtain the concentration of).

As is clear from Table 4, one of the two adjacent layers of silver halide grains has a silver iodide content of 10 in the inner layer.
When the emulsion (E-4) satisfying the condition of not less than mol% was compared with the emulsion (E-3) not satisfying the condition, the former sample was also sensitized and color-sensitized. By adding the compound of the present invention to an emulsion using the silver halide grains of the present invention in the same manner as in 1, it was possible to obtain a silver halide photographic light-sensitive material having high sensitivity and excellent reciprocity law failure characteristics. .

〔The invention's effect〕

As described above, by using the silver halide grain of the present invention and the compound comprising the polyhydric alcohol of the present invention in combination, the reciprocity failure characteristic is improved without degrading other photographic performance while maintaining high sensitivity. It can be used as a silver halide photographic light-sensitive material.

Continuation of the front page (56) Reference JP-A-59-149349 (JP, A) JP-A-60-143331 (JP, A) JP-A-59-178447 (JP, A) JP-B-51-3241 (JP , B1) US Patent 2960404 (US, A)

Claims (2)

[Claims] 1. A multi-layered silver halide grain containing at least silver iodide as silver halide, wherein the difference in the silver iodide content between at least one pair of adjacent two layers is within the grain. A silver halide photographic light-sensitive material containing silver halide grains having a content of 5 mol% or more and a polyhydric alcohol having a melting point of 40 ° C. or higher and having at least two hydroxyl groups. 2. The silver halide according to claim 1, wherein one of the two adjacent layers of the silver halide grains has a silver iodide content of 10 mol% or more in the inner layer. Photographic material.