JP2000275803A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material excellent in preservability and gradation by incorporating a specified compound into one layer and at least one of ions of polyvalent metal atoms, etc., into a silver halide emulsion layer. SOLUTION: At least one of compounds of the formula R11OOC(CH2)mCOOR12 (I), the formula R21OOC(CnH2n-2)COOR22 (II), the formula R31OOC(CH2)pCOOR32 (III), formula IV and the formula X-((CO2)q-O(CO)R51)r (V) is incorporated into at least one layer and at least one of ions of multivalent metal atoms, complexes of multivalent metal atoms or ions of complexes of multivalent metal atoms is incorporated into at least one of silver halide emulsion layers. In the formulae, R11, R12, R21 and R22 are each 4-10C linear or branched alkyl, R31 and R32 are each 3-24C linear or branched alkyl, R51 is 4-16C linear or branched alkyl, R41 is alkyl or the like, R42 and R43 are each H or the like, the total number of carbon atoms in R41-R43 is >=10, X is a 5- to 7-membered saturated hydrocarbon ring, (m), (n) and (p) are each an integer of 2-10, (q) is an integer of 0-2 and (r) is an integer of 1-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved sensitivity, granularity, storability and gradation reproducibility.

[0002]

2. Description of the Related Art Photographic equipment such as cameras has become increasingly popular in recent years, and opportunities for taking photographs using silver halide photographic materials have been increasing. Demands for higher sensitivity and higher image quality are increasing.

One of the dominant factors in increasing the sensitivity and image quality of silver halide photographic light-sensitive materials is silver halide grains. Silver halide grains aiming at higher sensitivity and higher image quality. Particle development has traditionally been pursued in the art.

However, the sensitivity tends to decrease as the size of silver halide grains is reduced to improve image quality, as is generally practiced. To achieve both high sensitivity and high image quality. Had limitations.

Techniques for improving the sensitivity / grain size ratio per silver halide grain have been studied in order to achieve higher sensitivity and higher image quality. As one of them, a technique using tabular silver halide grains is disclosed in JP-A-58-11.
No. 1935, No. 58-111936, No. 58-111
No. 937, No. 58-113927, No. 59-9943
No. 3 and the like. When these tabular silver halide grains are compared with so-called normal silver halide grains such as octahedral, tetrahedral, or hexahedral grains, when the silver halide grains have the same volume, the surface area increases, and thus Many sensitizing dyes can be adsorbed on the silver particle surface, and there is an advantage that the sensitivity can be further increased.

JP-A-6-230491, JP-A-6-235
988, 6-258745, 6-289516
And the like have also studied using tabular silver halide grains having a higher aspect ratio than before.

Further, Japanese Patent Application Laid-Open No. 63-92942 discloses a technique for providing a core having a high silver iodide content inside tabular silver halide grains, and Japanese Patent Application Laid-Open No. 63-163541 discloses a technique for forming a core between twin planes. A technique using tabular silver halide grains having a ratio of grain thickness to long distance of 5 or more is disclosed, and shows effects on sensitivity and graininess, respectively.

Further, Japanese Patent Application Laid-Open No. 63-106746 discloses that
Tabular silver halide grains having a substantially layered structure in a direction parallel to two opposite main planes are disclosed in
No. 279237 has a layered structure separated by a plane substantially parallel to two opposite main planes, and the average silver iodide content of the outermost layer is the average silver iodide of the whole silver halide grains. It describes a technique using tabular silver halide grains at least 1 mol% higher than the content.

Japanese Patent Application Laid-Open No. 3-121445 discloses a silver halide grain composed of an interface layer having parallel twin planes and regions having different iodine contents from each other.
No. 305343 discloses a tabular silver halide grain having a development start point near the vertex.
Silver halide grains having a (0) plane and a (111) plane are disclosed.

[0010] In addition, JP-A-1-183644 describes that
A technique using tabular silver halide grains, characterized in that the silver iodide distribution of silver halide containing silver iodide is completely uniform is disclosed.

Further, there is disclosed a technique for controlling carriers by metal doping, that is, a technique for improving photographic characteristics by mainly including a polyvalent metal oxide in silver halide grains.

JP-A-3-196135 and JP-A-3-189
No. 641 and the like disclose a silver halide emulsion produced in the presence of an oxidizing agent for silver, and the effect on sensitivity and fog when a silver halide photographic material using the same is used.

Further, for example, Japanese Patent Application Laid-Open No. 63-220238
In Japanese Patent Application Laid-Open No. Hei 3-175440, a technique using a silver halide emulsion containing tabular silver halide grains in which the positions of dislocation lines are defined is disclosed in JP-A-3-175440. A technique using a silver halide emulsion containing silver halide grains is disclosed in Japanese Patent Publication No. 3-186.
No. 95 discusses a technique using silver halide grains having a clear core / shell structure, and Japanese Patent Publication No. 3-31245 discusses a technique relating to silver halide grains having a core / shell three-layer structure. It has been studied as a sensitivity enhancement technique.

JP-A-6-11781 and 6-1178
No. 2, No. 6-27564, No. 6-250309, No. 6-250310, No. 6-250311, No. 6-2
Nos. 50313, 6-242527, etc., realize high sensitivity and improved fog / pressure resistance by using an iodide ion releasing compound in forming silver halide grains.

However, these conventional techniques have limitations in achieving both high sensitivity and high image quality, and are insufficient to satisfy recent demands on photosensitive materials. Was rare.

[0016]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in sensitivity, graininess, storability and gradation reproducibility.

[0017]

The above object of the present invention is achieved by the following means.

1. On the support, at least one layer contains at least one of the compounds represented by the following general formulas (I) to (V), and at least one of the silver halide emulsion layers has a polyvalent metal atom ion or a polyvalent metal atom ion. A silver halide photographic light-sensitive material comprising at least one kind of a valence metal atom complex or a polyvalent metal atom complex ion.

Formula (I) R ₁₁ OOC (CH ₂ ) _m COOR _{12 wherein} R ₁₁ and R ₁₂ each represent a linear or branched alkyl group having 4 to 10 carbon atoms; Represents an integer of 10. General formula (II) R ₂₁ OOC (C _n H _2n-2 ) COOR ₂₂ [wherein, R ₂₁ and R ₂₂ each represent a linear or branched alkyl group having 4 to 10 carbon atoms, and n represents 2 Represents an integer of 10 to 10. General formula (III) R ₃₁ OOC (CH ₂ ) _p COOR ₃₂ [wherein, R ₃₁ and R ₃₂ each represent a linear or branched alkyl group having 3 to 24 carbon atoms. p represents an integer of 2 to 10. ]

[0020]

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[In the formula, R ₄₁ represents an alkyl group or an alkenyl group. R ₄₂ and R ₄₃ each represent a hydrogen atom or a group represented by R ₄₁ . Provided that R ₄₁ , R ₄₂ and R ₄₃
The total carbon number of the group represented by is at least 10 or more. General formula (V) X-((CH ₂ ) _q —O (CO) R ₅₁ ) _r wherein X represents a 5- to 7-membered saturated hydrocarbon, and q represents 0
Represents an integer of 2 to 2, and r represents an integer of 1 to 3. R ₅₁ represents a linear or branched alkyl group having 4 to 16 carbon atoms. ] 2. At least one layer of the above general formula (I) to
(V), wherein at least one of the silver halide emulsion layers contains a tabular silver halide emulsion having an average thickness of less than 0.07 μm. Silver halide photographic light-sensitive material.

3. Silver halide having at least one compound represented by formulas (I) to (V) in at least one layer thereof and having dislocation lines in at least one of the silver halide emulsion layers on the support; A silver halide photographic material comprising an emulsion.

4. On the support, at least one layer contains at least one of the compounds represented by formulas (I) to (V), and at least one silver halide emulsion layer has an outermost layer of silver halide grains. Average silver iodide content of
₁ (mol%), wherein the silver halide grains contain a silver halide emulsion satisfying I ₁ > I ₂ and having a dislocation line when the average silver iodide content of the silver halide grains is I ₂ (mol%). Silver halide photographic material.

5. On the support, at least one layer contains at least one of the compounds represented by formulas (I) to (V), and at least one silver halide emulsion layer contains iodine inside silver halide grains. A silver halide photographic light-sensitive material comprising a silver halide emulsion having a plurality of silver halide phases differing in silver halide content by 3 mol% or more.

6. Halogen containing at least one of the compounds represented by formulas (I) to (V) in at least one layer of the support and reduction sensitizing at least one of the silver halide emulsion layers A silver halide photographic material comprising a silver halide emulsion containing silver particles.

7. On the support, at least one layer contains at least one of the compounds represented by formulas (I) to (V), and at least one layer of the silver halide emulsion layer has a halogen on the surface of silver halide grains. A silver halide photographic material comprising a silver halide emulsion having silver halide projections.

8. On the support, at least one layer contains at least one of the compounds represented by formulas (I) to (V), and at least one layer of the silver halide emulsion layer has a grain size of silver halide grains. A silver halide photographic light-sensitive material, characterized in that the silver halide emulsion contains a monodispersed silver halide emulsion.

9. On the support, at least one layer contains at least one of the compounds represented by the above general formulas (I) to (V), and at least one layer of the silver halide emulsion layer contains tabular silver halide grains. A silver halide photographic light-sensitive material containing a silver halide emulsion having an average distance between two or more twin planes parallel to the main plane of 500 ° or less.

10. At least one of the compounds represented by the above general formulas (I) to (V) is provided in at least one layer on the support.
A silver halide photographic material comprising a seed and a silver halide emulsion containing silver chloride in at least one of the silver halide emulsion layers.

11. At least one of the compounds represented by the above general formulas (I) to (V) is provided in at least one layer on the support.
Containing species, and I ₃ (mol%) the average silver iodide content outermost layer of the silver halide grains in at least one layer of silver halide emulsion layers in the main planar portion, I ₄ (mol% in the side surface portion ), Wherein the tabular silver halide grains satisfying I ₃ > I ₄ contain a silver halide emulsion in which the number is 50% or more (number).

12. At least one of the compounds represented by the above general formulas (I) to (V) is provided in at least one layer on the support.
A silver halide photographic light-sensitive material containing a seed, wherein at least one of the silver halide emulsion layers contains a silver halide emulsion having an average aspect ratio of silver halide grains of less than 3.

13. At least one of the compounds represented by the above general formulas (I) to (V) is provided in at least one layer on the support.
A silver halide photographic light-sensitive material containing at least one of normal silver halide emulsions and at least one tabular silver halide emulsion in at least one of the silver halide emulsion layers. material.

14. At least one of the compounds represented by the above general formulas (I) to (V) is provided in at least one layer on the support.
A silver halide photographic light-sensitive material comprising a seed and wherein at least one of the silver halide emulsion layers contains a tabular silver halide emulsion having a (100) major plane.

Hereinafter, the present invention will be described in detail.

The silver halide photographic material of the present invention is characterized in that at least one layer contains at least one of the compounds represented by formulas (I) to (V).

The compounds represented by formulas (I) to (V) will be described.

In the general formulas (I) and (II), R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ each independently represent a linear or branched alkyl group having 4 to 10 carbon atoms. Examples of the alkyl group include butyl, iso-butyl, 2-ethylhexyl, octyl, t-octyl, s
ec-octyl, nonyl, iso-nonyl, decyl, i
Each group such as so-decyl is exemplified.

In the general formula (I), m is 2 to 10
Represents an integer, but is more preferably an integer of 4 to 8.

In the general formula (II), n is 2 to 10
Represents an integer of 2, but is more preferably an integer of 2 to 4.

In the general formula (II), -OOC (C
The _n H _2n-2) COO- preferred diacid residue represented by, for example, malonic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, 2-pentene diacid, 2-hexene diacid, 3 -Diacid residues from acids such as hexenedioic acid.

In the general formula (III), R ₃₁ and R ₃₂
Is a linear or branched alkyl group having 3 carbon atoms
Represents a straight-chain or branched alkyl group having 24 to 24 carbon atoms, and more preferably has 4 to 10 carbon atoms.

Examples of the linear or branched alkyl group having 3 to 24 carbon atoms represented by R ₃₁ and R ₃₂ include a propyl group, a butyl group, an iso-butyl group, a pentyl group, a heptyl group and a 2-alkyl group. Examples include an ethylhexyl group, an octyl group, a nonyl group, an iso-nonyl group, a decyl group, a pentadecyl group, and a tetracosyl group.

In the general formula (IV), the alkyl group or alkenyl group represented by R ₄₁ may or may not be substituted. R ₄₂ and R ₄₃ are each independently a hydrogen atom,
Or it represents a group represented by R _41, more preferably at least one is hydrogen atom, that both is hydrogen Further preferred.

In the general formula (V), 5 to 5 represented by X
Examples of the seven-membered saturated hydrocarbon include cyclopentane, cyclohexane, and cycloheptane.
Cyclohexane is more preferred.

Q is an integer of 0 to 2, preferably 0 to 1, and r is an integer of 1 to 3, preferably 1 to 2.

The linear or branched alkyl group represented by R ₅₁ has 4 to 16 carbon atoms, and more preferably 4 to 12 carbon atoms. Examples of the linear or branched alkyl group represented by R ₅₁ include butyl, iso-butyl, pentyl, hexyl, heptyl, 1-ethylpentyl, octyl, nonyl, and iso-nonyl. Group, decyl group, iso-decyl group, undecyl group, dodecyl group, hexadecyl group and the like.

The typical examples of the compounds represented by formulas (I) to (V) are shown below, but the present invention is not limited to these compounds.

I-1 Di-butyl adipate I-2 Di-iso-butyl adipate I-3 Di- (2-ethylhexyl) adipate I-4 Di-octyl adipate I-5 I-octyl-decyl adipate I-6 (2-ethylhexyl) -adipate-decyl I-7 di-iso-nonyl adipate I-8 di- (2-ethylhexyl) azelate I-9 di-nonyl azelate I-10 di-butyl sebacate I-11 di- (2-ethylhexyl) sebacate I-12 di-octyl sebacate II-1 di-butyl maleate II-2 di- (2-ethylhexyl) maleate II-3 di-iso-nonyl maleate II-4 Di-butyl fumarate II-5 Di- (2-ethylhexyl) fumarate II-6 Di-butyl itaconate II-7 Di-itaconate Ethylhexyl)

[0049]

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[0050]

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[0051]

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[0052]

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The compounds represented by formulas (I) to (V) of the present invention are preferably added to a light-sensitive silver halide emulsion layer containing a coupler. It may be added in any range with respect to the coupler contained in the silver emulsion layer, but is preferably 0.1 to 5 by weight.
Is preferably added within the range, more preferably 0.1.
It is good to use in the range of 1 to 0.8.

The compound represented by any of formulas (I) to (V) may be added to the light-sensitive material by any method. However, the compound may be dissolved in an auxiliary solvent together with the coupler to form a protective colloid. It is common to disperse according to a commonly known dispersion method, and to add after removing the auxiliary solvent.

When the compounds represented by the general formulas (I) to (V) are used as a solvent having a high boiling point, they may be used alone, or may be represented by the general formulas (I) to (V). May be used in combination with other compounds, or may be used in combination with a high boiling point solvent other than the compounds represented by formulas (I) to (V).

In the silver halide photographic light-sensitive material according to the first aspect of the present invention, at least one of the silver halide emulsion layers contains a polyvalent metal atom ion, a polyvalent metal atom complex or a polyvalent metal atom. It is characterized by containing a silver halide emulsion containing at least one complex ion.

The silver halide emulsion containing at least one kind of polyvalent metal atom ion, polyvalent metal atom complex or polyvalent metal atom complex ion comprises silver halide grains inside or on the surface of the silver halide grains. At least one kind of polyvalent metal atom ion, polyvalent metal atom complex, or polyvalent metal atom complex ion other than silver or halide ion contained in the face-centered cubic crystal lattice structure of silver halide Is preferred.

As the above-mentioned polyvalent metal atom ion, polyvalent metal atom complex or polyvalent metal atom complex ion,
e, Co, Ni, Ru, Rh, Pd, Re, Os, I
r, Pt, Mg, Al, Ca, Sc, Ti, V, Cr,
Mn, Cu, Zn, Ga, Ge, As, Se, Sr,
Y, Mo, Zr, Nb, Cd, In, Sn, Sb, B
a, La, W, Au, Hg, Tl, Pb, Bi, Ce and U, metal atoms, ions from the third to seventh periods (most commonly, the fourth to sixth periods) of the periodic table. At least one selected from the complex, a salt containing the complex (including a complex salt), and a compound containing the same can be used, but it is preferable to select from a single salt or a metal complex.

When selected from metal complexes, a six-coordinate complex,
Five-coordinate complexes, four-coordinate complexes, and two-coordinate complexes are preferable, and octahedral six-coordinate complexes and planar four-coordinate complexes are more preferable.

[0060] As a ligand which forms a complex, CN ^-,
CO, NO ₂ ^-, 1,10-phenanthroline, 2,2 '
-Bipyridine, SO ₃ ⁻ , ethylenediamine, NH ₃ , pyridine, H ₂ O, NCS ⁻ , NCO ⁻ , O ₃ , SO ₄ ²⁻ , O
_{^{H -, N 3 -, S}} 2 -, F -, Cl -, Br -, I - and the like can be used.

In order to incorporate a polyvalent metal into the silver halide emulsion used in the present invention, the following known techniques can be applied.

For example, B. H. Carroll, "Ir
Idium Sensitization, A Lit
erature review ”, Photograph
hic Science and Engineeri
ng, Vol. 24, No. 6, November / December 1980, pp. 265-267, U.S. Pat. No. 1,951,933,
No. 2,628,167, No. 3,687,676
Nos. 3,761,267 and 3,890,15
No. 4, No. 3,901,711, No. 3,901,7
No. 13, No. 4,173,483, No. 4,269,
No. 927, No. 4,413,055, No. 4,47
No. 7,561, No. 4,581,327, No. 4,6
No. 43,965, No. 4,806,462, No. 4,
No. 828,962, No. 4,835,093, No. 4,902,611, No. 4,981,780, No. 4,997,751, No. 5,057,402,
Nos. 5,134,060 and 5,153,110
No. 5,164,292 and 5,166,04
No. 4, No. 5,204,234, No. 5,166,0
No. 45, No. 5,229,263, No. 5,252
No. 451, No. 5,252,530, EPO No. 024
No. 4184, No. 0488737, No. 048860
No. 1, No. 0368304, No. 0405938,
The techniques described in JP-A Nos. 05096774 and 0563946, Japanese Patent Application No. 2-249588, and WO 93/02390 can be applied. Further, U.S. Pat. No. 4,847,
No. 191, No. 4,933,272, No. 4,981,7
No. 81, No. 5,037,732, No. 937,180
Nos. 4,945,035, 5,112,732
No., EPO No. 0509674, No. 0513738
No., WO 91/10166, and WO 92/16876
No. 298,320, U.S. Pat.
The techniques described in 360,712 and 5,024,931 can be applied.

In addition, Research Disclosure
ure, Volume 367, November 1994, Item 36
736 provides a straightforward description of the criteria for selecting shallow electron trap dopants. In the present invention, among the at least one selected from the group consisting of polyvalent metal atoms, their ions, their complexes, and their ions, it is preferable to use the following six-coordinate complex ions.

[ML ₆ ] ^{n In the} formula, M is a charged frontier orbital polyvalent metal ion, preferably Fe ⁺² , Ru ⁺² , Os ⁺² , Co ⁺³ , Rh ⁺³ , Ir
⁺³ , Pd ⁺⁴ or Pt ⁺⁴ ; L ₆ represents an independently selectable six-coordinate complex ligand, with the proviso that
At least four of the ligands are anionic ligands;
At least one (preferably at least 3 and optimally at least 4) of the ligands is more electronegative than any halide ligand; and n is-, 2-,
Represents 3- or 4-. Specific examples of hexacoordinate complex ions capable of providing a shallow electron trap are shown below.

SET-1 [Fe (CN) ₆ ] ^4- SET-2 [Ru (CN) ₆ ] ^4- SET-3 [Os (CN) ₆ ] ^4- SET-4 [Rh (CN) ₆ ] ^{3 -} SET-5 [Ir (CN) _6] ^3- SET-6 [Fe (pyrazine) (CN) _5] ^4-SET-7 [RuCl (CN) _5] ^4-SET-8 [OsBr (CN) _5] ^4-SET-9 [RhF (CN) _5] ^3- SET-10 [IrBr (CN) _5] ^3- SET-11 [FeCO (CN) _5] ^3- SET-12 [RuF ₂ (CN) _4] ^{4 -} SET-13 [OsCl ₂ (CN) _4] ^4-SET-14 [RhI ₂ (CN) _4] ^3- SET-15 [IrBr ₂ (CN) _4] ^3- SET-16 [Ru (CN) ₅ ( OCN)] ^4-SET-17 _{[Ru (CN) 5 (N 3} ) ] ^4-SET-18 [Os (CN) ₅ (S N)] ^4-SET-19 [Rh (CN) ₅ (SeCN)] ^3- SET-20 [Ir (CN) ₅ (HOH)] ^2-SET-21 [Fe (CN) ₃ Cl _3] ^3- SET -22 _{[Ru (CO) 2 (CN)} 4 ] ^- SET-23 [Os (CN) Cl _5] ^4-SET-24 [Co (CN) _6] ^3- SET-25 [Ir (CN) ₄ (oxalate )] ^3- SET-26 [In (NCS) ₆ ] ^3- SET-27 [Ga (NCS) ₆ ] ^{3- In the} present invention, when an Ir compound is used, preferred examples of the compound include K ₂ IrCl ₆ and K ₃ IrCl ₆ , K ₂ Ir
Br _{6 and the} like.

In the present invention, specific examples of other polyvalent metal compounds preferably used include InCl ₃ and K ₄
Fe (CN) ₆ , K ₃ Fe (CN) ₆ , K ₄ Ru (C
N) ₆ , Pb (NO ₃ ) _{2 and the} like.

In the present invention, at least one selected from the group consisting of a polyvalent metal atom, its ion and its complex, and its ion is used, but Ru, Os, Fe, R
Each atom such as h, Co, In, Ga, Ge, Pd or Pt, its ion and its complex are particularly preferably used.

In the present invention, in order for the silver halide emulsion to contain at least one selected from the group consisting of a polyvalent metal atom, an ion thereof, a complex thereof, and an ion thereof, doping is performed during physical ripening of the silver halide grains. May be performed, doping may be performed during the formation of silver halide grains (generally, during addition of a water-soluble silver salt and a water-soluble alkali halide), or the formation of silver halide grains may be temporarily stopped. The doping may be performed in this state, and then the particle formation may be further continued. Further, doping may be performed after the formation of the silver halide grains, and at least one selected from the group consisting of polyvalent metal atoms, their ions, their complexes, and their ions may be introduced into the surface of the silver halide grains. The introduction of at least one selected from the group consisting of a polyvalent metal atom, its ion and its complex, and its ion, the nucleation and physical ripening in the presence of the polyvalent metal atom, its ion and its complex, It can be carried out by forming particles.

The concentration of at least one selected from the group consisting of the polyvalent metal atom, its ion, its complex, and its ion used in the present invention is generally 1 × 10 ^-7 mol per mol of silver halide. The range is preferably 1 × 10 ⁻² mol or less, more preferably 1 × 10 ⁻⁶ mol or more and 1 × 10 ⁻³ mol or less, and 2 × 10 ⁻⁶ to 1 × 1 mol.
A range of ^0-4 moles is particularly preferred.

In the present invention, to make the silver halide emulsion contain a polyvalent metal, the polyvalent metal may be directly dispersed in the emulsion, or may be dissolved in a solvent such as water, methanol or ethanol alone or in a mixed solvent. A method in which an additive is generally added to a silver halide emulsion in the art can be applied. At least one selected from the group consisting of a polyvalent metal atom, an ion thereof, a complex thereof, and an ion thereof may be added to the silver halide emulsion together with the silver halide fine particles. Those containing at least one selected from the group consisting of metal atoms, their ions, their complexes, and their ions can also be added to the silver halide emulsion.

Regarding the production method of adding silver halide fine particles containing at least one selected from the group consisting of polyvalent metal atoms, their ions, their complexes, and their ions, see Japanese Patent Application No. 10-014194. The method described can be referred to.

In the silver halide photographic light-sensitive material according to claim 2 of the present invention, at least one of the silver halide emulsion layers has a tabular silver halide emulsion having an average thickness of less than 0.07 μm. It is characterized by containing.

The tabular silver halide emulsion having an average thickness of less than 0.07 μm means that the tabular silver halide grains occupy 50% or more of the total projected area of the silver halide grains, and Is a silver halide emulsion having an average thickness of less than 0.07 μm. The tabular silver halide grains preferably account for at least 70% of the total projected area. Average thickness of tabular silver halide grains is 0.01 μm or more and 0.07 μm
It is preferably less than.

In the present invention, tabular silver halide grains are silver halide grains having an aspect ratio of 2 or more. Tabular silver halide grains have an aspect ratio of 3 to 10.
0 is preferable and 5 to 50 is more preferable.

The aspect ratio of silver halide grains can be obtained by the following formula by determining the grain size and grain thickness of each silver halide grain by the method described below.

Aspect ratio = particle diameter / particle thickness The average thickness according to the second aspect of the present invention is 0.
Tabular silver halide grains of less than 07 μm are referred to in the art as ultrathin tabular grains.

The ultrathin tabular grains are described in US Pat.
No. 0,403 or European Patent Application Publication No. 0,403.
362, 699A3 and the like.

In the case of a camera sensitivity film, the tabular grains contain at least 0.25 mol% of iodide based on silver.
(Preferably at least 1.0 mol%). These low levels of iodide are also contemplated in the ultrathin tabular grains of the emulsions of the present invention. However, ultra-thin particle iodide is not required to realize the speed-granularity benefits of the present invention. Ultrathin silver bromide grains are very susceptible to morphological collapse (eg, enlargement) during emulsion preparation or storage after preparation, so that iodide is used instead as a convenience to morphologically stabilize ultrathin tabular grains. May be incorporated. The ultrathin tabular grains of the emulsions of the present invention in all cases contain less than 10 mol% iodide, preferably less than 6 mol% iodide, optimally less than 4 mol% iodide. Ultrathin tabular grains can contain small amounts of chloride ions. As disclosed in U.S. Pat. No. 5,372,927 to Delton, it contains from 0.4 to 20 mol% chloride and up to 10 mol% iodide, based on total silver, with the remainder of the halide being bromide. Are disclosed in U.S. Pat. Nos. 5,061,609 and 5,061,616 (Pi
ggin, etc., corresponding to Curves A and B of Grain A, which comprises 5-90% of the total silver within the pAg-temperature (° C.) boundary of Curve A (preferably within the boundary of Curve B) of Curve A. Can be prepared. Under these precipitation conditions, the presence of chloride ions actually helps reduce the thickness of the tabular grains. It is preferred to use precipitation conditions where chloride ions (when present) can help reduce tabular grain thickness, but chloride ions are compatible with retention of tabular grain average thickness less than 0.07 μm To the extent it can be added during normal ultrathin tabular grain precipitation. Ultrathin tabular grains, which account for at least 90% of the total grain projected area, contain at least 70 mole% bromide and at least 0.25% iodide, based on silver. These ultrathin tabular grains include silver iodobromide, silver iodochlorobromide and silver chloroiodobromide grains. All references to the composition of ultrathin tabular grains exclude silver halide epitaxy. The iodide in the ultrathin tabular grains is conveniently placed in the tabular grains,
It can be evenly distributed. Antoniade
Examples of emulsions such as s illustrate a relatively uniform iodide distribution. U.S. Pat. No. 4,433,048 (Solber
g et al.) disclose a non-uniform iodide that can reduce granularity without reducing speed. Antoniades et al., Zola and Bry
The ultrathin tabular grains produced according to the teachings of ant and Delton all have (111) major faces. Such tabular grains typically have a triangular or hexagonal major surface. The tabular structure of the grains results from the inclusion of parallel twin planes.

Ultrathin tabular grains in which tabular grains account for greater than 97% of total grain projected area are Antonia
It can and is preferably prepared by the preparation methods taught by Des et al. Antoniades et al. Have a total grain projected area of 9
Report emulsions in which more than 9% (substantially all) are occupied by tabular grains. Similarly, Delto
n reports that "substantially all" of the grains that settled when forming the ultrathin tabular grain emulsions were tabular. Providing emulsions in which tabular grains account for a high percentage of the total grain projected area is important to achieve the highest achievable image sharpness levels, especially in multilayer color photographic films. It is also important to utilize silver efficiently and to achieve the most desirable speed-granularity relationship.

The tabular silver halide grains having an average thickness of less than 0.07 μm according to the second aspect of the present invention preferably have a grain size of 0.7 μm or more and 10 μm or less.

The advantage realized by maintaining the average particle size at least 0.7 μm is that Antoniades
Etc. are shown in Tables III and IV. Emulsions with very large average grain sizes are sometimes prepared for scientific grain studies, but for photographic applications the grain size is usually less than 10 μm, and most often less than 5 μm. The optimum particle size range for medium to high image structure qualities is in the range of 1-4 μm.

At an average grain thickness of 0.07 μm, there is almost no change in reflectance between the green regions of the spectrum.
Furthermore, the difference between the minus blue reflectance and the blue reflectance is not large compared to tabular grain emulsions having an average grain thickness in the range of 0.08 to 0.20 μm. Film construction in that green and red recording emulsions (and to a lesser extent blue recording emulsions) can be constructed using the same or similar tabular grain emulsions by decoupling the magnitude of the reflectance from the exposure wavelength in the visible region. Is simplified. If the average thickness of the tabular grains is further reduced to less than 0.07 μm, the average reflectance observed in the visible spectrum will also decrease. Therefore, it is preferable to keep the average grain thickness less than 0.05 μm. Generally, the minimum average tabular grain thickness conveniently achieved by the precipitation method is preferred. Thus, the average tabular grain thickness is about 0.03-0.05.
Ultrathin tabular grain emulsions in the μm range are readily realized. U.S. Pat. No. 4,672,027 (Daubendi)
ek et al.) report an average tabular grain thickness of 0.017 μm. Utilizing the grain growth method taught by Antoniades et al., These emulsions were grown without appreciable thickness increase, for example, with an average thickness of 0.02 μm.
m to at least 0.7 μm
Can grow up to. The minimum thickness of tabular grains is limited by the spacing between the first two parallel twin planes formed in the grains during precipitation. The smallest twin plane spacing of 0.002 μm (ie, 2 nm or 20 angstroms) is
ades, etc., were observed in Kofron.
Suggest a practical minimum tabular grain thickness of about 0.01 μm. Preferred ultrathin tabular grain emulsions are those in which the variability between grains is kept at a low level. Antoniad
es et al. report ultrathin tabular grain emulsions in which more than 90% of the tabular grains have a hexagonal major surface. Also, A
ntoniades has a coefficient of variation of 25% with respect to particle size
Ultrathin tabular grain emulsions of less than and sometimes less than 20% have also been reported. It can be seen that photographic sensitivity and granularity increase with increasing average particle size. The speed is doubled (i.e. 0.3 log E increase in speed, where E
It is established that with each increase in exposure (look-seconds), the granularity of emulsions exhibiting the same speed-granularity relationship increases by 7 granularity units. In the ultrathin tabular grain emulsions of the present invention, it was observed that the presence of even a small proportion of larger grain size significantly increased the graininess of the emulsion. Antoniades et al. Preferred a low coefficient of variation emulsion because limiting the coefficient of variation would necessarily result in tabular grain sizes approaching the average. According to the present invention, the coefficient of variation is not the best way to determine the granularity of an emulsion. The need for a low emulsion coefficient of variation limits both populations larger and smaller than the average grain size, while only the former provides a higher level of granularity. . The reliability of the overall coefficient of variation measurements in the art is based on the assumption that the particle size-frequency distribution (whether the variance is wide but narrow) is a normal error function distribution that is inherent in the precipitation method and cannot be easily controlled. ing. An
Specifically, the method of precipitating ultrathin tabular grains taught by Toniades et al. may be modified to selectively reduce the size-frequency distribution of ultrathin tabular grains having a grain size larger than the average grain size of the emulsion. Intended. Since the frequency distribution of particles having a particle size smaller than the average is not relatively small, the overall coefficient of variation does not decrease appreciably.
However, the benefits of reducing emulsion granularity have been clearly demonstrated. The reduction of the disproportionation size range in the particle size-frequency distribution of ultrathin tabular grains larger than the average grain size (hereinafter referred to as "> average grain size") can be achieved by the following method. It has been found that this can be realized by changing the precipitation method. That is, the nucleation of ultrathin tabular grains is performed using a gelatinous peptizer that has not been treated to reduce the natural methionine content, while the existing gelatinous peptizer and the later introduced gelatinous peptizer After substantially removing the methionine content from the above, the particles are grown. A convenient approach to accomplish this is to interrupt precipitation after nucleation and before growth has progressed to a sufficient degree to introduce a methionine oxidizing agent. Any of the conventional techniques for oxidizing the gelatinous peptizer methionine can be used. U.S. Pat. No. 4,713,320 (Mask
Asky) (hereinafter "Maskasky III") teaches that methionine levels are reduced by oxidation to less than 30 umol per gram of gelatin, preferably to less than 12 umol by using a strong oxidizing agent. In fact, the oxidizing agent treatment used by Maskasky III reduces methionine below the detection limit. Agents used to oxidize methionine in gelatinous peptizers include, for example, NaOCl, chloramine, potassium monopersulfate, hydrogen peroxide and peroxide releasing compounds, and ozone. US Patent 4,94
No. 2,120 (King et al.) Teaches oxidizing the methionine component of a gelatinous peptizer with an alkylating agent. European Patent Application No. 0,434,012 (T
Akada et al.) disclose precipitation in the presence of a thiosulfonate of one of the following formulas:

(BI) R-SO ₂ S-M (B-II) R-SO ₂ S-R _k (B-III) R-SO ₂ S-L _m -SSO ₂ -R ₂ (wherein , R, R _k and R ₂ are the same or different and are an aliphatic group, an aromatic group or a heterocyclic group, M is a cation, L is a divalent linking group, and m is 0 or l. With the proviso that R, R _k , R ₂ and L combine to form a ring). Gelatinous peptizers include gelatin, for example, alkali-treated gelatin (livestock, bone or hide gelatin) or acid-treated gelatin (pork hide gelatin) and gelatin derivatives, for example, acetylated or phthalated gelatin.

The silver halide photographic light-sensitive material according to the third aspect of the present invention is characterized in that at least one of the silver halide emulsion layers contains a silver halide emulsion having dislocation lines. .

In the invention according to claim 3 of the present invention,
A silver halide emulsion having dislocation lines means that 30% of the total projected area of silver halide grains contained in the silver halide emulsion.
This refers to the case where the corresponding silver halide grains have dislocation lines. Further, that the silver halide grains have dislocation lines, by the following observation method using a transmission electron microscope,
This refers to the case where at least one or more dislocation lines are observed in a grain.

Dislocation lines of silver halide grains are described, for example, in J. Am. F. Hamilton, Photo. Sci. E
ng. 11 (1967) 57 and T.I. Shiozaw
a, J. et al. Soc. Photo. Sci. Japan35
(1972) 213 can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for an electron microscope so as to prevent damage by electron beams (such as printout). Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particle, the more difficult it is for an electron beam to penetrate. Therefore, a clearer observation can be obtained by using a high acceleration voltage type electron microscope. From the grain photograph obtained by such a method, the number and position of dislocation lines in each grain can be known.

The tabular silver halide emulsion according to the present invention comprises:
It is preferable that silver halide grains corresponding to 50% or more of the projected area of the silver halide grains have dislocation lines.
% Is more preferable. Further, the number of dislocation lines of the particles having dislocation lines is preferably 5 or more, more preferably 10 or more, and particularly preferably 20 or more.

Further, the form of the dislocation line can be appropriately selected. For example, a dislocation line that exists linearly in a specific direction of the crystal orientation of the grains or a dislocation line that is bent can be selected.
Furthermore, a dislocation line exists only in the fringe portion (outer peripheral portion) of the particle, or exists only in a specific portion of the particle, or exists only in the main plane. It can also be selected from a form in which a line exists or a form in which dislocation lines are concentrated near a vertex.
In the tabular silver halide emulsion according to the present invention, dislocation lines are preferably present at least in the fringe portion of the grains, and it is also preferred that dislocation lines are present in the fringe portion and the main plane portion.

As a method for introducing dislocation lines into silver halide grains, for example, a method of adding an aqueous solution containing iodide ions such as potassium iodide and a water-soluble silver salt solution by double jetting, or a method of introducing silver iodide fine grains. Adding method, adding only solution containing iodide ion,
A known method such as a method using an iodide ion-releasing agent as described in JP-A No. 6-183, can be used to form a dislocation originating a dislocation line at a desired position. Among these methods, a method of adding an aqueous solution containing iodide ions and a water-soluble silver salt solution by double jet, a method of adding silver iodide fine particles, and a method of using an iodide ion releasing agent are preferable.

The iodide ion releasing agent is a compound capable of releasing iodide ions in the silver halide emulsion after being added to the emulsion, and includes a compound represented by the following general formula (A).

Formula (A) RI In the formula, R represents a monovalent organic residue which releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile. Examples of iodide ion releasing agents that can be used for the silver halide emulsion related to the present invention are shown below.

[0092]

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[0093]

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[0094]

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[0095]

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[0097]

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In the silver halide photographic light-sensitive material according to the fourth aspect of the present invention, at least one of the silver halide emulsion layers has an average silver iodide content of the outermost layer of silver halide grains of I. ₁ (mol%) and a silver halide emulsion satisfying I ₁ > I ₂ when the average silver iodide content of the silver halide grains is I ₂ (mol%).

In the fourth aspect of the present invention,
The outermost layer of the silver halide grains refers to a silver halide phase including the surface of the silver halide grains and extending from the surface of the silver halide grains to a depth of 50 °.

The average silver iodide content I ₁ (mol%) of the outermost layer of the silver halide grains is determined by the following method.

In the fourth aspect of the present invention,
The halogen composition of the outermost layer of the silver halide grains is determined by an XPS method (X-ray Photoelectron Spec).
troscopy (X-ray photoelectron spectroscopy) as follows. That is, the sample was cooled to −110 ° C. or less in an ultrahigh vacuum of 1 × 10 e ⁻⁸ torr or less, and MgKα was irradiated as a probe X-ray at an X-ray source voltage of 15 kV and an X-ray source current of 40 mA, and Ag3d5 / 2, Br3d, I3d
Measure for 3/2 electrons. The integrated intensity of the measured peak is used as a sensitivity factor (Sensity Factor).
r), and the halide composition of the outermost layer is determined from these intensity ratios.

The XPS method has hitherto been known as a method for determining the silver iodide content on the surface of silver halide grains as disclosed in JP-A-2-241.
No. 88 and the like. However, when the measurement was carried out at room temperature, the sample was destroyed by the X-ray irradiation, so that an accurate silver iodide content of the outermost layer could not be obtained. We succeeded in accurately determining the silver iodide content of the outermost layer by cooling the sample to a temperature at which no destruction occurs. as a result,
In particular, for particles such as core / shell particles having different compositions between the surface and the inside, or for particles in which a high iodine layer or a low iodine layer is localized on the outermost surface, the measured value at room temperature is a value obtained by halogenation by X-ray irradiation. It became clear that the true composition was greatly different due to the decomposition of silver halide and the diffusion of halide (particularly iodine).

The XPS method used here is specifically as follows.

Protease (pronase) was added to the emulsion.
A 05% by weight aqueous solution was added, and the mixture was stirred at 45 ° C. for 30 minutes to decompose gelatin. This is centrifuged to sediment the emulsion particles and the supernatant is removed. Next, distilled water is added to disperse the emulsion particles in distilled water, and the supernatant is removed by centrifugation. The emulsion particles are redispersed in water and thinly coated on a mirror-polished silicon wafer to obtain a measurement sample. The surface iodine was measured by XPS using the sample thus prepared. To prevent the destruction of the sample by X-ray irradiation,
The sample was placed in a chamber for XPS measurement at -110 to -120.
Cooled to ° C.

As a probe X-ray, MgKα was irradiated at an X-ray source voltage of 15 kV and an X-ray source current of 40 mA, and Ag3d5
/ 2, Br3d and I3d3 / 2 electrons.
The integrated intensity of the measured peak is used as a sensitivity factor (Sensit
The halide composition of the outermost layer was determined from these intensity ratios.

In the fourth aspect of the present invention,
Preferably, 30> I ₁ > 1, more preferably 20> I ₁ > 3.

In the fourth aspect of the present invention,
The silver iodide content of the silver halide grains was determined by the EPMA method (El
electron Probe Micro Analyz
er method). Specifically, a sample in which silver halide grains are well dispersed so as not to be in contact with each other is prepared, and irradiated with an electron beam while being cooled to −100 ° C. or lower with liquid nitrogen, and emitted from individual silver halide grains. By determining the characteristic X-ray intensity of silver and iodine, the silver iodide content of each silver halide grain can be determined.

The silver iodide content of each silver halide grain determined by the above method was 100%.
The average silver iodide content I ₂ (mol%) is determined and averaged for at least two silver halide grains.

[0111] In the invention according to claim 4 of the present invention,
30> I ₂ > 0.5, preferably 20> I ₂ > 1
Is more preferable.

In the silver halide emulsion according to the fourth aspect of the present invention, it is preferable that 20> I ₁ / I ₂ > 1.3, and 10> I ₁ / I ₂ > 1.5. Is more preferable.

In the production of the silver halide emulsion according to the fourth aspect of the present invention, the production method described in Japanese Patent Application No. 9-349421 is preferably used for controlling the surface iodine of silver halide grains. Can be

In the fourth aspect of the present invention,
In the silver halide emulsion, silver iodobromide as silver halide,
Any of the usual silver halides such as silver iodochlorobromide and silver iodochloride can be used, but silver iodobromide and silver iodochlorobromide are particularly preferred.

In the fourth aspect of the present invention,
The average silver iodide content of the silver halide grains contained in the silver halide emulsion is preferably from 1 to 40 mol%, more preferably from 2 to 20 mol%.

In the silver halide photographic light-sensitive material according to the fifth aspect of the present invention, at least one of the silver halide emulsion layers has a silver iodide content of 3 mol% or more inside the silver halide grains. It is characterized by containing a silver halide emulsion having a plurality of different silver halide phases.

In the invention according to claim 5 of the present invention,
A silver halide emulsion having a plurality of silver halide phases having silver iodide contents differing by 3 mol% or more inside the silver halide grains is defined as having a silver iodide content inside the silver halide grains excluding the surface of the silver halide grains. A silver halide emulsion containing silver halide grains having two or more silver halide phases having different ratios of 3 mol% to 100 mol%, preferably 5 mol% to 100 mol%.

When the silver iodide content is 3
In a silver halide emulsion having a plurality of silver halide phases different by at least mol%, the silver iodide content in the silver halide phase having a high silver iodide content is preferably from 5 mol% to 100 mol%. , 10 mol% or more and 100 mol%
The following is preferred.

In the silver halide emulsion having a silver halide phase containing high silver iodide inside the silver halide grains, a so-called core / shell type emulsion in which silver iodide is concentrated inside the grains is preferred. One. Emulsions in which a high silver iodide phase is localized inside the grains are also one of the preferred embodiments.
Emulsions having a plurality of high iodide phases inside the grains, or emulsions having a relatively high silver iodide content in the shell portion relative to the core portion are also preferable.

In the silver halide photographic light-sensitive material according to the sixth aspect of the present invention, a silver halide emulsion containing reduction-sensitized silver halide grains is contained in at least one of the silver halide emulsion layers. It is characterized by containing.

In the invention according to claim 6 of the present invention,
The reduction sensitization is carried out by adding a reducing agent to the aqueous protective colloid solution in which silver halide milk grains are grown, or by adding pA to the aqueous protective colloid solution in which silver halide grains are grown.
The silver halide grains are ripened or grown under a low pAg condition of 7.0 or less or a high pH condition of 7.0 or more. These methods may be performed in combination.

When a reducing agent is used in the invention according to claim 6 of the present invention, thiourea dioxide, ascorbic acid and its derivatives, stannous salts, borane compounds, hydrazine derivatives, formamidine sulfinic acid, silane compounds, amines Thiourea dioxide, ascorbic acid and its derivatives, and stannous salts are preferably used.

When a reducing agent is used in the invention according to claim 6 of the present invention, the addition amount is preferably from 10 ^-2 to 10 ^-8 mol per mol of silver halide, but is preferably from 10 ^-3 to 10 ^-7 mol. More preferred.

In the invention according to claim 6 of the present invention,
When the reduction sensitization is carried out by using a protective colloid aqueous solution in which silver halide grains are grown under a low pAg condition of pAg 7.0 or less, a silver salt is added to the protective colloid aqueous solution to obtain an appropriate pAg. After that, the silver halide grains are preferably ripened or grown. The silver salt is preferably a water-soluble silver salt, and particularly preferably an aqueous solution of silver nitrate. The pAg at the time of aging is suitably 7.0 or less, and preferably 2.0 to 5.0. (Here, the pAg value is a common logarithm of the reciprocal of the Ag + concentration.) In the invention according to claim 6, reduction sensitization is carried out using p aqueous solution of a protective colloid in which silver halide grains are grown.
When the process is performed under a high pH condition of H7.0 or more, an alkaline compound is added to the aqueous protective colloid solution to adjust the pH to an appropriate value, and then the silver halide grains are ripened or grown. As the alkaline compound, for example, sodium hydroxide, potassium hydroxide, ammonia and the like can be used, but it is preferable that the compound is other than the ammonium compound.

In the invention according to the sixth aspect of the present invention, the reduction sensitization of the silver halide emulsion is carried out by using a protective colloid aqueous solution in which the silver halide grains are grown under a high pH condition of pH 7.0 or more. Most effectively achieved.

The method for adding the reducing agent, the silver salt for reduction ripening, and the alkaline compound may be rush addition or may be added over a certain period of time. In this case, uniform addition may be performed, or function addition may be performed. Further, the required amount may be added several times.
Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, it may be present in the reaction vessel, or may be mixed with the soluble halide solution and added together with the halide. Further, it may be added separately from the soluble silver salt and the soluble halide.

In the sixth aspect of the present invention, the reduction sensitization is preferably carried out at a pH of 7.0 or higher in an aqueous protective colloid solution in which silver halide grains are grown. The pH is more preferably 7.5 or more and 11.0 or less,
The value is most preferably 8.0 or more and 10.0 or less.

In the invention of the sixth aspect of the present invention, an oxidizing agent can be used for deactivating the reducing agent and for other purposes.

Hydrogen peroxide (water) and its adduct: H
₂ O ₂ , NaBO ₂ , H ₂ O ₂ -3H ₂ O, 2NaCO ₃ -3
_{H 2 O 2, Na 4 P} 2 O 7 -2H 2 O 2, 2Na 2 SO 4 -H 2 O
Such as ₂ -2H ₂ O. Peroxy acid salts: K ₂ S ₂ O ₃ , K ₂ C ₂
O ₃ , K ₄ P ₂ O ₃ , K ₂ [Ti (O ₂ ) C ₂ O ₄ ] -3H
Examples include ₂ O, peracetic acid, ozone, I ₂ , and thiosulfonic acid.

In the invention according to the sixth aspect of the present invention, the emulsion may have the above-mentioned oxidizing agent for a purpose other than deactivation of the reducing agent. The addition amount of the oxidizing agent, the type of the reducing agent, reduction sensitization conditions, timing of addition of oxidizing agent, is influenced in its amount by the addition conditions of the oxidizing agent, the reducing agent per mole ^10-3 to using ⁵ moles are preferred.

The oxidizing agent may be added at any time during the silver halide emulsion production process. It can be added prior to the addition of the reducing agent.

As a method for adding an oxidizing agent, a method in which an additive is generally added to a silver halide emulsion in the art can be applied. For example, it can be previously dissolved in an appropriate organic solvent represented by alcohols, or added as an aqueous solution.

After the oxidizing agent is added, a reducing substance may be newly added to neutralize the excess oxidizing agent. These reducing substances are substances capable of reducing the oxidizing agent, and include sulfinic acids, di- and trihydroxybenzenes, chromans, hydrazines and hydrazides, p-phenylenediamines, aldehydes, aminophenols, Examples include enediols, oximes, reducing sugars, phenidones, sulfites, and ascorbic acid derivatives. The amount of the reducing substance is preferably 10 ^-3 to 10 ³ mol amount 1 mole of oxidizing agent used is.

In the silver halide photographic light-sensitive material according to the invention of claim 7, a silver halide having at least one silver halide emulsion layer having silver halide projections on the surface of silver halide grains. It is characterized by containing an emulsion.

The silver halide emulsion having silver halide projections on the surface of the silver halide grains is defined as a silver halide emulsion having silver halide projections on the surface of the silver halide grains. Means 30% or more of the silver halide emulsion, and preferably 50% or more of the total projected area is silver halide grains having silver halide projections on the surface of the silver halide grains. 7
More preferably, 0% or more are silver halide grains having silver halide projections on the surface of the silver halide grains.

In the invention according to claim 7 of the present invention,
The silver halide projections on the surface of the silver halide grains are preferably epitaxial, and the silver halide grains having the silver halide projections are preferably tabular silver halide grains.

The silver halide projections are epitaxially arranged on selected portions of silver halide grains (hereinafter sometimes referred to as “host grains”) serving as a substrate, and emitted by photon absorption in imagewise exposure. It is generally said that the competition of the conduction band electrons for the sensitized site is reduced, and thus the sensitivity is improved. US Patent 4,435,501
Discloses improvement in sensitivity by epitaxially depositing a silver salt on selected sites on the surface of host tabular grains. The US patent states that the increase in sensitivity is due to limiting the epitaxial deposition of the silver salt to a small fraction of the surface area of the host tabular grains. That is, the epitaxial arrangement of the tabular grains on a limited portion of the major plane is more efficient than the epitaxial arrangement covering all or most of the major plane, and more preferably, substantially limited to the edges of the host grains. Epitaxial arrangements with limited coverage on the principal plane and more efficient and preferred are those limited to or near the corners of host grains or other discrete sites. The spacing of the corners of the main plane of the host particle itself reduces the photoelectron competition sufficiently to achieve near maximum sensitivity. U.S. Pat. No. 4,435,501 teaches that reducing the rate of epitaxial deposition can reduce the number of sites of epitaxial placement on host particles.

Therefore, also in the present invention, the silver halide projections epitaxially arranged on the surface area of the host grains are preferably limited to a small portion of the surface area of the host grains, and are preferably limited to the corners or the vicinity thereof. Particularly preferred. Specifically, it is preferably less than 50%, more preferably less than 30%. Further, the silver content of the silver halide projections arranged epitaxially is preferably 0.3 to 25%, more preferably 0.5 to 15%, based on the silver content of the host grains.

In one of the most preferred embodiments of the present invention, the silver halide projections arranged epitaxially are preferably formed at the corners of the host grains or at restricted positions near the corners. A known method can be applied as the method. In the above-mentioned U.S. Pat. No. 4,435,501, a spectral sensitizing dye or aminoazaindene is used as a site director.
or) is disclosed, and it is preferably applicable in the present invention.

In order to avoid structural collapse of the host grains, the silver halide projections arranged epitaxially are
The total solubility is preferably higher than the total solubility of the silver halide forming the host grains. Therefore, it is preferable that the silver halide projections to be epitaxially arranged are specifically silver chloride. Silver chloride, like silver bromide, forms a face-centered cubic lattice structure, thus facilitating epitaxial deposition.

To maintain the structural integrity of the host grains, the epitaxial deposition is preferably performed under conditions that limit the solubility of the halide forming the host grains. However, there is a case where the halide of the silver halide projection portion arranged epitaxially is derived from the host grain. That is, the silver chloride projections contain a small amount of bromide and, in some cases, iodide.

In the silver halide photographic light-sensitive material according to the present invention, the silver halide emulsion in which at least one of the silver halide emulsion layers has a monodispersed silver halide particle diameter. It is characterized by containing.

In the present invention, the expression that the grain size of the silver halide grains is monodisperse means that the coefficient of variation of the grain size (the grain size in terms of projected area circle) of the silver halide grains is 20% or less, and is preferable. Is 16% or less.

In the present invention, when the silver halide grains are tabular silver halide grains, the diameter is defined as the diameter of a circle having an area equal to the area projected on the grain perpendicular to the main plane. In the case where the silver halide grains are non-tabular silver halide grains, the diameter of a circle having an area equal to the projected area of the grains (projected area circle-converted grain size). ).

The variation coefficient of the grain size is a value defined by the following equation. The grain size is determined by arbitrarily measuring 500 or more silver halide grains contained in the silver halide emulsion by the method described later. It calculates using the value obtained by the above.

Coefficient of variation (%) of particle size = (standard deviation of particle size / average value of particle size) × 100 US Pat. No. 4,797,354 and JP-A-2-83
No. 8 describes a method for producing monodisperse hexagonal tabular grains having a high tabularization ratio. Also, European Patent No. 514,742
The article describes a method for producing tabular grains having a coefficient of variation of the grain size distribution of less than 10% using a polyalkylene oxide block copolymer. These techniques can be applied to the preparation of a silver halide emulsion relating to the present invention. Further, tabular silver halide grains having a high uniformity of the thickness such that the coefficient of variation of the grain thickness is 30% or less are also a preferable embodiment.

In preparing a silver halide emulsion having silver halide particles having a monodispersed particle size, a low-molecular-weight gelatin having an average molecular weight of 70,000 or less is used as a dispersion medium, particularly at the time of forming nuclei of silver halide particles. Preferably, low molecular weight gelatin having an average molecular weight of 50,000 or less is more preferably used. Examples of the gelatin include alkali-treated gelatin, acid-treated gelatin, oxidized gelatin, and Bull. S
oc. Sci. Photo. Japan. , No. 16
(1966), p. 30 and the like, and NH4 described in JP-A-9-197595 and the like.
Gelatin having two groups chemically modified is also preferably used.

In the silver halide photographic light-sensitive material according to the ninth aspect of the present invention, at least one of the silver halide emulsion layers has at least two layers parallel to the main plane of the tabular silver halide grains. It is characterized by containing a silver halide emulsion having an average twin plane distance of 500 ° or less.

In the ninth aspect of the present invention,
The average distance between two or more twin planes parallel to the main plane of the tabular silver halide grains is preferably 300 ° or less and 10 ° or more,
120 ° or less and 10 ° or more are more preferred.

The tabular silver halide grains according to the ninth aspect of the present invention have two or more twin planes parallel to the main plane. The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a silver halide emulsion is coated on a support so that the tabular silver halide grains to be contained are oriented substantially parallel to the main plane, to prepare a sample. This is cut using a diamond cutter to obtain a thin section having a thickness of about 0.1 μm.
By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

In the ninth aspect of the present invention,
The average of the distance between two or more twin planes parallel to the main plane is determined by observing the section using the above-mentioned transmission electron microscope, and the tabular silver halide showing a cross section cut almost perpendicular to the main plane. It can be obtained by arbitrarily selecting 100 or more grains, determining the distance between twin planes, and performing averaging.

According to the ninth aspect of the present invention,
The silver halide emulsion can be produced by any of an acidic method, a neutral method and an ammonia method, but the acidic method or the neutral method is preferred. In the present invention, the distance between twin planes is a factor that affects the supersaturated state at the time of nucleation, for example, a combination of various factors such as gelatin concentration, temperature, iodine ion concentration, pBr, ion supply speed, stirring speed, and gelatin type. Can be controlled by appropriate selection. In general, as nucleation is performed in a highly supersaturated state, the distance between twin planes can be reduced. The details of the supersaturation factor can be referred to, for example, the descriptions in JP-A-63-92942 or JP-A-1-213637.

The silver halide photographic light-sensitive material according to the tenth aspect of the present invention is characterized in that at least one of the silver halide emulsion layers contains a silver halide emulsion containing silver chloride. I do.

The silver halide emulsion containing silver chloride is defined as a silver halide emulsion in which the average silver chloride content of the silver halide grains in the silver halide emulsion is from 0.1 mol% to 10 mol%. That means.

In the tenth aspect of the present invention, the average silver chloride content of silver halide grains in a silver halide emulsion containing silver chloride is preferably from 5 mol% to 100%. , 50 mol% or more and 100% or less.

The constituents other than silver chloride are preferably silver bromide and / or silver iodide, and the silver halide emulsion includes silver chlorobromide, silver chloride and silver chloroiodobromide.

It is preferable that the silver halide emulsion according to the tenth aspect of the present invention is localized in a specific portion of a solid solution crystal such as silver chlorobromide or silver chloroiodide.

When the silver halide emulsion according to the tenth aspect of the present invention is silver chlorobromide, the silver bromide is preferably localized at the vertex of the silver halide crystal or in the vicinity thereof. Such a silver halide emulsion is prepared by adsorbing a sensitizing dye or an inhibitor onto silver chloride or silver chlorobromide crystal grains and then ripening by adding silver bromide fine particles, or adding a water-soluble bromide solution. It can be obtained by addition and halogen substitution.

Further, when the silver halide emulsion is silver chloroiodobromide, the silver iodide is preferably localized inside the grains. A silver halide emulsion in which silver iodide is localized inside the grains can be obtained by depositing silver chloride or silver chlorobromide on a core containing silver iodide. For the deposition of silver chloride or silver chlorobromide, a known silver halide crystal growth method such as a double jet method or an Ostwald ripening method can be used.

In the silver halide photographic light-sensitive material according to the eleventh aspect of the present invention, the average silver iodide content of the outermost layer of silver halide grains is mainly determined in at least one of the silver halide emulsion layers. I ₃ (mol%) on the flat part, I on the side part
_{When 4} (mol%), tabular silver halide grains satisfying I ₃ > I ₄ contain a silver halide emulsion in which the number is 50% or more (number).

In the invention according to the eleventh aspect of the present invention, the average silver iodide content of the outermost layer of each of the main plane portion and the side surface portion of the silver halide grain is measured by the following method.

The tabular silver halide grains in the silver halide emulsion are decomposed by gelatin with a protease, taken out, embedded in methacrylic resin, and continuously cut out with a diamond cutter to a section of about 500 mm in thickness. Of these sections, those in which a tomographic plane perpendicular to two parallel principal planes of the tabular silver halide grains appear, including a principal plane surface on the tomographic planes of the tabular silver halide grains,
The silver halide phase from the surface parallel to the main plane surface to a depth of 50 ° is referred to as a main plane portion, and the portion of the outermost layer of the silver halide crystal other than the main plane portion is referred to as a side surface portion. The main plane portion and the side portion are made of EPMA which is well known in the art.
The spot diameter is set to 50 ° or less, preferably 20 ° using the method.
The silver iodide content is measured by the following point analysis.

In the silver halide emulsion according to the eleventh aspect of the present invention, the relationship between I ₃ and I ₄ is such that I ₃ / I ₄ >
1.3 is preferable, I ₃ / I ₄ > 2.0 is more preferable, and I ₃ / I ₄ > 2.5 is most preferable. Further, I ₃ is preferably less than 30 mol%, and more preferably less than 20 mol%.

As one embodiment of the production of the silver halide emulsion according to the eleventh aspect of the present invention, a tabular silver halide grain serving as a base is once prepared, and the tabular silver halide grain is prepared. A method in which a low iodide silver halide phase is preferentially grown first in the lateral direction and then a high iodide silver halide phase is grown in the main plane direction, or conversely, A method in which a high iodide silver halide phase is preferentially grown in the main plane direction, and a method in which a low iodide silver halide phase is grown in the lateral direction is used well, and the following various methods and conditions are used. And forming a very thin silver halide layer while precisely controlling the composition.

To preferentially grow tabular silver halide grains in the lateral direction or in the main plane direction, silver ions and halide ions during the growth of the silver halide grains, or halogens during the growth due to dissolution thereof. It is important to select the concentration of an additive solution containing silver halide fine particles for supplying silver ions and halide ions to silver halide grains, the growth temperature, pBr, pH, gelatin concentration, and the like. The shape of the tabular base particles, the halogen composition,
It can be controlled to some extent by the combination of the (100) face / (111) face ratio of the side face and the like.

For example, the preferred pBr for growing preferentially in the lateral direction is 1.0 to 2.5, and the gelatin concentration is 0.1 to 2.5.
The pH is more preferably from 2.0 to 5.0 for forming high aspect ratio tabular silver halide grains having almost no (100) face on the side surface. On the other hand, pB preferable for preferentially growing in the main plane direction
r is 2.5 to 4.5.

In order to precisely and uniformly control the thickness and composition of the silver halide crystal outermost layer and the silver halide composition, silver ions and halide are added to the growing silver halide grains by dissolution rather than by the ion supply method. A method of supplying silver halide fine particles for supplying ions is suitable. The method described below can be used for preparing the silver halide fine particles. The silver halide fine particles themselves are preferably subjected to washing with a sedimentation / coagulant or the like described below, desalting operation or operation of removing unnecessary substances such as salts and ions by membrane separation. It is preferable that an operation of removing unnecessary substances such as salts and ions is performed by a membrane separation technique without using a flocculant.

When silver halide phases having different halogen compositions are separately formed in the lateral direction / principal plane direction, a washing operation, a desalting operation or an operation of removing unnecessary substances such as salts and ions by membrane separation are appropriately used. After being used to form one silver halide phase, residual, excessive or unnecessary halogen ions are removed to prevent unintended conversion from occurring in the subsequent manufacturing process, and to prevent the other silver halide phase from being generated. At the time of formation, control of the halogen composition can be facilitated. The operation of removing unnecessary substances such as salts and ions by the water washing, desalting method or membrane separation is performed after the formation of the base particles and after the growth in any one side direction / main plane direction, or halogenation of any composition. It is preferably carried out after the formation of the silver layer, and particularly preferably each time the respective silver halide forming steps are completed.

Salts obtained by the above-mentioned water washing, desalting method or membrane separation,
For the operation of removing unnecessary substances such as ions, the method described below can be applied, but it is particularly preferable to perform the operation of removing unnecessary substances such as salts and ions by a membrane separation method without using a precipitation / coagulant.

In the production of the silver halide emulsion according to the eleventh aspect of the present invention, in order to suppress the growth of tabular silver halide grains in the main plane direction or the side direction, the growth of the silver halide grains is carried out. In addition to controlling the conditions, it is also preferable to use additives called silver halide growth control agents, crystal habit control agents or inhibitors in the art. For example, after a low silver iodide-containing surface phase is grown in a lateral direction on a tabular silver halide grain, U.S. Pat.
No. 71, 5,147,772, 5,147,77
No. 3, JP-A-6-308644, and the like, a polyalkylene oxide-related compound or the like used at the time of nucleation for the purpose of monodispersion of tabular silver halide grains is added. Growth can be suppressed, and then the growth of a high silver iodide-containing surface phase in the main plane direction can be facilitated, and the development of tabular silver halide grains according to the present invention can be promoted.

When silver halide phases having different halogen compositions in the lateral direction / principal plane direction are separately formed, for example, a conversion method by solely adding an iodide salt or another halide salt, or a method described in, for example, JP-A-58-108526. issue,
The epitaxial junction method described in JP-A-59-133540 and JP-A-59-162540 can also be used.

Further, when a silver halide phase having a different halogen composition in the lateral direction / principal plane direction is separately formed, the difference in the crystal surface between the main plane and the side plane is used to make a plane selective adsorption known in the art. Adsorbable substances such as a dye having a hydrophobic property and an inhibitor are adsorbed on a specific crystal surface of silver halide grains, and a silver halide phase having an arbitrary halogen composition is formed on the non-adsorbed surface by the method described above or below. Is also a preferred method.

The operations for producing different silver halide phases having different halogen compositions in the various lateral and principal plane directions are performed from the start of silver halide grain formation to crystal growth of silver halide grains, physical ripening, and desalting. The color sensitization and the chemical sensitization can be carried out in any one or more steps, as necessary, until the coating liquid preparation step is completed. 9 in silver
It is preferably carried out in a step after the completion of 0% or more, particularly preferably after the formation of the tabular silver halide grains as the base and before the completion of color sensitization and chemical sensitization.

In the production of the silver halide emulsion according to the eleventh aspect of the present invention, the following general formula (C-I)
It is preferable to use the compound represented by

Formula (C-I) A-Ａ- (L) _m- (Z) _n ｝ _{r In the} formula, A represents an adsorptive group to silver halide, and L represents 2 or 3
Z represents a substituent capable of releasing a halogen ion, m represents 0 or 1, n represents 1 or 2, and r represents an integer of 1 to 3.

In the silver halide photographic light-sensitive material according to the twelfth aspect of the present invention, at least one of the silver halide emulsion layers has an average aspect ratio of silver halide grains of less than 3 It is characterized by containing an emulsion.

The silver halide emulsion having an average aspect ratio of less than 3 in the invention according to the twelfth aspect of the present invention means that the silver halide grains having an average aspect ratio of less than 3 are halogens having 50% or more of the total projected area. The term "silver halide emulsion" means that silver halide grains having an average aspect ratio of less than 3 preferably account for 70% or more of the total projected area.

The silver halide grains having an average aspect ratio of less than 3 are normal crystal halides having a regular crystal structure such as cubic, octahedral, tetradecahedral, 24 tetrahedral and 36 hexahedral. Silver grains or normal silver halide grains having a regular crystal structure with rounded vertices and ridges, or spherical or twinned silver halide grains having twin planes parallel to the inside of the grain Preferably, there is.

In the silver halide photographic light-sensitive material according to the thirteenth aspect of the present invention, at least one of a normal crystal silver halide emulsion and a tabular silver halide emulsion is provided in at least one of the silver halide emulsion layers. Characterized by containing at least one of the following.

The normal-crystal silver halide emulsion in the invention according to the thirteenth aspect of the present invention refers to a regular crystal such as a cubic, octahedral, tetradecahedral, 24 tetrahedral, or 36 hexahedral. The normal crystal silver halide grains having a structure, or the vertices and ridges of the normal crystal silver halide grains having these regular crystal structures, or the vertices and ridges of these normal crystal silver halide grains having rounded edges. A silver halide emulsion in which silver halide grains whose surface is so rounded that the crystal habit can no longer be discriminated and whose shape is spherical are occupied by 50% or more of the total projected area, and preferably 70% by weight. It is.

In the silver halide photographic light-sensitive material according to the fourteenth aspect of the present invention, at least one of the silver halide emulsion layers contains a tabular silver halide emulsion having a (100) major plane. It is characterized by containing.

In the invention according to the fourteenth aspect of the present invention, the term "tabular silver halide emulsion having a (100) plane as the main plane" means that all tabular silver halide grains having the (100) plane as the main plane are present. A silver halide emulsion occupying 30% or more of the projected area. The tabular silver halide emulsion having a (100) principal plane in the invention according to claim 14 of the present invention comprises:
It is preferable that the tabular silver halide grains having a (100) main plane have a total projected area of 50% or more.

The tabular silver halide grain emulsion according to the fourteenth aspect of the present invention, wherein the main plane is the (100) plane,
First, a small-sized cubic seed grain emulsion can be prepared and formed by growing the emulsion.

The formation of the small-size cubic seed grain emulsion can be carried out by a conventional technique. Preferred seed grain emulsions are prepared by the double jet method. That is, a silver salt aqueous solution such as silver nitrate and a sodium or potassium halide aqueous solution are simultaneously injected into one reaction vessel. The concentration of these aqueous solutions can be, for example, from about 0.2 mol to saturation, but it is preferred that stirring be performed quickly and uniformly, less than 4 mol / l, preferably 2 to 0.1 mol / l. It is preferred to use a concentration.

To form the preferred seed particles, it is preferable to adjust the pAg in the reaction vessel during precipitation. In order to achieve this, it is preferable to keep the pAg in the range of 2.5 to 8.5. If the pAg is smaller or larger than this range, particles having twin planes are formed, which is not preferable. Further, from the viewpoint of production stability, pAg in which the equilibrium point, that is, the concentrations of silver and halide ions are stoichiometrically equal is not preferable. In order to finally obtain a silver halide emulsion having a high aspect ratio, pAg is 6.5.
To 8.3, more preferably 7.0.
８8.0. As used herein, the term "aspect ratio" refers to the ratio of the thickness between the principal planes to the average edge length forming the principal planes of the grains, and the term "principal plane" refers to the ratio of the crystal surface forming the substantially rectangular parallelepiped emulsion grains. Of these, the plane is defined as a set of parallel surfaces having the largest area, and the fact that the main plane is the (100) plane can be determined by an electron beam diffraction method or an X-ray diffraction method. A substantially cuboid emulsion grain has a principal plane of (1
It means that it may be formed from the (00) plane but may have from 1 to 8 (111) crystal planes. That is, the rectangular parallelepiped 8
One to eight of the corners may have a rounded shape. The “average edge length” is defined as the length of one side of a square having an area equal to the projected area of each grain as viewed in a micrograph of the emulsion grain sample.

The seed grain precipitation temperature affects the optimum value of pAg, but can be any temperature known to be useful for preparing emulsions of the desired grain size. Preferred temperatures are in the range of about 25-75C, more preferably below 45C.

During the formation of the seed particles, the pH is preferably maintained in the range of about 2.0 to 5.0 in order to suppress ripening. For adjusting the pH, nitric acid, sulfuric acid or acetic acid can be used.

After precipitation, tabular grains are prepared by Ostwald ripening of the cubic seed grain emulsion.

During aging, it is preferable to adjust the pAg in the reaction vessel. By adjusting the pAg during aging to 5.2 to 6.2, the aspect ratio can be adjusted.
If Ag is smaller than this, the aspect ratio of the tabular grains obtained is too small, and if it is larger, ripening is inhibited. A more preferred range of pAg for obtaining tabular grains having a high aspect ratio is 5.5 to 5.8.

The ripening temperature affects the optimum value of pAg, but can be any temperature known to be useful for preparing emulsions of the desired grain size. Preferred temperatures are in the range of about 50-80 ° C.

The pH is about 5.0 to promote ripening.
It is preferable to keep in the range of 9.0 to 9.0. Sodium hydroxide and potassium hydroxide can be used to adjust the pH.

[0191] Claim 1 of the present invention prepared by the above method
The tabular silver halide grains having a (100) plane as the principal plane used in the invention described in Item 4 are at least 50%, preferably 70% or more, and more preferably at least 50% of the total projected area of the silver halide grains present in the emulsion. Preferably, 80% or more has an aspect ratio of 2 or more and 20 or less, and preferably 5 or more and 15 or less. Further, the particle size is preferably 0.2 μm or more and 3.0 μm or less in sphere equivalent diameter,
Preferably, the coefficient of variation is equal to or less than 25% in sphere equivalent diameter. If the aspect ratio is 2 or less, a sufficient effect cannot be obtained in terms of sensitivity. When the aspect ratio exceeds 20, there is a problem in terms of density fluctuation. The coefficient of variation is 25%
If it exceeds, it is not preferable in sensitivity.

In the present invention, the projected area and thickness of each grain for calculating the grain size and the aspect ratio of the silver halide grain can be determined by the following method. A sample is prepared by coating a latex ball with a known particle size as an internal standard on a support and silver halide particles so that the main plane is oriented parallel to the substrate, and the particles are shaded by carbon deposition from a certain angle. After that, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area and thickness of each particle are determined using an image processing device or the like. In this case, the projected area of the particle can be calculated from the projected area of the internal standard, and the thickness of the particle can be calculated from the internal standard and the length of the shadow of the particle.

The silver halide grains contained in the silver halide photographic light-sensitive material of the present invention may have a regular crystal structure such as cubic, octahedral or tetradecahedral, or may have a spherical or plate-like shape. It may have such an irregular crystal form. In these particles, any ratio of the crystal habit (100) plane and the (111) plane can be used. Further, a composite of these crystal forms may be used, and particles of various crystal forms may be mixed. Twin silver halide grains having two opposing parallel twin planes can also be used.

The twins are silver halide crystals having one or more twin planes in one grain, and the classification of the twins is described in a report by Klein and Moiser, “Photographic. Correspondents (Photograph)
ishe Korrespondentz) ", Volume 99,
The details are described on page 99, volume 100, and page 57.

When tabular silver halide grains are used, tabular silver halide grains preferably account for 50% or more of the total projected area of the silver halide grains, more preferably 60% or more, and still more preferably. 80% or more.

In the present invention, when tabular silver halide grains having a (111) main plane are used, the ratio of tabular silver halide grains having two twin planes parallel to the main plane is determined by the number of silver halide grains. It is preferably at least 60%,
It is more preferably at least 70%, further preferably at least 80%.

In the present invention, the average grain size of the silver halide grains is preferably from 0.2 to 10 μm, more preferably from 0.3 to 7.0 μm.
m is more preferred, and 0.4 to 5.0 μm is most preferred.

In the present invention, an arbitrary silver halide emulsion such as a polydisperse emulsion having a wide particle size distribution and a monodisperse emulsion having a narrow particle size distribution is used, and the above-mentioned monodisperse emulsion is preferable. .

In the present invention, any composition can be used as the silver halide in the silver halide emulsion.

In the present invention, the silver halide grains contained in the photographic emulsion have an average silver iodide content of 0.5 to 40 mol%.
And more preferably 1 to 20 mol%
It is.

In the present invention, when gelatin is used as the dispersion medium, lime-treated gelatin, acid-treated gelatin, ion-exchanged gelatin and the like can be used. Gelatin having an adenine content of 0.2 ppm or less described in U.S. Pat. For details on the gelatin production method, see "The Macromolecular Chemistry of
Gelatin "(Academic Press, 1964)
And so on.

Examples of substances which can form protective colloids other than gelatin include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfate and the like. Cellulose derivatives of the following: sugar derivatives such as sodium alginate and starch derivatives; homo- or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinyl pyrrolidone, polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinyl imidazole, polyvinyl pyrazole, etc. And various kinds of synthetic or semi-synthetic hydrophilic polymer substances.

In the production of photographic emulsions, various methods well-known in the art can be used to form host grains. That is, single jet method, double jet method
A jet method, a triple jet method, a silver halide fine particle supply method, or the like can be used in any combination. The pH, pA in the liquid phase in which silver halide is produced,
A method of controlling g according to the growth rate of silver halide can also be used.

For the production of the photographic emulsion of the present invention, a seed emulsion may be used. When a seed emulsion is used, the silver halide grains in the seed emulsion may have a regular crystal structure such as cubic, octahedral, or tetradecahedral, or may have a spherical or plate-like shape. It may have an irregular crystal form. In these particles, any ratio can be used for the crystal habit (100) plane and (111) plane. Further, a composite of these crystal forms may be used, and particles of various crystal forms may be mixed.

Regardless of whether a seed emulsion is used or no seed emulsion is used, silver halide nucleus formation and ripening can be performed by methods known in the art.

For the preparation of a photographic emulsion, a silver halide solvent known in the art can be used. If possible, when forming a host tabular grain, the use of a silver halide solvent can improve the ripening after nucleation. It is better to avoid it. Examples of silver halide solvents include (a) US Pat.
157, 3,531,289, 3,574,6
No. 28, JP-A-54-1019 and JP-A-54-15891.
No. 7, and JP-B-58-30571; (b) JP-A-53-82408;
Thiourea derivatives described in JP-A-5-29829 and JP-A-57-77736, and (c) halogenation having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319 and the like. Silver solvent, (d) JP-A-5
Imidazoles described in No. 4-100717, (e)
Sulfites, (f) thiocyanates, (g) ammonia, (h) hydroxyalkyl-substituted ethylenediamines described in JP-A-57-196228 and the like, (i)
Substituted mercaptotetrazoles described in JP-A-57-202531, etc .; (j) water-soluble bromide;
And a benzimidazole derivative described in JP-A-8-54333.

For producing the photographic emulsion of the present invention, any of an acidic method, a neutral method and an ammonia method can be used, but the acidic method or the neutral method is preferred.

In the production of a photographic emulsion, halide ions and silver ions may be mixed at the same time, or one of them may be mixed while the other is present. In consideration of the critical growth rate of silver halide crystals, halide ions and silver ions can be added sequentially or simultaneously while controlling the pAg and pH in the mixing vessel. In any step of silver halide formation, the halogen composition of the silver halide grains may be changed by using a conversion method.

In the production of the silver halide emulsion according to the present invention, desalting is carried out during or after the formation of silver halide grains for the purpose of suppressing the progress of physical ripening or removing unnecessary salts by the following method. Is preferred.

The desalting can be carried out, for example, by the method described in Research Disclosure (hereinafter abbreviated as RD) No. 17643 No. II. More specifically, in order to remove unnecessary soluble salts from the precipitated product or the emulsion after physical ripening, a Nudel washing method performed by gelling gelatin may be used,
Further, a precipitation method using an inorganic salt, an anionic surfactant, an anionic polymer (such as polystyrenesulfonic acid), or a gelatin derivative (such as acylated gelatin or carbamoylated gelatin) can be used.

In addition, desalination using ultrafiltration described in Chemical Engineering Handbook, 5th revised edition (edited by the Society of Chemical Engineers, Maruzen), pages 924 to 954, etc., can be more preferably used.

Regarding the method of ultrafiltration desalination, one of the RD
02, 10208 and 131, 13122, Shoko 5
Nos. 9-43727 and 62-27008;
-113137, 57-209823, 59-
43727, 62-11137, 61-21
No. 9948, No. 62-23035, No. 63-4013
No. 7, 63-40039, JP-A-3-140946
And the methods described in JP-A Nos. 2-172816, 2-172817 and 4-22942 can be referred to.

In the preparation of a photographic emulsion, conditions other than those described above are described in JP-A-61-6643 and JP-A-61-14.
No. 630, No. 61-112142, No. 62-1570
No. 24, No. 62-18556, No. 63-92942
Nos. 63-151618 and 63-163451
Nos. 63-220238 and 63-31244
No., RD 365, 36544, 367, 36736,
Appropriate conditions can be selected with reference to Vol.

In constructing a color light-sensitive material using the silver halide emulsion of the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used.

The additive used in such a step is R
D17643, page 23, section III to page 24, section VI-M, RD1
8716, pages 648 to 649 and RD308119, 9
It is described in page 96, section III-A to page 1000, section VI-M.

Known photographic additives that can be used in the present invention are also described in RD17643, page 25, VIII-A to page 27.
Section XIII, RD18716, pages 650 to 651, RD30
8119, page 1003, paragraphs VIII-A to 1012, XXI-E
Those described in the section can be used.

Various couplers can be used in the color light-sensitive material. Specific examples thereof are RD17643, 25
Page VII-C to G, RD308119, page 1001 VII-
It is described in sections C to G.

The additive used in the present invention is RD3081
19, page 1007, section XIV.

In the present invention, the aforementioned RD 17643,
Page 28, section XVII, RD 18716, pages 647-8, and RD
The support described in section 308119, page 1009, XVII can be used.

The light-sensitive material includes RD308119, 1
An auxiliary layer such as a filter layer or an intermediate layer described in section VII-K on page 002 can be provided.

The photosensitive material is RD308119, VII
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section -K can be adopted.

The silver halide emulsion according to the present invention can be used for various color light-sensitive materials typified by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. Can be preferably applied.

The light-sensitive material of the present invention is obtained by using
The development can be carried out by a conventional method described in XIX, pages 3, 28 to 29, page IX, RD18716, page 651, and RD308119, pages 1010 to 1011, page XIX. The silver halide photographic material of the present invention can be produced by referring to the following conditions other than the above.

[0225] The locations described in RD308119 are shown below.

[Item] [Page RD308119] Iodine composition 993 IA Section Manufacturing method 993 IA and 994 E Crystal wall Normal crystal 999 IA Twin crystal 999 IA Section Epitaxial 933 I- Section A Halogen composition uniform 993 IB Section Not uniform 993 IB Section Halogen conversion 994 IC Halogen substitution 994 IC Section Metal content 994 ID Monodispersion 990 IF Section Solvent addition 996 Item IF Latent image formation position Surface 995 I-G Inside 995 I-G Applicable photosensitive material negative 995 I-H Positive (including internal fog particles) 995 I-H Item Emulsion mixed 995 I- Section J Desalting 995 II-A The silver halide emulsion of the present invention can be subjected to physical ripening, chemical ripening and spectral sensitization. Are described in RD17643, RD18716 and RD308119, and can be used in the silver halide emulsion of the present invention.

Hereinafter, RD17643, RD18716
And RD308119.

[Item] [RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A section 23 648 Spectral sensitizer 996 IV-AA, B, C, D, 23-24 648- 649 H, I, J section Supersensitizer 996 IV-AE, J section 23 to 24 648 to 649 Antifoggant 998 VI 24 to 25 649 Stabilizer 998 VI 24 to 25 649 Known methods usable in the present invention Are also described in Research Disclosure below. The relevant sections are described below.

[Items] [Page of RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VlI-J item 25 Brightener 998 V 24 Ultraviolet absorber 1003 VIII- Section I, XIII-C Section 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plastic 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) 1001 XXB Item Silver halide photographic light-sensitive material of the present invention Providing a red, green and blue-sensitive silver halide emulsion layer, It may contain a coupler in the layer. It is preferable that the coloring dye formed from the coupler contained in each of these layers has a spectral absorption maximum separated by at least 20 nm. As the coupler, it is preferable to use a cyan coupler, a magenta coupler, and a yellow coupler. As a combination of each emulsion layer and a coupler, a combination of a yellow coupler and a blue photosensitive layer, a combination of a magenta coupler and a green photosensitive layer, a combination of a cyan coupler and a red photosensitive layer are used, but are not limited to these combinations. , And other combinations.

In the present invention, a DIR compound can be used. Specific examples of DIR compounds that can be used include, for example, D-1 to D-34 described in JP-A-4-114153, and these compounds can be preferably used in the present invention.

DIR that can be used in the present invention
Specific examples of the compounds other than those described above include, for example, U.S. Pat. Nos. 4,234,678, 3,227,554, 3,647,291, and 3,955.
8,993, 4,419,886,
No. 3,933,500, JP-A-57-5683
7, No. 51-13239, U.S. Pat.
72, 363, 2,070,266, and Research Disclosure, December 21, 1981, No. 21228.

Specific examples of the coupler that can be used in the present invention are described in RD308119 and RD17643. Hereinafter, RD308119, RD1764
3 shows relevant description places.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 Sections VII-D VIIC to G Magenta coupler 1001 VII-D Sections VIIC to G Cyan coupler 1001 VII-D Sections VIIC to G Colored coupler 1002 VII-C VIIG DIR coupler 1001 VII-F VIIF BAR coupler 1002 VII-F Release of other useful residues 1001 VII-F Coupler Alkali-soluble coupler 1001 VII-E Additive used in the present invention Is RD308119 XIV
Can be added by the dispersion method described in the above.

As the support of the silver halide photographic light-sensitive material of the present invention, the above-mentioned RD1764328, RD1871
The supports described in XIX at pages 6647-648 and RD308119 can be used.

In the silver halide photographic light-sensitive material of the present invention,
An auxiliary layer such as a filter layer or an intermediate layer described in RD308119 VII-K can be provided.

The silver halide photographic light-sensitive material of the present invention can have various layer constitutions such as a forward layer, a reverse layer and a unit constitution described in RD308119 VII-K.

To develop the silver halide color light-sensitive material of the present invention, for example, T.I. H. James, Theory of the Photographic Process 4th Edition (The Theory of The Photog)
rafic ProcessForth Edition
n) Pages 291 to 334 and Journal of the
American Chemical Society (Journa1
of the American Chemical
Society, 73, 3,100 (195
The developer known per se described in 1) can be used, and RD17643 28-2 described above can be used.
Page 9, RD18716 page 615 and RD308119
Development can be carried out by the usual method described in XIX.

[0238]

The present invention will be specifically described below with reference to examples.
The present invention is not limited to these examples.

Example 1 (Preparation of seed emulsion T-1) Seed emulsion T-1 having two parallel twin planes was prepared by the following method.

(E-1 solution) Deionized alkali-treated gelatin (weight average molecular weight 15,000) 244.0 g Potassium bromide 156.6 g 10% methanol solution of surfactant (EO-1) 0.48 ml EO-1 : HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 34.0 L with water (F-1 solution) Silver nitrate 1200 g 3716 ml with water (G-1 solution) Deionized alkali-treated gelatin (weight average molecular weight 15,000) 31.6 g potassium bromide 906.0 g 4.0 liters with water (H-1 solution) ammonia water (28%) 299 ml (liquid I-1) 8.0 liters of water (liquid J-1) 400.0 g of ossein gelatin 4832 ml with water (liquid K-1) 69.2 g of potassium bromide 38 with water 38 ml (L-1 solution) 56 using the stirrer weight% aqueous acetic acid 1000ml JP 62-160128 Patent forth, 3
Solution I-1 was added to solution E-1 which was vigorously stirred at 0 ° C., and then solution F-1 and solution G-1 were mixed by double jet method.
Per minute to produce silver halide nuclei.

Thereafter, the solution J-1 was added, the temperature was raised to 68 ° C. over 41 minutes, and the solution H-1 was further added and ripened for 5 minutes. Thereafter, the K-1 solution was further added, and 1 minute later, L-solution was added.
The pH was adjusted to 4.7 using one solution, and desalting was immediately performed.

When this seed emulsion was observed with an electron microscope, a monodisperse seed having an average grain size (projected area circle equivalent grain size) of 0.31 μm having two twin planes parallel to each other and a grain size distribution of 16% was obtained. It was an emulsion.

(Preparation of Emulsion Em-1) Em-1 was prepared using the following solution.

(H-3 Solution) Ossein gelatin 223.6 g 10% methanol solution of surfactant (EO-1) 3.6 ml Seed emulsion (T-1) 0.774 mol equivalent 5904 ml with water (I-3) Liquid) 3.5N silver nitrate aqueous solution 6490 ml (J-3 liquid) 3.5N potassium bromide aqueous solution 7500 ml (K-2 liquid) 3.0% by weight of gelatin and silver iodide fine particles (average particle diameter 0.05 μm) Fine grain emulsion (preparation method is shown below) Required amount (preparation method) 6.0 containing 0.06 mol of potassium iodide
To 5000 ml of a weight% gelatin solution, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide was added at a constant speed over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate. 12.53k finished weight
g.

(L-3 solution) 1.75N aqueous solution of potassium bromide required amount (M-3 solution) 56% by weight aqueous acetic acid solution required amount (N-3 solution) 3.5N aqueous solution of potassium bromide 500ml H in the reaction vessel -3 liquid is added, and with vigorous stirring,
Solution I-3, Solution J-3 and Solution K-2 were added by the simultaneous mixing method in accordance with the combinations shown in Table 1, seed crystals were grown, and a core / shell type silver halide emulsion was prepared.

Here, the addition rates of the I-3 solution, the J-3 solution and the K-2 solution are varied in a function with respect to the addition time in consideration of the critical growth rate. The generation of small particles and the deterioration of the particle size distribution due to Ostwald ripening between growing particles were prevented.

In the crystal growth, first, the first addition was performed while controlling the solution temperature in the reaction vessel to 75 ° C. and the pAg to 8.8, and then the solution temperature in the reaction vessel was reduced to 60 ° C. in 15 minutes. Solution 3 was added in 4 minutes, Solution K-2 was added in an amount corresponding to 2% of the total silver used, and then a second addition was performed. Second
The addition was performed by setting the solution temperature in the reaction vessel to 60 ° C. and pAg to 9.
8. The pH was controlled at 5.8. For control of pAg and pH, if necessary, L-3 solution,
M-3 solution was added.

After the particles are formed, desalting is carried out in accordance with the method described in JP-A-5-72658, gelatin is added and dispersed, pAg 8.06 at 40 ° C., pH 5.0.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, they were hexagonal tabular monodispersed silver halide grains having an average particle size of 1.30 μm and a particle size distribution of 17% and an average aspect ratio of 8.0. there were. The tabular silver halide grains had dislocation lines on the outer periphery.

[0250]

[Table 1]

(Preparation of Emulsion Em-2) In the preparation of Emulsion Em-1, when the growth of silver halide grains was 50% in terms of the amount of silver halide, InCl ₃ was added to 3.6 × 10 5 per mol of silver halide. Emulsion Em-2 was prepared in the same manner except that an aqueous solution containing ^-5 mol was added.

(Preparation of Emulsion Em-3) In the preparation of Emulsion Em-1, K ₄ Fe (CN) ₆ was added per mol of silver halide at the time when silver halide grain growth was 50% by silver halide amount. Emulsion Em-3 was prepared in the same manner except that an aqueous solution containing 3.6 × 10 ^-5 mol was added.

(Preparation of Emulsion Em-4) In the preparation of Emulsion Em-1, K ₄ Ru (CN) ₆ was added per mol of silver halide at the time when silver halide grain growth was 50% in silver halide amount. Emulsion Em-4 was prepared in the same manner except that an aqueous solution containing 3.6 × 10 ^-5 mol was added.

(Preparation of Emulsion Em-5) In the preparation of Emulsion Em-1, K ₄ Ru (CN) ₆ was added per mol of silver halide at the time when silver halide grain growth was 50% in terms of the amount of silver halide. Adding an aqueous solution containing 3.6 × 10 ^-5 mol, and adding an aqueous solution containing 1.5 × 10 ^-7 mol of K ₂ IrCl ₆ per mol of silver halide at the time when the amount of silver halide is 80%. Except for the above, emulsion Em-5 was prepared in the same manner.

<Preparation of Color Photosensitive Material> On a triacetyl cellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to prepare a multilayer color photographic material sample. The amount of each material added is shown in grams per 1 m ^2. However, silver halide and colloidal silver were converted to the amount of silver and represented by the number of moles per mole of silver in the same emulsion layer of sensitizing dye.

Emulsions Em-1 to Em-5 were respectively used in the following sample formulas, in the form of emulsion k in the fifth layer, and the high boiling point solvent (HBS) OIL- in the third to fifth layers was used.
2 was changed to the types and addition amounts shown in Tables 2 and 3, and
The samples shown in Table 1 were prepared. These emulsions Em-1 to E
m-5 is optimally color sensitized by the method described in the following sample formulation,
Used after chemical sensitization.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV Absorber UV-1 0.3 Colored Magenta Coupler CM-1 0.123 Colored Cyan Coupler CC-1 0.044 High Boiling Solvent OIL-1 0.167 Gelatin 1.33 Second layer (intermediate layer) Stain inhibitor AS-1 0.16 High boiling point solvent OIL-1 0.20 Gelatin 0.69 Third layer (Low sensitivity red-sensitive layer) Silver halide a 0.12 silver iodobromide b 0.29 sensitizing dye SD-1 2.37 × 10 ^-5 sensitizing dye SD-2 1.2 × 10 ^-4 sensitizing dye SD-3 2.4 × ^10-4 sensitizing dye SD-4 2.4 × ^10-6 Cyan coupler C-1 0.32 Colored cyan coupler CC-1 0.038 High boiling point solvent OIL-2 0.28 Stain inhibitor AS-2 0.0. 002 Gelatin 0.73 4th layer Medium-speed red-sensitive layer) Silver iodobromide c 0.10 Silver iodobromide d 0.86 Sensitizing dye SD-1 4.5 × 10 ^-5 Sensitizing dye SD-2 2.3 × 10 ^-4 Sensitizing dye SD-3 4.5 × 10 ^-4 Cyan coupler C-2 0.52 Colored cyan coupler CC-1 0.06 DIR compound DI-1 0.047 High boiling point solvent OIL-2 0.46 Antifouling agent AS-2 0.004 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide k 1.18 Sensitizing dye SD-1 3.0 × 10 ^-5 Sensitizing dye SD- ²¹ 0.5 × 10 ^-4 sensitizing dye SD-3 3.0 × 10 ^-4 cyan coupler C-2 0.047 cyan coupler C-3 0.09 colored cyan coupler CC-1 0.036 DIR compound DI-10 .024 High boiling point solvent OIL-2 0.27 Stain inhibitor AS-2 0.006 Tin 1.28 6th layer (intermediate layer) High boiling point solvent OIL-1 0.29 Stain inhibitor AS-1 0.23 Gelatin 1.00 7th layer (low-sensitivity green color-sensitive layer) Silver iodobromide a 0.19 silver iodobromide b 0.062 sensitizing dye SD-4 3.6 × 10 ^-4 sensitizing dye SD-5 3.6 × 10 ^-4 magenta coupler M-1 0.18 colored magenta coupler CM- 1 0.033 High boiling solvent OIL-1 0.22 Stain inhibitor AS-2 0.002 Stain inhibitor AS-3 0.05 Gelatin 0.61 Eighth layer (intermediate layer) High boiling solvent OIL-1 26 Antifouling agent AS-1 0.054 Gelatin 0.80 Ninth layer (Medium-speed green-sensitive layer) Silver iodobromide e 0.54 Silver iodobromide f 0.54 Sensitizing dye SD-6 7 × 10 ^-4 sensitizing dye SD-7 7.4 × 10 ^-5 sensitizing dye SD-8 5.0 × 10 ^{− 5} Magenta coupler M-1 0.17 Magenta coupler M-2 0.33 Colored magenta coupler CM-1 0.024 Colored magenta coupler CM-2 0.029 DIR compound DI-2 0.024 DIR compound DI-3 005 High boiling point solvent OIL-1 0.73 Stain inhibitor AS-2 0.003 Stain inhibitor AS-3 0.035 Gelatin 1.80 10th layer (highly sensitive green color-sensitive layer) Silver iodobromide f 1 .19 Sensitizing dye SD-6 4.0 × 10 ^-4 Sensitizing dye SD-7 8.0 × 10 ^-5 Sensitizing dye SD-8 5.0 × 10 ^-5 Magenta coupler M-1 0.065 Colored Magenta coupler CM-1 0.022 Colored magenta coupler CM-2 0.026 DIR compound DI-2 0.003 DIR compound DI-3 0.003 High boiling solvent OIL -1 0.19 High boiling point solvent OIL-2 0.43 Antifouling agent AS-2 0.014 Antifouling agent AS-3 0.017 Gelatin 1.23 11th layer (yellow filter layer) Yellow colloidal silver 0.05 High boiling point solvent OIL-1 0.18 Stain inhibitor AS-1 0.16 Gelatin 1.00 12th layer (low-sensitivity blue-sensitive layer) Silver iodobromide a 0.08 Silver iodobromide b 0.22 Sensitizing dye SD-9 6.5 × 10 ^-4 Sensitizing dye SD-10 2.5 × 10 ^-4 Yellow coupler Y-1 0.77 DIR compound DI-4 0.017 High boiling point solvent OIL-1 31 Antifouling agent AS-2 0.002 Gelatin 1.29 13th layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.41 Silver iodobromide i 0.61 Sensitizing dye SD-9 4 × 10 ^-4 sensitizing dye SD-10 1.5 × 10 ^-4 yellow cap L Y-1 0.23 High boiling point solvent OIL-1 0.10 Stain inhibitor AS-2 0.004 Gelatin 1.20 14th layer (1st protective layer) Silver iodobromide j 0.30 UV absorber UV -1 0.055 Ultraviolet absorber UV-2 0.110 High boiling point solvent OIL-2 0.30 Gelatin 1.32 15th layer (second protective layer) Polymer PM-1 0.15 Polymer PM-2 0.04 Slip agent WAX-1 0.02 Dye D-1 0.001 Gelatin 0.55 The characteristics of the above silver iodobromide are shown below (emulsions a to j below).
Mean the one side length of a cube having the same volume). The following silver iodobromide j was used without sensitization.

Emulsion No. Average grain size (μm) Average AgI amount (mol%) Diameter (equivalent to circle) / thickness ratio Silver iodobromide a 0.30 2.0 5.0 Silver iodobromide b 0.40 3.0 6.4 Iodine Silver bromide c 0.60 2.0 6.1 Silver iodobromide d 0.74 2.0 5.0 Silver iodobromide e 0.60 3.0 6.0 Silver iodobromide f 0.65 2 0.0 6.5 Silver iodobromide h 0.65 3.0 6.0 Silver iodobromide i 1.00 3.0 5.0 Silver iodobromide j 0.05 2.0 1.0 Each of the above emulsions The above-mentioned sensitizing dye is added to the mixture, and after aging, triphenylphosphine selenide, sodium thiosulfate,
Chloroauric acid and potassium thiocyanate were added and subjected to chemical sensitization so as to optimize the fog-sensitivity relationship.

In addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-1 (polyvinylpyrrolidone, weight average molecular weight: 1)
000), AF-2 (polyvinylpyrrolidone, weight average molecular weight: 1,100,000), inhibitor AF-3,
AF-4, AF-5, hardeners H-1, H-2 and preservative Ase-1 were added.

The structures of the compounds used in the above samples are shown below.

SU-1: C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK SU-2: C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₃
Br ^- SU-3: sodium di (2-ethylhexyl) sulfosuccinate SU-4: sodium tri-i-propylnaphthalenesulfonate ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene ST-2: Adenine AF-3: 1-Phenyl-5-mercaptotetrazole AF-4: 1- (4-Carboxyphenyl) -5-mercaptotetrazole AF-5: 1- (3- acetamidophenyl) -5-mercaptotetrazole H-1: _{[(CH 2 = CHSO 2 CH 2} ) 3 CCH 2 SO 2 C
H ₂ CH ₂ ] ₂ NCH ₂ CH ₂ SO ₃ K H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium OIL-1: tricresyl phosphate OIL-2: di (2-ethylhexyl) Phthalate AS-1: 2,5-bis (1,1-dimethyl-4-hexyloxycarbonylbutyl) hydroquinone AS-2: Dodecyl gallate AS-3: 1,4-bis (2-tetradecyloxycarbonylethyl) Piperazine

[0262]

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[0263]

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[0264]

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[0265]

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[0266]

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[0267]

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[0268] Samples immediately after preparation and 65% 20% after preparation
Each of the samples stored in the RH for one week was subjected to a step wedge exposure for 1/200 second and 3.2 CMS using white light, and then immediately subjected to the following color development processing to obtain a characteristic curve.

The sensitivity was indicated by a relative value, where the value of the sample 1001 exposed and developed immediately after the red sensitivity (reciprocal of the amount of exposure giving a density of fog + 0.10) was taken as 100.

The granularity was determined by the RMS granularity (fog density +
A cyan density of 0.30 was scanned with a microdensitometer having an aperture scanning area of 250 μm 2, which was 1000 times the change in density value, and the value of a sample 1001 exposed and developed immediately after fabrication was set to 100. It was shown as a relative value.

<< Color development processing >> (Processing step) Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes and 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 1 minute 55 ± 5.0 ° C.-* The replenishment amount is a value per 1 m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developing solution and color developing replenisher Developer replenisher Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium bicarbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g iodide Potassium 1.2 mg-Hydroxylamine sulfate 2.5 g 3.1 g Sodium chloride 0.6 g-4-Amino-3-methyl-N-ethyl-N-([beta] -hydroxylethyl) aniline sulfate 4.5 g 6.3 g Diethylenetriaminepentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Add water to make 1 liter, and add potassium hydroxide or 20%
The color developing solution is adjusted to pH 10.06 and the replenisher is adjusted to pH 10.18 using sulfuric acid.

Bleach and Bleach Replenisher Bleach Replenisher Water 700 ml 700 ml 1,3-diaminopropanetetraacetate ammonium (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g water To 1 liter, and adjust the pH of the bleaching solution to 4.4 and the pH of the replenishing solution to 4.0 using ammonia water or glacial acetic acid.

Fixer and Fixer Replenisher Fixer Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Aqueous solution using ammonia water or glacial acetic acid, pH 6.2
Then, the pH of the replenisher is adjusted to 6.5, and then water is added to make 1 liter.

Stabilizing Solution and Stabilizing Replenisher Water 900 ml p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g siloxane (UCC L-77) 0.1 g ammonia water 0.5 ml water was added to make up to 1 liter.
Adjust to pH 8.5 with% sulfuric acid.

Tables 2 and 3 show the produced samples and their evaluation results.

[0278]

[Table 2]

[0279]

[Table 3]

As is clear from Tables 2 and 3, samples 1021 to 1026, 1031 to 1036, and 1
041 to 1046 and 1051 to 1056 (the structure of the invention described in claim 1 of the present invention) are comparative samples 1001 to 101.
6 showed excellent performance.

Example 2 An emulsion (Em-11) was prepared using the following solution.

(A-22 solution) Gelatin (average molecular weight 15,000) 35.9 g Potassium bromide 23.1 g 6200 ml with water (B-22 solution) 1.9 N silver nitrate aqueous solution 149.4 ml (C-22 solution) 3.5N silver nitrate aqueous solution 6281 ml (E-22 solution) Potassium bromide 33.8 g 149.4 ml with water (F-22 solution) Potassium bromide 1978 g Potassium iodide 145.3 g Water with 5000 ml (G-22 solution) Bromide Potassium 1212 g potassium iodide 52.3 g water 3000 ml (I-22 solution) potassium bromide 208.3 g water 1000 ml (K-22 solution) gelatin 33.9 g potassium bromide 6.16 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% methanol solution 0.33 953 ml with water (L-22 solution) Gelatin 339.8 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% methanol solution 1.3 ml 17228 ml with water (M-22 solution) 624.8 g potassium bromide 1500 ml with water Add the A-22 solution into a reaction vessel, and vigorously stir at 30 ° C. while stirring B-22. The solution and the E-22 solution were added at a constant speed in 70 seconds by the simultaneous mixing method. Thereafter, K-22 solution was added, and the temperature was raised to 70 ° C. After the temperature was raised, L-22 solution was added, and pAg was adjusted to 8.2 with C-22 solution.
4169 ml of the 22 solution and the F-22 solution were acceleratedly added (final addition speed was 8 times the initial addition speed) over 112 minutes while maintaining pAg 8.2 by the simultaneous mixing method. afterwards,
The temperature was lowered to 60 ° C. Subsequently, pAg9.
7 and then accelerated addition of the remainder of the C-22 solution and the G-22 solution in a simultaneous mixing method for 55 minutes (final addition speed is twice the initial addition speed) to prepare a tabular silver halide emulsion. did.

For pAg control, I-22 solution was added as needed.

After the particles are formed, desalting is performed according to the method described in JP-A-5-72658, and gelatin is added and dispersed, and pAg 8.06, pH 5.0 at 40 ° C.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, they were tabular silver halide grains having an average grain size (equivalent grain size in projected area circle) of 1.2 μm and an average thickness of 0.17 μm. Was.

Emulsion (Em-1) was prepared using the following solution.
2) was prepared.

(A-23 solution) Gelatin 7.5 g Potassium bromide 9.5 g 12.0 l with water (B-23 solution) 1.0 N silver nitrate aqueous solution 27.0 ml (C-23 solution) Potassium bromide 3.16 g 27.0ml potassium iodide 67mg water (D-23 solution) Oxone _{(TM) (2KHSO 5 · KHSO 4 ·} K 2 SO 4, Aidrich Ltd.) 300 mg water at 40 ml (E-23 solution) gelatin (methionine content Is 8 μmol / g of gelatin) 180 g 3000 ml with water (F-23 solution) 1N potassium bromide aqueous solution 245 ml (G-23 solution) 2N silver nitrate aqueous solution 850 ml (H-23 solution) potassium bromide 228.5 g potassium iodide 13.3 g 1000 ml with water (I-23 solution) 3.5N silver nitrate aqueous solution 4657 ml (J-23 solution) Potassium bromide 1999g Potassium iodide 116.2g 5000ml with water Add the A-23 solution to the reaction vessel, adjust the pH to 2 with sulfuric acid, and stir vigorously at 40 ° C while mixing the B-23 solution and C
-23 liquid was added by the double jet method. Then D-
23 liquid was added, and it heated up to 55 degreeC. After the temperature was raised, the mixture was aged for 10 minutes, the E-23 solution was added, and the pH was adjusted to 6 with an aqueous potassium hydroxide solution. F-23 solution was added, followed by pA
While maintaining g, Liquid G-23 and Liquid H-23 were added by the simultaneous mixing method, and then Liquid I-23 and Liquid J-23 were added by the simultaneous mixing method.

After the particles were formed, the mixture was desalted by a conventional method, dispersed by adding gelatin, and pAg 8.06, p
An emulsion of H5.8 was obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, they were tabular silver halide grains having an average grain size (grain size in terms of projected area circle) of 1.9 μm and an average thickness of 0.06 μm. Was.

Emulsions Em-11 and Em-12 were prepared in Example 1.
Of the fifth layer emulsion k and the fourth layer
Samples were prepared in the same manner as in Example 1 except that emulsions c and d in the layers were used and OIL-2 of the high boiling point solvent (HBS) in the third to fifth layers was changed in the same manner as in Example 1. Table 4 shows the prepared samples and evaluation results.

[0291]

[Table 4]

As is clear from Table 4, Samples 1112 to 1117 according to the present invention (the structure of the invention described in claim 2 of the present invention) were Comparative Samples 1101 to 1107 and 1111.
Showed excellent performance.

Example 3 Preparation of Silver Halide Emulsion (Preparation of Emulsion Em-21) [Nucleation / Nucleation Ripening Step] The following gelatin aqueous solution-1 in a reaction vessel was kept at 30 ° C. The following silver nitrate aqueous solution-1 and halide aqueous solution-1 were added at a constant flow rate for one minute by a double jet method while vigorously stirring using a mixing and stirring apparatus described in the publication to form nuclei.

[0294] (aqueous gelatin solution -1) alkali-processed inert gelatin (average molecular weight 100,000) 32.4 g Potassium bromide 9.9 g H ₂ O 13.0 L (aqueous silver nitrate solution -1) nitrate 50.43g H ₂ O 225. 9 ml (halide solution -1) potassium bromide 35.33g H ₂ O 224.7ml the addition finished, immediately following aqueous gelatin solution -2 addition, the temperature was raised to 60 ° C. over a period of 30 minutes, the pH 5 .
It was adjusted to 0 and kept in that state for 20 minutes.

(Aqueous Gelatin Solution-2) Alkali-treated inert gelatin (average molecular weight 100,000) 17.5 g Potassium bromide 3.18 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 ( _{CH 2 CH 2 O) n H} (m + n = 9.77) 10 wt% methanol solution 0.20ml H ₂ O 673.5ml [grain growth step -1] after the aging step is completed, followed by double jet in Silver nitrate aqueous solution-2 and halide aqueous solution-
2 was added with increasing flow rate. After the addition was completed, an aqueous solution of gelatin-3 was added, and subsequently, an aqueous solution of silver nitrate-3 and an aqueous solution of halide-3 were added at an increased flow rate. During this time, the silver potential of the solution (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled at 6 mV using a 1N potassium bromide solution.

[0296] (aqueous silver nitrate solution -2) nitrate 639.8g H ₂ O 2866.2ml (halide solution -2) Potassium bromide 448.3g H ₂ O 2850.7ml (aqueous gelatin solution -3) alkali-processed inert gelatin (average 175.9 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by weight methanol solution 0 .67ml H ₂ O 4260.1ml (aqueous silver nitrate solution -3) nitrate 989.8g H ₂ O 1437.2ml (halide solution -3) potassium bromide 679.6g iodide 19.35g H ₂ O 1412.0ml [particles Growth step-2] After completion of the particle growth step-1, 1N
Adjust the pH to 5.0 with aqueous nitric acid, then 3.
The silver potential in the reaction vessel was adjusted to −19 mV using a 5N aqueous potassium bromide solution, and then a silver nitrate aqueous solution-4 and a halide aqueous solution-4 were added while accelerating the flow rates.

[0297] (aqueous silver nitrate solution -4) nitrate 720.0g H ₂ O 1045.6ml (halide solution -4) Potassium bromide 499.3g iodide 7.0g H ₂ O 1027.1ml Incidentally, the particle growth step -1 2, the addition rates of the aqueous silver nitrate solution and the aqueous halide solution were adjusted so that no new silver halide grains were formed, and that the grain size distribution did not deteriorate due to Ostwald ripening between the growing silver halide grains. Optimal control.

After completion of the growth, desalting and washing are performed.
Add gelatin and disperse well.
8. The pAg was adjusted to 8.1. When the obtained emulsion was examined by a replica method, it was a silver halide emulsion composed of hexagonal tabular grains having an average grain size of 1.4 μm, a grain size distribution of 22% and an average aspect ratio of 7. When observed using a transmission electron microscope, no particles having dislocation lines existed in Em-21.

(Preparation of Emulsion Em-22) Em-22 was prepared in the same manner as Em-21, except for the following. E
When m-22 was examined by a replica method, the average particle size was 1.4.
It was a silver halide emulsion composed of hexagonal tabular grains having a particle size distribution of 22 μm and an average aspect ratio of 7. The state of dislocation lines formed in the silver halide grains was examined using a transmission electron microscope. As a result, 90% or more (number) of grains having 5 or more dislocation lines per grain were found in Em-22. did. Many dislocation lines were formed in the fringe portions of the tabular grains.

[Particle Growth Step-2] After the completion of the particle growth step-1, the following aqueous solution-A1 and then the aqueous solution-B1 were added, and the pH was adjusted to 9.3 with a 1N aqueous potassium hydroxide solution for 4 minutes. The iodine ions were released while ripening.
Thereafter, the pH was adjusted to 5.0 using a 1N aqueous nitric acid solution, and then the silver potential in the reaction vessel was adjusted to −19 mV using a 3.5N aqueous potassium bromide solution. Aqueous halide solution-4 was added while accelerating the flow rate.

(Aqueous solution-A1) Sodium p-iodoacetamidobenzenesulfonate 102.7 g H ₂ O 770.1 ml (Aqueous solution-B1) Sodium sulfite 35.6 g H ₂ O 352.9 ml (Aqueous silver nitrate solution-4) Silver nitrate 720. 0g H ₂ O 1045.6ml (halide solution -4) samples in the same manner as in example 1 using potassium potassium bromide 494.4g iodide 14.1g H ₂ O 1027.1ml emulsions Em-21 and Em-22 Was prepared. Table 5 shows the prepared samples and evaluation results.

[0302]

[Table 5]

As is evident from Table 5, Samples 1212 to 1217 according to the present invention (structure of the invention according to the third aspect of the present invention) were Comparative Samples 1201 to 1207 and 1211.
Showed excellent performance.

Example 4 (Preparation of Emulsion Em-31)
-31 was prepared.

(H-31 solution) Ossein gelatin 223.6 g 10% methanol solution of surfactant (EO-1) 3.6 ml Seed emulsion (T-1 prepared in Example 1) 0.774 mol equivalent of water 5904 ml (I-31 solution) 3.5N silver nitrate aqueous solution 6490 ml (J-31 solution) 3.5N potassium bromide aqueous solution 7500 ml (K-31 solution) 3.0% by weight of gelatin and silver iodide fine particles (average particle size) Fine emulsion (0.05 μm) (used in the preparation of Em-1 in Example 1) Required amount (L-31 solution) 1.75N aqueous potassium bromide solution Required amount (M-31 solution) 56% by weight acetic acid Required amount of aqueous solution (N-31 solution) 3.5N aqueous potassium bromide solution 500ml Add H-31 solution into the reaction vessel, and stir vigorously to display I-31 solution, J-31 solution and K-31 solution. The addition is performed by the double jet method according to the combination shown in 6,
Seed crystals were grown to prepare a core / shell type silver halide emulsion.

Here, I-31 solution, J-31 solution, K-3
Considering the critical growth rate, the addition rate of one solution is changed in a function-wise manner with respect to the addition time, and the generation of small particles other than the seed particles that are growing and the particle size distribution due to Ostwald ripening between the growing particles are performed. Deterioration did not occur.

In the crystal growth, first, the first addition was performed while controlling the solution temperature in the reaction vessel to 75 ° C. and the pAg to 8.8, and then the solution temperature in the reaction vessel was reduced to 60 ° C. in 15 minutes. -31 solution was added in 4 minutes, and 0.5 part of K-31 solution was added.
After 1 mole was added over 15 minutes, a second addition was made. In the second addition, the solution temperature in the reaction vessel was set to 60 ° C., and the pAg was set to 9.
8. The pH was controlled at 5.8. For control of pAg and pH, if necessary, L-3 solution,
M-3 solution was added.

After the formation of the particles, the following operation of ultrafiltration A was performed, and then the temperature was raised to 60 ° C., the pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution, and the following Q-31 solution was subjected to total halogenation. Emulsion (Em-31) was prepared in the same manner except that 5.0 mol% was added to silver, the mixture was aged for 30 minutes, and the following operation of ultrafiltration A was performed.

(Ultrafiltration A) A silver halide emulsion was treated with an ultrafiltration module (manufactured by Asahi Kasei Kogyo Co., Ltd .;
Type AL using 000 polyacrylonitrile membrane
P-1010), the mixture was repeatedly circulated through water and concentrated while being circulated, and finally adjusted to pBr 3.0 at 40 ° C.

(Liquid Q-31) A fine grain emulsion preparation method comprising 3.0% by weight of gelatin and silver bromide fine grains (average grain size: 0.05 μm) is shown below.

6.0 containing 0.06 mol of potassium bromide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2000 ml of an aqueous solution containing 7.06 mol of potassium bromide were added at a constant rate to 5000 ml of a weight% gelatin solution over 10 minutes. The pH during the formation of the fine particles was adjusted to 3.0 using nitric acid.
And the temperature was controlled at 30 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate, and the operation of ultrafiltration A was performed subsequently.

After the particles are formed, desalting is performed according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and pAg 8.06, pH 5.0 at 40 ° C.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, they were hexagonal tabular monodispersed silver halide grains having an average particle size of 1.30 μm and a particle size distribution of 17% and an average aspect ratio of 8.0. there were. The tabular silver halide grains had dislocation lines on the outer periphery.

[0314]

[Table 6]

The silver halide grains in the emulsion Em-31 were as follows:
I ₁ / I ₂ = 0.4.

(Preparation of Emulsion Em-32) Emulsion (Em-3
In the preparation of 1), solution I-31, solution J-31, and K-3
The same procedure was carried out up to the formation of particles by addition of one liquid. After the operation of the ultrafiltration A was performed, the temperature was raised to 60 ° C., and pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution. -3
Solution 2a was added at 3.0 mol% based on the total silver halide and ripened for 20 minutes, and then pB with a 2N aqueous potassium bromide solution.
r was adjusted to 1.0, the following Q-32b solution was added at 5% to silver halide, ripened for 30 minutes, and then subjected to the above-mentioned ultrafiltration A operation. Em-3
2) was prepared.

(Liquid Q-32a) A fine grain emulsion preparation method comprising 3.0% by weight of gelatin and silver iodobromide fine grains (average grain size: 0.05 μm, silver iodide content: 10 mol%) is shown below.

6.0 containing 0.06 mol of potassium bromide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate in 5000 ml of a weight% gelatin solution and an aqueous solution 2 containing 6.35 mol of potassium bromide and 0.706 mol of potassium iodide 2
000 ml was added at a constant speed over 10 minutes. During the formation of fine particles, the pH was controlled at 3.0 using nitric acid, and the temperature was controlled at 30 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate, and the operation of ultrafiltration A was performed subsequently.

(Solution Q-32b) A fine grain emulsion preparation method comprising 3.0% by weight of gelatin and silver bromide fine grains (average grain size: 0.05 μm) is shown below.

6.0 containing 0.06 mol of potassium bromide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2000 ml of an aqueous solution containing 7.06 mol of potassium bromide were added at a constant rate to 5000 ml of a weight% gelatin solution over 10 minutes. The pH during the formation of the fine particles was adjusted to 3.0 using nitric acid.
And the temperature was controlled at 30 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate, and the operation of ultrafiltration A was performed subsequently.

The silver halide grains in the emulsion Em-32 were as follows:
I ₁ / I ₂ = 1.6. The tabular silver halide grains had dislocation lines on the outer periphery.

Preparation of photosensitive material A sample was prepared in the same manner as in Example 1 except that the emulsions Em-31 and Em-32 were used. Table 7 shows the prepared samples and the evaluation results.

[0323]

[Table 7]

As is clear from Table 7, Samples 1312 to 1317 according to the present invention (the structure of the invention described in claim 4 of the present invention) were Comparative Samples 1301 to 1307 and 1311.
Showed excellent performance.

Example 5 Preparation of Emulsion (Em-41) In the preparation of emulsion (Em-31) in Example 4,
Solution I-31, solution J-31 and solution K-31 were added according to the combination shown in Table 8, and addition of solution K-31 from the end of the first addition to the start of the second addition. An emulsion having a silver halide phase having a silver iodide content of 0 mol% at the center and a silver halide phase having a silver iodide content of 2 mol% outside thereof in the same manner except that no silver halide phase is carried out. (E
m-41) was prepared.

[0326]

[Table 8]

Preparation of Emulsion (Em-42) In the preparation of the emulsion (Em-31) in Example 4,
Solution I-31, solution J-31 and solution K-31 were added according to the combination shown in Table 8, and addition of solution K-31 from the end of the first addition to the start of the second addition. Is carried out in the same manner except that the silver halide phase having a silver iodide content of 0 mol% and the silver halide phase having a silver iodide content of 2 mol% outside the center of the grain, except that no iodine is carried out. Silver halide phase having a silver content of 12 mol%, silver iodide content of 2 mol%
(Em-42) having a silver halide phase in order.

[0328]

[Table 9]

Emulsions Em-41 and E prepared in Example 4
A sample was prepared in the same manner as in Example 1 using m-42. Table 10 shows the prepared samples and the evaluation results.

[0330]

[Table 10]

As is clear from Table 10, Samples 1412 to 1417 (the structure of the invention described in claim 5 of the present invention) relating to the present invention are comparative samples 1401 to 1407 and 141.
1 showed excellent performance.

Example 6 Preparation of Emulsion (Em-51) In the preparation of emulsion (Em-31) in Example 4,
Immediately before the first addition of the I-31 solution, the J-31 solution and the K-31 solution, the following I-4 solution was added, and immediately after the first addition, the following J solution was added.
Emulsion (Em-51) was prepared in the same manner except that Solution -4 was added and reduction sensitization was performed.

(I-4 solution) 100 ml of an aqueous solution containing 1 × 10 ⁻⁵ mol of thiourea dioxide per mol of silver halide (J-4 solution) 2.5 ml of aqueous solution of sodium ethylthiosulfonate per mol of silver halide Aqueous solution containing 10 ^-4 mol 100 ml Using the emulsions Em-31 and Em-51 prepared in Example 4, the sample formulation 1001 in Example 1
Used in place of emulsion h and emulsion i in the
Samples were prepared by changing the types and amounts of OIL-1 in the layer and the thirteenth layer to those shown in Table 11. Emulsion Em-1 prepared in Example 1 was used as emulsion k of the fifth layer. Emulsions Em-31 and Em-51 were used after being optimally subjected to color sensitization and chemical sensitization by the method described in Sample Formulation 1001. The prepared samples were evaluated for blue sensitivity and granularity in the same manner as in Example 1.

Table 11 shows the prepared samples and the evaluation results.

[0335]

[Table 11]

As is clear from Table 11, Samples 1512-1517 (the structure of the invention described in claim 6 of the present invention) relating to the present invention are comparative samples 1501-1507, 151
1 showed excellent performance.

Example 7 Preparation of Emulsion (Em-61) The emulsion (Em-22) prepared in Example 3 was dissolved at 40 ° C., and a 1N silver nitrate aqueous solution and a 1N potassium iodide aqueous solution were mixed at a flow ratio of 8: 1. Simultaneous addition was performed to prepare pBr 4.0. Subsequently, a 1N aqueous sodium chloride solution was emulsified (Em-24).
0.02 mol was added per 1 mol, and the aforementioned spectral sensitizing dyes SD-3 and SD-2 were added at a ratio of 2: 1 so that the total coverage was 70%. And a 0.5 sodium chloride aqueous solution at a constant speed in an emulsion (Em).
-24) 0.05 mol per mol was added simultaneously. By this operation, epitaxials were formed mainly at the corners and edges of the tabular silver halide grains.

Subsequently, spectral sensitizing dyes SD-1 to SD-3
Was added in the required amount to perform spectral sensitization optimally.

Using Emulsions Em-22 and Em-61 prepared in Example 3, samples were prepared in the same manner as in Example 1. Table 12 shows the prepared samples and evaluation results.

[0340]

[Table 12]

As is clear from Table 12, Samples 1612 to 1617 (the structure of the invention according to claim 7 of the present invention) relating to the present invention correspond to Comparative Samples 1601 to 1607 and 161.
1 showed excellent performance.

Example 8 Preparation of Emulsion (Em-71) In the preparation of emulsion (Em-22) in Example 3,
An emulsion (Em-71) was prepared in the same manner except that the silver potential during the addition of the aqueous silver nitrate solution-2 and the aqueous halide solution-2 in [Grain Growth Step-1] was controlled to 0 mV.
When the obtained emulsion was examined by a replica method, the average particle size was 1.5 μm, the particle size distribution was 26%, and the average aspect ratio was 7.5.
Was a silver halide emulsion composed of hexagonal tabular grains. The state of dislocation lines formed in the silver halide grains was examined using a transmission electron microscope.
90% or more (number) of particles having more than one dislocation line existed. Many dislocation lines were formed in the fringe portions of the tabular grains.

Preparation of Emulsion (Em-72) Em-72 was prepared in the same manner as in Em-22 except that the emulsion (Em-22) in Example 3 was not described below. When Em-72 was examined by a replica method, the average aspect ratio was 1.3 μm and the average aspect ratio was 14% with a particle size distribution of 14%.
5 was a silver halide emulsion comprising hexagonal tabular grains. Further, the state of dislocation lines formed in the silver halide grains was examined using a transmission electron microscope. As a result, 90% or more (number) of grains having 15 or more dislocation lines were found in Em-72. Many dislocation lines were formed in the fringe portions of the tabular grains.

[Nucleation and ripening step] The following gelatin aqueous solution-5 in a reaction vessel was maintained at 30 ° C, and the pH was adjusted to 1.96 with 1N sulfuric acid.
While stirring vigorously using the mixing and stirring device described in JP-A No. 28-28, the silver nitrate aqueous solution-1 was used by a double jet method.
And halide solution-1 were added at a constant flow rate for one minute to form nuclei.

(Aqueous Gelatin Solution-5) Oxidized low molecular weight gelatin (average molecular weight: 42,000) 32.4 g Potassium bromide 9.92 g H ₂ O 12938.0 ml After completion of the above addition, the above gelatin solution-2 was added, and 1N
The temperature was raised to 60 ° C. over a period of 30 minutes while maintaining the silver potential at 6 mV using a potassium bromide solution. Aqueous ammonia was added to adjust the pH to 9.3, and the mixture was maintained for 7 minutes. Then, the pH was adjusted to 6.1 using a 1N aqueous nitric acid solution.

Preparation of Emulsion (Em-73) In the preparation of emulsion (Em-22) in Example 3,
E. Except for using the following (aqueous gelatin-6) instead of (aqueous gelatin-1) in the [nucleation / ripening step]
Emulsion (Em-73) was prepared in the same manner as m-22. When the obtained emulsion was examined by a replica method, the average particle size was 1.4 μm, the particle size distribution was 13%, and the average aspect ratio was 8.8.
0 was a silver halide emulsion composed of hexagonal tabular grains.
The state of dislocation lines formed in the silver halide grains was examined using a transmission electron microscope.
90% or more (number) of particles having five or more dislocation lines existed. Many dislocation lines were formed in the fringe portions of the tabular grains.

(Aqueous Gelatin Solution-6) Alkali-treated inert gelatin (average molecular weight 100,000) 32.4 g Potassium bromide 12.0 g PLURONIC-31R1 (manufactured by BASF, polyalkylene oxide compound) 7.0 g H ₂ O 13. A sample was prepared in the same manner as in Example 1 using 0l Em-71 to Em-73. Table 13 shows the prepared samples and the evaluation results.

[0348]

[Table 13]

As is clear from Table 13, Samples 1711 to 1722 according to the present invention (the structure of the invention described in the eighth aspect of the present invention) showed superior performance to Comparative Samples 1701 to 1709.

Example 9 Preparation of Twin Seed Emulsion (T-2) (solution a-1) Ossein gelatin 80.0 g Potassium bromide 53.1 g Potassium iodide 24.0 g 7.2 l with water (b-1) Solution) Silver nitrate 1800 g with water 6.0 l (solution c-1) Potassium bromide 1327 g 1-phenyl-5-mercaptotetrazole (added with 1.0% methanol solution) 0.3 g with water 3.0 l (solution d-1) ) Ammonia water (28%) 705 ml (e-1 solution) Acetic acid (56%) required amount Solution b-1 and solution c-1 were added to solution a-1 which was vigorously stirred at 40 ° C.
The liquid was added by a double jet method in 30 seconds to perform nucleation. Thereafter, the temperature was lowered to 20 ° C., d-1 solution was added, and aging was performed for 5 minutes. After aging, the pH was adjusted to 6.0 with solution e-1 and desalting was performed according to a conventional method. The average grain size of this seed emulsion was 0.24 μm.

Preparation of Twin Seed Emulsion (T-3) (a-2 solution) Ossein gelatin 80.0 g Potassium bromide 47.4 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% methanol solution 0.48 ml with water 8.0 l (solution b-2) 1200 g of silver nitrate 1600 ml with water (solution c-2) ossein Gelatin 32.2 g Potassium bromide 840 g Water 1600 ml (d-2 solution) Ammonia water (28%) 470 ml (e-2 solution) Acetic acid (56%) Required amount Using a stirrer described in JP-A-62-160128. , 4
A-2 solution stirred at 1000 rpm at 0 ° C.
Solution-2 and solution c-2 were added by a double jet method over 14 minutes to form nuclei. Thereafter, the temperature was lowered to 20 ° C., the d-2 solution was added, and aging was performed for 5 minutes.

After the completion of the ripening, the pH was adjusted to 6.0 with solution e-2, and desalting was carried out according to a conventional method. The average grain size of this seed emulsion was 0.23 μm.

Preparation of Twin Seed Emulsion (T-4) (a-3 solution) Ossein gelatin 80.0 g Potassium bromide 61.6 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% methanol solution 0.48 ml with water 8.0 l (solution b-3) 1200 g of silver nitrate 1600 ml with water (solution c-3) ossein Gelatin 32.2 g Potassium bromide 790 g Potassium iodide 70.3 g Water 1600 ml (d-3 solution) Ammonia water (28%) 470 ml (e-3 solution) Acetic acid (56%) Required amount JP-A-62-160128 Using the stirrer described, 4
The solution a-3 stirred at 600 rpm at 0 ° C.
Solution 3 and solution c-3 were added by a double jet method over 5 minutes to form nuclei. Thereafter, the temperature is lowered to 20 ° C. and d
-3 solution was added and ripened for 5 minutes.

After the completion of the ripening, the pH was adjusted to 6.0 with solution e-3, and desalting was carried out according to a conventional method. The average grain size of this seed emulsion was 0.20 μm.

Preparation of Emulsion (Em-81) Emulsion (Em-81) was prepared using the following solution.

(A-4 solution) Ossein gelatin 67.0 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) ) Of 10% methanol solution 0.6 ml seed emulsion (T-2) 0.33 mol with water 3.5 l (solution b-4) 0.5N silver nitrate aqueous solution 948 ml (solution c-4) 52.9 g of potassium bromide In-gelatin 35.6 g 948 ml with water (d-4 solution) 3.5N silver nitrate aqueous solution 4471 ml (e-4 solution) Potassium bromide 1882 g ossein gelatin 200 g 4471 ml with water (f-4 solution) 3% by weight of gelatin and iodine Emulsion (*) composed of silver halide fine particles (average particle size: 0.05 μm) 1.39 mol (*) The preparation method is described below.

6.0 containing 0.06 mol of potassium iodide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2000 ml of an aqueous solution containing 7.06 mol of potassium iodide were added to 5000 ml of an aqueous gelatin solution of 10% by weight over 10 minutes. During the formation of the fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of fine particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

(G-4 solution) 1.75N Potassium bromide aqueous solution required amount Add the a-4 solution to the reaction vessel and, while stirring vigorously, add the solutions b-4 to f-4 according to the combination shown in Table 14. Was added by the double jet method.

The temperature inside the reaction vessel was 75 ° C., and the pAg was 9.
It was kept at zero. g-4 if necessary for pAg control
The liquid was used.

After grain growth, desalting was carried out in accordance with a conventional method, and then dispersed in gelatin, and at 40 ° C., pH 5.8, pAg
Adjusted to 8.8. The silver halide grains in the obtained silver halide emulsion are tabular silver halide grains having an average grain size of 1.4 μm, an average aspect ratio of 7.0, and a grain size distribution of 23%, and are 2 parallel to the main plane. The average of the distance between two or more twin planes was 600 °.

[0361]

[Table 14]

Preparation of Emulsion (Em-82) Emulsion (Em-81) was prepared in the same manner as in the preparation of emulsion (Em-81), except that Solution a-5 was used instead of Solution a-4.
-82) was prepared.

(A-5 solution) 67.0 g of ossein gelatin 0.6% of 10% methanol solution of surfactant (EO-1) Seed emulsion (T-3) 0.31 mol 3.5 l of water was obtained. The silver halide grains in the silver halide emulsion are tabular silver halide grains having an average grain size of 1.6 μm, an average aspect ratio of 8.0, and a grain size distribution of 24%, and two or more silver halide grains parallel to the main plane. The average twin plane distance was 250 °.

Preparation of Emulsion (Em-83) Emulsion (Em-81) was prepared in the same manner as in the preparation of emulsion (Em-81) except that Solution a-6 was used in place of Solution a-4.
-83) was prepared.

(A-6 solution) 67.0 g of ossein gelatin 0.6 ml of 10% methanol solution of surfactant (EO-1) 0.28 mol of seed emulsion (T-4) 3.5 l of water were obtained. The silver halide grains in the silver halide emulsion are tabular silver halide grains having an average grain size of 1.6 μm, an average aspect ratio of 8.0, and a grain size distribution of 26%, and two or more silver halide grains parallel to the main plane. The average distance between twin planes was 100 °.

Example 1 using Em-81 to Em-83
A sample was prepared in the same manner as described above. Table 15 shows the prepared samples and the evaluation results.

[0367]

[Table 15]

As is clear from Table 15, Samples 1811 to 1822 (the structure according to the ninth aspect of the present invention) related to the present invention showed superior performance to Comparative Samples 1801 to 1809.

Example 10 Preparation of Emulsion Em-91 In the preparation of Emulsion Em-22 in Example 3, after the completion of the grain growth step-2, the following ultrafiltration A was performed. Then, at 60 ° C., p with 2N aqueous potassium bromide solution
The Ag was adjusted to 8.8, 0.7 mol equivalent of the silver halide of the following K-6 solution was added in 10 minutes, and the mixture was aged for 20 minutes. An emulsion (Em-91) was prepared in the same manner as described above except that the pAg was adjusted to 8.06 and the pH to 5.8 at 40 ° C.

(Ultrafiltration A) A silver halide emulsion was treated with an ultrafiltration module (Asahi Kasei Kogyo Co., Ltd .;
Type AL using 000 polyacrylonitrile membrane
Water circulation and concentration were repeated while circulating through P-1010) to reduce the salt concentration to 1/80.

(K-6 solution) A fine grain emulsion preparation method comprising 3.0% by weight of gelatin and silver chloride fine grains (average grain size: 0.08 µm) is described below.

Containing 0.06 mol of sodium chloride
To 5000 ml of a 0% by weight gelatin solution, 2,000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2,000 ml of an aqueous solution containing 7.06 mol of sodium chloride were added at a constant speed over 10 minutes. During the formation of fine particles, the pH was controlled at 3.0 using nitric acid, and the temperature was controlled at 30 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution, subjected to the ultrafiltration B, and added to a 40% aqueous sodium chloride solution.
It adjusted to pAg7.5 at ° C.

A sample was prepared in the same manner as in Example 1 except that the emulsions Em-22 and Em-91 prepared in Example 3 were used. Table 16 shows the prepared samples and the evaluation results.

[0374]

[Table 16]

As is clear from Table 16, Samples 1911 to 1916 (the constitution according to the ninth aspect of the present invention) related to the present invention showed superior performance to Comparative Samples 1901 to 1908.

Example 11 Preparation of Emulsion (Em-101) Emulsion (Em-101) was prepared using the following solution.

(A-7 solution) Sodium chloride 2.0 g Ossein gelatin 10.0 g 5.0 l with water (B-7 solution) Silver nitrate 37.5 g 100 ml with water (C-7 solution) Sodium chloride 13.0 g water 100 ml (solution D-7) 0.01 mol of compound (AA-1)

[0378]

Embedded image

Ossein gelatin 120 g 2.0 l with water (E-7 solution) 563 g of silver nitrate 3750 ml with water (F-7 solution) 194 g of sodium chloride 5.0 g of sodium iodide 3750 ml with water 37.5 ml of A-7 solution was added to the reaction vessel. Then, the mixture was kept at 30 ° C., and the B-7 solution and the C-7 solution were added at a constant speed for 1 minute by a simultaneous mixing method with vigorous stirring. Then, D-7 solution was added,
The temperature was raised to 5 ° C. Thereafter, the E-7 solution and the F-7 solution were acceleratedly added (the final flow rate was 15 times the initial flow rate) by a simultaneous mixing method while maintaining the EAg at +120 mV. Thereafter, desalting is carried out by a conventional method, and pH 6.2, pA
g was adjusted to 7.5.

When the silver halide grains in this emulsion were observed with an electron microscope, a flat plate having a (111) plane having an average grain size of 1.40 μm, a grain size distribution of 25% and an average aspect ratio of 8.0 as a main plane was obtained. Silver halide grains.

Emulsions Em-21 and E prepared in Example 3
Using m-101, samples were prepared and evaluated in the same manner as in Example 1, as shown in Table 17. However, the development process
Using the following (Development treatment A), the sample 200 immediately after the sample preparation
The sensitivity and the granularity of No. 6 were shown as relative values with each being 100.

<< Development Processing A >> Processing Step (35 ° C.) Color development 1 minute 30 seconds Bleaching 1 minute 30 seconds Water washing 30 seconds Fixing 1 minute 00 seconds Water washing 30 seconds Stabilization 1 minute 00 seconds Drying Processing used in each processing step The liquid composition is as follows.

Color developer Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediamine Tetraacetic acid 1.0 g Disodium catechol-3,5-diphosphonate 1.0 g N-ethyl-N-β-hydroxyethyl-3-methyl-4-aminoanine sulfate 4.5 g Fluorescent whitening agent (4,4 ′ -Diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to make the total volume 1 l, and the pH is adjusted to 10.10.

Bleaching solution Ferric ammonium salt of ethylenediaminetetraacetic acid 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and the pH was adjusted using ammonium water.
Adjust to 6.0.

Fixing solution Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to 1 liter, and the pH was adjusted to 6.0 using acetic acid.

Stabilizing solution Formalin (37% aqueous solution) 1.5 ml Konidax (manufactured by Konica Corporation) 7.5 ml Make up to 1 liter by adding water.

Table 17 shows the contents of the manufactured samples and the evaluation results.

[0388]

[Table 17]

As is clear from Table 17, Samples 2001 to 2007 using Em-21 have extremely low sensitivity.
The density required for image formation could not be obtained. Samples 2011 to 2016 (the structure of the invention described in claim 10 of the present invention) related to the present invention showed superior performance to comparative samples 2001 to 2008.

Example 12 Preparation of Emulsion (Em-111) In the preparation of emulsion (Em-22) in Example 3,
In the grain growth step-2, the following (halide aqueous solution-8) was used in place of (halide aqueous solution-4), and after the addition of (silver nitrate aqueous solution-4) and (halide aqueous solution-8), 3.
The silver potential in the reaction vessel was adjusted to −40 mV using a 5N aqueous solution of potassium bromide, and 0.85 mol of the following K-8 solution was added to 2
Emulsion (Em-111) was prepared in the same manner except that the mixture was added at 0 minute, aged for 20 minutes, and then desalted and washed similarly.

(Aqueous halide solution-8) Potassium bromide 453.9 g Potassium iodide 70.4 g H ₂ O 1024 ml (K-8 solution) 3.0% by weight of gelatin and silver bromide fine particles (average particle diameter 0.05 μm) )) Is described below.

6.0 containing 0.06 mol of potassium bromide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2000 ml of an aqueous solution containing 7.06 mol of potassium bromide were added at a constant rate to 5000 ml of a weight% gelatin solution over 10 minutes. The pH during the formation of the fine particles was adjusted to 3.0 using nitric acid.
And the temperature was controlled at 30 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

Emulsion Em-111 had 90% (number) of tabular silver halide grains satisfying I ₃ > I ₄ , and I ₃ / I ₄
70% (number) of tabular silver halide grains having a ratio of> 2.5.

A sample was prepared in the same manner as in Example 1 except that the emulsions Em-22 and Em-111 prepared in Example 3 were used.

In the emulsion Em-22, tabular silver halide grains satisfying I ₃ > I ₄ were 10% (number).

Table 18 shows the prepared samples and the evaluation results.

[0397]

[Table 18]

As is clear from Table 18, Samples 2111 to 2116 according to the present invention (the structure of the invention described in claim 11 of the present invention) showed superior performance to Comparative Samples 2101 to 2108.

Example 13 Preparation of Emulsion (Em-121) Emulsion (Em-121) was prepared using the following solution.

(A-13 solution) Ossein gelatin 9.29 g Potassium bromide 2.85 g 3718 ml with water (B-13 solution) 1.25 N silver nitrate aqueous solution 932 ml (C-13 solution) 1.25 N potassium bromide aqueous solution 1200 ml (D-13 solution) 3.5N silver nitrate aqueous solution 4713 ml (E-13 solution) Potassium bromide 1428.7 g Potassium iodide 40.7 g Water 3500 ml (F-13 solution) Potassium bromide 824.7 g Potassium iodide 11. 6 g with water 2000 ml (G-13 solution) Ossein gelatin 39.9 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9. with 10% methanol solution 1.33ml water 77) 967ml (H-13 solution) ossein gelatin _{65.3g HO (CH 2 CH 2 O} ) m _{CH (CH 3) CH 2 O} ) 19.8 (CH 2 CH 2 O) n H (m + n = 9.77) of 10% methanol solution 1.78ml water at 585 ml (I-13 solution) 10% potassium hydroxide aqueous solution required Amount (J-13 solution) Ammonia water (28%) 25.8 ml (K-13 solution) Acetic acid (56%) Required amount (L-13 solution) Potassium bromide 208.3 g Water 1000 ml (M-13 solution) Potassium bromide 416.5 g 1000 ml with water (N-13 solution) Emulsion (*) 0.53 mol (*) consisting of 3% by weight of gelatin and silver iodide fine particles (average particle size: 0.05 μm) Shown in

6.0 containing 0.06 mol of potassium iodide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2000 ml of an aqueous solution containing 7.06 mol of potassium iodide were added to 5000 ml of an aqueous gelatin solution of 10% by weight over 10 minutes. During the formation of the fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of fine particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

Solution A-13 was placed in a reaction vessel, and kept at 30 ° C., and while stirring vigorously, 68 ml of each of solutions B-13 and C-13 was added at a constant speed by a simultaneous mixing method over 1 minute. Thereafter, solution G-13 was added, and the temperature was immediately raised to 60 ° C. Subsequently, solution J-13 was added, the pH was adjusted to 9.3 with solution I-13, and the mixture was aged for 7 minutes and adjusted to pH 6.1 with solution K-13. Then, the remainder of the liquid B-13 was mixed with the liquid C-13 by 37.
While maintaining the pAg at 9.0 for one minute, accelerated addition was performed by a simultaneous mixing method (the final speed was 12 times the initial speed). H-13
The solution was added, and 3197 ml of the solution D-13 was added to the E-solution.
Accelerated addition by the simultaneous mixing method while maintaining pAg at 9.0 for 110 minutes together with the 13 solution (final speed is 5
Times). Thereafter, the pH was adjusted to 5.0 with K-13 solution,
The pAg was adjusted to 9.7 with the M-13 solution, and the N-13 solution was added. Thereafter, the remainder of the D-13 solution and the F-13 solution were accelerated and added in 70 minutes by a simultaneous mixing method (the final speed was 1.5 times the initial speed).

After the grain growth, desalting was carried out according to a conventional method, and then dispersed in gelatin at 40 ° C., pH 5.8, pAg
Adjusted to 8.8. The silver halide grains in the obtained silver halide emulsion were hexagonal tabular silver halide grains having an average grain size of 2.0 μm, an average aspect ratio of 7.0, and a grain size distribution of 18%.

Preparation of Seed Emulsion (T-14) A seed emulsion (T-14) was prepared using the following solution.

(A-14 solution) Ossein gelatin 80 g Potassium bromide 47.4 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% methanol solution 20 ml with water 8.0 l (solution B-14) silver nitrate 1200 g with water 1600 ml (solution C-14) ossein gelatin 32.2 g potassium bromide 840 g with water 1600 ml (D-14 Solution) Ammonia water (28%) 470 ml (E-14 solution) Acetic acid (56%) required amount A-14 solution vigorously stirred at 40 ° C, B-14 solution and C
-14 solution was added by a simultaneous mixing method over 11 minutes to generate nuclei. During this time, pBr was maintained at 1.6. Thereafter, the temperature was lowered to 30 ° C. in 12 minutes, and ripened for 18 minutes. Thereafter, solution D-14 was added, and the mixture was aged for 5 minutes.
The pH was adjusted to 6.0 with -14 solution, and desalting was performed by a conventional method.

The silver halide grains in this seed emulsion were spherical silver halide grains having an average grain size of 0.43 μm and two twin planes parallel to each other.

Preparation of Emulsion (Em-122) Emulsion (Em-122) was prepared using the following solution.

(A-15 solution) Ossein gelatin 268.2 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) ) 10% methanol solution 1.5 ml Seed emulsion (T-14) 0.255 mol aqueous ammonia (28%) 528 ml acetic acid (56%) 795 ml 5930 ml with water (solution B-15) 3.5N aqueous ammoniacal silver nitrate solution ( 2713 ml (liquid C-15), potassium bromide 1458 g ossein gelatin 140 g 3500 ml with water (liquid D-15) 3 wt% gelatin and silver iodide fine particles (average particle size 0) (*) 0.844 mol (*) The preparation method is described below.

6.0 containing 0.06 mol of potassium iodide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2000 ml of an aqueous solution containing 7.06 mol of potassium iodide were added to 5000 ml of an aqueous gelatin solution of 10% by weight over 10 minutes. During the formation of the fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of fine particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

(E-15 solution) 1.75N Potassium bromide aqueous solution required amount (F-15 solution) Acetic acid (56%) required amount Put A-15 solution in a reaction vessel, maintain at 70 ° C., and vigorously stir. Solution B-15, solution C-15 and solution D-15 were added over 140 minutes by the simultaneous mixing method.

Here, the addition rates of the B-15 solution, C-15 solution and D-15 solution were changed as a function of time so as to match the critical growth rate. Was added in the same manner.

The pAg and the pH during crystal growth were adjusted to E-1.
The control was carried out as shown in Table 19 using 5 liquids and F-15 liquid.

[0413]

[Table 19]

After the particles are formed, desalting is carried out by a conventional method, then dispersed in gelatin, and at 40 ° C., pH 5.8, pAg8.
Adjusted to 8. The silver halide grains in the obtained silver halide emulsion were octahedral silver halide grains having an average grain size of 1.3 μm and a grain size distribution of 14%.

Using emulsions Em-121 and Em-122, the thirteenth sample formulation 1001 in Example 1 was used.
Used in place of emulsion h and emulsion i in the
Samples were prepared by changing the types and amounts of OIL-1 in the layer and the thirteenth layer to those shown in Table 20. Emulsion Em-1 prepared in Example 1 was used as emulsion k of the fifth layer. Emulsions Em-121 and Em-122 were used after being optimally subjected to color sensitization and chemical sensitization according to the method described in Sample Formulation 1001. The prepared samples were evaluated for blue sensitivity and granularity in the same manner as in Example 1.

[0416] Table 20 shows the manufactured samples and the evaluation results.

[0417]

[Table 20]

As is evident from Table 20, Samples 2211 to 2216 according to the present invention (the structure of the invention described in claim 12 of the present invention) showed superior performance to Comparative Samples 2201 to 2208.

Example 14 Preparation of Seed Emulsion (T-18) A seed emulsion (T-18) was prepared using the following solution.

(A-18 solution) Ossein gelatin 59.6 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) ) 10% methanol solution 53.0 ml potassium bromide 3.1 g magnesium sulfate 5.4 g water 6.0 l (solution B-18) 2N silver nitrate aqueous solution 597 ml (solution C-18) 4N silver nitrate aqueous solution 2350 ml (solution D-18) ) Ossein gelatin 15.4 g Potassium bromide 175 g Potassium iodide 5.0 g Water 750 ml (E-18 solution) Ossein gelatin 60.0 g Potassium bromide 1400 g Potassium iodide 39.9 g Water (F-18 solution) ) 208.3 g of potassium bromide 1000 ml with water Add solution A-18 into a reaction vessel, and stir vigorously at 40 ° C while stirring B-18. A 230ml and D-18 solution was constant rate added in 5 minutes by the simultaneous mixing method. Subsequently, the remainder of the B-18 solution and the D-18 solution were acceleratedly added (final speed was twice the initial speed) in 6 minutes by the simultaneous mixing method. Thereafter, the C-18 solution and the E-18 solution were mixed together by the simultaneous mixing method.
Accelerated addition (final speed was 4 times the initial speed) was performed in 5 minutes. P during addition
8. H was set to 2.0 with nitric acid, and pAg was set to 9.
It was kept at zero.

After the particles are formed, desalting is carried out by a conventional method, and then gelatin is added and dispersed.
An emulsion having Ag 8.06 and pH 5.8 was obtained.

When the silver halide grains in this emulsion were observed by an electron microscope, they were monodispersed silver halide grains having an average grain size (grain size in terms of projected area circle) of 0.11 μm and a grain size distribution of 19%. .

Preparation of Emulsion (Em-131) Emulsion (Em-131) was prepared using the following solution.

(A-19 solution) Ossein gelatin 9.2 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) ) 10% methanol solution 1.5 ml 4-hydroxy-6-methyl 1,3,3a, 7-tetrazaindene 0.5 g ammonia water (28%) 30 ml acetic acid (56%) 36 ml seed emulsion (T-18) 2000 ml with 0.436 mol water (solution B-19) 1.5 N aqueous ammoniacal silver nitrate solution (pH adjusted to 9.0 with ammonium nitrate) 2900 ml (solution C-19) ossein gelatin 35.0 g potassium bromide 1429 g iodine Potassium bromide 40.7 g 4-hydroxy-6-methyl 1,3,3a, 7-tetrazaindene 4.0 g 3500 ml with water (D-19 solution) Potassium bromide 208.3 g 1000 ml with water (E-19 solution) Acetic acid (56%) Required amount Add the A-19 solution into the reaction vessel and stir vigorously at 40 ° C. while stirring the B-19 solution and C-19 solution. (The final speed of the accelerated addition was twice the initial speed in 30 minutes) by the simultaneous mixing method. During the addition, the pH during the first ten minutes was 8.
0 and 7.0 thereafter, and the pAg was adjusted to 8.8 using the D-19 solution for the first 10 minutes, and 9.7 thereafter.
Was controlled.

After the particles are formed, desalting is carried out by a conventional method, and then gelatin is added and dispersed.
An emulsion having Ag 8.06 and pH 5.8 was obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, a monodisperse tetrahedral silver halide having an average grain size (projected area circle equivalent grain size) of 0.32 μm and a grain size distribution of 17% was obtained. Particles.

Preparation of Seed Emulsion (T-20) Seed emulsion (T-20) was prepared using the following solution.

(A-20 solution) Ossein gelatin 80 g Potassium bromide 47.4 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% methanol solution 0.48 ml with water 8.0 l (solution B-20) 1200 g of silver nitrate 1600 ml with water (solution C-20) ossein gelatin 32.2 g potassium bromide 790 g potassium iodide 70. 3g with water 1600ml (D-20 solution) Ammonia water (28%) 470ml (E-20 solution) Acetic acid (56%) required amount A-20 solution vigorously stirred at 40 ° C, B-20 solution and C
-20 solution was added for 7 minutes by the simultaneous mixing method to generate nuclei. During this time, pBr was maintained at 1.6. Thereafter, the temperature was lowered to 20 ° C. in 30 minutes, and then D-20 solution was added. After aging for 5 minutes, the pH was adjusted to 6.0 with E-14 solution, and desalting was performed by a conventional method.

The silver halide grains in this seed emulsion were silver halide grains having an average grain size of 0.24 μm and having two twin planes parallel to each other.

Preparation of (Emulsion Em-132) An emulsion (Em-132) was prepared using the following solution.

(A-21 solution) Ossein gelatin 47.3 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) ) 10% methanol solution 3.5 ml Seed emulsion (T-20) 2.41 mol ammonia water (28%) 431 ml acetic acid (56%) 484 ml water 3270 ml (solution B-21) 3.5N silver nitrate aqueous solution (by ammonium nitrate) 5846 ml (C-21 solution) Potassium bromide 2916 g Ossein gelatin 280 g Water 7000 ml (D-21 solution) 3% by weight of gelatin and silver iodide fine particles (average particle diameter 0.05 μm) 1.) Emulsion (*) 1.98 mol (*) The preparation method is shown below.

6.0 containing 0.06 mol of potassium iodide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2000 ml of an aqueous solution containing 7.06 mol of potassium iodide were added to 5000 ml of an aqueous gelatin solution of 10% by weight over 10 minutes. During the formation of the fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of fine particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

(E-21 solution) 1.75N Potassium bromide aqueous solution required amount (F-21 solution) Acetic acid (56%) required amount Put A-21 solution in a reaction vessel, keep at 70 ° C., and vigorously stir. The B-21 solution, the C-21 solution, and the D-21 solution were added by the simultaneous mixing method over 77 minutes.

Here, the addition rates of the B-21 liquid, C-21 and D-21 liquids were changed in a function-wise manner with time so as to match the critical growth rate. Was added in the same manner.

[0435]

[Table 21]

The pAg and the pH during the crystal growth were adjusted to E-2.
Control was carried out as shown in Table 21 using Solution 1 and Solution F-21.

After the particles are formed, desalting is carried out by a conventional method, and then dispersed in gelatin at 40 ° C., pH 5.8, pAg8.
Adjusted to 8. The silver halide grains in the obtained silver halide emulsion were monodisperse tetrahedral silver halide grains having an average grain size of 0.47 μm and a grain size distribution of 13%.

Preparation of Emulsion (Em-133) A comparative emulsion Em-133 was prepared using the following solution.

(A-16 solution) Gelatin (average molecular weight 15,000) 35.9 g Potassium bromide 23.1 g 6.2 l with water (B-16 solution) 1.9 N silver nitrate aqueous solution 149.4 ml (C-16 Liquid) 1.9 N silver nitrate aqueous solution 4628 ml (D-16 liquid) 1.9 N silver nitrate aqueous solution 147.8 ml (E-16 liquid) Potassium bromide 33.8 g Water 149.4 ml (F-16 liquid) Potassium bromide 886. 3 g Potassium iodide 25.2 g 4000 ml with water (G-16 solution) 452.2 g potassium bromide 2,000 ml with water (H-16 solution) 46.6 g potassium iodide 147.8 ml with water (1-16 solution) Bromide 208.3 g of potassium 1000 ml of water (K-16 solution) 33.9 g of ossein gelatin 6.16 g of potassium bromide HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by weight methanol solution 0.33 ml 953 ml with water (L-16 solution) Ossein gelatin 339.8 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by weight methanol solution 1.3 ml 17228 ml with water (M-16 solution) Potassium bromide 624.8 g 1500 ml with water Add A-16 solution to the reaction vessel, stir vigorously at 30 ° C., and mix B-16 solution and E-16 solution in 70 seconds by the simultaneous mixing method. Quick addition. Thereafter, K-16 solution was added, and the temperature was raised to 70 ° C. After the temperature was raised, L-16 solution was added, and pAg was adjusted to 8.2 with C-16 solution.
3072 ml of the 16 solution and the F-16 solution were acceleratedly added (final addition speed was 6 times the initial addition speed) for 60 minutes while maintaining pAg 8.2 by a simultaneous mixing method. Then 60
The temperature was lowered to ° C. Subsequently, pAg was adjusted to 9.7 with the M-16 solution, and the entire amount of each of the D-16 solution and the H-16 solution was added at a constant speed for 2 minutes by the simultaneous mixing method. Then, C-16
The remainder of the solution and the G-16 solution were added at an accelerated rate of 23 minutes by the simultaneous mixing method (the final addition rate was twice the initial addition rate) to prepare a tabular silver halide emulsion. Solution I-16 was added as needed for pAg control.

After the particles are formed, desalting is performed according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and pAg 8.06, pH 5.0 at 40 ° C.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, a hexagonal flat plate having an average grain size (projected area circle-equivalent grain size) of 0.90 μm and a grain size distribution of 18% and an average aspect ratio of 7.0 was obtained. Monodispersed silver halide grains.

Preparation of Emulsion (Em-134) A comparative emulsion Em-134 was prepared using the following solution.

(A-17 solution) Gelatin (average molecular weight 15,000) 51.8 g Potassium bromide 33.3 g 8.9 l with water (B-17 solution) 1.9 N silver nitrate aqueous solution 216 ml (C-17 solution) 1.9N aqueous silver nitrate solution 2387 ml (D-17 solution) 48.8 g of potassium bromide 216 ml with water (E-17 solution) 664.7 g of potassium bromide 18.9 g of potassium iodide 3000 ml of water (F-17 solution) Bromide 208.3 g of potassium 1000 ml with water (G-17 solution) 48.9 g of ossein gelatin 8.9 g of potassium bromide HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH _{2 O) n H (m + n} = 9.77) 10 wt% methanol solution 0.47ml water at 1376ml (H-17 solution) ossein gelatin 490.6g HO (CH ₂ C _{2 O) m [CH (CH} 3) CH 2 O] 19.8 (CH 2 CH 2 O) n H (m + n = 9.77) A to 24.8l reaction vessel at 10 wt% methanol solution 1.9ml water Solution -17 was added, and while stirring vigorously at 30 ° C., solution B-17 and solution D-17 were added at a constant speed in 70 seconds by the simultaneous mixing method. Thereafter, G-17 solution was added, and the temperature was raised to 70 ° C. After the temperature was raised, H-17 solution was added, and pAg was adjusted to 8.2 with C-17 solution.
The remainder of solution 17 and solution E-17 were pAg
While maintaining 8.2, accelerated addition was performed in 40 minutes (final addition speed was 4 times the initial addition speed) to prepare a tabular silver halide emulsion.

For the control of pAg, F-17 solution was added as needed.

After the particles are formed, desalting is performed according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and at 40 ° C., pAg 8.06, pH 5.0.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, a hexagonal flat plate having an average grain size (grain size in terms of projected area circle) of 0.65 μm and a grain size distribution of 18% and an average aspect ratio of 6.0 was obtained. Monodispersed silver halide grains.

Emulsions Em-131 to Em-134 were used instead of emulsions a and b in the twelfth layer in the sample formulation 1001 in Example 1,
The types shown in Tables 22 and 23 represent OIL-1 in the three layers,
The samples shown in Tables 22 and 23 were prepared by changing the amount of addition.
Emulsion Em-1 prepared in Example 1 was used as emulsion k of the fifth layer. Emulsions Em-131 to Em-1
Sample No. 34 was used after being optimally subjected to color sensitization and chemical sensitization by the method described in Sample Formulation 1001.

[0448] Sample immediately after preparation and 65% 20% after preparation
Each of the samples stored in the RH for one week was subjected to a step wedge exposure for 1/200 second and 3.2 CMS using white light, and then immediately subjected to the above color development processing to obtain a characteristic curve.

The sensitivity was indicated by a relative value, with the value of sample 2301 exposed and developed immediately after the preparation of blue sensitivity (the reciprocal of the exposure amount giving a fog density of +1.5) as 100.

Further, for the characteristic curve D- (LogE), the Ji value of the yellow image was obtained by the following method, and the gradation reproducibility was evaluated.

Color density curve D- (logE) for yellow
ΔlogE = −1.5 more than the exposure amount logE ₀ that gives the density d ₀ of the minimum density (Dmin) +1.0.
In the range up to log E ₅ in Δlog E = −
Exposure points logE _i (i = 0,
1, 2, 3, 4) and concentration d _i give corners logE _i
At (i = 0, 1, 2, 3, 4, 5) g _i = (d _i −d _i−1 ) / − (log E _i −log E _i−1 )
And h = (d ₅ −d ₀ ) / − (log E ₅ −log E ₀ ), j _i = g _i / h are obtained, and the numerical value having the largest deviation from 1.00 is determined as Ji of each color. Is shown as a relative value with the value of the sample 2301 immediately after the sample preparation as 100.

Table 2 shows the contents of the manufactured samples and the evaluation results.
2 and 23.

[0453]

[Table 22]

[0454]

[Table 23]

As is clear from Tables 22 and 23, samples 2331 to 2336 according to the present invention (claim 13 of the present invention)
Of the invention described in (1) is a comparative sample 2301 to 2329.
Showed excellent performance.

Example 15 Preparation of Emulsion (Em-141) An average particle size of 1.2 μm, an average aspect ratio of 7, and a silver iodide content according to the method of producing Em-C disclosed in JP-A-5-5967. The emulsion (Em-141) was composed of silver iodobromide hexagonal tabular grains having 2.4 mol% of (111) major plane.

Preparation of Emulsion (Em-142) Gelatin (200 g) was dissolved in 10 l of distilled water, and the pH was adjusted to 3 with nitric acid while stirring vigorously at 40 ° C. in a reaction vessel.
The mixture was adjusted to 0, and 150 ml of each of a 1N aqueous solution of silver nitrate and a 1N aqueous solution of potassium bromide were added for 20 seconds by the double jet method. Thereafter, the pAg was adjusted to 6.6 with an aqueous silver nitrate solution and the pH was adjusted to 6.0 with an aqueous sodium hydroxide solution, and the temperature was raised to 75 ° C. After the temperature was raised, the pAg was adjusted to 5.8 and aged for 2 hours. Subsequently, over 30 minutes, 373 ml of each of a 0.01 N aqueous silver nitrate solution and a 0.01 N aqueous potassium iodide solution were added by a simultaneous mixing method. After completion of the addition, desalting and washing were performed by a conventional method.

The resulting emulsion Em-142 had an average particle size of 1.1 μm, an average aspect ratio of 7, and a silver iodide content of 2.
This emulsion was composed of 4 mol% of silver iodobromide tabular grains having a (100) major plane.

A sample was prepared in the same manner as in Example 1 except that the emulsions Em-141 and Em-142 were used. Table 24 shows the prepared samples and the evaluation results.

[0460]

[Table 24]

As is clear from Table 24, Samples 2411 to 2416 according to the present invention were compared with Comparative Samples 2401 to 2416.
08 showed excellent performance.

[0462]

According to the present invention, a silver halide photographic material excellent in sensitivity, granularity, storage stability and gradation reproducibility can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/06 502 G03C 1/06 502 1/08 1/08 1/09 1/09

Claims (14)

[Claims] 1. A support comprising at least one compound represented by the following general formulas (I) to (V) in at least one layer thereof, and at least one layer of a silver halide emulsion layer comprising a polyvalent compound. A silver halide photographic light-sensitive material containing at least one kind of metal atom ion, polyvalent metal atom complex or polyvalent metal atom complex ion. Formula (I) R ₁₁ OOC (CH ₂ ) _m COOR ₁₂ [wherein R ₁₁ and R ₁₂ each represent a linear or branched alkyl group having 4 to 10 carbon atoms, and m is an integer of 2 to 10 Represents General formula (II) R ₂₁ OOC (C _n H _2n-2 ) COOR ₂₂ [wherein, R ₂₁ and R ₂₂ each represent a linear or branched alkyl group having 4 to 10 carbon atoms, and n represents 2 Represents an integer of 10 to 10. General formula (III) R ₃₁ OOC (CH ₂ ) _p COOR ₃₂ [wherein, R ₃₁ and R ₃₂ each represent a linear or branched alkyl group having 3 to 24 carbon atoms. p represents an integer of 2 to 10. [Formula 1] [In the formula, R ₄₁ represents an alkyl group or an alkenyl group.
R ₄₂ and R ₄₃ each represent a hydrogen atom or a group represented by R ₄₁ . However, the total number of carbon atoms of the groups represented by R ₄₁ , R ₄₂ and R ₄₃ is at least 10 or more. General formula (V) X-((CH ₂ ) _q —O (CO) R ₅₁ ) _r wherein X represents a 5- to 7-membered saturated hydrocarbon, and q represents 0
Represents an integer of 2 to 2, and r represents an integer of 1 to 3. R ₅₁ represents a linear or branched alkyl group having 4 to 16 carbon atoms. ] 2. The support according to claim 1, wherein at least one layer of the support contains at least one of the compounds represented by formulas (I) to (V), and at least one of the silver halide emulsion layers has an average thickness. A silver halide photographic light-sensitive material comprising a tabular silver halide emulsion having a thickness of less than 0.07 μm. 3. A support comprising at least one of the compounds represented by formulas (I) to (V) in at least one layer thereof and dislocation lines in at least one of the silver halide emulsion layers. A silver halide photographic material comprising a silver halide emulsion having the formula: 4. A silver halide emulsion layer comprising at least one of the compounds represented by the above general formulas (I) to (V) in at least one layer thereof, and at least one of the silver halide emulsion layers having a halide. The average silver iodide content of the outermost layer of the silver grains is I ₁ (mol%), and the average silver iodide content of the silver halide grains is I ₂ (mol%).
A silver halide photographic light-sensitive material comprising a silver halide emulsion satisfying I ₁ > I ₂ when (mol%) and having a dislocation line. 5. A silver halide emulsion layer comprising at least one of the compounds represented by formulas (I) to (V) in at least one layer and at least one silver halide emulsion layer on a support. A silver halide photographic material containing a silver halide emulsion having a plurality of silver halide phases having silver iodide contents differing by 3 mol% or more inside silver grains. 6. A support containing at least one of the compounds represented by the above general formulas (I) to (V) in at least one layer thereof and reducing at least one of the silver halide emulsion layers. A silver halide photographic light-sensitive material comprising a silver halide emulsion containing silver halide grains. 7. A silver halide emulsion layer comprising at least one of the compounds represented by the above general formulas (I) to (V) in at least one layer thereof, and at least one of the silver halide emulsion layers being halogenated. A silver halide photographic material comprising a silver halide emulsion having silver halide projections on the surface of silver grains. 8. A silver halide emulsion layer comprising at least one of the compounds represented by formulas (I) to (V) in at least one layer of the support and at least one layer of a silver halide emulsion layer. A silver halide photographic light-sensitive material comprising a silver halide emulsion in which silver particles have a monodispersed particle size. 9. A support comprising at least one of the compounds represented by formulas (I) to (V) in at least one layer thereof, and at least one of the silver halide emulsion layers having a tabular shape. A silver halide photographic light-sensitive material comprising a silver halide emulsion having an average distance between two or more twin planes parallel to the main plane of silver halide grains of 500 ° or less. 10. A silver halide emulsion comprising at least one of the compounds represented by formulas (I) to (V) in at least one layer of the support and at least one silver halide emulsion layer. A silver halide photographic material comprising a silver halide emulsion containing: 11. A support comprising at least one of the compounds represented by formulas (I) to (V) in at least one layer thereof, and at least one of the silver halide emulsion layers comprising a halide. the average silver iodide content of the outermost layer in the main flat portion I ₃ of the silver particles (mol%), when I ₄ a (mol%) in a side portion, the tabular silver halide grains is I _3> I ₄ A silver halide photographic light-sensitive material comprising a silver halide emulsion having a content of 50% or more (number). 12. A silver halide emulsion layer comprising at least one of the compounds represented by the above general formulas (I) to (V) in at least one layer thereof, and at least one of the silver halide emulsion layers comprising a halide. A silver halide photographic material comprising a silver halide emulsion having an average aspect ratio of silver particles of less than 3. 13. A silver halide emulsion layer comprising at least one of the compounds represented by formulas (I) to (V) in at least one layer and a normal crystal in at least one layer of the silver halide emulsion layer. A silver halide photographic material comprising at least one silver halide emulsion and at least one tabular silver halide emulsion. 14. A support containing at least one of the compounds represented by formulas (I) to (V) in at least one layer thereof and a main plane in at least one of the silver halide emulsion layers. A silver halide photographic material comprising a tabular silver halide emulsion having a (100) plane.