JP2529881B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which has excellent photographic properties and storage stability and can be processed quickly. .

2. Description of the Related Art In a silver halide color photographic light-sensitive material, it is already known to release a development accelerator or a fogging agent from a certain type of coupler during color development processing. JPA
No. 57-150845, Japanese Patent Application No. 57-161515 and JP-A No. 59-1708
No. 40 discloses a coupler which releases a fogging agent by a reaction with an oxidized product of a color developing agent. By releasing the fogging agent imagewise, a contrast enhancement effect and a development accelerating effect are claimed. Also disclosed in JP-A-60-1007029 is a compound which releases an imagewise fogging agent by a redox reaction with an oxidized developer by black-and-white development using a black-and-white developing agent such as hydroquinone, metol, 3-pyrazolidone and the like. It has a high sensitivity of the negative emulsion.
It is described that it is effective for high contrast. However, the effect was not yet sufficient.

On the other hand, in the direct positive image formation using the light fogging method or the chemical fogging method, the developing speed is slower and the processing time is longer than that in the case of a normal negative type. A method of increasing the temperature to shorten the processing time has been used. However, there is generally a problem that the minimum image density (Dmin) of the direct positive image obtained when the pH is high is increased. Further, under high pH conditions, there is a problem that the developing agent is easily deteriorated by air oxidation, and as a result, the developing activity is remarkably reduced.

As a means for increasing the development speed of direct positive image formation, another method using a hydroquinone derivative (US Pat. No. 3,22
7,552), and those using a mercapto compound having a carboxylic acid group or a sulfonic acid group (JP-A No. 50-170843) are known, but the effect of using these compounds is small and effective. No technique has been found for increasing the image density (Dmax). In particular, there is a demand for a technique capable of obtaining a sufficient maximum image density even when processed with a developer having a low pH.

Further, in order to increase the maximum density of the obtained direct positive image, especially in the core / shell type silver halide emulsion, surface chemical sensitization treatment is carried out, but the minimum density increase caused by excessive chemical sensitization or In order to avoid problems such as reduction of sensitivity and generation of images due to high exposure amount area, surface chemical sensitization usually has to be stopped at an appropriate point, and surface chemical sensitization nuclei formed at that time are usually It was weaker than that of the negative type, and there was a problem in its stability over time.

(Problems to be Solved by the Invention) 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-, which has been well known in the past for improving such drawbacks. A method of adding a stabilizer such as mercaptotetrazole has been studied, but in order to prevent the performance change with time, a large amount of addition is required, so that it is possible to avoid adversely affecting the obtained photographic performance. There wasn't. Specifically, this is a decrease in the maximum density of the positive image due to the action of the development inhibitor, an increase in re-reversal sensitivity, and a decrease in spectral sensitivity.

Further, it has been attempted to add a hydroquinone derivative in order to suppress the maximum of the minimum image density (Japanese Patent Laid-Open No. 63-80250), but the effect is not sufficient, and when it is applied to a negative type photosensitive material. However, a sufficient high-sensitivity contrast cannot be obtained, and it has been desired to solve these problems.

Therefore, the first object of the present invention is to provide a silver halide photographic light-sensitive material which gives an image having a high-sensitivity highlight area and a high contrast.

Secondly, to provide a silver halide photographic light-sensitive material exhibiting stable performance even when stored under high temperature and high humidity.

Thirdly, it is to provide a silver halide photographic light-sensitive material which can be rapidly processed.

(Means for Solving the Problems) The objects of the present invention are to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and an auxiliary layer on a support, and the following general formula (II) And at least one compound releasing a nucleating agent, a nucleation accelerator, or a precursor thereof during development, and an internal latent image type silver halide emulsion. It has been achieved by the characteristic direct positive type silver halide photographic light-sensitive material.

(II) In the general formula (II), R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 8 or less carbon atoms, an alkoxy group, an alkylthio group or an amide group, and R ⁵ represents a hydrogen atom or an alkyl group having 11 or less carbon atoms. . The total carbon number of R ³ , R ⁴ and R ⁵ is 8 or more 22
It is the following.

The compound represented by the general formula (II) will be described below.

In the general formula (II), R ³ and R ⁴ are hydrogen atoms or alkyl groups having 8 or less carbon atoms (for example, methyl, ethyl, t-butyl,
sec-hexyl, t-octyl), alkoxy group (eg methoxy, ethoxy, butoxy, 2-ethylhexyloxy), alkylthio group (eg methylthio, butylthio, octylthio), amide group (eg acetylamino, butanoylamino, 2- R ⁵ represents a hydrogen atom or an alkyl group having 11 or less carbon atoms (eg, methyl, n-propyl, iso-propyl, heptyl, undecyl, 1-ethylpentyl, etc.)
Represents The total carbon number of R ³ , R ⁴ and R ⁵ is 8 or more and 22 or less.

Preferred as R ³ and R ⁴ is an alkyl group having 6 or less carbon atoms.

R ⁵ is preferably an alkyl group having 7 or less carbon atoms.

In the general formula (II), the total number of carbon atoms of R ³ , R ⁴ and R ⁵ is 8
It is preferably in the range of 17 or more and 17 or less.

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

The synthesis of the compound of the general formula (II) is described in JP-A-52-146235.
It can be carried out according to the methods described in JP-B No. 56-21,145, JP-B No. 59-37497 and the like.

The compound of general formula (II) may be added to either the emulsion layer or the intermediate layer, but is preferably added to the emulsion layer.

1 × 10 ⁻² to 1 × 10 ⁻⁹ mol can be added per 1 m ² , preferably 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁷ mol,
More preferably, it is 1 × 10 ^-5 mol to 1 × 10 ^-7 mol.

The nucleating agent or development accelerator (hereinafter, referred to as “FA”) used in the present invention, or a compound that releases a precursor thereof (hereinafter, referred to as “FR” compound), may be combined with an oxidized developer during development. A substance that releases the FA or a precursor thereof by a coupling reaction or an oxidation-reduction reaction.

The FR compounds that can be used in the present invention include the following.

(I) A coupler that couples with an oxidation product of an aromatic primary amine developing agent to release FA or a precursor thereof.

(Ii) A coupler which is coupled with an oxidation product of an aromatic primary amine developing agent to give a diffusible coupling product, and the coupling product functions as FA or a precursor thereof.

(Iii) A redox compound that releases FA or its precursor by a redox reaction with an oxidation product of an aromatic primary amine developing agent or a subsequent reaction of the reaction.

The above compounds (i), (ii) and (iii) are represented by the following general formulas [1], [2] and [3], respectively.

[1] Cp- (TIME) _n -FA [2] BALL-Cp- (TIME) _n -FA [3] RED- (TIME) _n -FA In the above formula, Cp is an aromatic primary amine development. Represents a coupler residue capable of undergoing a coupling reaction with an oxidized form of a drug, BA
LL represents a diffusion resistant group that can be separated from Cp by a coupling reaction with an oxidized product of an aromatic primary amine developing agent,
RED represents a compound residue capable of undergoing a redox reaction with an oxidized product of an aromatic primary amine developing agent.

TIME is represented by a timing group that further releases FA after leaving Cp or RED by a coupling reaction.

n represents 0 or 1, FA is a group capable of leaving from Cp or RED by a coupling reaction when n is 0, and FA can be released from TIME when n is 1 (in the above formula, In the case of the compound represented by [2], FA does not have to leave Cp or TIME after the coupling reaction).

Here, FA represents a so-called fogging agent or development accelerator which acts on silver halide grains during development to generate fog nuclei capable of starting development. Examples of FA include groups that act on silver halide grains during development to produce fog nuclei or act on silver halide grains to produce silver sulfide nuclei, which are fog nuclei capable of initiating development. be able to.

A group preferable as FA is a group containing a group having adsorptivity to silver halide grains, and can be represented as follows.

AD- (L) _m -X AD represents a group having adsorptivity to silver halide, L represents a divalent group, and m represents 0 or 1.
X represents a reducing group or a group capable of acting on silver halide to form silver sulfide. However, when X is the latter, it may also have the function of AD, and in this case, AD- (L) _m -X is not always necessary.

When FA is a group represented by AD- (L) _m -X, TIME,
The position of binding to Cp or RED may be any position of AD- (L) _m -X.

In the general formula [1], it is bonded to the Cp coupling position of-(TIME) _n -FA, and the bond is cleaved during the coupling reaction.

In the general formula [2], BALL is bonded to the coupling position of Cp, and the bond is cleaved during the coupling reaction. Moreover, since-(TIME) _n -FA is bound to the non-coupling position of Cp, the bond is not immediately cleaved by the coupling.

In the general formula [3],-(TIME) _n -FA is bonded to a position where RED can be released from RED by a redox reaction with an oxidized aromatic primary amine developer or a subsequent reaction thereof.

On the other hand, in the case of the general formula [1], the group represented by TIME is
It may be a trivalent group. That is, one of the trivalent bonds binds to FA, one of the remaining two bonds to the coupling position of Cp, and the bond with TIME is cut off, but it binds to the non-coupling site. The bond with TIME is not cleaved, and the cleaved bond portion (anion) of TIME cleaves the bond with FA due to electron transfer and / or intramolecular nucleophilic substitution reaction of TIME. Can be released. Therefore, in the case of such a compound, not only a trivalent group but also an intramolecular electron transfer and / or
Alternatively, it is necessary to have a structure capable of releasing FA by an intramolecular nucleophilic substitution reaction.

Hereinafter, for general formulas [1], [2] and [3],
This will be described in more detail.

In the general formula [1], the coupler residue represented by Cp has a partial structure of a non-colored coupler and a black-colored coupler in addition to the yellow, magenta and cyan couplers described below.

Representative examples of yellow couplers among the couplers here are U.S. Pat.Nos. 2,875,057, 2,407,210, and 3,265,
No. 506, No. 2,298,443, No. 3,048,194, No. 3,447,928
No. 4,149,886, British Patent 1,204,680, Japanese Patent Laid-Open No. 52-
It is described in No. 154631. Among these yellow couplers, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferable.

Therefore, as the yellow coupler residue (Cp), those represented by the following general formulas [Ia] to [IIIa] are preferable.

In addition, * represents the bonding position of the M'group or TIME group (hereinafter the same applies to the general formula [XIXa]).

Here, R ₁ represents a diffusion resistant group having a total carbon number of 8 to 32,
R ₂ represents a hydrogen atom, one or more halogen atoms, a lower alkyl group, a lower alkoxy group or a nondiffusible group having 8 to 32 total carbon atoms. When R ₂ is 2 or more, they may be the same or different.

R ₃ has the same meaning as R _1, and R ₄ has the same meaning as R ₂ .

A representative example of a magenta coupler is U.S. Pat.
788, 2,369,489, 2,343,703, 2,311,082
No. 3,152,896, No. 3,519,429, No. 3,062,653,
2,908,573, 3,558,319, Japanese Patent Publication No. 47-27411,
JP-A-59-171956, 59-162548, 60-33552
No. 60-43659, No. 60-172982 and the like. Among those magenta couplers, pyrazolone or pyrazoloazoles (pyrazolopyrazole,
Pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole and the like) are preferable.

Therefore, as a magenta coupler residue (Cp),
Those represented by the following general formulas [IVa] to [VIIa] are preferable.

Here, R ₂ represents a diffusion resistant group having a total carbon number of 8 to 32,
R _'2 represents one or more halogen atoms, lower alkyl group, a lower alkoxy group, a phenyl group or substituted phenyl group. Z represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring).

Representative examples of cyan couplers are described in U.S. Pat.
No. 2,895,826, No. 3,002,836, No. 3,034,892,
2,474,293, 2,423,730, 2,367,531, and 3,041,236, JP-A-56-99341, and JP-A-57-155538
Nos. 57-204545, 58-189154 and 59-3195
No. 3, No. 58-118643, No. 58-187928, No. 58-213748
No. 61-167952, U.S. Pat.Nos. 4,333,999, 4,690,8
No. 89 etc. Of those cyan couplers, phenols or naphthols are preferable.

Therefore, as the cyan coupler residue (Cp), those represented by the following general formulas [VIIIa] to [XIIIa] are preferable.

Here, R ₁ represents a diffusion resistant group having a total carbon number of 8 to 32,
R ″ ₂ represents one or more halogen atoms, a lower alkyl group or a lower alkoxy group, and when R ″ ₂ is 2 or more, they may be the same or different.

R _'3 is a monovalent radical, preferably an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, an alkoxycarbonyl group.

Q is a group necessary for forming a 5- to 7-membered ring, and is preferably a substituted or unsubstituted methylene group, dimethylene group, imino group or ether group.

 Further, Cp may be a so-called colorless coupler.

Representative examples of colorless couplers are described in U.S. Pat.
No. 4,204,867 and JP-A-52-152721.

Representative examples of these non-color-forming coupler residues have a skeleton represented by the following general formulas [XIVa] to [XVIa].

Here, R ₁ represents a diffusion resistant group having a total carbon number of 8 to 32,
R ″ ₂ represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group.

Here, R ₁ represents a diffusion resistant group having a total carbon number of 8 to 32,
V represents an oxygen atom, a sulfur atom or a nitrogen atom.

Here, R ″ ₃ and R ′ ₄ are independently bonded at an alkoxycarbonyl group, an aminocarbonyl group, an acyl group, a sulfonic acid or sulfinic acid derivative corresponding to the above, a cyano group, an ammonium mil group, and an N-position. Represents a nitrogen-containing heterocycle, etc. R ″ ₃ and R ′ ₄ may combine to form a 5- or 6-membered ring.

In addition to the above, Cp may be a coupler residue that develops a black color by reacting with an oxidized product of a developing agent. Examples of those couplers include U.S. Patents 1,939,231 and 2,18.
1,944, 2,333,106, 4,126,461, West German patent (O
LS) 2,644,194 and 2,650,764.
Specifically, those coupler residues are represented by the following general formulas [XVIIa] to [XIXa].

Here, R ₅ is an alkyl group having 3 to 20 carbon atoms, or a phenyl group (the phenyl group may be substituted with a hydrogen group, a halogen atom, an amino group, an alkyl group having 1 to 20 carbon atoms or an alkoxy group). ) Is represented. R _6's each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ₇ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or another monovalent organic group, and when R ₇ is 2 or more, they may be different from each other.

Cp represented by the above general formulas [Ia] to [XIXa] may be a dimer or higher multimer at a portion other than the coupling site, or may be bonded to a polymer at that portion. Good.

In the general formula [2], the coupler residue represented by Cp has the partial structure represented by the above general formulas [Ia] to [XIXa], BALL is bound to the * mark, and it is one of the other sites. -(TIME) _m -M 'is bound to.

In the general formula [2], the nondiffusible group represented by BALL may have a size and shape that give the coupler nondiffusibility, and may be a polymer having a plurality of leaving groups linked to each other, In addition, an alkyl group that imparts non-diffusibility and /
Alternatively, it may have an aryl group. In the latter case, the total number of carbon atoms of the alkyl group and / or the aryl group is preferably about 8 to 32. BALL has a group for bonding to the coupling position of Cp, and typical examples thereof include -O-, -S-, -N = N-, And -N <which constitutes a heterocycle.

In the general formula [3], the group represented by RED has a skeleton of hydroquinone, catechol, o-aminophenol or p-aminophenol, and undergoes a redox reaction with an oxidant of the developing agent, followed by alkaline hydrolysis. -(T
IME) _m -M 'group (in the following general formulas [XXa] to [XXVa], represents a group which releases this (abbreviated as "FR")).

 Specific examples thereof are shown in general formulas [XXa] to [XXVa].

In the above formula, R ₈ is a hydrogen atom, a halogen atom,
Alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, cyano group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carboxyl group, sulfo group, sulfonyl group, acyl group, carbonamide group, sulfonamide It represents a group, a hydroxy group, an acyloxy group or a heterocyclic group, and when two or more R ₈ are present, they may be the same or different. Also, 2
R _{8 s} may form a ring.

 T₁Is -OT during development processing₁The bond is broken and -O To
A group that releases, for example, an acyl group or an alkoxycarbo group.
Nyl group, aryloxycarbonyl group, carbamoyl group,
2-cyanoethyl group, 2-methanesulfonylethyl group, etc.
Can be given.

R ⁹ represents an acyl group or a sulfonyl group.

U.S. Pat. No. 4,24 is used as the camming group represented by TIME.
No. 8,962, JP-A-57-56837, etc., which are separated from Cp or RED by a coupling reaction or an oxidation-reduction reaction and then release FA by an intramolecular substitution reaction, UK Patent 2,072,363A, No.57-154234, No.57-188035
Nos. 56-114946, 57-56837, 58-209736
No. 58-209737, 58-209738, 58-209740
No. 58-98728, etc., which release FA by electron transfer through a conjugated system, and a cup with an oxidized aromatic primary amine developer as disclosed in JP-A-57-111536. Examples thereof include those which are coupling components capable of releasing FA by a ring reaction. These reactions may take place in one stage or in multiple stages.

Further, as described above, a trivalent TIME binding to a coupling site, a non-coupling site, and FA is also preferable (an example in which a yellow coupler is incorporated is disclosed in
-209740).

When FA is a group containing AD- (L) _m -X, AD may be directly bonded to the carbon atom at the coupling position, or L at X
However, if it can be removed by the coupling reaction, it may be bonded to the coupling carbon. What is known as a so-called 2-equivalent leaving group may be interposed between the coupling carbon and AD. These 2-equivalent leaving groups include an alkoxy group (eg methoxy), an aryloxy group (eg phenoxy), an alkylthio group (eg ethylthio), an arylthio group (eg phenylthio), a heterocyclic oxy group (eg tetrazolyloxy), Heterocyclic thio groups (eg pyridylthio), heterocyclic groups (eg hydantoinyl, pyrazolyl, triazolyl, benzotriazolyl). In addition, FA described in British Patent Publication No. 2,011,391 can be used.

As a group capable of adsorbing to silver halide represented by AD, a nitrogen-containing heterocycle having a dissociable hydrogen atom (pyrrole, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole,
Benzotriazole, uracil, tetraazaindene,
(Imidazotetrazole, pyrazolotriazole, pentaazaindene, etc.), heterocycle having at least one nitrogen atom and other heteroatoms (oxygen atom, sulfur atom, selenium atom, etc.) in the ring (oxazole, thiazole, thiazoline, thiazolidine) , Thiazoazole, benzothiazole, benzoxazole, benzselenazole, etc.),
Heterocycle having a mercapto group (2-mercaptobenzthiazole, 2-mercaptopyrimidine, 2-mercaptobenzoxazole, 1-phenyl-5-mercaptotetrazole, etc.), quaternary salt (tertiary amine, pyridine, quinoline, benzthiazole, Quaternary salts such as benzimidazole and benzoxazole), thiophenols, alkylthiols (such as cysteine), (Eg, thiourea, dithiocarbamate, thioamide, rhodanine, thiazolidinethione, thiohydantoin, thiobarbituric acid, etc.).

Examples of the divalent linking group represented by L in FA include alkylene, alkenylene, phenylene, naphthylene, -O-,
-S -, - SO -, - SO 2 -, - N = N-, carbonyl,
It is composed of one selected from amides, thioamides, sulfonamides, ureidos, thioureidos, heterocycles, phosphoric acid amides, phosphoric acid esters and the like.

If one of the divalent linking groups constituting L is appropriately selected from groups capable of being cleaved by the action of a component (eg, hydroxide ion, hydroxylamine, sulfite ion, etc.) in the developer, the fogging action can be adjusted. And can be deactivated.

Examples of the group represented by X include reducing compounds (hydrazine, hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-phenylenediamine, 1-phenyl-3-pyrazolidinone, enamine, aldehyde, polyamine, acetylene, aminoborane, 4 such as tetrazolium salt and ethylenebispyridinium salt
Primary salt such as carbazic acid) or a compound capable of forming silver sulfide during development (eg, thiourea, thioamide, dithiocarbamate, rhodanine, thiohydantoin, thiazolidinethione). And the like having a partial structure of Among the groups represented by X, those which are present in the groups capable of forming silver sulfide during development have themselves an adsorptivity for silver halide grains, and can also serve as an adsorptive group AD.

Further, particularly preferred FA is represented by the following general formula [XXV
I] and [XXVII].

General formula (XXIIa) General formula (XXIIIa) In the formula, R ₇₁ represents an acyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or a sulfamoyl group, and R ₇₂ represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, an alkylsulfonyl group. Represents an arylsulfonyl group or an aryloxycarbonyl group,
R ₇₃ represents a halogen atom, an alkoxy group, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a carbonamide group, a phosphoramide group or a sulfonamide group. m represents an integer of 0 to 4, and when m is 2 or more, R _{73 s} may be the same or different, and two or more R ₇₃ may form a fused ring. L has the same meaning as previously described, ie 2
Represents a valent linking group, and n represents 0 or 1. Z ₁ represents a non-metallic atomic group necessary for forming a monocyclic or condensed-ring heterocyclic ring, and Z ₂ represents a non-metallic atomic group necessary for forming a monocyclic or condensed-ring heterocyclic ring formed together with N. Express.

Examples of substituents are described in more detail below. R ₇₁ is an acyl group (formyl, acetyl, propionyl, trifluoroacetyl, pyruvoyl, 2-hydroxymethylbenzoyl group, 2-methylsulfonylbenzoyl group, etc.), carbamoyl group (dimethylcarbamoyl, etc.), alkylsulfonyl group (methanesulfonyl group, etc. Group), an arylsulfonyl group (benzenesulfonyl etc.), an alkoxycarbonyl group (methoxycarbonyl etc.), an aryloxycarbonyl group (phenoxycarbonyl etc.) or a sulfamoyl group (methylsulfamoyl etc.), a hydrogen atom as R ₇₂ , Acyl group (trifluoroacetyl, etc.),
An alkoxycarbonyl group (methoxycarbonyl, etc.), an alkylsulfonyl group (methanesulfonyl, etc.), an arylsulfonyl group (benzenesulfonyl, toluenesulfonyl, etc.) or an aryloxycarbonyl group (phenoxycarbonyl, etc.) is used as R ₇₃ , a halogen atom (fluorine, Chlorine, etc.), alkoxy groups (methoxy, methoxyethoxy, etc.), alkyl groups (methyl, hydroxymethyl, etc.), alkenyl groups (allyl, etc.), aryl groups (phenyl, etc.), aryloxy groups (phenoxy, etc.), alkylthio groups (methylthio, etc.). Etc.), arylthio groups (phenylthio etc.), carbonamide groups (acetamide etc.) or sulfonamide groups (methanesulfonamide etc.).

Examples of the FR compound used in the present invention are described in JP-A-57-150845.
No. 59-50439, 59-157638, 59-170840
And Nos. 60-37556, 60-147029 and 60-128446.

 Specific examples of the compound used in the present invention are shown below.

The amount of the FR compound used in the present invention is 10 ^-9 to 10 ^-1 mol, preferably 10 ^-1 mol, per mol of silver of silver halide contained in the layer containing the FR compound or in the layer adjacent thereto.
10 ^-5 to 10 ^-1 mol.

In the present invention, a known method, for example, a method described in U.S. Pat. No. 2,322,027 is used to introduce the FR compound into the silver halide emulsion layer.

Further, the dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

When the FR compound has an acid group such as carboxylic acid and sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention,
Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used.

Silver halide grains in photographic emulsions are cubic, octahedral,
So-called regular particles having regular crystals such as tetradecahedron may be used, or may have irregular crystal forms such as spheres, crystal defects such as twin planes, or composite forms thereof. May be. Also, a mixture of particles having various crystal forms may be used.

The silver halide grains may be fine grains having a grain size of about 0.1 μm or less or large grains having a projected area diameter of about 10 μm, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. An emulsion may be used.

The silver halide photographic emulsion usable in the present invention can be produced by a known method, for example, Research Disclosure, Vol. 176, No. 17643 (December, 1978), pp. 22-23, "1.
Emulsion preparation and types "and ibid, Vol. 187, No. 18716 (November, 1979), p.648.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Ch.
emie et Physique Photographique Paul Montel, 196
7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry
(Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman'e).
t, al, Making and Coating Photographic Emulsion, Foca
l Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and as a method of reacting a soluble silver salt with a soluble silver halide, a one-sided mixing method, a simultaneous mixing method,
Any combination of them may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. A method of maintaining a constant pAg in a liquid phase in which silver halide is formed as a kind of the double jet method,
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.

Known silver halide solvents (eg, ammonia,
Rodankari or U.S. Pat.No. 3,271,157, JP-A-51-1
Physical ripening in the presence of thioethers and thione compounds described in JP-A-2360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717 or JP-A-54-155828. Can also be performed. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size distribution can be obtained.

The silver halide emulsion comprising the regular grains,
It can be obtained by controlling pAg and pH during particle formation.
For more information, see, for example, Photographic Science and Eng
ineering), Vol. 6, pp. 159-165 (1962);
Of Photographic Science (Journal Photog
Raphic Science), 12: 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

Typical monodisperse emulsions that can be used in the present invention are silver halide grains having an average grain size of more than about 0.05 μm and at least 95% by weight of which are within ± 40% of the average grain size. It is. Further, the average particle size is 0.15 to 2 μm
An emulsion may be used in which at least 95% by weight or at least 95% (by number of grains) of silver halide grains are within the range of average grain size ± 20%. Methods for preparing such emulsions are described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748. Also JP 4
Nos. 8-8600, 51-39027, 51-83097, 53-137
No. 133, No. 54-48521, No. 54-99419, No. 58-37635
Monodispersed emulsions can also be preferably used as described in JP-A No. 58-49938 and the like.

Tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described by Gaft, Gutoff, Photographic Science and Engineering,
Volume 14, Pages 248-257 (1970): U.S. Pat. No. 4,434,226
No. 4,414,310, 4,433,048, 4,439,520, and British Patent No. 2,112,157. When tabular grains are used,
There are advantages such as improved covering power and improved color sensitization efficiency by a sensitizing dye.
It is described in detail in No. 4,434,226.

It is also possible to use grains in which the crystal form is controlled by using certain additives for the sensitizing dye in the grain forming process.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146.
U.S. Pat. Nos. 3,505,068, 4,444,877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. These emulsion grains are described in U.S. Patent Nos. 4,094,684 and 4,142,900.
No. 4,459,353, British Patent No. 2,038,792, U.S. Patent Nos. 4,349,622, 4,395,478, 4,433,501, 4,4.
63,087, 3,656,962, 3,852,067, JP-A-59-
No. 162540 is disclosed.

Furthermore, the surface of the crystal is chemically ripened to form photosensitive nuclei (Ag ₂ S, Agn, A
It is also possible to use those having a so-called internal latent image type grain structure in which silver halide is further grown around after forming (u etc.).

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be present together.

In the present invention, it is preferable to use an internal latent image type emulsion which has not been fogged in advance, and to fog it by light before or during processing, or to fog it using a nucleating agent to obtain a direct positive image.

The pre-fogged internal latent image type silver halide emulsion used in the present invention is an emulsion in which the surface of silver halide grains is not pre-fogged and which contains silver halide mainly forming a latent image inside the grains. However, more specifically, a certain amount of a silver halide emulsion is coated on a transparent support,
When a sample exposed to light for a fixed time of 0.01 to 10 seconds was developed in the following developer A (internal type developer) at 20 ° C. for 6 minutes, the maximum density measured by a usual photographic density measuring method was used. However, it is preferable that the similarly exposed sample has a concentration which is at least 5 times larger than the maximum concentration obtained when the sample is developed in the following developer B (surface type developer) at 18 ° C. for 5 minutes, and more preferably at least It has a 10 times greater concentration.

Internal developer A Metol 2g sodium sulfite (anhydrous) 90 g Hydroquinone 8g sodium carbonate (monohydrate) 52.5 g KBr 5 g KI 0.5 g Water to make 1 surface developer B Metol 2.5 g l-ascorbic acid 10g NaBO ₂ · 4H ₂ O 35g KBr 1g Add water 1 As a specific example of the above-mentioned internal latent image type emulsion, British Patent No. 10
11062, U.S. Pat.Nos. 2,592,250, and 2,456,94
Examples of the core / shell type silver halide emulsion include a conversion type silver halide emulsion and a core / shell type silver halide emulsion described in JP-A No. 47-32813. No. 47-32814, No. 52-134721, No. 52
-156614, 53-60222, 53-66218, 53-66
Nos. 727, 55-127549, 57-136641, 58-70221
No. 59-208540, No. 59-216136, No. 60-107641
No. 60, No. 60-247237, No. 61-2148, No. 61-3137, Japanese Patent Publication No. 56-18939, No. 58-1412, No. 58-1415, No. 58.
-6935, 58-108528, Japanese Patent Application No. 61-36424, U.S. Pat.Nos. 3,206,313, 3,317,322, 3761266, and 3761276.
No. 3850637, No. 3923513, No. 4035185, No. 43954
Emulsions described in No. 78, No. 4504570, European Patent 0017148, Research Disclosure No. 16345 (November 1977) and the like can be mentioned.

In order to remove the soluble silver salt from the emulsion before and after physical ripening, Nudel water washing, flocculation sedimentation method or ultrafiltration method can be used.

The emulsion used in the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are described in Research Disclosure No. 17643 (December 1978) and No. 18716 described above.
(November 1979), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosure Magazines,
The points described in the table below are shown.

In the present invention, various color couplers can be used to form a color image. A color coupler is a compound that forms a coupling or reactant with an oxidized form of an aromatic primary amine color developing agent to form or release a substantially non-diffusible dye. Preferably, it is a compound. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are described in "Research Disclosure" magazine.
No.17643 (issued in December 1978) p25, section VII-D, same No.187
17 (issued in November 1979) and Japanese Patent Application No. 61-32462 and the patents cited therein.

Card couplers, couplers in which the coloring dye has an appropriate diffusivity, achromatic couplers, and DIR couplers that release the development inhibitor along with the coupling reaction, in order to correct unnecessary absorption in the short wavelength region of the dye that is produced. Polymerized couplers can also be used.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

Color fog inhibitors or color mixture inhibitors can be used in the light-sensitive material of the present invention.

Representative examples thereof are described in JP-A-62-215272, pages 185 to 193.

In the present invention, a color-enhancing agent can be used for the purpose of improving the color-forming property of the coupler. Representative examples of compounds are disclosed in
62-215272, pp. 121-125.

The light-sensitive material of the present invention includes dyes, ultraviolet absorbers, plasticizers, fluorescent brighteners, matting agents, antifoggants, coating aids, hardeners that prevent irradiation and halation.
An antistatic agent, a slipperiness improving agent, etc. can be added.
Typical examples of these additives are Research Disclosure No. 17643, pages VIII to XIII (published in December 1978), p25 to 2
7 and 18716 (issued in November 1979) p647-651.

The present invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support.
The order of these layers can be arbitrarily selected as required. The preferred layer sequence is red-sensitive, green-sensitive, blue-sensitive from the support side or green-sensitive, red-sensitive and blue-sensitive from the support side.
Further, each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. . Usually, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer, but different combinations can be used depending on circumstances.

The light-sensitive material according to the present invention has an auxiliary layer, but in addition to the silver halide emulsion layer, an auxiliary layer such as a protective layer, an intermediate layer, a filter layer, an antihalation agent, a back layer and a white reflective layer may be appropriately provided. preferable.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are described in Research Disclosure No. 17643XVII (19).
Issued in December 1978) Those described in p28 and European patents 0,10
It is coated on a support described in JP-A No. 2,253 and JP-A No. 61-97655. Also, Research Disclosure No. 17643XV
The application method described on pages 28 to 29 can be used.

The present invention can be applied to various color light-sensitive materials.

It can also be applied to full-color copiers and color hard copies for storing CRT images. The present invention is also No. 1 in "Research Disclosure" magazine.
It can also be applied to a black-and-white light-sensitive material using a three-color coupler mixture described in 7123 (issued in July 1978).

 Furthermore, the present invention can be applied to black and white photographic light-sensitive materials.

Black and white (B / W) photographic light-sensitive materials to which the present invention can be applied include B / W direct positive photographic light-sensitive materials described in JP-A-59-208540 and JP-A-60-260039 (for example, for X ray). Sensitive materials, duplicating sensitive materials, micro sensitive materials, photographic sensitive materials, printing sensitive materials) and the like.

The fogging treatment of the present invention is performed by the following “light fogging method” and / or “chemical fogging method”. The entire surface exposure, that is, the fog exposure in the "light fog method" of the present invention is performed after the imagewise exposure and during the developing treatment and / or the developing treatment.
The image-exposed light-sensitive material is immersed in a developing solution or a pre-bath of the developing solution, or is exposed before being taken out of these solutions and dried, but is most preferably exposed in the developing solution.

As a light source for fogging exposure, a light source having a light-sensitive wavelength of a light-sensitive material may be used, and generally, a fluorescent lamp, a tungsten lamp, a xenon lamp, sunlight or the like can be used.
These specific methods are described in, for example, British Patent 1,151,363.
No. 45, No. 45-12710, No. 45-12709, No. 58-6936
No., JP-A-48-9727, JP-A-56-137350, JP-A-57-129438
Nos. 58-62652, 58-60739, 58-70223 (corresponding U.S. Pat. No. 4,440,851), and 58-120248 (corresponding European Patent 89101A2). For a light-sensitive material having photosensitivity in all wavelength ranges, for example, a color light-sensitive material is preferably a light source having a high color rendering property (as close as possible to white) as described in JP-A-56-137350 and JP-A-58-70223. Light illuminance is 0.01-2000 lux, preferably 0.05-
30 lux, more preferably 0.05 to 5 lux is suitable. The light-sensitive material using a higher sensitivity emulsion,
Photosensitivity with low illuminance is preferred. The illuminance may be adjusted by changing the luminous intensity of the light source, dimming by various filters, changing the distance between the photosensitive material and the light source, or changing the angle between the photosensitive material and the light source. Further, the illuminance of the fog light can be continuously or stepwise increased from low illuminance to high illuminance.

It is preferable to immerse the light-sensitive material in a developing solution or a solution of its pre-bath so that the solution sufficiently penetrates into the emulsion layer of the light-sensitive material before irradiation with light. The time from the penetration into the liquid to the light fog exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, and more preferably 10 seconds to 30 seconds.

The exposure time for fogging is generally from 0.01 seconds to 2 minutes, preferably from 0.1 seconds to 1 minute, more preferably from 1 second to 40 seconds.

In the present invention, the nucleating agent used when performing the so-called "chemical fogging method" can be contained in the photosensitive material or in the processing solution of the photosensitive material. Preferably, it can be contained in a photosensitive material.

Here, the "nucleating agent" is a substance which acts when the surface of an internal latent image type silver halide emulsion which has not been fogged in advance is subjected to a surface development treatment to directly form a positive image. In the present invention, it is particularly preferable to perform fogging treatment using a nucleating agent.

When it is contained in the light-sensitive material, it is preferably added to the inner latent silver halide emulsion layer, but as long as the nucleating agent is diffused during coating or processing and adsorbed to the silver halide,
It may be added to other layers such as an intermediate layer, an undercoat layer and a back layer.

When the nucleating agent is added to the processing solution, it may be contained in the developing solution or in the low pH pre-bath as described in JP-A-58-178350.

 Moreover, you may use together 2 or more types of nucleating agents.

Regarding the nucleating agent used in the present invention, a compound represented by the general formula [N-
Use of the compounds represented by [I] and [N-II] is preferred.

General formula [NI] (In the formula, Z represents a non-metal atom group necessary for forming a 5- to 6-membered heterocycle, Z may be substituted with a substituent, R ¹ is a fatty group, and R ² is A hydrogen atom, an aliphatic group or an aromatic group, R ¹ and R ² may be substituted with a substituent, and R ² is further bonded to the heterocycle completed by Z to form a ring. Provided that at least one of the groups represented by R ¹ , R ² and Z contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R ¹ and R ² are 6-membered. A ring is formed to form a dihydropyridinium skeleton, and at least one of the substituents of R ¹ , R ² and Z may have an adsorption promoting group to silver halide, Y is a charge balance N is 0 or 1.

[N-I-1] C ₂ H ₅ O- Br ^- [N-I-6] H ^- CF ₃ SO ₃ ^- (In the formula, R ²¹ represents an aliphatic group, an aromatic group, or a heterocyclic group; R ²² represents a hydrogen atom, an alkyl group, an aralkyl group,
Represents an aryl group, an alkoxy group, an aryloxy group, or an amino group; G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an iminomethylene group (HN =
R ²³ and R ²⁴ are both hydrogen atoms or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group or an acyl group. However G, may form a hydrazone structure (N-N = C) in a form, including R ^22, R ²⁴ and hydrazine nitrogen. Further, the above-mentioned groups may be substituted with a substituent when possible. ) The nucleating agent may be added to any hydrophilic colloid layer,
It is preferably added to the photosensitive layer.

The addition amount is 1 × 10 ⁻² to 1 × 10 ⁻⁹ mol, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁸ mol, and more preferably 1 × 10 ⁻⁴ to 1 ×, per 1 mol of Ag. It is in the range of 10 ^-7 mol.

In the present invention, the following nucleation accelerator can be used to further promote the action of the nucleating agent.

Examples of the nucleation accelerator include tetrazaindenes, triazaindenes and pentazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group, and JP-A-63-163. 1066
Compounds described in JP-A-56 (pages 6 to 16) can be added.

Specific examples of the nucleation accelerator are shown below, but the invention is not limited thereto.

(A-1) 3-mercapto-1,2,4-triazolo [4,5-
a] Pyridine (A-2) 3-mercapto-1,2,4-triazolo [4,5-
a] Pyrimidine (A-3) 5-mercapto-1,2,4-triazolo [1,5-
a] pyrimidine (A-4) 7- (2-dimethylaminoethyl) -5-mercapto-1,2,4-triazolo [1,5-a] pyrimidine (A-5) 3-mercapto-7-methyl- 1,2,4-triazolo [4,5-a] pyrimidine (A-6) 3,6-dimercapto-1,2,4-triazolo [4,
5-b] pyridazine (A-7) 2-mercapto-5-methylthio-1,3,4-
Thiadiazole (A-8) 3-Mercapto-4-methyl-1,2,4-triazole (A-9) 2- (3-Dimethylaminopropylthio)-
5-Mercapto-1,3,4-thiadiazole hydrochloride (A-10) 2- (2-morpholinoethylthio) -5-mercapto-1,3,4-thiodiazole hydrochloride The nucleation accelerator is used in the light-sensitive material. Alternatively, it can be contained in the processing solution, but it is preferably contained in the internal latent image type silver halide emulsion layer and other hydrophilic colloid layers (intermediate layer, protective layer, etc.) among the light-sensitive materials. Particularly preferred is a layer in or adjacent to a silver halide emulsion layer.

The color developer used for the development processing of the light-sensitive material of the present invention,
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent, but p-
A phenylenediamine compound is preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N.
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates.
Two or more of these compounds can be used in combination depending on the purpose.

The pH of these color developing solutions is 9 to 12, preferably
9.5 to 11.5.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), the purpose, and the rinsing water temperature.
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Volume 64, p248 to 253 (May 1955 issue).

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing.
For incorporation, it is preferable to use various precursors of color developing agents.

On the other hand, to develop a black and white photosensitive material in the present invention,
Various known developing agents can be used. That is, polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol, pyrogallol and the like; aminophenols such as p-aminophenol and N-methyl-
p-aminophenol, 2,4-diaminophenol and the like;
3-pyrazolidones, such as 1-phenyl-3-pyrazolidones, 1-phenyl-4,4'-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5 -Dimethyl-1-phenyl-3-pyrazolidone and the like; ascorbic acids and the like,
A single or a combination can be used. Also, JP-A-58-
The developer described in No. 55928 can also be used.

For detailed examples of developing agents, preservatives, buffers, and developing methods for black and white light-sensitive materials and their usage, see "Research Disclosure", No. 17643 (1978).
Published in December) XIX to XXI.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to examples. The invention is not limited to these examples only.

Example 1 A paper support laminated on both sides with polyethylene (thickness 10
A color photographic light-sensitive material was prepared by coating the following first to fourteenth layers on the front side (0 micron) and the fifteenth to sixteenth layers on the back side. The polyethylene on the first layer coating side contains titanium oxide as a white pigment and a trace of ultramarine blue as a bluing dye (the chromaticity of the surface of the support is L ^* , a ^* , b
^* 88.0, -0.20, -0.75 in the system. ).

(Composition of photosensitive layer) The components and the coating amount (g / m ² unit) are shown below. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was produced according to the production method of Emulsion EM1. However, as the 14th layer emulsion, a Lippmann emulsion which was not surface chemically sensitized was used.

1st layer (antihalation layer) Black colloidal silver 0.10 Gelatin 0.70 2nd layer (intermediate layer) Gelatin 0.70 3rd layer (low sensitivity red sensitive layer) Spectral sensitization with red sensitizing dye (ExS-1,2,3) Silver bromide (average grain size 0.25μ, size distribution [variation coefficient] 8
%, Octahedron) 0.04 Silver chlorobromide spectrally sensitized with a red sensitizing dye (ExS-1,2,3) (5 mol% silver chloride, average grain size 0.40μ, size distribution)
10%, octahedron) 0.08 Gelatin 1.00 Cyan coupler (Exc-1, 2, 3 1: 1: 0.2) 0.30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalents) 0.18 Coupler dispersion medium (Cpd- 6) 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) 0.12 4th layer (high-sensitivity red-sensitive layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) ( Average particle size 0.60μ, size distribution 15%, octahedron) 0.
14 Gelatin 1.00 Cyan coupler (ExC-1, 2, 3 1: 1: 0.2) 0.30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalents) 0.18 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent ( Solv-1, 2, 3 equivalents) 0.12 Fifth layer (intermediate layer) Gelatin 1.00 Anti-color mixing agent (Cpd-7) 0.08 Anti-color mixing agent solvent (Solv-4, 5 equivalents) 0.16 Polymer latex (Cpd-8) 0.10 6th layer (low-sensitivity green-sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.25μ, size distribution 8%, octahedron) 0.04 Green sensitizing dye ( ExS-4) spectrally sensitized silver chlorobromide (silver chloride 5 mol%, average particle size 0.40μ, size distribution
10%, octahedron) 0.60 Gelatin 0.80 Magenta coupler (ExM-1, 2, 3 equivalents) 0.11 Anti-fading agent (Cpd-9, 26 equivalents) 0.15 Anti-staining agent (Cpd-10, 11, 12 10) : 7: 7 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 equivalents) 0.15 7th layer (high sensitivity green sensitive layer) Spectral with green sensitizing dye (ExS-4) Sensitized silver bromide (average grain size 0.65μ, size distribution 16%, octahedron) 0.10 gelatin 0.80 magenta coupler (ExM-1, 2, 3 equivalents) 0.11 anti-fading agent (Cpd-9, 26 equivalents) ) 0.15 Anti-staining agent (Cpd-10, 11, 12 in 10: 7: 7 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 equivalents) 0.15 8th layer (intermediate layer) ) Same as the 5th layer 9th layer (yellow filter layer) Yellow colloidal silver 0.12 Gelatin 0.07 Color mixture inhibitor (Cpd-7) 0.03 Color mixture inhibitor solvent (Solv-4, 5 etc.) ) 0.10 Polymer latex (Cpd-8) 0.07 10th layer (intermediate layer) Same as 5th layer 11th layer (low sensitivity blue sensitive layer) Odor spectrally sensitized with blue sensitizing dye (ExS-5, 6) Silver halide (average grain size 0.40μ, size distribution 8%, octahedron) 0.
07 Silver chlorobromide spectrally sensitized with blue sensitization base (ExS-5, 6) (silver chloride 8 mol%, average grain size 0.60μ, size distribution 11%, octahedron) 0.14 gelatin 0.80 yellow coupler (ExY -1, 2 equivalents) 0.35 Anti-fading agent (Cpd-14) 0.10 Anti-staining agent (Cpd-15) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 12th layer (high sensitivity blue) Sensitive layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.85μ, size distribution 18%, octahedron).
15 Gelatin 0.60 Yellow coupler (ExY-1, 2 equivalents) 0.30 Anti-fading agent (Cpd-14) 0.10 Anti-staining agent (Cpd-15) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 13th layer (UV absorbing layer) Gelatin 1.00 UV absorbing agent (Cpd-2, 4, 16 equivalents) 0.50 Color mixing inhibitor (Cpd-7, 17 equivalents) 0.03 Dispersion medium (Cpd-6) 0.02 UV absorbing solvent (Solv-2, 7 equivalents) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27
10: 10: 13: 15: 20 ratio) 0.05 14th layer (protective layer) Fine silver chlorobromide (97 mol% silver chloride, average size 0.1μ)
0.03 Acrylic modified copolymer of polyvinyl alcohol 0.01 Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent 0.05 gelatin 1.80 gelatin hardening agent (H-1, H-2 equivalent) 0.18 15th layer (back layer) gelatin 2.50 UV absorber (Cpd-2, 4) , 16 equivalents) 0.50 Dye (equivalent to Cpd-18, 19, 20, 21, 27) 0.06 16th layer (back side protective layer) Polymethylmethacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5 μ) equivalent 0.05 gelatin 2.00 gelatin hardening agent (H-1, H-2 equivalent) 0.14 How to make emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate is vigorously added to an aqueous gelatin solution. The mixture was simultaneously added with stirring at 75 ° C over 15 minutes to obtain octahedral silver bromide grains having an average grain size of 0.40μ. 0.2 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mole of silver, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were successively added to this emulsion at 40 ° C at 75 ° C. The chemical sensitization treatment was performed by heating for a minute. The grains thus obtained were used as cores and further grown in the same precipitation environment as in the first time, to finally obtain an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.7μ. The coefficient of variation of particle size was about 10%. To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) were added per mol of silver, and the mixture was heated at 60 ° C. for 50 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion. Obtained.

In each light-sensitive layer, ExZK-1 and ExZK-2 were used as nucleating agents at 10 ^-3 and 10 ^-2 % by weight, respectively, with respect to silver halide, and Cpd-22 as a nucleation accelerator was used at 10 ^-2 % by weight. . Further, in each layer, alkanol XC (Dupon Co.) and sodium alkylbenzenesulfonate were used as emulsification / dispersion aids, and succinic acid ester and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. In the layers containing silver halide and colloidal silver, (Cpd-23, 24, 25) was used as a stabilizer. This sample was designated as sample number No.A. The compounds used in the examples are shown below.

Solv-1 Di (2-ethylhexyl) sebacate Solv-2 Trinonyl phosphate Solv-3 Di (3-methylhexyl) phthalate Solv-4 Triclodyl phosphate Solv-5 Dibutyl phthalate Solv-6 Trioctyl phosphate Solv-7 Di (2 -Ethylhexyl) phthalate H-11,2-bis (vinylsulfonylacetamide)
Ethane H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine Na salt ExZK-1 NI-10 ExZK-2 N-II-14 Processing step A Processing step time Temperature color development 100 seconds 38 ℃ Bleaching Fixing 40〃 33〃 Washing (1) 40〃 33〃 Washing (2) 40〃 33〃 Drying 30〃 80〃 Washing water is replenished in the washing bath (2), then the washing bath (2) The so-called countercurrent replenishment system was adopted in which the overflow liquid of (1) was introduced into the washing bath (1).

 The composition of each treatment liquid was as follows.

Color developer Mother liquor D-sorbit 0.15 g Sodium naphthalenesulfonate / formalin condensate 0.
15 g Ethylenediaminetetrakismethylenephosphonic acid 1.5 g Diethylene glycol 12.0 ml Benzyl alcohol 13.5 ml Potassium bromide 0.80 g Benzotriazole 0.003 g Sodium sulfite 2.4 g N, N-bis (carboxymethyl) hydrazine 6.0 g D-glucose 2.0 g Triethanolamine 6.0 g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulphate 6.4 g Potassium carbonate 30.0 g Fluorescent brightener (diaminostilbene type) 1.0 g Water added 1000 ml pH (25 ° C) 10.25 Bleach-fixing solution mother liquor ethylenediamine 4 acetic acid 2 sodium Dihydrate 4.0 g Ethylenediaminetetraacetic acid / Fe (III) / Ammonium /
Dihydrate 70.0 g Ammonium thiosulfate (700 g / l) 180 ml Sodium p-toluenesulfinate 20.0 g Sodium bisulfite 20.0 g 5-Mercapto-1,3,4-triazole 0.5 g Ammonium nitrate 10.0 g Water 1000 ml pH (25 6.20 Rinse water Tap water was mixed in a mixed bed column filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). Water was passed to adjust the concentration of calcium and magnesium ions to 3 mg / l, and subsequently 20 mg / l of sodium isocyanurate dichloride and 1.5 g / l of sodium nitrate were added.
The pH of this solution was in the range of 6.5-7.5.

Sample Nos. 1 to 8 were prepared in the same manner as Sample No. A except that the FR compound of the present invention and the compound of the general formula (II) were used in each photosensitive layer as shown in Table 1.

After subjecting these samples to wedge exposure, process step A was performed. The magenta image densities Dmax and Dmin and the gradation of the toes were measured and shown in Table 1.

FR compound addition: 3.5 × 10 ^-3 mol / Ag mol in each photosensitive layer.

Compound of general formula (II): 4.5 × 10 ^-3 mol / A for each photosensitive layer
gmol.

Highlight gradation: Dmin + 0.2 (optical density) and Dmin + 0.5
The average gradation between.

Sample Nos. 1, 3, 5, and 7 in which the FR compound of the present invention and the compound of the general formula (II) were used in combination had a lower Dmin than Sample Nos. 2, 4, 6, and 8 in which only the FR compound was used. And, the gradation of the highlight part was hard and was preferable. Sample No.A
Compared with, Dmax was high, Dmin was low, and the gradation of the highlight part was hard, which was preferable.

Similar results were obtained with cyan and yellow image densities.

Example-2 Sample No. B was prepared in the same manner as Sample No. A of Example-1 except that the support was a polyethylene terephthalate film (100 μm thick) with an undercoat layer, and the following changes were made.

 The first and second layers were removed.

The coating layers of the 3rd, 4th, 6th, 17th, 11th and 12th layers are 1.5
Doubled.

Further, the compound of the present invention was added as shown in Table 2 to prepare sample Nos. 1 and 2.

These samples were stored (incubated) for 2 days in an atmosphere of 45 ° C. and 80% RH, and exposed before and after them in the same manner as in Example-1, and then subjected to processing step B.

In the process step B, except that the time of each step is 1.5 times,
It is the same as the processing step A.

The cyan density of the obtained image was measured and is shown in Table 2.

Sample No. 1 in which both the FR compound and the compound of the general formula (II) were used was preferable because the increase in Dmin due to incubation was smaller than that in Sample No. 2 containing only the FR compound. Further, compared to Sample B, both the decrease of Dmax and the increase of Dmin were small and preferred.

Similar results were obtained with magenta and yellow image densities.

(Effects of the Invention) The silver halide photographic light-sensitive material according to the present invention can provide a sufficiently high maximum image density, low minimum image density, and a toned image. Moreover, the above light-sensitive material provides stable photographic performance even when stored under high temperature and high humidity.
The practical advantage is great.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-60-191241 (JP, A) JP-A-62-150344 (JP, A) JP-A-61-267757 (JP, A) JP-B 43- 10256 (JP, B1)

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and an auxiliary layer on a support, and at least one compound represented by the following formula (II) and a compound prepared during development. A direct positive type silver halide photographic light-sensitive material comprising at least one compound releasing a nucleating agent, a nucleation accelerator, or a precursor thereof and an internal latent image type silver halide emulsion. (II) In the general formula (II), R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 8 or less carbon atoms, an alkoxy group, an alkylthio group or an amide group, and R ⁵ represents a hydrogen atom or an alkyl group having 11 or less carbon atoms. . The total carbon number of R ³ , R ⁴ and R ⁵ is 8 or more and 22 or less.