JP2003107619A - Internal latent image type direct positive silver halide emulsion and color diffusion transfer photosensitive material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an internal latent image type direct positive silver halide emulsion having a high S/N (signal-to-noise) ratio, free of lowering of high illuminance sensitivity and having improved reciprocity law failure at low illuminance and to provide a color diffusion transfer photosensitive material using the emulsion. SOLUTION: In a not previously fogged internal latent image type direct positive silver halide emulsion having a core/shell structure comprising a chemically sensitized core and a chemically sensitized shell, a compound of the formula (X)k -(L)m -(A-B)n is contained in the silver halide emulsion. In the formula, X is a group attracted to silver halide or a light absorbing group having at least one atom selected from the group comprising N, S, P, Se and Te; L is a divalent linking group having at least one atom selected from the group comprising C, N, S and O; A is an electron donative group; B is a releasable group or H and is released or deprotonated after oxidation to generate a radical A.; k and m are each an integer of 0-3; and n is 1 or 2.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an internal latent image type direct positive silver halide emulsion and a color diffusion transfer light-sensitive material using the same.

[0002]

2. Description of the Related Art The photographic method using silver halide has excellent sensitivity and gradation characteristics as compared with other photographic methods such as electrophotographic method and diazo photographic method, and has been widely used. . Among them, a method of directly forming a positive image is known. This is described, for example, in US Pat.
No. 76 and Japanese Patent Publication No. 60-55821, an internal latent image type direct positive silver halide emulsion is developed by a surface developing solution (a latent image forming site inside a silver halide grain is substantially left undeveloped. When developing with a liquid, a positive image is obtained by giving uniform exposure or by using a nucleating agent. Such a direct positive silver halide emulsion is superior to the negative type emulsion in that a positive image can be obtained by a single processing. Generally, an internal latent image type direct positive silver halide emulsion is prepared by mixing a soluble silver salt and a soluble halide in an aqueous gelatin solution to form silver halide grains (core grains).
Is formed, and after the core particles are chemically sensitized,
Silver halide deposition for shell formation is performed, then desalting is performed, and if necessary, chemical sensitization is performed to prepare. For example, Japanese Examined Patent Publication (Kokoku) No. 52-34213 (U.S. Pat. No. 3,761,276) describes an internal latent image type emulsion which is useful as a direct positive emulsion. This emulsion contains a doping agent inside a silver halide grain. It is characterized by including and chemically sensitizing the grain surface. This is Po again
It is also taught in U.S. Pat. No. 3,317,322 to Rter et al. However, the internal latent image type direct positive silver halide emulsion prepared in this manner also causes a sensitivity decrease phenomenon (low illuminance reciprocity law failure) that occurs when the exposure illuminance is lowered.
Was still larger than the negative emulsion, leaving room for improvement.

In the industrial field, an internal latent image type direct emulsion positive silver halide emulsion is often used in a color diffusion transfer light-sensitive material. Among color diffusion transfer light-sensitive materials, instant photographic light-sensitive materials are used for various purposes and have become important recording materials. Among the uses of instant photographic light-sensitive materials, certificate photography, trial photography of reversal film photography, etc. occupy important weight, but these photography conditions are often taken indoors using tungsten light, I was forced to make a long exposure with illuminance.
Under such circumstances, users have long sought an improved color diffusion transfer photosensitive material having a low illuminance reciprocity law failure.

It is generally known that doping of an iridium compound having a halogen as a ligand is effective for improving the reciprocity law failure of a silver halide emulsion under low illuminance. For example, Japanese Examined Patent Publication (Kokoku) No. 43-4935 discloses that by adding an iridium compound during the preparation of silver halide grains, the gradation variation is small over a wide exposure time range. Further, US Pat. No. 4,997,751 describes that reciprocity law failure is improved by adding iridium from the surface of silver halide grains. However, when an internal latent image type direct emulsion positive silver halide emulsion was doped with an iridium compound, there were the following problems and it was not put into practical use. The first problem is that the maximum density is reduced and the reciprocity law failure is improved, but the S / N is deteriorated. The second problem is that the low illuminance sensitivity is increased by doping the iridium compound, but the high illuminance sensitivity is decreased as the doping amount of the iridium compound is increased.

Japanese Unexamined Patent Publication No. 2-269,337 discloses Ir, P.
An internal latent image type direct positive silver halide emulsion, which is soft under high-intensity exposure and hard under low-intensity exposure by adding heavy metal cations such as b and Rh, is disclosed. The emulsion is prepared by doping polyvalent metal ions into grains. It also mentions that the reciprocity property of can be changed. However, in this patent, although there is a description about gradation, there is no description about S / N, and since the maximum concentration is lowered by doping polyvalent metal ions into the particles, a technique for practical use has not been reached. Didn't.

[0006]

The object of the present invention is to provide a high S
It is an object of the present invention to provide an internal latent image type direct positive silver halide emulsion improved in low illuminance reciprocity law failure, and a color diffusion transfer light-sensitive material using the same.

[0007]

The present inventor has found that the above problems can be solved by the following constitution. (1) An internal latent image type direct positive silver halide emulsion having a core / shell structure consisting of a chemically sensitized core and a chemically sensitized shell, which is not previously fogged, in the silver halide emulsion. An internal latent image type direct positive silver halide emulsion containing a compound represented by the following general formula (I). In the general formula (I) (X) _k- (L) _m- (AB) _n , X is halogenated having at least one atom selected from the group consisting of N, S, P, Se and Te. Represents a silver adsorption group or a light absorption group. L is C, N, S and O
Represents a divalent linking group having at least one atom selected from the group consisting of: A represents an electron donating group, B represents a leaving group or a hydrogen atom, after oxidation, are desorbed or deprotonated to generate a radical A ^·. k and m each independently represent an integer of 0 to 3, and n represents 1 or 2. (2) The tabular silver halide grains having an aspect ratio (diameter equivalent to a circle of silver halide grains / grain thickness) of the silver halide emulsion described in the item (1) is 5 or more and 100 or less, and the projected area of all silver halide grains is Internal latent image type direct positive silver halide emulsion characterized by containing 50% or more of the above, and having an average grain diameter of tabular silver halide grains of 0.3 μm or more. (3) The internal latent image type direct positive silver halide emulsion as described in the item (1) or (2), wherein the silver halide at the end of grain formation before the desalting step is silver bromide. (4) At least one photosensitive silver halide emulsion layer unit is provided on a support, and the internal latent image according to any one of (1) to (3) is contained in at least one emulsion layer. A color diffusion transfer light-sensitive material comprising a mold direct positive silver halide emulsion.

[0008]

The present invention will be described in more detail below.

First, the compound of the general formula (I) will be explained. In the general formula (I) (X) _k- (L) _m- (AB) _n , X is halogenated having at least one atom selected from the group consisting of N, S, P, Se and Te. Represents a silver adsorption group or a light absorption group. L is C, N, S and O
Represents a divalent linking group having at least one atom selected from the group consisting of: A represents an electron donating group, B represents a leaving group or a hydrogen atom, after oxidation, are desorbed or deprotonated to generate a radical A ^·. k and m each independently represent an integer of 0 to 3, and n represents 1 or 2.

The compound used in the present invention will be described in detail. In formula (I), the silver halide adsorbing group represented by X has at least one selected from the group consisting of N, S, P, Se and Te, and preferably has a silver ion ligand structure. It is a thing. When k is 2 or more, a plurality of X may be the same or different. Examples of the silver ion ligand structure include the following.

In the general formula (X-1) -G ₁ -Z ₁ -R ₁ , G ₁ is a divalent linking group, which is substituted with a divalent heterocyclic group or a divalent heterocyclic group. Unsubstituted alkylene group, alkenylene group, alkynylene group, arylene group,
It represents a divalent group bonded to any of the SO ₂ groups. Z
₁ represents an S, Se or Te atom. R ₁ represents a hydrogen atom or a counter ion necessary when it becomes a dissociation product of Z ₁ , and represents a sodium ion, a potassium ion, a lithium ion and an ammonium ion.

General formulas (X-2a), (X-2b)

[Chemical 1]

The general formulas (X-2a) and (X-2b) form a ring, and the form thereof is a 5- to 7-membered hetero saturated ring, hetero unsaturated ring, or unsaturated carbocyclic ring. Z _a is O, N,
Represents an S, Se or Te atom, and n ₁ represents an integer of 0 to 3. R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. When n ₁ is 2 or more, a plurality of Z _a may be the same or different.

[0014] Formula _{(X-3) -R 3 -} (Z 2) n in ₂ -R ₄ Formula, Z ₂ is S, Se or Te atom, n ₂ is 1
Represents an integer of 3. R ₃ is a divalent linking group, and is an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group, or a divalent heterocyclic group and an alkylene group, an alkenylene group, an alkynylene group, an arylene group, It represents a divalent group bonded to any of the SO ₂ groups.
R ₄ represents an alkyl group, an aryl group or a heterocyclic group.
When n ₂ is 2 or more, a plurality of Z ₂ may be the same or different.

General formula (X-4)

[Chemical 2]

In the formula, R ₅ and R ₆ each independently represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

General formulas (X-5a), (X-5b)

[Chemical 3]

In the formula, Z ₃ represents an S, Se or Te atom, E ₁ represents a hydrogen atom, NH ₂ , NHR ₁₀ , N.
It represents (R ₁₀ ) ₂ , NHN (R ₁₀ ) ₂ , OR ₁₀ or SR ₁₀ . E ₂ is a divalent linking group, and is NH, NR ₁₀ , NHN
Represents R ₁₀ , O or S. R ₇ , R ₈ and R ₉ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and R ₈ and R ₉ may be bonded to each other to form a ring. R ₁₀ is a hydrogen atom, an alkyl group,
It represents an alkenyl group, an aryl group or a heterocyclic group.

General formulas (X-6a), (X-6b)

[Chemical 4]

In the formula, R ₁₁ is a divalent linking group and represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group or a divalent heterocyclic group. G ₂ and J are each independently COOR ₁₂ , SO ₂ R ₁₂ , COR ₁₂ , SO
Represents R ₁₂ , CN, CHO or NO ₂ . R ₁₂ represents an alkyl group, an alkenyl group or an aryl group.

The general formula (X-1) will be described in detail. In the formula, the linking group represented by G ₁ is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, 3
-Oxapentylene, 2-hydroxytrimethylene),
A substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (for example, cyclopropylene, cyclopentylene, cyclohexylene), a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms (for example, ethene, 2-butenylene),
Examples thereof include an alkynylene group having 2 to 10 carbon atoms (eg ethyne) and a substituted or unsubstituted arylene group having 6 to 20 carbon atoms (eg unsubstituted p-phenylene, unsubstituted 2,5-naphthylene).

In the formula, the SO ₂ group represented by G ₁ is
In addition to the SO ₂ — group, a substituted or unsubstituted linear or branched alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cyclic alkylene group having 3 to 6 carbon atoms or 2 carbon atoms
And a —SO ₂ — group bonded to the alkenylene group of 10 to 10.

Further, the divalent linking group represented by G ₁ includes a divalent heterocyclic group, or a divalent heterocyclic group and an alkylene group, an alkenylene group, an alkynylene group, an arylene group or an SO ₂ group. A divalent group bonded to any of them, or a heterocyclic portion of these groups benzo- or naphtho-condensed (for example, 2,3-tetrazolediyl,
1,3-triazolediyl, 1,2-imidazoldiyl, 3,5-oxadiazolediyl, 2,4-thiazolediyl, 1,5-benzimidazolediyl,
2,5-benzothiazolediyl, 2,5-benzoxazoldiyl, 2,5-pyrimidinediyl, 3-phenyl-2,5-tetrazolediyl, 2,5-pyridinediyl, 2,4-furandiyl, 1, 3-piperidinediyl, 2,4-morpholinediyl).

In the above formula, G ₁ may have a substituent as much as possible. The substituents are shown below, and these substituents are referred to as substituent Y here.

As the substituent, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl, ethyl, isopropyl, n-propyl, t-butyl), an alkenyl group (eg, allyl, 2-
Butenyl), alkynyl group (eg propargyl), aralkyl group (eg benzyl), aryl group (eg phenyl, naphthyl, 4-methylphenyl), heterocyclic group (eg pyridyl, furyl, imidazolyl, piperidinyl, morpholyl), alkoxy group ( For example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, ethoxyethoxy, methoxyethoxy), aryloxy group (for example, phenoxy, 2-naphthyloxy), amino group (for example, unsubstituted amino, dimethylamino, diethylamino, dipropylamino, dibutyl). Amino, ethylamino, aniline), acylamino group (eg acetylamino, benzoylamino), ureido group (eg unsubstituted ureido, N-methylureido), urethane group (eg methoxycarbonylamino) Phenoxycarbonylamino), sulfonylamino group (eg methylsulfonylamino, phenylsulfonylamino), sulfamoyl group (eg unsubstituted sulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (eg unsubstituted) Carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl), sulfonyl group (eg mesyl, tosyl), sulfinyl group (eg methylsulfinyl, phenylsulfinyl), alkyloxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl), aryloxy Carbonyl group (eg phenoxycarbonyl), acyl group (eg acetyl, benzoyl, formyl, pivaloyl), acyloxy group (eg acetoxy, benzoyl) Oxy), phosphoric acid amide group (for example, N, N-diethylphosphoric acid amide), cyano group, sulfo group, thiosulfonic acid group, sulfinic acid group, carboxy group, hydroxy group, phosphono group, nitro group, ammonio group, phosphonio group , A hydrazino group and a thiazolino group. When there are two or more substituents, they may be the same or different, and the substituent may further have a substituent.

Preferred examples of the general formula (X-1) are shown below. In the preferable general formula (X-1), G ₁ has 6 to ₁ carbon atoms.
5 to 7 bonded to a substituted or unsubstituted arylene group of 0, a substituted or unsubstituted alkylene group or an arylene group, or benzo-fused or naphtho-fused
Heterocyclic groups forming a member ring are mentioned. Examples of Z ₁ include S and Se, and examples of R ₁ include a hydrogen atom, sodium ion, and potassium ion.

More preferably, G ₁ has 6 to 8 carbon atoms.
A heterocyclic group bonded to a substituted or unsubstituted arylene group of, or benzo-fused to form a 5- or 6-membered ring, and most preferably 5 to 6 bonded to an arylene group or benzo-fused. It is a heterocyclic group forming a 6-membered ring. More desirable Z ₁ is S, and R ₁ is a hydrogen atom or sodium ion.

The general formulas (X-2a) and (X-2b) will be described in detail. In the formula, the alkyl group, alkenyl group and alkynyl group represented by R _{2 have} 1 to 1 carbon atoms.
10 substituted or unsubstituted linear or branched alkyl groups (for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, n-butoxypropyl, methoxymethyl), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (for example, cyclopropyl, cyclopentyl, cyclohexyl), An alkenyl group having 2 to 10 carbon atoms (eg, allyl, 2-butenyl, 3-pentenyl), 2 carbon atoms
Examples thereof include an alkynyl group having 10 to 10 (eg, propargyl, 3-pentynyl), an aralkyl group having 6 to 12 carbon atoms (eg, benzyl) and the like. An aryl group has 6 carbon atoms
To 12 substituted or unsubstituted aryl groups (eg, unsubstituted phenol, 4-methylphenol) and the like. The above R ₂ may further have a substituent Y or the like.

Preferred examples of formulas (X-2a) and (X-2b) are shown below. In the formula, preferably R ₂ is a hydrogen atom,
A substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms,
Z _a is O, N or S, and n ₁ is an integer of ₁ to 3.

More preferably, R ₂ is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, Z _a is N or S, and n ₁ is 2 or 3.

Next, the general formula (X-3) will be described in detail. In the formula, the linking group represented by R ₃ is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, isopropylene, tetramethylene, hexamethylene, 3-oxapentylene, 2-hydroxytrimethylene), a substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (eg, cyclopropylene, cyclopentynylene, cyclohexylene), substituted or unsubstituted having 2 to 20 carbon atoms. Substituted alkenylene group (eg, ethene, 2-butenylene), alkynylene group having 2 to 10 carbon atoms, substituted or unsubstituted arylene group having 6 to 20 carbon atoms (eg, unsubstituted p-phenylene, unsubstituted 2 , 5-naphthylene), and examples of the heterocyclic group include a substituted or unsubstituted heterocyclic group, and Fine alkylene group, an alkenylene group, an arylene group, or even those heterocyclic groups are attached (e.g., 2,5-pyridinediyl, 3-phenyl -
2,5-pyridinediyl, 1,3-piperidinediyl,
2,4-morpholinediyl).

In the formula, the alkyl group represented by R ₄ is a substituted or unsubstituted straight chain or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n-). Butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl,
2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, methoxymethyl), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (for example, cyclopropyl, cyclopentyl). , Cyclohexyl)
Examples of the aryl group include a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg, unsubstituted phenyl and 2-methylphenyl).

Examples of the heterocyclic group include an unsubstituted or alkyl group, an alkenyl group, an aryl group, or a heterocyclic group further substituted (for example, pyridyl, 3-phenylpyridyl, piperidyl, morpholyl). The above R ₄ may further have a substituent Y or the like.

Preferred examples of the general formula (X-3) are shown below. In the formula, preferably R ₃ is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and R ₄ is a substituted or unsubstituted C 1 to 6 or Unsubstituted alkyl group or C6 to C1
0 is a substituted or unsubstituted aryl group, and Z ₂ is S
Alternatively, it is Se and n ₂ is 1-2.

More preferably, R ₃ is an alkylene group having 1 to ₄ carbon atoms, R ₄ is an alkyl group having 1 to ₄ carbon atoms, Z ₂ is S and n ₂ is 1.

Next, the general formula (X-4) will be described in detail. In the formula, the alkyl group and alkenyl group represented by R ₅ and R ₆ include a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, isopropyl, n-propyl). , N-butyl, t-
Butyl, 2-pentyl, n-hexyl, n-octyl,
t-octyl, 2-ethylhexyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, n-butoxypropyl, methoxymethyl), substituted with 3 to 6 carbon atoms or Examples thereof include an unsubstituted cyclic alkyl group (eg cyclopropyl, cyclopentyl, cyclohexyl) and an alkenyl group having 2 to 10 carbon atoms (eg allyl, 2-butenyl, 3-pentenyl).
Examples of the aryl group include a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg, unsubstituted phenyl, 4-methylphenyl), and examples of the heterocyclic group include an unsubstituted or alkylene group, an alkenylene group, an arylene group, Or those further substituted with a heterocyclic group (eg pyridyl, 3
-Phenylpyridyl, furyl, piperidyl, morpholyl). In the above formula, R ₅ and R ₆ may further have a substituent Y or the like.

Preferred examples of the general formula (X-4) are shown below. In the formula, preferably R ₅ and R ₆ are a substituted or unsubstituted alkyl group having 1 to ₆ carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. More preferably, R ₅ and R ₆ are aryl groups having 6 to 8 carbon atoms.

Next, general formulas (X-5a) and (X-5)
The b) will be described in detail. In the formula, E₁Group represented by
As NH₂, NHCH₃, NHC₂H_Five, NHPh, N
(CH₃)₂, N (Ph)₂, NHNHC₃H₇, NHNH
Ph, OC_FourH₉, OPh, SCH ₃, Etc., E₂
As NH, NCH₃, NC₂H_Five, NPh, NHN
C₃H₇, NHNPh, etc. (where Ph = F
Phenyl group (the same applies below)).

General formulas (X-5a) and (X-5b)
Examples of the alkyl group and alkenyl group represented by R ₇ , R ₈ and R ₉ include a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-
Butyl, 2-pentyl, n-hexyl, n-octyl,
t-octyl, 2-ethylhexyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, n-butoxypropyl, methoxymethyl), substituted with 3 to 6 carbon atoms or Examples thereof include an unsubstituted cyclic alkyl group (eg cyclopropyl, cyclopentyl, cyclohexyl) and an alkenyl group having 2 to 10 carbon atoms (eg allyl, 2-butenyl, 3-pentenyl). As the aryl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg, unsubstituted phenyl, 4
-Methylphenyl), the heterocyclic group is unsubstituted or substituted with an alkylene group, an alkenylene group, an arylene group, or a heterocyclic group, (for example,
Pyridyl, 3-phenylpyridyl, furyl, piperidyl, morpholyl). R ₇ , R ₈ and R ₉ may further have a substituent Y or the like.

Preferred examples of formulas (X-5a) and (X-5b) are shown below. In the formula, preferably E ₁ is an alkyl-substituted or unsubstituted amino group or an alkoxy group, E ₂ is an alkyl-substituted or unsubstituted amino linking group, and R ₇ , R ₈ and R ₉ have 1 to 1 carbon atoms. A substituted or unsubstituted alkyl group having 6 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and Z ₃ is S or S
It is e.

More preferably, E ₁ is an alkyl-substituted or unsubstituted amino group, E ₂ is an alkyl-substituted or unsubstituted amino linking group, and R ₇ , R ₈ and R
₉ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and Z ₃ is S.

Next, general formulas (X-6a) and (X-6)
The b) will be described in detail. In the formula, G₂And represented by J
COOCH₃, COOC₃H₇, COOC ₆
H₁₃, COOPh, SO₂CH₃, SO₂C_FourH₉, COC₂
H_Five, COPh, SOCH₃, SOPh, CN, CHO,
NO₂Etc.

In the formula, the linking group represented by R ₁₁ is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, propylene, tetramethylene and hexa). Methylene, 3-oxapentylene, 2-hydroxytrimethylene), a substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (for example, cyclopropylene, cyclopentylene, cyclohexylene), and substituted having 2 to 20 carbon atoms Alternatively, an unsubstituted alkenylene group (eg, ethene, 2-butenylene), an alkynylene group having 2 to 10 carbon atoms (eg, ethyne), a substituted or unsubstituted arylene group having 6 to 20 carbon atoms (eg, unsubstituted p-phenylene, Substituted 2,5-naphthylene).

Further, the divalent linking group represented by R ₁₁ includes a divalent heterocyclic group or a divalent heterocyclic group and an alkylene group, an alkenylene group, an alkynylene group, an arylene group or an SO ₂ group. A divalent group bonded to any of them (eg 2,5-pyridinediyl, 3-phenyl-2,5-pyridinediyl, 2,4-furandiyl, 1,3-piperidinediyl, 2,4-morpholinediyl) Is mentioned.
In the formula, R ₁₁ may further have a substituent Y or the like.

Preferred examples of the general formulas (X-6a) and (X-6b) are shown below. In the formula, preferably G ₂ and J are carboxylic acid esters and carbonyls having 2 to 6 carbon atoms, and R ₁₁ is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms or a substituted alkylene group having 6 to 10 carbon atoms. Alternatively, it is an unsubstituted arylene group.

More preferably, G ₂ and J are carboxylic acid esters having 2 to 4 carbon atoms, and R ₁₁ is 1 carbon atom.
A substituted or unsubstituted alkylene group having 4 to 4 or a substituted or unsubstituted arylene group having 6 to 8 carbon atoms.

The preferred order of the general formula of the silver halide adsorbing group represented by X is (X-1)>(X-2a)> (X-2
b)>(X-3)>(X-5a)>(X-5b)> (X
-4)>(X-6a)> (X-6b).

Next, the light absorbing group represented by X in the general formula (I) will be described in detail. In the general formula (I), examples of the light absorbing group represented by X include the following. General formula (X-7)

[Chemical 5]

In the formula, Z ₄ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and L ₂ , L ₃ , and L ₄
And L ₅ represents a methine group. p ₁ represents 0 or 1,
n ₃ represents an integer of 0 to 3. M ₁ represents a charge-balancing counterion, m ₂ represents 0 to 10 necessary for neutralizing the charge of the molecule.
Represents the number of. The nitrogen-containing heterocycle formed by Z ₄ may be condensed with an unsaturated carbocycle such as a benzene ring.

In the formula, the 5- or 6-membered nitrogen-containing heterocycle represented by Z ₄ includes a thiazolidine nucleus, a thiazole nucleus, a benzothiazole nucleus, an oxazoline nucleus, an oxazole nucleus,
Benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine),
Imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus , An oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, a pyrimidine nucleus and the like. The 5- or 6-membered nitrogen-containing heterocycle represented by Z ₄ may have the aforementioned substituent Y.

In the formula, L ₂ , L ₃ , L ₄ and L ₅ each independently represent a methine group. The methine group represented by L ₂ , L ₃ , L ₄ and L ₅ may have a substituent, and examples of the substituent include a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms (eg, methyl group). , Ethyl, 2-carboxyethyl), a substituted or unsubstituted aryl group having 6 to 20 carbon atoms (eg, phenyl, o-carboxyphenyl), a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms (eg, N, N-diethyl barbituric acid), a halogen atom (eg chlorine, bromine, fluorine, iodine), an alkoxy group having 1 to 15 carbon atoms (eg methoxy, ethoxy), 1 to 1 carbon atoms.
15 alkylthio groups (eg methylthio, ethylthio), C 6-20 arylthio groups (eg phenylthio), C 0-15 amino groups (eg N, N-
Diphenylamino, N-methyl-N-phenylamino,
N-methylpiperazine) and the like. Moreover, you may form a ring with another methine group. Alternatively, it may form a ring with other moieties.

In the formula, M ₁ is included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the light absorbing group. Typical cations include inorganic cations such as hydrogen ion (H ⁺ ) and alkali metal ions (eg, sodium ion, potassium ion, lithium ion), ammonium ion (eg, ammonium ion, tetraalkylammonium ion, pyridinium ion). , Ethylpyridinium ion) and the like. The anion may be either an inorganic anion or an organic anion, a halogen anion (eg, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (eg, p-toluene sulfonate ion, p -Chlorobenzene sulfonate ion), an aryl disulfonate ion (for example, 1,3-benzenedisulfonate ion,
1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picric acid Ions, acetate ions, and trifluoromethanesulfonate ions. Further, an ionic polymer or a light absorbing group having an opposite charge may be used.

In the present invention, for example, the sulfo group is represented by SO ₃ ⁻ and the carboxy group is represented by CO ₂ ⁻ , but when the counter ion is a hydrogen ion, they are represented by SO ₃ H and CO ₂ H, respectively. it can. In the formula, m ₂ represents the number necessary for balancing the charges, and is 0 when forming a salt in the molecule.

Preferred examples of the general formula (X-7) are shown below. As preferable general formula (X-7), Z ₄ is a benzoxazole nucleus, benzothiazole nucleus, benzimidazole nucleus or quinoline nucleus, and L ₂ , L ₃ , L ₄ and L ₅ are unsubstituted methine groups. , P ₁ is 0, and n ₃ is 1 or 2.

More preferably, Z ₄ is a benzoxazole nucleus or a benzothiazole nucleus, and n ₃ is 1.
A particularly preferred Z ₄ is a benzothiazole nucleus.

In the general formula (I), preferable k is 0 or 1.
And more preferably 1.

Specific examples of the X group used in the present invention are shown below, but the compounds used in the present invention are not limited thereto.

[0058]

[Chemical 6]

[0059]

[Chemical 7]

[0060]

[Chemical 8]

[0061]

[Chemical 9]

[0062]

[Chemical 10]

[0063]

[Chemical 11]

Next, the linking group represented by L in formula (I) will be described in detail. In the general formula (I), the linking group represented by L is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, propylene, tetramethylene, Hexamethylene, 3-oxapentylene, 2-
Hydroxytrimethylene), a substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (for example, cyclopropylene, cyclopentylene, cyclohexylene), a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms (for example, Ethene, 2-butenylene), alkynylene group having 2 to 10 carbon atoms (eg ethyne), substituted or unsubstituted arylene group having 6 to 20 carbon atoms (eg unsubstituted p-phenylene, unsubstituted 2,5-naphthylene). ), A heterocyclic linking group (for example, 2,6-pyridinediyl), a carbonyl group,
Examples thereof include thiocarbonyl group, imide group, sulfonyl group, sulfonic acid group, ester group, thioester group, amide group, ether group, thioether group, amino group, ureido group, thioureido group and thiosulfonyl group. Also,
These linking groups may be linked to each other to form a new linking group. When m is 2 or more, a plurality of Ls may be the same or different.

L may further have the above-mentioned substituent Y and the like. Examples of the preferred linking group L include a C1-10 unsubstituted alkylene group and a C1-10 alkylene group linked to an amino group, an amide group, a thioether group, a ureido group or a sulfonyl group, and more preferably. Is an unsubstituted alkylene group having 1 to 6 carbon atoms and an alkylene group having 1 to 6 carbon atoms linked to an amino group, an amide group or a thioether group.

In the general formula (I), m is preferably 0 or 1, and more preferably 1.

Next, the electron donating group A will be described in detail. And generating electrons radical A ^· is generated A-B portion undergoes oxidation and fragmentation to generate electrons more radical A ^· is subjected to oxidation, the following reaction process of high sensitivity.

[0068]

[Chemical 12]

Since A is an electron-donating group, it is preferable that the substituent on the aromatic group in any structure be selected so that A is in a state of having an excess of electrons. For example, when the aromatic ring is not electron-rich, an electron-donating group is introduced. Conversely, when the aromatic ring is extremely electron-rich, an electron-withdrawing group is introduced to adjust the oxidation potential of each. It is preferably adjusted.

Preferred A groups are of the general formula: General formula (A-1), (A-2), (A-3)

[Chemical 13]

In the general formulas (A-1) and (A-2), R
₁₂And R₁₃Are each independently a hydrogen atom or
Is an unsubstituted alkyl group, aryl group, alkylene group or
And arylene group, R₁₄Is an alkyl group, COOH,
Halogen, N (R₁₅)₂, OR₁₅, SR₁₅, CHO, C
OR₁₅, COOR₁₅, CONHR₁₅, CON
(R₁₅) ₂, SO₃R₁₅, SO₂NHR₁₅, SO₂NR₁₅,
SO₂R₁₅, SOR₁₅, CSR₁₅Represents Ar₁Is allie
It represents a len group or a heterocyclic group. R₁₂And R₁₃And R₁₂And Ar
₁May combine with each other to form a ring. Q₂Is O, S, S
represents e or Te, m₃And m_FourRepresents 0 or 1
Then n_FourRepresents an integer of 1 to 3. L₂Is NR (where
R represents a substituted or unsubstituted alkyl group. ), N
Represents Ar, O, S and Se. R₁₂And R₁₃, R₁₂And Ar
₁The cyclic form formed by bonding with each other is 5 to 7-membered.
Represents a heterocyclic group or an unsaturated ring. R₁₅Is a hydrogen atom,
It represents a alkyl group or an aryl group. Ring of general formula (A-3)
Is a substituted or unsubstituted 5- to 7-membered unsaturated ring
Alternatively, it represents a heterocyclic group.

General formulas (A-1), (A-2) and (A
-3) will be described in detail. Wherein R ₁₂ and R ₁₃
The alkyl group represented by is a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n-
Butyl, t-butyl, 2-pentyl, n-hexyl, n
-Octyl, t-octyl, 2-ethylhexyl, 2-
Hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, methoxymethyl), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (for example, cyclopropyl, cyclopentyl, cyclohexyl). Examples of the aryl group include substituted or unsubstituted aryl groups having 6 to 12 carbon atoms (eg, unsubstituted phenyl and 2-methylphenyl).

Examples of the alkylene group include a substituted or unsubstituted linear or branched alkylene group having 1 to 10 carbon atoms (for example, methylene, ethylene, trimethylene, tetramethylene, methoxyethylene), and the arylene group includes carbon. Examples of the substituted or unsubstituted arylene group of the formulas 6 to 12 (eg, unsubstituted phenylene, 2-methylphenylene, naphthylene).

In the general formulas (A-1) and (A-2), R
_The group represented by ₁₄ is an alkyl group (for example, methyl,
Ethyl, isopropyl, n-propyl, n-butyl, 2
-Pentyl, n-hexyl, n-octyl, 2-ethylhexyl, 2-hydroxyethyl, n-butoxymethyl), COOH group, halogen atom (for example, fluorine atom,
Chlorine atom, bromine _{atom), OH, N (CH 3} ) 2, NP
h ₂ , OCH ₃ , OPh, SCH ₃ , SPh, CHO, C
OCH ₃ , COPh, COOC ₄ H ₉ , COOCH ₃ , CO
NHC ₂ H ₅ , CON (CH ₃ ) ₂ , SO ₃ CH ₃ , SO ₃ C ₃
H ₇ , SO ₂ NHCH ₃ , SO ₂ N (CH ₃ ) ₂ , SO ₂ C ₂ H
₅ , SOCH ₃ , CSPh, CSCH ₃ may be mentioned.

As Ar ₁ represented by the general formulas (A-1) and (A-2), a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg, phenyl, 2-methylphenyl, naphthyl), substituted Or an unsubstituted heterocyclic group (for example, pyridyl, 3-phenylpyridyl, piperidyl,
Morpholyl).

Examples of L ₂ represented by the general formula (A-1) include NH, NCH ₃ , NC ₄ H ₉ , NC ₃ H ₇ (i) and NP.
_{h, NPh-CH 3, O} , S, Se, Te and the like.

Examples of the cyclic form of the general formula (A-3) include an unsaturated 5- to 7-membered carbon ring and a heterocycle (eg, furyl, piperidyl, morpholyl).

R in the general formulas (A-1) and (A-2)
₁₂ , R ₁₃ , R ₁₄ , Ar ₁ , L ₂ , and the general formula (A-3)
The above-mentioned substituent Y and the like may further be provided on the inside of the ring.

General formulas (A-1), (A-2) and (A
-3) A preferable example is shown. In formulas (A-1) and (A-2), R ₁₂ and R ₁₃ are preferably substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, alkylene groups, or substituted or unsubstituted having 6 to 10 carbon atoms. A substituted aryl group, wherein R ₁₄ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an amino group mono- or di-substituted with an alkyl group having 1 to 4 carbon atoms, carboxylic acid, halogen or carbon number 1 to 4 carboxylic acid ester, Ar ₁ is a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and Q is
₂ is O, S, or Se, m ₃ and m ₄ are 0 or 1, n ₄ is 1 to 3, and L ₂ is an alkyl-substituted amino group having 0 to 3 carbon atoms. General formula (A-3)
Among them, the preferred cyclic form is a 5- to 7-membered heterocycle.

In the general formulas (A-1) and (A-2), more preferably, R ₁₂ and R ₁₃ are a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms or an alkylene group, and R
₁₄ is an unsubstituted alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
Is a monoamino-substituted or diamino-substituted alkyl group, Ar ₁ is a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, Q ₂ is O or S, and m ₃ and m ₄ are 0. , N ₄ is 1 and L ₂ has 0 to 3 carbon atoms.
Is an alkyl-substituted amino group of. General formula (A-
In 3), a more preferable cyclic form is a 5- or 6-membered heterocycle.

The moieties at which the A group is bonded to the L group (or the X group when m = 0) are Ar ₁ and R ₁₂ or R ₁₃ .

Specific examples of the A group used in the present invention are shown below, but the compounds used in the present invention are not limited thereto.

[0083]

[Chemical 14]

[0084]

[Chemical 15]

[0085]

[Chemical 16]

[0086]

[Chemical 17]

[0087]

[Chemical 18]

[0088]

[Chemical 19]

Next, the group B will be described in detail. After when B is hydrogen atom oxidation, by intramolecular base is deprotonated to generate a radical A ^·.

Preferred B groups are those having a hydrogen atom and the following general formula: General formula (B-1), (B-2), (B-3)

[Chemical 20]

General formulas (B-1), (B-2) and (B
-3), W represents Si, Sn or Ge, R ₁₆ each independently represents an alkyl group, and Ar ₂ each independently represents an aryl group.

The general formulas (B-2) and (B-3) can be combined with the adsorption group X.

General formulas (B-1), (B-2) and (B
-3) will be described in detail. In the formula, the alkyl group represented by R ₁₆ is a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms (for example, methyl,
Ethyl, isopropyl, n-propyl, n-butyl, t
-Butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, n-butoxyethyl, methoxymethyl), substituted with 6 to 12 carbon atoms or An unsubstituted aryl group (eg, phenyl, 2-methylphenyl) can be mentioned.

R in the general formulas (B-2) and (B-3)
₁₆ and Ar ₂ may further have the above-mentioned substituent Y and the like.

General formulas (B-1), (B-2) and (B
The preferable example of -3) is shown below. In formulas (B-2) and (B-3), R ₁₆ is preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and Ar ₂ is a substituted or unsubstituted alkyl group having 6 to 10 carbon atoms. Is an aryl group of
W is Si or Sn.

In formulas (B-2) and (B-3), it is more preferable that R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms and Ar ₂ is 6 to 8 carbon atoms. It is a substituted or unsubstituted aryl group, and W is Si.

General formulas (B-1), (B-2) and (B
In (3), most preferred are COO ^{− in} (B-1) and Si— (R ₁₆ ) ₃ in (B-2).

In the general formula (I), preferable n is 1. In the general formula (I), when n is 2, two (A-
B) may be the same or different.

The examples of the A-B group used in the present invention are shown below, but the present invention is not limited thereto.

[0100]

[Chemical 21]

[0101]

[Chemical formula 22]

[0102]

[Chemical formula 23]

[0103]

[Chemical formula 24]

[0104]

[Chemical 25]

[0105]

[Chemical formula 26]

Counterions necessary for charge balance of the above compounds AB include sodium ion, potassium ion, triethylammonium ion, diisopropylammonium ion, tetrabutylammonium ion,
And tetramethylguanidinium ion.

The preferable oxidation potential of AB is 0 to 1.5 V.
And more preferably 0 to 1.0 V, and further preferably 0.3 to 1.0 V.

Radical A ^· (E generated from bond cleavage reaction
The preferable oxidation potential of ₂ ) is -0.6 to -2.5V, more preferably -0.9 to -2V, and further preferably -0.9 to -1.6V.

The method for measuring the oxidation potential is as follows. E
₁ can be performed by the cyclic voltammetry method. The electron donor A is dissolved in a solution of acetonitrile / 0.1M or water containing lithium chlorate in 80% / 20% (volume%). A glassy carbon disk is used as the working electrode, a platinum wire is used as the counter electrode and a saturated calomel electrode (SCE) is used as the reference electrode. 0.1V / at 25 ° C
It is measured at a potential scanning speed of 2 seconds. The oxidation potential vs. SCE is taken at the peak potential of the cyclic voltammetry wave.
The E ₁ values of these AB compounds are European Patent No. 93,731.
It is described in A1.

Radical oxidation potential measurements are made by transient electrochemical and pulse radiolysis methods. These are described in J. Am. Chem. Soc. 1988, 110 ,.
132, ibid., 1974, 96 ,. 1287, 1974,
96 ,. 1295.

Specific examples of the compound represented by formula (I) are shown below, but the compounds used in the present invention are not limited to these.

[0112]

[Chemical 27]

[0113]

[Chemical 28]

[0114]

[Chemical 29]

[0115]

[Chemical 30]

[0116]

[Chemical 31]

[0117]

[Chemical 32]

[0118]

[Chemical 33]

[0119]

[Chemical 34]

[0120]

[Chemical 35]

[0121]

[Chemical 36]

[0122]

[Chemical 37]

[0123]

[Chemical 38]

[0124]

[Chemical Formula 39]

[0125]

[Chemical 40]

As a method for synthesizing the compound represented by the general formula (I), US Pat. Nos. 5,747,235 and 5,747,2
35, European Patents 786,692A1, 893,731.
It can be easily synthesized by the method described in A1, 893, 732A1, WO99 / 05570, or the like, or a method similar thereto.

The compound represented by formula (I) can be added to a light-sensitive emulsion layer and a non-light-sensitive layer such as a non-light-sensitive emulsion layer and an intermediate layer, but it is added to the light-sensitive emulsion layer. Preferably, it is most preferably used by directly adding to the emulsion during the production of the emulsion. The addition amount of the compound represented by formula (I) is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁷ to 1 mol per mol of silver halide in the emulsion layer. It is 1 × 10 ⁻³ mol.

The compound represented by the general formula (I) used in the present invention is, in addition to water, a suitable organic solvent which can be mixed with water (for example, alcohols, ethers, glycols,
It can be added after being dissolved in a mixed solvent with ketones, esters, amides, etc.).

The internal latent image type direct emulsion positive silver halide emulsion used in the present invention will be described below.

Internal latent image type direct positive silver halide emulsion (hereinafter sometimes abbreviated as internal latent image type silver halide emulsion)
Is a silver halide emulsion that forms a latent image mainly inside the silver halide grains when imagewise exposed, and specifically, a certain amount of the silver halide emulsion is coated on a transparent support,
This was exposed to light for a fixed time of 0.01 to 1 second, and the maximum density obtained when developed in Developer A (“internal type” developer) below at 20 ° C. for 5 minutes was A second sample exposed in the same manner was developed with the following developer B (“surface type”).
It is defined as having a density which is at least 5 times greater than the maximum density obtained when developed in a developing solution) at 20 ° C. for 5 minutes. Here, the maximum density is measured by a usual photographic density measuring method. Developer A N-methyl-p-aminophenol sulfite 2 g Sodium sulfite (anhydrous) 90 g Hydroquinone 8 g Sodium carbonate (monohydrate) 52.5 g Potassium bromide 5 g Potassium iodide 0.5 g Water was added 1 liter Developer B N-methyl-p-aminophenol sulfite 2.5 g 1-ascorbic acid 10 g potassium metaborate 35 g potassium bromide 1 g Water to be added 1 liter As an internal latent image type silver halide emulsion, for example, US Pat. 456,953, 2,592,250 and the like, conversion type silver halide emulsions, and the first phase and the first phase as described in U.S. Pat. No. 3,935,014 and the like. Laminated structure type silver halide emulsions having different two-phase halogen composition, doped with metal ions, or Such core / shell type silver halide emulsion coated with shell sensitized core particles. Of these, the present invention uses a core / shell type silver halide emulsion as the internal latent image type silver halide emulsion, examples of which are US Pat. Nos. 3,206,313 and 3,317,322.
Issue No. 3,761,266 Issue No. 3,761,276
Nos. 3,850,637 and 3,923,513
No. 4,035,185, No. 4,184,878
Nos. 4,395,478, 4,504,570
JP-A-57-136641 and 61-3137.
No. 63-151618, JP-A-1-131547.
And the like are listed. In order to directly obtain a positive image, a uniform second exposure is applied to the entire surface of the photosensitive layer after image-exposure of the above-mentioned internal latent image type silver halide emulsion and before or during development processing ("light fog method"). Development process in the presence of a nucleating agent ("chemical fogging", e.g. Research Disclosur, U.S. Pat. No. 1,151,363).
e), Vol. 151, No. 15162, pp. 76-78). In the present invention, a method of directly obtaining a positive image by the "chemical fogging method" is preferable. In the present invention, an internal latent image type direct positive silver halide emulsion which has not been fogged in advance is used. The nucleating agent used in the present invention will be described later. As described above, in order to directly obtain a positive image using the internal latent image type silver halide emulsion, after the image exposure, before the development processing or during the development processing, the entire surface is uniformly exposed to the second exposure, or It is obtained by carrying out development processing in the presence of a nucleating agent. Examples of the nucleating agent include US Pat. Nos. 2,563,785 and 2,588,9.
82, hydrazines, US Pat.
7,552, hydrazides and hydrazones, British Patent 1,283,835, JP-A-52-69.
No. 613, No. 55-138742, No. 60-1183.
No. 7, No. 62-210451, No. 62-291637.
U.S. Pat. Nos. 3,615,615 and 3,719,4.
No. 94, No. 3,734,738, No. 4,094,68
No. 3, No. 4,115,122, No. 4,306,016
Heterocyclic quaternary salt compounds described in U.S. Pat. No. 4,471,044, etc., and sensitizing dyes described in U.S. Pat. No. 3,718,470 having a substituent having a nucleating action in a dye molecule. , US Pat. No. 4,030,925, 4,031,12
No. 7, No. 4,245,037, No. 4,255,511
Issue 4, Issue 4,266,013, Issue 4,276,364
Thiourea-bonded acylhydrazine compounds described in U.S. Pat. No. 2,012,443, etc., and U.S. Pat. Nos. 4,080,270, 4,278,748, and British Patent 2,011,391B. An acylhydrazine-based compound having a thioamide ring or a heterocyclic group such as triazole or tetrazole bonded as an adsorptive group described in the above is used. The amount of the nucleating agent used here is preferably an amount that gives a sufficient maximum density when the internal latent image type emulsion is developed with a surface developing solution. In practice, the appropriate content may vary over a wide range since it depends on the characteristics of the silver halide emulsion used, the chemical structure of the nucleating agent and the development conditions, but the silver content in the internal latent silver halide emulsion may vary. A range of about 0.1 mg to 5 g per mole is practically useful, preferably about 0.5 mg to about 2 g per mole of silver. When it is contained in the hydrophilic colloid layer adjacent to the emulsion layer, the same amount as described above may be contained with respect to the amount of silver contained in the inner latent type emulsion having the same area.

In the present invention, silver halide grains having various shapes can be used. As an example, those having a regular crystal form such as a cube, octahedron, tetradecahedron and rhombic dodecahedron, and those having an irregular crystal form such as a sphere and a plate, Examples thereof include those having the following plane ((hkl) plane), and a mixture of grains of these crystal forms. For particles with higher surfaces, see the Journal of Imaging Science.
247 of the maging Science magazine, Volume 30 (1986)
See pages 254. The silver halide grains used in the present invention, even if they are normal crystals that do not contain twin planes, are edited by The Photographic Society of Japan, Fundamentals of The Photographic Industry, Silver Salt Photography (Corona Publishing Co.), p. 163, for example, single twin containing one twin plane, parallel multiple twin containing two or more parallel twin planes, non-parallel containing two or more non-parallel twin planes. It can be selected and used from multiple twins and the like according to the purpose. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected if necessary. In case of normal crystal (10
A cube consisting of (0) faces, an octahedron consisting of (111) faces,
JP-B-55-42737, JP-A-60-222842
The dodecahedral grains composed of (110) planes disclosed in Japanese Patent No. 3,095,049 can be used. Furthermore, Journal of Imaging Science, Vol. 30, p. 247, 198.
(Hll) plane particles typified by (211) and typified by (331) as reported in 2006 (hh1)
The surface particles, the (hk0) surface particles typified by the (210) surface and the (hk1) surface particles typified by the (321) surface may be selected and used according to the purpose although some preparation methods are required. Tetrahedral particles in which (110) plane and (111) plane coexist in one grain, particles in which (100) plane and (110) plane coexist, or particles in which (111) plane and (110) plane coexist. For example, particles in which two surfaces or a large number of surfaces coexist can be selected and used according to the purpose.

As the silver halide composition of these grains, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodide, and silver chloride is used. However, silver bromide and silver iodobromide are preferred. Further, other silver salts such as silver thiocyanate, silver cyanate, silver sulfide,
Silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains.

The silver halide grains may have different phases in the inside and the surface layer, or may have a uniform phase.
The silver halide composition in the grain may be uniform, may have a different silver halide composition between the inside and the outside, or may have a layered structure (JP-A-57-154).
No. 232, No. 58-108533, No. 58-2484
69, 59-48755, 59-52237.
U.S. Pat. Nos. 3,505,068 and 4,433.
048, 4,444,877, European Patent No. 10
0,984 and British Patent No. 1,027,146.
issue). Also, particles having dislocation lines may be used.

In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or have a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. A uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a variation coefficient of 20% or less is preferable.
Another preferred form is an emulsion where there is a correlation between grain size and halogen composition.

It is important to control the halogen composition near the surface of the grain. Increase the content of silver iodide near the surface,
Alternatively, increasing the silver chloride content changes the adsorbability of the dye and the developing rate, and can be selected according to the purpose.
When changing the halogen composition in the vicinity of the surface, it is possible to select either a structure that encloses the entire grain or a structure that attaches only a part of the grain. For example, (100) plane and (11
1) The case where the halogen composition is changed only on one surface of the tetradecahedral grain composed of faces, or the halogen composition is changed on one of the main plane and the side surface of the tabular grain.

The grain size of the emulsion used in the present invention is determined by the circle equivalent diameter of the projected area using an electron microscope, the sphere equivalent diameter of the grain volume calculated from the projected area and grain thickness, or the sphere equivalent diameter of the volume by the Coulter counter method. Can be evaluated. It can be selected from ultrafine particles having a sphere-equivalent diameter of 0.05 μm or less and coarse particles having a diameter of more than 10 μm. Particles of 0.1 μm or more and 3 μm or less are preferable. The grain size distribution of the silver halide grains is arbitrary, but may be monodisperse. Here, monodisperse means
It is defined as a dispersion system in which 95% of the total mass or the total number of silver halide grains contained therein falls within ± 60% of the number average grain size, preferably within 40%.
Here, the number average grain size is the number average diameter of the projected area diameters of silver halide grains. Monodisperse emulsions are described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748. These monodisperse emulsions are mixed and used. May be.

Two or more kinds of silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions and the like can be used in combination, and they can be used in different emulsion layers and / or in the same emulsion layer. It is possible to

In the present invention, tabular silver halide grains can be used. Regarding tabular silver halide grains, Cleave has already written "Theory and Practice of Photography" (Cleve, P
hotography Theory and Practice (1930)), 13
One page; Gatov, Photographic Science and Engineering (Gutoff, Photographic Scien
ce and Engineering), 14: 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520. No. 4,414,306, 4,459,353, British Patent No. 2,112,157.
JP-A-59-99433 and JP-A-62-209445.
The production method and the use technique are disclosed in the publication. Particularly, tabular internal latent image type direct positive silver halide emulsions are disclosed in U.S. Pat. Nos. 4,395,478 and 4,50.
4,570, 4,996,137, Japanese Patent Publication No. 64-
8327, JP-A-1-131547 and the like. These tabular internal latent image type direct positive emulsions are excellent in that they have a good sharpness, a rapid development progress, and a direct positive image having a small development temperature dependency.

The shape of tabular grains contained in the silver halide emulsion used in the present invention can be selected from triangle, hexagon, circle and the like. A regular hexagon with approximately six sides of equal length, as described in U.S. Pat. No. 4,996,137, is a preferred form. In the present invention, tabular grains are
The aspect ratio (equivalent circle diameter of silver halide grains / grain thickness) is usually from 2 to 100, and the tabular grains account for 50% of all silver halide grains in the emulsion used in the present invention ( It is preferable that the area is equal to or larger than the projected area of the particles. Preferably, the aspect ratio is 5 or more and 100
The silver halide grains having an aspect ratio of 5 or more and 8 or less are more preferably 50 or less of all the silver halide grains in the emulsion.
%, The emulsion is preferably present at 70% or more, more preferably 70% or more, and particularly preferably 85%.
It is an emulsion that exists above. Here, the equivalent circle diameter in tabular grains means the equivalent circle diameter of two opposing parallel or nearly parallel principal planes (the diameter of a circle having the same projected area as the principal plane), and the grain thickness Shows the distance between planes.
On the other hand, when the aspect ratio exceeds 100, there is a problem that the emulsion may be deformed or destroyed in the process of completing this emulsion as a coated product, which is not preferable.

The equivalent circle diameter of the tabular grains is 0.3 μm or more,
Preferably 0.3 to 10 μm, more preferably 0.3 μm
m or more and 5 μm or less, more preferably 0.5 to 5.0 μm
m, and more preferably 0.5 to 3.0 μm. The tabular grain thickness is less than 1.5 μm, preferably 0.05-1.
It is 0 μm. Further, an emulsion having a grain thickness variation coefficient of 30% or less and high thickness uniformity is also preferable. Further, grains described in JP-A-63-163451, in which the grain thickness and the interplanar distance between twin planes are defined, are also preferable. The grain diameter and grain thickness of tabular grains can be measured by US Pat. No. 4,434,2.
It can be determined by an electron micrograph of particles as in the method described in No. 26.

The grain size distribution of tabular grains is arbitrary, but monodisperse grains are preferred. Here, monodisperse means that 95% of the total mass or the total number of silver halide grains contained therein is within ± 60% of the number average grain size,
It is preferably defined as a dispersion that falls within 40% in size. Here, the number average grain size is the number average diameter of the projected area diameters of silver halide grains. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A-63-151618, and these monodisperse emulsions may be mixed and used.

The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in European Patent Nos. 96,727B1 and 64412B1, or West German Patent No. 2,306,447C2. , JP Sho 60
The surface may be modified as disclosed in US Pat. A structure having a flat particle surface is generally used, but intentionally forming irregularities is sometimes preferable. JP-A-58-106532, 60-22132
Part of the crystals described in US Pat. No. 0, for example, a method of drilling holes in the centers of vertices or planes, or US Pat.
Raffle particles described in 643,966 are examples.

The silver halide grains used in the present invention are
Research Disclosure (RD) No. 1764
3 (Dec. 1978), pp. 22-23, "I. Emulsion preparation and types", ibid. 1
8716 (November 1979), p. 648, ibid. Three
07105 (November 1989), pages 863-865,
And Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P. Glafkides, Chimie et Pysique Photograph
ique, Paul Montel, 1967), "Photographic emulsion chemistry" by Duffin, published by Focal Press (GF Duffin, Photog
raphic Emulsion Chemistry, Focal Press, 196
6), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et al, Making and
Coating Photographic Emulsion, Focal Press, 196
It can be prepared using the method described in 4) or the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. Method of forming grains in the presence of excess silver ion (so-called reverse mixing method)
Can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. Also, tabular grains are described in Gatov, Photographic Science and Engineering (Guto
ff, Photographic Science and Engineering), 14th
Vol. 248-257 (1970); U.S. Pat. No. 4,
No. 434, 226, No. 4,414, 310, No. 4, 4
It can be easily prepared by the methods described in 33,048, 4,439,520 and British Patent 2,112,157.

The silver halide emulsion comprising the above regular grains can be obtained by controlling the pAg and pH during grain formation. For more information, for example,
Science and Engineering (Photographic S
cience and Engineering), Volume 6, 159-165 (1962); Journal of Photographic Science, 1
Volume 2, Pages 242-251 (1964), U.S. Pat. No. 3,
655,394 and British Patent 1,413,748.
No. Regarding monodisperse emulsions, JP-A Nos. 48-8600, 51-39027 and 51-
83097, 53-137133, and 54-48.
No. 521, No. 54-99419, No. 58-37635.
No. 58-49938, Japanese Patent Publication No. 47-11386
No. 3,655,394 and British Patent No. 1,413,748.

A method of adding pre-precipitated silver halide grains to a reaction vessel for emulsion preparation is described in US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Is more preferable. These can be used as seed crystals, and are also effective when provided as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size. As an addition method, the whole amount can be added at once, divided into a plurality of times or added continuously, or the like. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface.

A method of converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,14.
2,900, European Patents 273,429, 273.
No. 430 and West German Laid-Open Patent No. 3,819,241 and the like, which is an effective particle forming method. A solution of soluble halogen or silver halide grains can be added to convert it to a more sparingly soluble silver salt. It is possible to select from a method such as conversion at once, conversion by dividing into plural times, or continuous conversion. In the present invention, the halogen composition at the end of grain formation before the desalting step is preferably silver bromide.

In addition to the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1,
469,480, U.S. Pat. No. 3,650,757,
A particle forming method in which the concentration is changed or the flow rate is changed as described in U.S. Pat. No. 4,242,455 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied if necessary. Furthermore, when adding a plurality of soluble silver salts having different solution compositions, or when adding a plurality of soluble halogen salts having different solution compositions, an addition method in which one is increased and the other is decreased is also an effective method. Is. A mixer for reacting a solution of a soluble silver salt and a soluble halogen salt is disclosed in US Pat. Nos. 2,996,287, 3,342,605 and 3,3.
The method can be selected from the methods described in 415,650, 3,785,777 and West German Laid-Open Patents 2,556,885, 2,555,364.

During the production of an emulsion containing tabular grains, a silver salt solution (eg AgN) added in order to accelerate grain growth.
A method of increasing the addition rate, the addition amount, and the addition concentration of the O ₃ aqueous solution) and the halide solution (for example, KBr aqueous solution) is preferable. Regarding these methods, for example, British Patent No. 1,335,925 and US Pat. No. 3,672,90 are described.
0, 3,650,757, 4,242,445
No. 5, JP-A-55-142329 and JP-A-55-15812.
The description of No. 4 etc. can be referred to.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. By doping with metal ions in this way, it is possible to increase the amount of overexposure without causing re-inversion and to lower the minimum concentration. When the grains are doped, they are preferably added at the time of grain formation, when the grain surface is modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Mg, Ca, Sr, Ba, Al, Sc, Y, L
a, Cr, Mn, Fe, Co, Ni, Cu, Zn, G
a, Ru, Rh, Pd, Re, Os, Ir, Pt, A
u, Cd, Hg, Tl, In, Sn, Pb, Bi and the like can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxyl groups or hexacoordinated complex salts and tetracoordinated complex salts, which can be dissolved during grain formation. For example, CdBr ₂ ,
_{CdCl 2, Cd (NO 3)} 2, Pb (NO 3) 2, Pd (CH 3
COO) ₂ , K ₃ [Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe (C
N) ₆ ], K ₃ IrCl ₆ , NH ₄ RhCl ₆ , K ₄ Ru (CN)
₆ and so on. The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but may use two types or a combination of three or more types.

The metal compound is preferably added after being dissolved in water or a suitable solvent such as methanol or acetone. Aqueous hydrogen halide solution (eg H 2 to stabilize the solution)
Cl, HBr, etc.) or an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.) can be used. If necessary, acids and alkalis may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. In addition, a water-soluble silver salt (eg AgNO ₃ ) or an aqueous alkali halide solution (eg NaCl, KBr, K)
It can also be added to I) and continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods. In the present invention, the metal complex is preferably present during the formation of silver halide grains.

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be effective. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanate, carbonate,
Phosphate and acetate may be present. Regarding these, US Pat. Nos. 2,448,060 and 2,628,
No. 167, No. 3,737,313, No. 3,772,0
No. 31, and Research Disclosure, 134
Vol., June 1975, 13452, etc.

The internal latent image type silver halide grain used in the present invention has a core / shell structure as described above. The shell manufacturing method is described in Examples of JP-A-63-151618 and U.S. Pat. Nos. 3,206,316 and 3,317,3.
No. 22, No. 3,761,276, No. 4,269,92
No. 7, No. 3,367,778 and the like can be referred to. Core / shell molar ratio (mass molar ratio) in this case
Is preferably 1/30 to 5/1, more preferably 1/30
20 to 2/1, and more preferably 1/20 to 1/1.

In the silver halide emulsion of the present invention, the core particles which have been chemically sensitized are coated with the shell and then chemically sensitized.
Chemical sensitization is a known method, for example, James, The Theory of the Photographic Process, 4th edition, published by Macmillan, 1977 (TH James, The
Theory of the Photographic Process, 4th ed., Macmi
llan, 1977), p. 67-76, and methods using active gelatin, and Research Disclosure, 120, April 1974, 12008; Research Disclosure, 34, June 1975, 1
3452, U.S. Pat. Nos. 2,642,361 and 3,2.
97,446, 3,772,031, 3,85
7,711, 3,901,714, 4,26
6,018, and 3,904,415, and British Patent 1,315,755, p.
Conducting by a method using Ag, 5 to 10, pH 4 to 8 and temperature of 30 to 80 ° C., using sulfur, selenium, tellurium, gold, platinum, palladium, iridium, rhodium, osmium, rhenium, or a plurality of combinations of these sensitizers You can

It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. The chemical sensitization aids used include compounds known to control fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aids are
US Pat. Nos. 2,131,038 and 3,411,91
No. 4, 3,554, 757, JP-A-58-1265.
36, 62-253159, and "Photographic Emulsion Chemistry" by Duffin, pp. 138-143 (published by Focal Press, 1966).

Japanese Examined Patent Publication No. 58-1410, Mois
ar) et al., Journal of Photographic Science, 25, 1977, pp. 19-27, silver halide emulsions can reduce and sensitize the inside of grains during the precipitation process. . The following reduction sensitization can also be used as the chemical sensitization. U.S. Pat. No. 3,891,
As described in US Pat. No. 2,518,698 and US Pat. No. 2,743, it is possible to carry out reduction sensitization by using, for example, hydrogen.
182 and 2,743,183 with reducing agents or low pAg (eg less than 5).
Alternatively, reduction sensitization can be performed by treatment with high pH (for example, greater than 8). Stannous salt as a typical reduction sensitizer,
Ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid,
Silane compounds and borane compounds are known. For reduction sensitization, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. The chemical sensitization methods described in US Pat. Nos. 3,917,485 and 3,966,476 can also be applied.

Further, JP-A-61-3134 and 61-3
The sensitizing method using an oxidizing agent described in No. 136 is also applied.
can do. The oxidizing agent for silver is metallic silver.
Used to convert a compound into silver ion.
U Especially the formation process and chemical sensitization process of silver halide grains
The extremely small silver particles produced as a by-product at
Compounds that can be replaced are effective. Silver Io generated here
Is sparingly soluble in water such as silver halide, silver sulfide, and silver selenide.
It may form a silver salt of, and is also easily soluble in water such as silver nitrate.
A silver salt may be formed. The oxidizer for silver is an inorganic substance
It may be organic material. As an inorganic oxidant
Is ozone, hydrogen peroxide and its adducts (eg Na
BO₂・ H₂O₂・ 3H₂O, 2NaCO₃・ 3H₂O₂, N
a_FourP₂O₇・ 2H₂O₂2Na₂SO_Four・ H₂O₂・ 2H
₂O), peroxyacid salts (eg K₂S ₂O₈, K₂C
₂O₆, K₂P₂O₈), A peroxy complex compound (for example,
K₂[Ti (O₂) C₂O_Four] 3H₂O, 4K₂SO_Four・ Ti (O
₂) OH / SO_Four・ 2H₂O, permanganate (eg, K
MnO_Four), Chromates (eg, K₂Cr₂O₇) Such as
Oxygenates, halogen elements such as iodine and bromine, perhalogens
Acid salts (eg potassium periodate), salts of high valent metals
(Eg potassium hexacyanoferrate) and thios
There are rufonates. Also, as an organic oxidant
Are quinones such as p-quinone, peracetic acid and perbenzoic acid.
Which organic peroxides, active halogen-releasing compounds (eg
For example, N-bromosuccinimide, chloramine T, chloramine T
Ramin B) is mentioned as an example. Used in the present invention
Preferred oxidizing agents are ozone, hydrogen peroxide and its additions.
Substances, halogen elements, inorganic oxidants for thiosulfonates
It is an organic oxidant for quinones. For the above-mentioned reduction sensitization and silver
It is a preferred embodiment to use an oxidizing agent in combination. Oxidation
Method of applying reduction sensitization after using an agent, the reverse method or
Select and use from the method of coexisting both at the same time
You can These methods are chemically sensitized even in the grain formation process.
It can be selected and used as appropriate.

Gelatin is advantageously used as the dispersion medium (protective colloid) used in the preparation of the emulsion used in the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl. Various synthetic hydrophilic polymer substances such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., such as single or copolymers Can be used. In addition to lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sc
i. Photo. Japan, No. 16, an enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. Although many impurity ions are contained in gelatin, it is also preferable to use gelatin in which the amount of inorganic impurity ions is reduced by ion exchange treatment.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of washing with water can be selected according to the purpose, but it is preferably selected in the range of 5 to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

In the present invention, spectral sensitization can be performed using a sensitizing dye. The sensitizing dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257,
JP-A-59-180550 and JP-A-60-140335.
No. 61-160739, RD17029 (197).
8) 12 to 13 pages, RD17643 (1978) 2
The sensitizing dyes described on page 3, etc. may be mentioned.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,9.
77,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377 and 3,76
9,301, 3,814,609, 3,83
7,862, 4,026,707, British Patents 1,344,281, 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, and Japanese Patent Laid-Open No. 5-12375.
2-110618 and 52-109925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. (For example, US Pat. Nos. 3,615,613 and 3,3
No. 615, 641, No. 3,617, 295, No. 3, 6
35,721, 2,933,390, 3,74
3,510, those described in JP-A-63-23145, etc.). The sensitizing dye may be added to the emulsion at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,628,969.
JP-A-58-113928 discloses that spectral sensitization can be performed simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 58-113928. As described above, the chemical sensitization can be carried out prior to the chemical sensitization, or the spectral sensitization can be started by the addition before the completion of the silver halide grain precipitation formation. Furthermore, US Pat. No. 4,22
Adding these said compounds separately as taught in US Pat. No. 5,666, ie adding some of these compounds prior to chemical sensitization and the rest after chemical sensitization. Is also possible, and US Pat. No. 4,183,7
It may be at any time during the formation of silver halide grains including the method disclosed in No. 56.

The addition amount is 10 per mol of silver halide.
It can be used in an amount of ^-8 to 10 ^-2 mol, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 µm, about 5 x 10 ^-5 to 2 x 10 ^-3 mol is more effective.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In the present invention, various antifoggants and photographic stabilizers can be used for the purpose of preventing sensitivity deterioration and fogging. For example, RD17643
(1978) 24-25, U.S. Pat. No. 4,629,
Nos. 678 and azaindenes, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, JP-A-62. −
The acetylene compounds described in 87957 are used. These additives are described in more detail in Research Disclosure Item 17643 (1978).
Year), the same Item 18716 (November 1979) and the same
It is described in Item 307105 (November 1989), and the relevant portions are summarized in the table below.

[0165]   Types of additives RD17643 RD18716 RD307105                     (December 1978) (November 1979) (November 1989) 1 Chemical sensitizer Page 23 Page 648 Right column Page 866 2 Sensitivity enhancer Page 648, right column 3 Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868    Supersensitizer: page 649, right column 4 Brightener 24 pages 647 pages 868 pages 5 Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870    Stabilizer 6 Light absorbers, pages 25 to 26, page 649, right column, page 873    Filter dye, page 650, left column    UV absorber 7 Anti-stain agent Page 25 Right column Page 650 Left column Page 872                                        ~ Right column 8 Dye image stabilizer page 25 page 650 page left column page 872 9 Hardener 26 pages 651 left column 874-875 pages 10 Binder page 26 same as above page 873-874 11 Plasticizers and lubricants Page 27 Page 650 Right column Page 876 12 Coating aid, pages 26-27 ibid., Pages 875-876    Surfactant 13 Antistatic agent Page 27 Same as above Pages 876-877 14 Matting agent pp. 878-879

Next, the color diffusion transfer photosensitive material of the present invention will be described. A typical form of the color diffusion transfer film unit is that the image receiving element and the photosensitive element are laminated on one transparent support, and it is not necessary to peel the photosensitive element from the image receiving element after the transfer image is completed. It is a form. More specifically, the image-receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a blue-sensitive emulsion layer, a combination of a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer, A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye image-forming compound, magenta in each of the above emulsion layers. A dye image-forming compound and a cyan dye image-forming compound are respectively combined to constitute (here, "infrared light-sensitive emulsion layer" means 700 nm or more, particularly 74 nm or more).
An emulsion layer having a maximum spectral sensitivity to light of 0 nm or more). A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the dye image forming compound-containing layer so that the transferred image can be viewed through the transparent support.

A light shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development processing can be completed in a bright place. Further, if desired, a peeling layer may be provided at an appropriate position so that all or part of the photosensitive element can be peeled from the image receiving element. Such an embodiment is disclosed in, for example, JP-A-56-56.
67840 and Canadian Patent 674,082.

In another embodiment of the laminate type which is peelable, at least (a) a layer having a neutralizing function, (b) a dye image receiving layer, on a white support described in JP-A-63-226649. The emulsion layer comprises (c) a release layer, (d) a light-sensitive element sequentially having at least one silver halide emulsion layer combined with a dye image-forming compound, an alkali processing composition containing a light-shielding agent, and a transparent cover sheet. There is a color diffusion transfer photographic film unit having a layer having a light shielding function on the side opposite to the side where the processing composition is developed.

In another form in which peeling is not required, the above-mentioned photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. .
U.S. Pat. No. 3,730,71 describes a mode in which an image receiving element, a white reflective layer, a peeling layer and a photosensitive element are laminated on the same support and the photosensitive element is intentionally peeled from the image receiving element.
No. 8.

On the other hand, there are roughly two representative forms in which a light-sensitive element and an image-receiving element are separately coated on two supports, one is a peeling type and the other is a peeling-free type. is there. Explaining these in detail, in a preferable embodiment of the peelable film unit, at least one image receiving layer is coated on one support, and the photosensitive element is coated on the support having a light shielding layer. Before the exposure is finished, the photosensitive layer coated surface and the mordant layer coated surface do not face each other, but after the exposure is finished (for example, during the development process), the photosensitive layer coated surface is inverted in the image forming apparatus to come into contact with the image receiving layer coated surface. It is devised to be. After the transfer image is completed on the mordant layer, the light-sensitive element is rapidly separated from the image-receiving element.

In a preferred embodiment of the peel-free type film unit, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-shielding layer. Thus, the photosensitive layer coated surface and the mordant layer coated surface face each other and are superposed.

A pressure rupturable container (processing element) containing an alkaline processing liquid may be combined with the above-described form. Among others, in a peel-free type film unit in which an image receiving element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. Further, in the form in which the light-sensitive element and the image-receiving element are separately coated on the two supports, it is preferable that the processing element is disposed between the light-sensitive element and the image-receiving element at the latest during the development processing. The processing element preferably contains either or both of a light-shielding agent (such as carbon black and a dye whose color changes with pH) and a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the color diffusion transfer type film unit, it is preferable that a neutralization timing mechanism comprising a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element, or the light sensitive element.

The constituent elements that can be used in the light-sensitive material of the present invention will be described in more detail below.

I. Photosensitive Sheet A) Support The support of the photosensitive sheet used in the present invention may be any smooth transparent support usually used for photographic light-sensitive materials, and may be cellulose acetate, polystyrene, polyethylene terephthalate, polycarbonate or the like. It is preferable to provide an undercoat layer. It is preferred that the support usually contains minor amounts of dyes or pigments such as titanium oxide, to prevent light piping. The thickness of the support is 5
The thickness is 0 to 350 μm, preferably 70 to 210 μm, and more preferably 80 to 150 μm. If necessary, a curl-balancing layer is provided on the back side of the support or JP-A No.
An oxygen barrier layer described in 6-78833 can be provided.

B) Image Receiving Layer The dye image receiving layer used in the present invention comprises a hydrophilic colloid containing a mordant. This may be a single layer or may have a multi-layered structure in which mordants having different mordant strengths are applied in layers. Regarding this, JP-A-61-25255
No. 1 is described. As the mordant, a polymer mordant is preferable. The polymer mordant is a polymer having a secondary or tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation, or the like and having a molecular weight of 5,000 or more, particularly preferably 10,000 or more. It is a thing. The amount of mordant applied is generally 0.5.
10 to 10 g / m ^2, preferably 1.0 to 5.0 g / m ^{2, and} particularly preferably ² to 4 g / m ² .

As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, etc. are used, and gelatin is preferred. In the image receiving layer, JP-A-62-30620
No. 62-302621 and JP-A-62-215272.
An anti-fading agent described in No. can be incorporated.

C) White Reflective Layer The white reflective layer forming the white background of the color image usually contains a white pigment and a hydrophilic binder. As the white pigment for the white reflective layer, barium sulfate, zinc oxide, barium stearate,
Silver flakes, silicates, alumina, zirconium oxide, sodium zirconium sulfate, kaolin, mica, titanium dioxide and the like are used. Further, non-film-forming polymer particles made of styrene or the like are also used. Further, these may be used alone or may be mixed and used within a range capable of obtaining a desired reflectance. A particularly useful white pigment is titanium dioxide.

The whiteness of the white reflective layer varies depending on the type of pigment, the mixing ratio of the pigment and the binder, and the coating amount of the pigment, but the light reflectance is preferably 70% or more. Generally, the greater the amount of pigment applied, the better the whiteness, but when the image-forming dye diffuses through this layer, the pigment resists the diffusion of the dye, so it should have an appropriate amount of application. Is desirable. Titanium dioxide 5-40g /
m ^2, preferably 10 to 25 g / m ² was applied, the white reflective layer light reflectance has a 78 to 85% with light having a wavelength of 540nm is preferred. Titanium dioxide can be selected from various commercially available brands and used. Among these, it is particularly preferable to use rutile type titanium dioxide. Most of the commercial products are
The surface treatment is performed with alumina, silica, zinc oxide or the like, and in order to obtain high reflectance, the surface treatment amount is preferably 5% or more. Examples of commercially available titanium dioxide include Ti-pure R931 (trade name) manufactured by DuPont and those disclosed in Research Disclosure No. 15162.

As a binder for the white reflective layer, an alkali-permeable polymer matrix such as gelatin, polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose can be used. A particularly preferred binder for the white reflective layer is gelatin. The ratio of white pigment to gelatin is 1/1 to 2
It is 0/1 (mass ratio), preferably 5/1 to 10/1 (mass ratio). In the white reflective layer, Japanese Examined Patent Publication No. 62-3062
It is preferable to incorporate an anti-fading agent such as No. 0 or No. 62-30621.

D) Light-shielding layer A light-shielding layer containing a light-shielding agent and a hydrophilic binder is provided between the white reflective layer and the photosensitive layer. As the light shielding agent, any material having a light shielding function is used, but carbon black is preferably used. US Pat. No. 4,61
You may use the decomposable dye as described in 5,966.
The binder for coating the light-shielding agent may be any as long as it can disperse carbon black, and gelatin is preferable. Examples of carbon black raw materials include D
onnel Voet "Carbon Black" MarcelDekker, Inc. (1
Any method such as a channel method, a thermal method and a furnace method as described in 976) can be used. The particle size of carbon black is not particularly limited, but is preferably 90 to 1800Å. The addition amount of the black pigment as the light-shielding agent may be adjusted depending on the sensitivity of the light-sensitive material to be shielded, but it is preferably about 5 to 10 in terms of optical density.

E) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image forming compound is provided above the light shielding layer. The constituent elements will be described below.

(1) Dye image forming compound Specific examples of the dye image forming compound are described in the following documents. Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609 and 4,139. , 383, 4,195,992, 4,148,641, 4,148,643, 4,336,322: JP-A-51-114930.
56-71072: Research Disclosure 1763.
No. 0 (1978) and No. 16475 (1977).

Examples of magenta dyes: US Pat. No. 3,453,353
No. 107, No. 3,544,545, No. 3,932,3
80, 3,931,144, 3,932,30
No.8, No.3,954,476, No.4,233,237
Nos. 4,255,509 and 4,250,246
No. 4,142,891, No. 4,207,104
No. 4,287,292, JP-A-52-10672.
No. 7, No. 53-23628, No. 55-36804,
56-73057, 56-71060, 55.
-134, JP-A-7-120901 and 8-286.
No. 343, No. 8-286344, No. 8-292537.
What is listed in the issue.

Examples of cyan dyes: US Pat. No. 3,482,9
72, 3,929,760, 4,013,63
No. 5, No. 4,268,625, No. 4,171,220
No. 4,242,435, 4,142,891
Issue No. 4,195,994, No. 4,147,544
No. 4,148,642; British Patent 1,551,1
38; JP-A-54-99431 and JP-A-52-8827.
No. 53-47823, No. 53-143323,
54-99431 and 56-71061; European Patents (EP) 53,037 and 53,040;
Those described in Research Disclosure 17,630 (1978) and 16,475 (1977).

Dye image-forming compounds which form a dye upon coupling can also be used. For example, JP-A-8-28634
No. 0, 9-152705, Japanese Patent Application No. 8-357190.
No. 8-357191, No. 9-17529 and the like. A positive type dye image forming compound can also be used. In this case, a negative emulsion may be used as the silver halide emulsion. As an example of this, Japanese Patent Laid-Open No. 4-156542
Nos. 4-155332, 4-172344, 4-172450, 4-318844, 356.
No. 046, No. 5-45824, No. 5-45825,
5-53279, 5-107710, 5-2
41302, 5-107708, 5-2326.
59, U.S. Pat. No. 5,192,649.

These compounds are disclosed in JP-A-62-2152.
It can be dispersed by the method described in No. 72, pages 144 to 146. Further, these dispersions include those disclosed in JP-A-62-2152.
No. 72, pages 137-144 may be included. Specific examples of these dye forming compounds include the following compounds. Dye in the following compounds represents a dye group, a temporarily shortened dye group, or a dye precursor group.

[0187]

[Chemical 41]

[0188]

[Chemical 42]

[0189]

[Chemical 43]

(2) Silver Halide Emulsion The silver halide emulsion used in the present invention is an internal latent image type direct positive emulsion which forms a latent image mainly inside the silver halide grains.

(3) Constitution of photosensitive layer For the reproduction of natural color by the color-subtraction method, the above-mentioned dye which provides a dye having a selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the above-mentioned spectral sensitizing dye. A photosensitive layer is used which consists of at least two layers with an image forming compound. The emulsion and the dye image-forming compound may be coated as separate layers, or they may be mixed and coated as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity region of the emulsion combined with it, another layer is preferable.
The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image forming compound layer. For example, Japanese Patent Laid-Open No. 60-1735
No. 41, a layer containing a nucleation development accelerator, JP-B-6
It is also possible to increase the color image density by providing a partition layer described in JP-A No. 0-15267, or to increase the sensitivity of the photosensitive element by providing a reflective layer.

The reflective layer is a layer containing a white pigment and a hydrophilic binder, preferably the white pigment is titanium oxide and the hydrophilic binder is gelatin. The amount of titanium oxide applied is 0.1 g / m ^{2 to} 8 g / m ² , preferably 0.1.
It is a ^{2g / m 2 ~4g / m 2} . Examples of the reflective layer are described in JP-A-60-91354.

In a preferred multilayer structure, a combination unit of blue-sensitive emulsion, a combination unit of green-sensitive emulsion and a combination unit of red-sensitive emulsion are sequentially arranged from the exposure side. An arbitrary layer can be provided between each emulsion layer unit as needed. In particular, it is preferable to provide an intermediate layer in order to prevent the unfavorable influence of the development effect of one emulsion layer on other emulsion layer units. In the present invention, an irradiation prevention layer, a UV absorber layer, a protective layer and the like are coated as necessary.

F) Peeling Layer In the invention, a peeling layer may be provided for peeling off the photosensitive sheet in the unit at any place after the treatment, if necessary. Therefore, this peeling layer must be easy to peel off after the treatment.

A material for this purpose is, for example, Japanese Patent Laid-Open No.
7-8237, 59-220727, 59-2
29555, 49-4653, U.S. Pat. No. 3,2.
20,835, 4,359,518, JP-A-49
-4334, 56-65133, 45-240.
75, U.S. Pat. Nos. 3,227,550 and 2,75.
9,825, 4,401,746, 4,36
Those described in No. 6,227 and the like can be used. As one specific example, a water-soluble (or alkali-soluble) cellulose derivative can be mentioned. For example, hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose and the like.
Another example is various natural polymers such as alginic acid, pectin, and gum arabic. Also, various modified gelatins such as acetylated gelatin and phthalated gelatin can be used. Yet another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethylmethacrylate,
Examples thereof include polybutyl methacrylate or copolymers thereof. The release layer can be a single layer or, for example,
It may be composed of a plurality of layers as described in JP-A-59-220727 and JP-A-60-60642.

The color diffusion transfer light-sensitive material of the present invention preferably has a neutralizing function between the support and the light-sensitive layer, between the support and the image-receiving layer, or on the cover sheet.

G) Support The support of the cover sheet used in the present invention may be any smooth transparent support commonly used for photographic light-sensitive materials, such as cellulose acetate, polystyrene, polyethylene terephthalate and polycarbonate. ,
It is preferable to provide an undercoat layer. The support preferably contains a trace amount of dye in order to prevent light piping.

H) Layer Having Neutralizing Function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize the alkali carried in from the treatment composition, and is necessary. Accordingly, it may have a multi-layered structure including layers such as a neutralization rate adjusting layer (timing layer) and an adhesion enhancing layer. The preferred acidic substance is a substance containing an acidic group having a pKa of 9 or less (or a precursor group which gives such an acidic group by hydrolysis), more preferably oleic acid described in US Pat. No. 2,983,606. Higher fatty acids such as US Pat. No. 3,362,819
Polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or anhydrides as disclosed in US Pat. No. 2,290,699; acrylic acid and acrylic acid as disclosed in French Patent 2,290,699. Ester isotopes;
No. 4,139,383 or Research Disclosure No. 16102 (19
Mention may be made of latex-type acidic polymers as disclosed in 77). Others, US Patent 4,08
No. 8,493, JP-A Nos. 52-153739 and 53-
No. 1023, No. 53-4540, No. 53-4541
The acidic substances disclosed in JP-A No. 53-4542 and the like can also be mentioned.

Specific examples of the acidic polymer include ethylene,
Examples thereof include copolymers of vinyl monomers such as vinyl acetate and vinyl methyl ether with maleic anhydride, and n-butyl esters thereof, copolymers of butyl acrylate and acrylic acid, cellulose, and acetate-hydrogenphthalate.

The polymer acid can be used as a mixture with a hydrophilic polymer. As such a polymer,
Examples include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polymethyl vinyl ether and the like. Of these, polyvinyl alcohol is preferable. Further, the polymer acid is a polymer other than a hydrophilic polymer,
For example, cellulose acetate or the like may be mixed.

The coating amount of the polymer acid is adjusted by the amount of alkali spread on the photosensitive element. The equivalent ratio of polymer acid and alkali per unit area is preferably 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye is changed or stains are generated on the white background portion, and if it is too large, the hue is changed or the light resistance is deteriorated. A more preferable equivalent ratio is 1.0 to 1.3. If too much or too little hydrophilic polymer is mixed, the quality of the photograph will be degraded. The mass ratio of the hydrophilic polymer to the polymer acid is 0.1 to 10, preferably 0.1.
It is 3 to 3.0.

Additives can be incorporated into the layer having a neutralizing function of the present invention for various purposes. For example, hardening agents well known to those skilled in the art for hardening this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. for improving the brittleness of the film can be added. Other as needed
Antioxidants, optical brighteners, development inhibitors and their precursors can also be added.

The timing layer used in combination with the neutralizing layer has a low alkali permeability such as gelatin, polyvinyl alcohol, a partial acetalization product of polyvinyl alcohol, cellulose acetate, and partially hydrolyzed polyvinyl acetate. Polymer; made by copolymerizing a small amount of hydrophilic comonomers such as acrylic acid monomer,
Latex polymers which increase the activation energy of alkali permeation; polymers having a lactone ring are useful.

Among them, JP-A-54-136328,
US Pat. Nos. 4,267,262 and 4,009,030
No. 4,029,849, and other timing layers using cellulose acetate; JP-A-54-128
No. 335, No. 56-69629, No. 57-6843.
U.S. Pat. Nos. 4,056,394 and 4,061,4
No. 96, No. 4,199,362, No. 4,250,24
No. 3, No. 4,256,827, No. 4,268,604
Latex polymers prepared by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid; disclosed in U.S. Pat. No. 4,229,516; polymers having a lactone ring disclosed in U.S. Pat. No. 4,229,516; -25735
Nos. 56-97346, 57-6842, European Patent (EP) 31,957A1, 37,72.
The polymers disclosed in 4A1 and 48412A1 are particularly useful.

In addition, the materials described in the following documents can also be used. US Pat. Nos. 3,421,893 and 3,455
No. 686, No. 3,575, 701, No. 3,778, 2
No. 65, No. 3,785,815, No. 3,847,61
No. 5, No. 4,088,493, No. 4,123,275
No. 4,148,653, 4,201,587
No. 4,288,523, 4,297,431
, West German Patent Applications (OLS) 1,622,936, 2,162,277, Research Disclosure 1516
2, No. 151 (1976). The timing layer using these materials may be used alone or in combination of two or more layers.

Further, in the timing layer made of these materials, for example, US Pat. No. 4,009,029, West German Patent Application (OLS) 2,913,164, and 3,014,6.
72, JP-A-54-155837, JP-A-55-138.
No. 745, etc., development inhibitors and / or precursors thereof, and US Pat. No. 4,201,5.
Hydroquinone precursor disclosed in No. 78,
It is also possible to incorporate other useful photographic additives or their precursors. Further, as a layer having a neutralizing function, JP-A-63-168648 and JP-A-63-168648
Providing an auxiliary neutralization layer as described in JP-A-168649 is effective in reducing the change in transfer density over time after the treatment.

I) Others In addition to the layer having a neutralizing function, a back layer, a protective layer, a filter dye layer and the like may be provided as a layer having an auxiliary function. The back layer is provided for adjusting curl and imparting slipperiness. Filter dyes may be added to this layer. The protective layer is mainly used to prevent adhesion to the back surface of the cover sheet and adhesion to the protective layer of the photosensitive material when the photosensitive material and the cover sheet are superposed. The cover sheet may contain a dye to adjust the sensitivity of the photosensitive layer. The filter dye is directly in the support of the cover sheet or a layer having a neutralizing function, further the back layer,
It may be added to the protective layer, the capture mordant layer or the like, or a single layer may be provided.

II. Alkali processing composition The processing composition used in the present invention is uniformly spread on the photosensitive element after exposure of the photosensitive element, and is placed on the back surface of the support or on the side opposite to the processing solution of the photosensitive layer to form a pair with the light shielding layer. Thus, the photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed by the components contained therein. Therefore, in the composition, an alkali, a thickener, a light-shielding agent, a developing agent, a development accelerator for controlling the development, a development inhibitor, and an antioxidant for preventing the deterioration of the developing agent. Contains etc. A light-shielding agent is always included in the composition for light-shielding.

Alkali is sufficient to adjust the pH of the liquid to 12 to 14, and alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide, lithium hydroxide),
Examples thereof include alkali metal phosphates (eg, potassium phosphate), guanidines, and quaternary amine hydroxides (eg, tetramethylammonium hydroxide), but potassium hydroxide and sodium hydroxide are preferred.

The thickening agent is used to spread the treatment liquid uniformly.
It is also necessary to maintain the close contact between the photosensitive layer and the cover sheet. For example, an alkali metal salt of polyvinyl alcohol, hydroxyethyl cellulose or carboxymethyl cellulose is used, and preferably hydroxyethyl cellulose or sodium carboxymethyl cellulose is used. As the light-shielding agent, any dye or pigment, or a combination thereof, can be used as long as it does not diffuse to the dye image-receiving layer to generate stain. Carbon black is a typical example.

As the preferable developing agent, any developing agent can be used so long as it cross-oxidizes the dye image-forming substance and does not substantially produce stain when oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor type. These developing agents may be contained in an appropriate layer of the light-sensitive sheet or may be contained in the alkaline processing liquid. Specific examples of the compound include aminophenols and pyrazolidinones. Of these, pyrazolidinones are particularly preferable because they generate less stain. For example, 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1- (3'-methyl-phenyl) -4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone and the like can be mentioned.

For any of the light-sensitive sheet, the cover sheet or the alkaline processing composition, the development accelerator described on pages 72 to 91 of JP-A-62-215272, the hardener on pages 146 to 155, and the composition described on pages 201 to 210. Surfactant, 210
To a 222-page fluorine-containing compound, 225-227 page thickener, 227-230 page antistatic agent, 23
A polymer latex described on pages 0 to 239, a matting agent described on page 240, and the like can be included. In addition, JP-A-6-2
73907, JP-A-7-134386, JP-A-7-
175193, 3 described in JP-A-7-287372
A primary amine latex can be included.

Further, these alkaline liquid compositions have a developed thickness (processing liquid amount per m ² after transferring the processing liquid) of 20 μm to ² μm.
It is desirable to develop on a photosensitive element at 00 μm. The processing temperature for processing the light-sensitive material is preferably 0 to 50 ° C, more preferably 0 to 40 ° C.

For details of the heat-developable color light-sensitive material (dye fixing element) in which the dye image-forming compound of the present invention is used, and the exposure / heating method and apparatus to be applied, see, for example, JP-A-7-219180, [0128]. From [01
59].

The silver halide emulsion of the present invention may also be used in a conventional light-sensitive material. Examples of applicable light-sensitive materials include light-sensitive materials for color and black-and-white printing paper, light-sensitive materials for color slides, and light-sensitive materials for microfilm.

[0216]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. Example 1 First, a method for preparing a silver halide emulsion will be described. The following types of silver halide emulsions 101 to 109 were prepared by the following emulsion grain preparation method.

Emulsion-101: potassium bromide 0.006 m
1 liter / liter of an aqueous solution of silver nitrate having a concentration of 0.16 mol / liter in 6 liters of a gelatin aqueous solution containing 0.09% by mass of low molecular weight gelatin having an average molecular weight of 20,000 or less.
25 ml and 363 ml of an aqueous solution containing 0.14 mol / liter of potassium bromide and 0.9% by mass of a low molecular weight gelatin having an average molecular weight of 20,000 or less were simultaneously mixed by the double jet method for 1 minute with vigorous stirring (first addition). .
During this time, the gelatin aqueous solution was kept at 35 ° C. After adding 3.8 g of potassium bromide, a gradient of 1.5 ° C. was applied for 7 minutes per minute.
The temperature was raised to 5 ° C. Ca content of 1 after reaching a temperature of 75 ° C
1.8 liters of gelatin solution containing 9.5% by mass of deionized gelatin of 00 ppm or less (first addition), Compound E
An aqueous solution containing 10.4 g of -1 was added. Then,
After adding 21 ml of 50% ammonium nitrate aqueous solution and 121 ml of 1 mol / liter sodium hydroxide aqueous solution and aging for 10 minutes, 10% of 100% acetic acid, 7.5 g of potassium bromide, and 40 mg of sodium benzenethiosulfate.
Was added. Then, the flow velocity accelerated while keeping the silver nitrate aqueous solution having a concentration of 0.6 mol / liter and the potassium bromide aqueous solution having a concentration of 0.6 mol / liter at pBr 2.05 (the flow velocity at the end is 1. (7 times) by the double jet method over 16 minutes (the second addition, the amount of the aqueous silver nitrate solution used was 500 ml).

Subsequently, 1.8 liters of a gelatin solution containing 9.5% by mass of deionized gelatin having a Ca content of 100 ppm or less (second addition), and then 15 mg of lead acetate (added in an aqueous solution) were added thereto to obtain 2 mol / liter. Concentration of silver nitrate solution and concentration of 2 mol / liter potassium bromide solution kept at pBr 2.70 at accelerated flow rate (flow rate at end is 2.6 times flow rate at start) for 110 minutes by double jet method (Third addition, the amount of aqueous silver nitrate solution used was 3.83 liters). After adding 39 g of potassium bromide, washing with water by a conventional flocculation method and adding deionized gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate,
The pH was adjusted to 6.5 and the pAg was adjusted to 9.3 so as to contain 1.7 mol of silver and 42 g of gelatin per kg of the emulsion. The emulsion thus formed is hereinafter referred to as a core emulsion. The diameter of a circle having an area equal to the projected area of each grain viewed from the principal plane direction is called a circle equivalent diameter. As a result of observation with an electron microscope, the average value of particle thickness hi (= Σhi × ni /
Σni) was 0.22 μm, and the average value of the equivalent circle diameters Di of the particles (= ΣDi × ni / Σni) was 1.6 μm. The average aspect ratio defined by the average value of the equivalent circle diameters Di / the average value of the particle thickness hi was 7.7.

The core emulsion 101, 4720 g, was added to 40
Dissolved at 25 ° C, water 2510 ml, 5% acetic acid solution 77 ml,
5.7 g of potassium bromide was added. After the temperature was raised to 75 ° C., sodium benzenethiosulfate 495 mg, potassium tetrachloroaurate 6.8 mg and compound E-2 6.6 mg were added, and after heating at 75 ° C. for 90 minutes, water 40 liters, deionized gelatin 1870 g, potassium bromide 460
g was added.

Subsequently, an accelerated flow rate was maintained while maintaining the pBr of 2.75 with an aqueous solution of silver nitrate having a concentration of 0.55 mol / l and an aqueous solution of potassium bromide having a concentration of 0.55 mol / l containing 35 mg / l of compound E-3 (end). The flow rate at that time was twice the flow rate at the start) and was added by the double jet method over 80 minutes (the amount of the silver nitrate aqueous solution used was 22.2 liters). Further, the flow velocity accelerated while keeping the aqueous solution of silver nitrate having a concentration of 1.7 mol / liter and the aqueous solution of potassium bromide having a concentration of 1.7 mol / liter at pBr 2.75 (the flow velocity at the end is 1.
(9 times) and added by the double jet method over 95 minutes (the amount of the aqueous silver nitrate solution used was 30 liters). After adding 870 g of potassium bromide, washing with water by a conventional flocculation method, adding deionized gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate, and then adjusting the pH to 6.5 and pAg 9.3. Emulsion 1
It was adjusted to contain 0.7 mol of silver, 62 g of gelatin per kg.

As a result of observation with an electron microscope, the grain thickness h
The average value of i (= Σhi × ni / Σni) 0.39 μm,
Average value of circle equivalent diameter Di of particles (= ΣDi × ni / Σn
i) It was 2.85 μm. Average value of circle equivalent diameter Di /
The average aspect ratio defined by the average value of the grain thickness hi was 7.4. Next, sodium thiosulfate 150mg
And 280 ml of an aqueous solution of 40 mg of sodium tetraborate dissolved in 1000 ml of water were added, and 430 mg of poly (N
-Vinylpyrrolidone), and chemically sensitizing the surface of the grain by heating at 70 ° C. for 100 minutes, and then potassium bromide is added at 5.8 × 10 ⁻³ mol per mol of silver to further sensitize. 3. Dye (1), sensitizing dye (2), sensitizing dye (3), sensitizing dye (4), and sensitizing dye (5) are 1.3 × 10 ⁻⁴ mol and 1 mol of silver, respectively. ^{0x10 -6} mol, 2.6x10 ^-5 mol, 2.4x10 ^-5 mol, 4.3
A final emulsion was prepared by adding 10 ⁻⁵ mol of X 10 ^{−5 and} ripening for 20 minutes and then cooling. The sensitizing dye (5) is an aqueous solution, and the sensitizing dye (1), the sensitizing dye (2), the sensitizing dye (3), and the sensitizing dye (4) are 5% gelatin mixed with the sensitizing dye powder. After being added to the aqueous solution, it was added in the form of a dissolver dispersion. The compounds used for emulsion preparation are shown below together.

[0222]

[Chemical 44]

[0223]

[Chemical formula 45]

[0224]

[Chemical formula 46]

[0225]

[Chemical 47]

Next, in the method for preparing Emulsion-101, except that the compound represented by the general formula (I) of the present invention was added in an amount shown in Table 1 per mol of silver nitrate by the specified addition method. -Emulsion -102 to 1 by the same method as that of -101
09 was prepared.

[0227]

[Table 1]

Photosensitive elements-101 to 109 having the constitutions shown in Tables 2 to 5 below were prepared, and exposure, development and density measurement were carried out to evaluate photographic performance. In the construction of the light-sensitive elements, the light-sensitive elements using the emulsions 101 to 109 prepared in the eighth layer were designated as light-sensitive elements-101 to 109, respectively. Table 6 shows a list of emulsions used in the other emulsion layers.
Each emulsion can be prepared with reference to the examples of JP-A-6-51423. Sensitizing dyes were added to these emulsions at the final stage of emulsion preparation. Table 7 shows the amount and method of addition of the sensitizing dyes.

[0229]

[Table 2]

[0230]

[Table 3]

[0231]

[Table 4]

[0232]

[Table 5]

[0233]

[Table 6]

[0234]

[Table 7]

The compounds used to make the photosensitive element are shown below.

[0236]

[Chemical 48]

[0237]

[Chemical 49]

[0238]

[Chemical 50]

[0239]

[Chemical 51]

[0240]

[Chemical 52]

[0241]

[Chemical 53]

[0242]

[Chemical 54]

[0243]

[Chemical 55]

[0244]

[Chemical 56]

[0245]

[Chemical 57]

The cover sheet was prepared as follows.

Preparation of Cover Sheet A transparent support having a thickness of 75 μm was coated in a layer structure as shown in Table 8 to prepare a cover sheet.

[0248]

[Table 8]

The chemical structural formulas and the like of the compounds used in the cover sheet are shown below.

[0250]

[Chemical 58]

[0251]

[Chemical 59]

The alkaline treatment composition was prepared according to the following formulation. Silver nitrate 0.10 g Carbon black (manufactured by Dainichiseika Co., Ltd.) 160 g Additive (23) 8.60 g Carboxymethyl cellulose Na salt 58.0 g Benzyl alcohol 2.50 g Additive (24) 2.10 g Potassium sulfite (anhydrous) ) 1.90 g 5-methylbenzotriazole 2.50 g 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 7.00 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10 0.0 g Potassium hydroxide 56.0 g Aluminum nitrate 0.60 g Zinc nitrate 0.60 g Additive (25) 6.60 g Additive (14) 1.80 g 1,2-benzisothiazolin-3-one 0.003 g

[0253]

[Chemical 60]

Next, after exposing the light-sensitive elements 101 to 109 from the emulsion layer side through a continuous gray wedge,
The cover sheet was overlaid and the alkali treatment composition was spread between both materials using a pressure roller so that the thickness was 51 μm. The exposure is performed under two conditions of 1/100 second exposure and 10 second exposure by adjusting the exposure illuminance so that the exposure amount is constant, and the sensitivity and the low illuminance exposure during high illuminance exposure (1/100 second exposure) Two points of sensitivity at (10 second exposure) were evaluated. The treatment is carried out at 25 ° C, and the dye density transferred after 2 hours is measured by a color densitometer (automatic densitometer
-Rite310TR, trade name, manufactured by X-Rite) was used to measure the maximum density of cyan and the midpoint sensitivity. The midpoint sensitivity was determined as follows. That is, the characteristic curve is drawn by displaying the logarithm of the exposure amount on the horizontal axis and each color density on the vertical axis. The midpoint sensitivity is defined as the sensitivity that gives an intermediate density between the highest density and the lowest density. The sensitivity is 10 times that of the sample 101.
It was set to 0 and indicated by its relative value (exact value). The results are summarized in Table 9.

[0255]

[Table 9]

As is apparent from Table 9, the emulsion of the present invention-
Photosensitive element prepared using 102-109-102-
In No. 109, an increase in dew sensitivity for 10 seconds was observed without a decrease in maximum density or a decrease in exposure sensitivity for 1/100 second. Rather, it is 1 for photosensitive elements -102, 103, 105-109.
/ 100 seconds It can be seen that the exposure sensitivity has increased.

When the emulsion of the present invention was applied to the green-sensitive emulsion layer and the blue-sensitive emulsion layer in the above-mentioned light-sensitive element, it was found that the same effects as those of the present Example in which the present invention was applied to the red-sensitive emulsion layer were exhibited. .

Example 2 First, a method for preparing a silver halide emulsion will be described. The following 60 types of silver halide emulsion grains (Emulsion-BH201 to Emulsion-BH208, Emulsion-BL201 to
Emulsion-BL208, Emulsion-GH201 to Emulsion-GH20
8. Emulsion-GL201 to Emulsion-GL208, Emulsion-RH
201-Emulsion-RH208, Emulsion-RL201-Emulsion-
RL208) was prepared.

Preparation of emulsion-H201 (octahedral internal latent image type direct positive emulsion-comparative example): potassium bromide 0.05M,
1.3 g of 3,6-dithia-1,8-octanediol,
A gelatin aqueous solution 1100 containing 0.13 mg of lead acetate and 70 g of deionized gelatin having a Ca content of 100 ppm or less
Controlling the 0.3M silver nitrate aqueous solution and the 0.3M potassium bromide aqueous solution into the ml while maintaining the temperature at 75 ° C, adjust the addition rate of the potassium bromide aqueous solution so that the pBr becomes 1.50 by the double jet method. Meanwhile, 86 ml of an aqueous silver nitrate solution was added over 3 minutes. After aging for a predetermined time, a 0.6 M silver nitrate aqueous solution and a 0.6 M potassium bromide aqueous solution were controlled by a control double jet method while adjusting the addition rate of the potassium bromide aqueous solution so that pBr became 1.40. , 630 ml of an aqueous silver nitrate solution was added over 45 minutes. Upon completion of the addition, octahedral silver bromide crystals (hereinafter referred to as core particles) having a uniform particle size with an average particle size (equivalent sphere diameter) of about 0.64 μm were produced.

Next, the core chemical sensitization was carried out under the following conditions. 1. Tank: A hemispherical bottom shape in which the metal surface is coated with Teflon (registered trademark) in a thickness of 120 μm with a fluororesin material FEP developed by Du Pont. 2. Stirrer: A seamless propeller type with a Teflon coated metal surface.

An aqueous solution of potassium bromide was added to the preparation solution of the core particle emulsion to adjust pBr to 1.15, and then sodium thiosulfate 9 mg and potassium tetrachloroaurate 90 mg and potassium bromide 1. 16 ml of an aqueous solution prepared by dissolving 2 g in 1000 ml of water was added, and the mixture was heated at 75 ° C. for 110 minutes for chemical sensitization. After 0.11 M potassium bromide was added to the emulsion solution chemically sensitized as described above, 1.0 M silver nitrate aqueous solution and 1.0 M silver nitrate solution were added while maintaining the temperature at 75 ° C. as in the core particle preparation. The aqueous potassium nitrate solution was added by a control double jet method while controlling the addition rate of the aqueous potassium bromide solution so that the pBr was 0.95, 440 ml of an aqueous silver nitrate solution was added over 40 minutes. This emulsion was washed with water by a conventional flocculation method, and the above-mentioned gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added to obtain a uniform particle size having an average particle size (equivalent sphere diameter) of about 0.8 μm. Further, octahedral silver bromide crystals (hereinafter referred to as internal latent image type core / shell grains) were obtained.

Emulsion-BH201, GH201, RH20
Preparation of 1 (octahedral internal latent image type direct positive emulsion-comparative example):
Next, to this internal latent image type core / shell emulsion, 150 mg of sodium thiosulfate and 40 mg of sodium tetraborate were added to 1000 parts of water.
7 ml of an aqueous solution dissolved in 8 ml of poly (N-
Vinylpyrrolidone) and heat aging at 75 ° C. for 100 minutes for shell chemical sensitization. At the end of the shell chemical sensitization, a sensitizing dye is added as shown in Table 10 to form an octahedral internal latent image type. Direct positive emulsion-BH201, GH20
1, RH201 was prepared.

Preparation of Emulsion-L201 (octahedral internal latent image type direct positive emulsion-comparative example): potassium bromide 0.07M,
1,8-Dihydrooxy-3,6-dithiaoctane 26
gelatin aqueous solution 11 mg containing 0.47 mg of lead acetate and 67 g of deionized gelatin having a Ca content of 100 ppm or less
Control the 0.6M silver nitrate aqueous solution and the 0.6M potassium bromide aqueous solution in 50 ml while maintaining the temperature at 75 ° C. Adjust the addition rate of the potassium bromide aqueous solution by the double jet method so that the pBr becomes 1.40. Meanwhile, 340 ml of an aqueous silver nitrate solution was added over 16 minutes. When the addition is completed, an octahedral silver bromide crystal having a uniform average particle size (sphere equivalent diameter) of about 0.32 μm (hereinafter referred to as core particle)
Was generated.

Next, the core chemical sensitization was carried out under the following conditions. 1. Tank: A hemispherical bottom shape with a metal surface coated with Teflon with a thickness of 120 μm using a fluororesin material FEP developed by Du Pont. 2. Stirrer: A seamless propeller type with a Teflon coated metal surface.

An aqueous solution prepared by dissolving 4.0 mg of sodium thiosulfate, 90 mg of potassium tetrachloroaurate and 1.2 g of potassium bromide in 1000 ml of water was added to the preparation liquid of the core particle emulsion.
Chemical sensitization was performed by adding ml and heating at 75 ° C. for 80 minutes. After chemical sensitization in this way,
As in the case of preparing the core particles, while maintaining the temperature at 75 ° C., a 1.0 M silver nitrate aqueous solution and a 1.0 M potassium bromide aqueous solution were used to obtain a pBr of 1.30 by a control double jet method.
790 ml of a silver nitrate aqueous solution was added over 64 minutes while controlling the addition rate of the potassium bromide aqueous solution so that This emulsion was washed with water by a conventional flocculation method, and the above gelatin and 2-phenoxyethanol, p were added.
-Methyl hydroxybenzoate was added to obtain octahedral silver bromide crystals (hereinafter referred to as internal latent image type core / shell grains) having an average grain size (sphere equivalent diameter) of about 0.55 μm and a uniform grain size. .

Emulsion-BL201, GL201, RL20
Preparation of 1 (octahedral internal latent image type direct positive emulsion-comparative example):
Next, 200 mg of sodium thiosulfate and 40 mg of sodium tetraborate were added to 1000 parts of water in the internal latent image type core / shell emulsion.
4.4 ml of an aqueous solution dissolved in ml was added, 54 mg of poly (N-vinylpyrrolidone) was further added, and the mixture was aged at 75 ° C. for 90 minutes. After completion of the heat aging, 0.007 M potassium bromide was added to complete the shell chemical sensitization.
After the completion of the shell chemical sensitization, a sensitizing dye was added as shown in Table 10 to form an octahedral internal latent image type direct positive emulsion-BL20.
1, GL201 and RL201 were prepared.

[0267]

[Table 10]

Next, Emulsion-BH201, GH201, RH
201, and emulsion-BL201, GL201, RL20.
Emulsion-BH201, GH except that the compound represented by the general formula (I) of the present invention was added by the specified addition method per 1 mol of silver nitrate in the preparation method of 1.
201, RH201, and Emulsion-BL201, GL20.
1. Emulsion-BH202-in exactly the same manner as RL201
BH208, Emulsion-GH202 to GH208, Emulsion-R
H202-RH208, and emulsion-BL202-BL2
08, emulsion-GL202 to GL208, emulsion-RL20
2 to RL208 were prepared.

[0269]

[Table 11]

Then, in the structure of the above-described photosensitive element-101, the seventh layer, the eighth layer, the thirteenth layer, the fourteenth layer, the nineteenth layer,
Photosensitive elements-201 to 208 were prepared by changing the emulsion of the 20th layer as shown in Table 12 below, and exposure, development and density measurement were carried out to evaluate photographic performance.

[0271]

[Table 12]

After exposing the light-sensitive elements 201 to 208 from the emulsion layer side through a continuous gray wedge, they are superposed with the cover sheet, and the alkali treatment composition is put between both materials so as to have a thickness of 51 μm. Deployed using. The exposure is performed under two conditions of 1/100 second exposure and 10 second exposure by adjusting the exposure illuminance so that the exposure amount is constant, and the sensitivity and the low illuminance exposure during high illuminance exposure (1/100 second exposure) Two points of sensitivity at (10 second exposure) were evaluated. The treatment is carried out at 25 ° C., and the dye density transferred after 2 hours is measured by a color densitometer (automatic densitometer X-Rite
310TR, trade name, manufactured by X-Rite), and the maximum density and midpoint sensitivity of each color of yellow, magenta, and cyan were measured. The midpoint sensitivity was determined as follows. That is, the characteristic curve is drawn by displaying the logarithm of the exposure amount on the horizontal axis and each color density on the vertical axis. The midpoint sensitivity is defined as the sensitivity that gives an intermediate density between the highest density and the lowest density. Sample 201
The sensitivity was defined as 100, and the relative value (exact value) was used.
The results are summarized in Table 13.

[0273]

[Table 13]

As is apparent from Table 13, Emulsion-BH202 to Emulsion-BH208 and Emulsion-BL202 of the present invention.
Emulsion-BL208, Emulsion-GH202 to Emulsion-GH20
8, Emulsion-GL202 to Emulsion-GL208, Emulsion-RH
202-Emulsion-RH208, Emulsion-RL202-Emulsion-
Photosensitive elements made using RL208-202-20
In No. 8, no increase in the maximum density and no decrease in the exposure sensitivity for 1/100 second were observed, and an increase in the dew sensitivity for 10 seconds was observed. rather,
Light-sensitive element containing a large amount of this compound-202, 203, 2
It is understood that in 06 to 208, not only the reciprocity law failure in low illuminance is improved, but also the exposure sensitivity for 1/100 second is increased.

The above emulsion (Japanese Patent Application No. 2001-14402) was used.
When the peeling type color diffusion transfer light-sensitive material described in 4) was summarized and the effect was confirmed, it was found that the same effect as this example was exhibited.

[0276]

INDUSTRIAL APPLICABILITY The internal latent image type direct positive silver halide emulsion of the present invention has an excellent effect that it has a high S / N ratio, high illuminance sensitivity does not decrease, and low illuminance reciprocity law failure is small. Play. Therefore, the color diffusion transfer light-sensitive material of the present invention using this internal latent image type direct positive silver halide emulsion does not lower the maximum density of the obtained image, and does not lower the high illuminance sensitivity and the low illuminance. Reciprocity failure is small. Therefore, the excellent effect of forming a sufficiently high-quality image is obtained even when shooting under indoor lighting.

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Claims (4)

[Claims] 1. An internal latent image type direct positive silver halide emulsion having a core / shell structure consisting of a chemically sensitized core and a chemically sensitized shell, wherein the silver halide is not previously fogged. An internal latent image type direct positive silver halide emulsion characterized in that the emulsion contains a compound represented by the following general formula (I). In the general formula (I) (X) _k- (L) _m- (AB) _n , X is halogenated having at least one atom selected from the group consisting of N, S, P, Se and Te. Represents a silver adsorption group or a light absorption group. L is C, N, S and O
Represents a divalent linking group having at least one atom selected from the group consisting of: A represents an electron donating group, B represents a leaving group or a hydrogen atom, after oxidation, are desorbed or deprotonated to generate a radical A ^·. k and m each independently represent an integer of 0 to 3, and n represents 1 or 2. 2. The silver halide emulsion according to claim 1 has an aspect ratio (diameter equivalent to circle of silver halide grain / grain thickness).
Internals characterized by containing tabular silver halide grains of 5 or more and 100 or less in an amount of 50% or more of the projected area of all silver halide grains and having an average grain diameter of 0.3 µm or more. Latent image type direct positive silver halide emulsion. 3. The internal latent image type direct positive silver halide emulsion according to claim 1 or 2, wherein the silver halide at the end of grain formation before the desalting step is silver bromide. 4. The internal latent image type image forming apparatus according to claim 1, which has at least one photosensitive silver halide emulsion layer unit on a support, and at least one emulsion layer unit in the emulsion layer. A color diffusion transfer light-sensitive material containing a direct positive silver halide emulsion.