JP2537079B2 - Direct positive photographic material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a direct positive photographic light-sensitive material, and more particularly to a direct positive photographic light-sensitive material in which the maximum image density is increased without raising the minimum image density Dmin. .

[Prior Art] A well-known method is to directly obtain a positive image by using an internal latent image type silver halide emulsion which has not been fogged in advance and performing surface development after fog processing after image exposure or while performing fog processing. Has been.

Here, the internal latent image type silver halide photographic emulsion is
A silver halide photographic emulsion of the type in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain upon exposure.

Various techniques have been known so far in this technical field. For example, U.S. Patent Nos. 2,592,250 and 2,466,9
No. 57, No. 2,497,875, No. 2,588,982, No. 3,317,322
Nos. 3,761,266, 3,761,276, 3,796,577 and British Patent Nos. 1,151,363, 1,150,553, 1,011,
The main thing is described in each specification of No. 062.

By using these known methods, a photographic photosensitive material having a relatively high sensitivity as a direct positive type can be produced.

For details of the mechanism for forming the direct positive image, for example,
TH The Ames, The Theory of the Photogra Process
Phic Prosess), 4th edition, Chapter 7, pp. 182-193 and U.S. Pat. No. 3,761,276.

[Problems to be Solved by the Invention] The direct positive image formation performed using a direct positive photographic light-sensitive material usually has a drawback that the developing speed is slower than the image formation using a negative photographic light-sensitive material.

Therefore, it has been proposed to add an acid group-containing mercapto compound as a means for improving the developing speed (Japanese Patent Laid-Open No. 60-170843), but the effect of improving the developing speed is small.

An object of the present invention is to obtain a direct positive photographic light-sensitive material capable of obtaining an image having a high maximum image density Dmax without increasing the minimum image density Dmin even if the development processing is performed at an increased development speed, that is, rapid development processing. To do.

[Means for solving the problem]

The above-mentioned object is to provide a photographic light-sensitive material having at least one pre-fogged internal latent image type silver halide emulsion layer on a support, and a coupling reaction and / or a redox reaction with an oxidized product of a developing agent during development. By a compound capable of releasing the rash agent represented by the following general formula [M] under alkaline conditions, and the following general formula [AI] and / or
Or a direct positive photographic light-sensitive material characterized by containing at least one nucleation accelerator represented by [A-II].

General formula [M] In the formula, R ^m1 represents a divalent aromatic group, R ^m2 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group, and G represents a carbonyl group or a sulfonyl group. , A sulfoxy group, a phosphoryl group, or an iminomethylene group (NH = C <), R
^m3 and R ^m4 both represent a hydrogen atom or one of them represents a hydrogen atom and the other represents one of an alkylsulfonyl group, an arylsulfonyl group and an acyl group.

A represents a group which promotes adsorption to silver halide;
Represents a divalent continuous group. n represents 0 or 1.

General formula [AI] General formula [A-II] Hereinafter, the present invention will be described in detail.

The compounds which can be used in the present invention and which can release the foggant represented by the general formula [M] under alkaline conditions by a coupling reaction with an oxidized product of a developing agent and / or a redox reaction during development include the following. Included.

(I) A coupler which couples with an oxidation product of an aromatic primary amine developing agent to release a fog agent represented by the general formula [M] or a precursor thereof.

(Ii) Coupling with an oxidation product of an aromatic primary amine developing agent to give a diffusible coupling product, the coupling product being represented by the fog agent represented by the general formula [M] or A coupler that functions as a precursor.

(Iii) A redox compound which releases the fog or the precursor thereof represented by the general formula [M] by a redox reaction with an oxidation product of a 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) _m -M '[2] BALL-Cp- (TIME) _m -M' [3] RED- (TIME) _m -M 'In the above formula, Cp is an aromatic first Represents a coupler residue capable of undergoing a coupling reaction with an oxidized product of a primary amine developing agent, BA
LL represents a diffusion-resistant group that can be separated from Cp by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, and RED represents a compound residue capable of undergoing a redox reaction with the oxidation product of a developing agent. Represent.

TIME represents a timing group that further releases M'after leaving Cp or RED by a coupling reaction.

m represents 0 or 1, and M ′ is Cp when m is 0.
Or a group that can be separated from RED, and when m is 1, TIM
It is a group that can be released from E. Here, M ′ is a group obtained by removing an arbitrary hydrogen radical from the general formula [M],
It is preferable to bond with TIME, Cp or RED at the position of the AgX adsorption group A.

In the general formula [1],-(TIME) _m -M 'is bonded to the coupling position of Cp, 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. Further, since-(TIME) _m -M 'is bonded to the non-coupling position of Cp, the bond is not immediately cleaved by the coupling.

In the general formula [3],-(TIME) _m -M 'means that RED is the redox reaction or the subsequent reaction with the oxidized product of the developer.
It is bound to a position that can be released from RED.

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 M ', one of the remaining two binds to the coupling position of Cp, and the other one binds to the uncoupling position of Cp. Is. The characteristic of the compound having such a structure is that during the coupling reaction with the aromatic primary amine developing agent, the bond with TIME that is bonded to the coupling site is cut off, but it is bonded to the non-coupling site. TI
The bond with ME is not cleaved, and the cleaved bond part (anion) of TIME is cleaved to bond with M'due to electron transfer and / or intramolecular nucleophilic substitution reaction of TIME to cleave M '. Can be released. Therefore, such a compound is required to have not only a trivalent group but also a structure capable of releasing M ′ by intramolecular electron transfer and / or intramolecular nucleophilic substitution reaction.

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

In the general formula [I], the coupler residue represented by Cp has a partial structure of a colorless coupler and a black coupler in addition to the yellow, magenta and cyan couplers listed below.

Here, a typical example of the yellow coupler is U.S. Pat.
2,875,057, 2,407,210, 3,265,506, 2,29
8,443, 3,048,194, 3,447,928, 4,149,886
No. 1,204,680, JP-A No. 52-154631, and the like.

The yellow coupler residue (Cp) has the following general formula [I
Those represented by a] to [IIIa] are preferable.

In addition, * represents the bonding position of the M'group or the TIME group (the same applies to the following 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.

Therefore, as the Madanta coupler residue (Cp),
Those represented by the following general formulas [IVa] to [VIIa] 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 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, 57-15538.
Nos. 57-204545, 58-189154 and 59-3195
No. 3, 58-118634, 58-187928, 58-213748
No. 61-167952, U.S. Pat.Nos. 4,333,999, 4,690,8
No. 89 etc.

As the cyan coupler residue (Cp), the following general formula [VI
Those represented by IIa] 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, preferably an alkyl, aryl, heterocyclic, acyl, sulfonyl, alkoxycarbonyl.

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

 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 colors [X IVa] to [X VIa].

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 each independently an alkoxycarbonyl group, an aminocarbonyl group, an acyl group,
A sulfonic acid or sulfinic acid derivative corresponding to the above,
It represents a cyano group, an ammonium mill group, a nitrogen-containing heterocycle bonded at the N-position, and the like. R ″ ₃ and R ′ ₄ combine to form 5-6
You may form a member ring.

Cp may be a coupler residue which develops black color by reacting with the above-mentioned oxidized product of the other 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 colors [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 [X IXa] is
A part other than the coupling site may form a dimer or higher multimer, or the part may bind to the polymer.

In the general formula [2], the coupler residue represented by Cp has the partial structure represented by the above general formulas [Ia] to [X IXa], BALL is bound to the * mark, and 1 at the other site. -(TIME) _m -M 'is bound to one.

In the general formula [2], the nondiffusible group represented by BALL may have a size and shape that impart non-diffusivity to the coupler, and may be a polymer field having a plurality of leaving groups linked together, Alkyl group 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,
About 8 to 32 pieces are preferable. 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], this is abbreviated as "FR") represents a group for releasing.

 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. Alternatively, two R _{8 s} may form a ring.

T ₁ is a group that cleaves the —O—T ₁ bond during development to release —O ⁻ , and examples thereof include acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, 2-cyanoethyl, and 2-methanesulfonylethyl. can give.

R ⁹ represents an acyl group or a sulfonyl group.

Preferred specific examples of the general formulas [XXa] to [XXVa] are shown below. Note that (*) in the nuclear structural formula indicates the position where FR is bonded.

FR is a group that forms the general formula [M] under alkaline conditions, and is represented by the following general formula. [] Represents M '.

General formula (FR) In the formula, TIME represents a timing group for releasing general formula M after FR is released, and m represents 0 or 1.

US Pat. No. 4,24 as a timing group represented by TIME
JP-A-57-154234, JP-A-57-154234 and JP-A-57-15437 for the intramolecular substitution reaction after elimination from Cp or RED by a coupling reaction or a redox reaction as described in JP-A-8,962 and JP-A-57-56837.
-188035, 56-114946, 57-56837, 58-2
09736, 58-209737, 58-209738, 58-209
No. 740, No. 58-98728, etc., which leaves M'by electron transfer through a conjugated system, and an oxidation product of an aromatic primary amine developing agent as disclosed in JP-A-57-111536. And the like, which are coupling components capable of leaving M'by the coupling reaction of. These reactions may take place in one stage or in multiple stages.

Further, as described above, a trivalent TIME that binds to the coupling site, the non-coupling site, and M'is also preferable.
58-209740).

As for M ', A may be directly bonded to the carbon atom at the coupling position, or any group other than A may be bonded to the coupling carbon as long as it can be eliminated by the coupling reaction. What is known as a so-called 2-equivalent leaving group may be interposed between the coupling carbon and A. 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).

Examples of the group capable of being adsorbed to silver halide represented by A include a nitrogen-containing heterocyclic ring having a dissociable hydrogen atom (pyrrole, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole,
Benzotriazole, uracil, tetraazaindene,
Imidazotetrazole, pyrazolotriazole, pentaazaindene, etc.), a heterocycle having at least one nitrogen atom and another heteroatom (oxygen, sulfur, selenium, etc.) in the ring (oxazole, thiazole, thiazoline, thiazolidine, thiadiazole, Benzothiazole, benzoxazole, benzselenazole, etc.), a heterocycle having a mercapto group (2-mercaptobenzothiazole, 2-
Mercaptopyrimidine, 2-mercaptobenzoxazole, 1-phenyl-5-mercaptotetrazole, 5
-Mercapto-1,3,4-thiadiazole, etc.), thiophenols, alkylthiols (cystine, etc.), (Eg, thiourea, dithiocarbamate, thioamide, rhodanine, thiazolidinethione, thiohydantoin, thiobarbituric acid, etc.).

Specific examples of A are described below. * Indicates the binding position to (TIME) _m .

L is a divalent linking group, and n represents an integer of 0 or 1. Examples of L include alkylene, alkenylene, arylene, divalent heterocyclic group, -O-, -S-, imino,
-COO -, - CONH -, - NHCONH -, - NHCOO -, - SO 2 NH
-, - CO -, - SO 2 -, - SO -, - NHSO 2 NH-, And composites thereof.

If one of the divalent linking groups constituting L is cleavable by the action of components in the developing solution (eg, hydroxide ion, hydroxyamine, sulfite ion, etc.), the fogging action can be adjusted. It is also possible to activate or deactivate it.

R ^m1 represents a divalent aromatic group, and examples thereof include a phenylene group and a naphthylene group.

R ^m1 may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted.

For example, alkyl, aralkyl, alkoxy, alkyl- or aryl-substituted amino, acylamino, sulfonylamino, ureido, urethane, aryloxy, sulfamoyl, carbamoyl, aryl, alkylthio,
Examples include arylthio, sulfonyl, sulfinyl, hydroxy, halogen atom, cyano, sulfo, carboxyl and phosphoric acid amide.

When possible, these groups may be linked to each other to form a ring.

R ^m1 is preferably a phenylene group, particularly 1,4-
A phenylene group is preferred.

Among the groups represented by R ^m2 , when G is a carbonyl group, a hydrogen atom, an alkyl group (for example, methyl, trifluoromethyl, 3-hydroxypropyl,
3-methanesulfonamidopropyl), aralkyl groups (eg o-hydroxybenzyl), aryl groups (eg phenyl, 3,5-dichlorophenyl, o-methanesulfonamidophenyl, 4-methanesulfonylphenyl,
2-hydroxymethylphenyl etc.) and the like, and a hydrogen atom is particularly preferable.

When G is a sulfonyl group, R ^m2 is preferably an alkyl group (eg methyl), an aralkyl group (eg o-hydroxyphenylmethyl), an aryl group (eg phenyl) or a substituted amino group (eg dimethylamino).

As the substituent for R ^m2, the substituents listed for R ^m1 can be applied, and for example, acyl, acyloxy, alkyl or aryloxycarbonyl, alkenyl, alkynyl, nitro and the like can also be applied.

These substituents may be further substituted with these substituents. If possible, these groups may be connected to each other to form a ring.

The alkylsulfonyl group of R ^m3 and R ^m4 has 1 carbon atom.
To 12 and examples thereof include methanesulfonyl, trifluoromethanesulfonyl, cyclohexanesulfonyl and the like. The arylsulfonyl group of R ^m3 and R ^m4 has a carbon number of 6 to 20, and examples thereof include benzenesulfonyl. The acyl group of R ^m3 and R ^m4 has 1 to 12 carbon atoms, and examples thereof include acetyl, trifluoroacetyl, p-cyanobenzoyl and the like.

A hydrogen atom is most preferable as R ^m3 and R ^m4 . G is most preferably a carbonyl group.

Specific examples of the compound which releases the rash agent represented by the general formula [M] used in the present invention are shown below, but the invention is not limited thereto.

The compound which releases the compound represented by the general formula [M] is
For example, it can be synthesized by a method similar to the method described in JP-A-57-150845, JP-A-59-157638 and JP-A-60-1007029.

 A specific synthesis example is shown below.

1. Synthesis of Exemplified Compound (1-1) 1-1. Synthesis of compound b Compound a 22.9 g (0.1M), CH ₃ CN 150 ml and pyridine 17.1
The mixture of ml (0.22M) is stirred under ice-cooling, and 17g (0.105M) of phenyl chlorocarbonate is added dropwise while keeping the temperature below 5 ° C. After the dropping, the mixture was stirred for 30 minutes at 5 ° C. and further stirred at room temperature for 1 hour, and then extracted by adding 500 ml of ethyl acetate, 10 ml of concentrated hydrochloric acid and 300 ml of water. The extract was washed twice with water, dried over Glauber's salt, and concentrated by an evaporator. 230 ml of acetonitrile was added, and the mixture was heated and cooled, and the precipitated crystals were filtered to obtain 23.8 g of compound b. Yield 75%.

1-2. Synthesis of compound c 15.7 g (0.05M) of compound b was dispersed in 150 ml of methylene chloride, and 7.4 g of sulfuryl chloride (0.
055M) was added dropwise. After the dropwise addition, the mixture was stirred at 5 ° C or lower for 30 minutes, further stirred at 15 ° C or lower for 1 hour, and then methylene chloride was distilled off under reduced pressure with an aspirator to give compound c.
An oily substance consisting of

1-3. Synthesis of compound e Iron powder 1 in a mixed solution of 120 ml of isopropanol and 17 ml of water
6.8 g and 1.7 g of ammonium chloride were added and the mixture was heated to reflux under a nitrogen stream, and compound d was gradually added as a powder. After the addition was completed, the mixture was heated under reflux for 1 hour, and the reaction solution was filtered. By cooling the filtrate with ice, 13.3 g of compound e was obtained. Yield 86.9
%. Melting point 154-156 ° C.

1-4. Synthesis of Compound g Compound f21.4 g (0.045 M) was dissolved in chloroform 150 ml, and a solution of compound c17.4 g (0.05 M) in chloroform 100 ml was added dropwise over about 15 minutes at 5 ° C or lower under ice cooling. After the dropping, the mixture was stirred for 30 minutes at 5 ° C. or lower, then at room temperature for 1 hour, and the reaction solution was concentrated under reduced pressure. 300 ml of ethyl acetate was added to the residue to dissolve it, washed with water, dried with sodium sulfate, and concentrated. Acetonitrile was added to the residue for crystallization to obtain 30.4 g of compound g. Yield 86%.

1-5. Synthesis of Exemplified Compound (1-1) Compound g 7.9 g (0.01 M), compound e 3.4 g (0.011 M) and imidazole 0.1 g were added with acetonitrile 50 ml and heated under reflux for 4 hours under a nitrogen stream. During this time, the solution changes from non-uniform to uniform. 150 ml of ethyl acetate was added to the reaction solution, which was washed 3 times with water, dried over sodium sulfate and concentrated. 6 g of the target Exemplified Compound (1-1) was obtained by adding methanol to the residue for crystallization.
Obtained. Yield 60%: melting point 176-178 ° C (decomposition).

2. Synthesis of exemplified compound (3-8) 2-1. Synthesis of compound j Compound h26. Synthesized by the method described in JP-A-61-230135.
Acetone 300g with 3g (0.05M) and compound b15.7g (0.05M)
It was dissolved in and reacted at room temperature for 3 hours. Acetone was concentrated under reduced pressure to obtain 34.5 g of glassy compound i. Compound i was dissolved in 150 ml of ethyl acetate, a solution of 35 g of Na ₂ S ₂ O _{4 in} 150 ml of water was added, and the mixture was reacted at room temperature for 1 hour with stirring. The ethyl acetate layer was separated, washed with water, and concentrated under reduced pressure to give 33.1 g of a glassy compound j. (Yield 92%) 2-2. Synthesis of Exemplified Compound (3-8) The target compound (3-8) was obtained in a yield of 45% by the same method as the exemplified compound (1-1) described in 1-5. Obtained.

Further, the addition amount of the compounds represented by the above general formulas [1] to [3] used in the present invention is from 10 ⁻⁹ to 1 mol of silver halide contained in the layer containing the compound or in the adjacent layer. It is 10 ^-1 mol, preferably 10 ^-5 to 10 ^-1 mol.

In the present invention, a known method such as the method described in U.S. Pat. No. 2,322,027 may be used to introduce the compound into the silver halide emulsion layer. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg acetyl citrate tributyl), Benzoic acid esters (eg, octyl benzoate), alkylamides (eg, diethyllaurylamide), fatty acid esters (eg, dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg, tributyl trimesate), etc., or a boiling point of about 30 ° C to 150
Dissolved in an organic solvent such as ethyl acetate, lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then dispersed in a hydrophilic colloid. To be done. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

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

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

Next, the nucleation accelerators represented by the general formulas [AI] and [A-II] will be described in detail.

The term "nucleating accelerator" as used herein means a nucleating agent (the term "nucleating agent" acts on the surface development treatment of an internal latent image type silver halide emulsion which has not been fogged in advance to directly form a positive image. Functioning as a substance that acts as a)
A substance that promotes the action of a nucleating agent, increases the maximum image density of a direct positive image, and / or shortens the development time necessary to obtain a constant direct positive image density. Two or more nucleation accelerators can be used in combination.

The nucleation accelerator used in the present invention has the general formula [A-
I] and / or [A-II].

In general formula [A-I], Q is preferably necessary for forming a 5- or 6-membered heterocycle composed of at least one atom selected from carbon atom, nitrogen atom, oxygen atom, sulfur atom and selenium atom. Represents a group of atoms. The heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of heterocycles include tetrazole, triazole, imidazole, thiadiazole, oxadiazole, selenadiazole, oxazole, thiazole, benzoxazole, benzothiazole,
Examples include benzimidazoles and pyrimidines.

M is a hydrogen atom, an alkali metal atom (for example, sodium, potassium) ammonium group (for example, trimethylammonium, dimethylbenzylammonium), M = H or a group which can be an alkali metal atom under alkaline conditions (for example, acetyl, cyanoethyl, methanesulfonyl). Ethyl).

In addition, these heterocycles include a nitro group, a halogen atom (eg, base, bromine), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, propyl, t-butyl, cyanoethyl), aryl. Group (for example, phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl, naphthyl), alkenyl group (for example, allyl), aralkyl group (for example, benzyl, 4-methylbenzyl, phenethyl), A sulfonyl group (eg methanesulfonyl),
Ethanesulfonyl, p-trienesulfonyl), carbamoyl group (eg unsubstituted carbamoyl, methylcarbamoyl, phenylcarbamoyl), sulfamoyl group (eg unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl), carbonamide group (eg acetamide) , Benzamide), sulfonamide groups (eg methanesulfonamide, benzenesulfonamide, p
-Toluenesulfonamide), acyloxy group (e.g. acetyloxy, benzoyloxy), sulfonyloxy group (e.g. methanesulfonyloxy), ureido group (e.g. unsubstituted ureido, methylureido, ethylureido, phenylureido), thioureido group (e.g. Unsubstituted thioureido, methylthioureido), acyl group (eg acetyl, benzoyl), oxycarbonyl group (eg methoxycarbonyl, phenoxycarbonyl), oxycarbonylamino group (eg methoxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarbonylamino) ), A carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a hydroxyl group or the like, but a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof. Salts, those who are not substituted with a hydroxyl group is preferred in terms of nucleation accelerating effect.

Preferred examples of the heterocyclic ring represented by Q include tetrazole, triazole, imidazole, thiadiazole and oxadiazole.

Y represents a divalent linking group consisting of an atom or an atom group selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of the divalent linking group include -S- and-
O-, And the like.

These linking groups may be a linear or branched alkylene group (for example, methylene, ethylene, propylene, butylene, hexylene, 1-methylethylene) between the above-mentioned heterocycles, or a substituted or unsubstituted arylene group (phenylene, naphthylene). ).

R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ are each a hydrogen atom, a substituted or unsubstituted alkyl group (for example, methyl, ethyl, propyl, n-butyl), a substituted or unsubstituted aryl group (eg, phenyl, 2-methylphenyl), a substituted or unsubstituted alkenyl group (eg, propenyl, 1-methylvinyl), or a substituted or unsubstituted aralkyl group ( For example, benzyl, phenethyl).

R represents an organic group containing at least one thioether group, amino group (including salt form), ammonium group, ether group or heterocyclic group (including salt form). Examples of such an organic group include a group in which a group selected from a substituted or unsubstituted alkyl group, an alkenyl group, an aralkyl group or an aryl group and the above group are combined, and a combination of these groups is used. Good. For example, dimethylaminoethyl, aminoethyl, diethylaminoethyl, dibutylaminoethyl, dimethylaminopropyl hydrochloride, dimethylaminoethylthioethyl, 4-dimethylaminophenyl, 4-dimethylaminobenzyl, methylthioethyl, ethylthiopropyl, 4- Methylthio-
3-cyanophenyl, methylthiomethyl, trimethylammonioethyl, methoxyethyl, methoxyethoxyethoxyethyl, methoxyethylthioethyl, 3,4-dimethoxyphenyl, 3-chloro-4-methoxyphenyl,
Morpholinoethyl, 1-imidazolylethyl, morpholinoethylthioethyl, pyrrolidinoethyl, piperidinopropyl, 2-pyridylmethyl, 2- (1-imidazolyl) ethylthioethyl, pyrazolylethyl, triazolylethyl, methoxyethoxyethoxyethoxyethoxy Carbonylaminoethyl is an example. n represents 0 or 1, m represents 0, 1 or 2, and preferably 1 or 2.

In the general formula (A-II), in the formula, Y, R, n,
M has the same meaning as those in formula (AI), m represents 1 or 2, and Q'represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring which can be formed with iminosilver. . Preferably, it represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring selected from carbon, nitrogen, oxygen, sulfur and selenium. This heterocyclic ring may be condensed as a carbon aromatic ring or a heteroaromatic ring. Examples of the heterocycle formed by Q ′ include indazoles, benzimidazoles,
Benzotriazoles, benzoxazoles, benzothiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, tetraazaindenes, triazaindenes, diazaindenes, pyrazoles, indoles and the like.

The nucleation accelerator represented by the general formula (AI) is preferably one represented by the following general formulas (A-III) to (A-VI).

General formula (A-III) In the formula, M, R, Y and n have the same meanings as those in formula (AI). X represents an oxygen atom, a sulfur atom or a selenium atom, preferably a sulfur atom.

General formula (A-IV) In the formula, R ′ represents a hydrogen atom, a halogen atom (eg chlorine, bromine), a nitro group, a mercapto group, an unsubstituted amino group, a substituted or unsubstituted alkyl group (eg methyl, ethyl), an alkenyl group (eg , Propenyl, 1-methylvinyl), aralkyl groups (eg benzyl, phenethyl), aryl groups (eg phenyl,
2-methylphenyl) or Y _n R.

R ″ represents a hydrogen atom, an unsubstituted amino group or Y _n R, and when R ′ and R ″ represent Y _n R, they may be the same or different from each other.

However, at least one of R ′ and R ″ represents Y _n R.

M, R, Y, and n have the same meanings as those in formula (AI), respectively.

General formula (AV) In the formula, R represents Y _n R. However, M, R,
Y and n have the same meanings as those in formula (AI), respectively.

General formula (A-VI) Hereinafter, the general formula (AI) of the present invention, specifically (A-
The compounds represented by III) to (A-VI) are shown below, but the compounds of the present invention are not limited thereto.

The nucleation accelerator used in the present invention is Berichte der.
Germany Chien Hemitsien Gezershyaft (Berich
te der Deutschen Chemischen Gesellschaft) 28 , 77
(1895), JP-A-50-37436, JP-A-51-3231, U.S. Pat. No. 3,295,976, U.S. Pat. No. 3,376,310, Berichte der Germany Chien Hemitsien Geselsyaft (Beri).
chte der Deutschen Chemischn Gesellschaft) 22 , 568
(1889), 29 , 2483 (1896), Journal of the Chemical Society (J.Chem.Soc.) 1932 , 1806, Journal of the American Chemical Society (J.Am.Chem.Soc.) ) 71 , 4000 (1949), US Patent 2,5
85,388, 2,541,924, Advances in Heterocyclic Chemistry (Advances in Hetero
Cyclic Chemistry) 9 , 165 (1968), Organic Synthesis IV, 569 (1963), Journal of the American Chemical Society (J.Am.Chem.Soc) 45 , 2390 (1923) , Chemische Berichte 9,465 (1876), Japanese Patent Publication No. 40-28496, Japanese Patent Application Laid-Open No. 50-89034, and U.S. Pat. No. 3,106,46.
No. 7, 3,420,670, 2,271,229, 3,137,578,
3,148,066, 3,511,663, 3,060,028, 3,2
No. 71,154, No. 3,251,691, No. 3,598,599, No. 3,148,06
No. 6, JP-B-43-4135, U.S. Pat.Nos. 3,615,616, 3,42
0,664, 3,071,465, 2,444,605, 2,444,606
No. 2,444,607, No. 2,935,404 and the like.

The addition amount of the nucleation accelerator is 10 ^-6 to 1 mol / mol of silver halide.
It is preferably 10 ^-2 mol, more preferably 10 ^-5 to 10 ^-2 mol.

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 a silver halide mainly forming a latent image inside the grains. More specifically, a specific amount of silver halide emulsion (0.5 to 3
g / m ² ) and exposed to it for a fixed period of time of 0.01 to 10 seconds.
The maximum density measured by a usual photographic density measurement method when developed for 5 minutes at a temperature of 20 ° C. in a developing solution B (surface type developing solution) described below was coated in the same amount as described above and exposed in the same manner. Are preferably at least 5 times larger than the maximum density obtained when the development is carried out for 6 minutes, more preferably at least 10 times larger.

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 A specific example of an internal latent emulsion prepared by adding water is disclosed in US Pat.
The conversion type silver halide emulsions described in the specification of U.S. Pat. No. 2,250,3,850,637.
No. 3, No. 3,923,513, No. 4,035,185, No. 4,395,478,
4,504,570, JP-A-52-156614, 55-127549.
No. 53-60222, 56-22681, 59-208540,
No. 60-107641, No. 61-3137, Japanese Patent Application No. 61-32462,
The core / shell type silver halide emulsions described in the patent disclosed in Research Disclosure No. 23510 (issued in November 1983) P236 can be mentioned.

The shape of the silver halide grains used in the present invention may be a regular crystal such as cubic, octahedral, dodecahedral or tetradecahedral, an irregular crystal shape such as spherical, etc. Plate-shaped particles having a thickness ratio of 5 or more may be used. Further, it may be an emulsion having a composite form of these various crystal forms, or an emulsion composed of a mixture thereof.

The composition of silver halide includes silver chloride and silver bromide mixed silver halide. The silver halide preferably used in the present invention does not contain silver iodide or contains 3 mol% or less of salt (iodine). It is silver bromide, (iodo) silver chloride or (iodo) silver bromide.

The average grain size of silver halide grains is 2 μl or less.
0.1 μl or more is preferable, but 1 μl or less and 0.15 μl or more is particularly preferable. The particle size distribution may be narrow or wide, but within ± 40% of the average particle size in terms of number of particles or weight to improve graininess and sharpness,
It is preferable to use a so-called "monodisperse" silver halide emulsion having a narrow grain size distribution such that 90% or more of all grains fall within ± 20%. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes or a plurality of emulsions having the same size but different sensitivities in emulsion layers having substantially the same color sensitivity. Can be mixed in the same layer or multi-layer coated in another layer. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc., alone or in combination. A detailed example is described in, for example, a patent described in Research Disclosure Magazine No. 17643-III (issued in December 1978) P23.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye in a conventional manner. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dye and supersensitizer may be used in combination. Specific examples are described in, for example, patents described in Research Disclosure Magazine No. 17643-IV (issued in December 1978) pp. 23-24.

The photographic emulsion used in the present invention may contain an antifoggant or stabilizer for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or for stabilizing photographic performance. For specific examples, see Research Disclosure No. 17643-VI (19
Published December 1978) and “Stabiliaution of
Photographic Silver Halide Emulsin "(Focal Pres
s), 1974, etc.

Various color couplers can be used in the present invention to directly form a positive color image. A color coupler is a compound that produces a coupling agent with an oxidized product of an aromatic primary amino color developing agent to produce or release a dye which is substantially non-diffusible, and is itself substantially non-diffusible. It is preferably 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 which can be used in the present invention are described in "Research Disclosure Magazine" No. 17643 (December 1978) P25, Item VII-D,
No. 18717 (issued in November, 1979) and Japanese Patent Application No. 61-32462, and the patents cited therein.

Color couplers, couplers with appropriate diffusivity of color forming dyes, colorless couplers, and DIR couplers that release a development inhibitor along with the coupling reaction, in order to correct unnecessary absorption in the short wavelength region of the dyes formed. 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 for preventing irradiation and halation, ultraviolet absorbers, plasticizers, fluorescent brighteners, matting agents, air antifoggants, coating aids, hardeners,
An antistatic agent, a slipperiness improving agent, etc. can be added.
Typical examples of these additives are Research Disclosure No. 17643-VIII- || (Published December 1978) P25-2
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 order of layer arrangement 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 is preferably provided with auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation agent, a back layer, and a white reflective layer in addition to the silver halide emulsion layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are those described in Research Disclosure No.17643-V VII (December 1978) P28 and European patents.
It is coated on the support described in JP-A No. 0,102,253 and JP-A No. 61-97655. Also, Research Disclosure Magazine No.17643
The application method described in XV section p28-29 can be used.

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

Typical examples include a color reversal film for slides or televisions, a color reversal paper, an instant color film, and the like. It can also be applied to full-color copiers and color hard copies for storing CRT images. The present invention is also disclosed in Research Disclosure, No. 17123 (19
This is also applicable to black-and-white light-sensitive materials using a mixture of three-color couplers described in, for example, Jpn.

 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 front exposure in the “light fogging method” of the present invention, that is, the fog exposure, is performed after the imagewise exposure and during the development processing and / or during the development processing.
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 within the photosensitive wavelength of the photosensitive material may be used. In general, any of a fluorescent lamp, a tungsten lamp, a xenon lamp, and sunlight can be used. These specific methods are described, for example, in British Patent 1,151,36.
No. 3, JP-B No. 45-12710, No. 45-12709, No. 58-6936
No., JP-A-48-9727, JP-A-56-137350, JP-A-57-129438
No. 58-62652, No. 58-60739, No. 58-70223 (corresponding US Pat. No. 4,440,851), and No. 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 light-sensitive material or in the processing liquid of the light-sensitive 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 nonmetallic atom group necessary for forming a 5- to 6-membered heterocycle, Z may be substituted with a substituent, R ⁴ is an aliphatic group, and R ⁵ is Is a hydrogen atom, an aliphatic group or an aromatic group, R ⁴ and R ⁵ may be substituted with a substituent, and R ⁵ is further bonded to the heterocyclic ring completed by Z to form a ring. Provided that at least one of the groups represented by R ⁴ , R ⁵ and Z contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R ⁴ and R ⁵ are 6-membered. A ring is formed to form a dihydropyridinium skeleton, and at least one of the substituents of R ⁴ , R ⁵ and Z may have an adsorption promoting group to silver halide, Y is a charge balance N is 0 or 1.

Specific examples of the compound represented by the general formula [N-1] are shown below.

(N-I-1) 5-ethoxy-2-methyl-1-propargylquinolinium bromide (N-I-2) 2,4-dimethyl-1-propargylquinolinium bromide (N-I-3) 3 , 4-Dimethyl-dihydropyrido [2,1-
b] Benzothiazolium bromide (N-I-4) 6-ethoxythiocarbonylamino-2
-Methyl-1-propargylquinolinium trifluoromethanesulfonate (NI-5) 6- (5-benzotriazolecarboxamide) -2-methyl-1-propargylquinolinium trifluoromethanesulfonate (NI-6) ) 6- (5-Mercaptotetrazole-1
-Yl) -2-methyl-1-propargylquinolinium iodide (N-I-7) 6-ethoxythiocarbonylamino-2
-(2-Methyl-1-propenyl) -1-propargylquinolinium trifluoromethanesulfonate (N-I-8) 10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (N -I-9) 7-ethoxythiocarbonylamino-10
-Propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (NI-10) 7- [3- (5-mercaptotetrazol-yl) benzamide] -10-propargyl-1,2, 3,
4-Tetrahydroacridinium perchlorate (N-I-11) 7- (5-mercaptotetrazole-1
-Yl) -9-methyl-10-propargyl-1,2,3,4-
Tetrahydroacridinium bromide (N-12) 7-ethoxythiocarbonylamino-10
-Propargyl-1,2-dihydroacridinium trifluoromethanesulfonate (N-I-13) 10-propargyl-7- [3- (1,2,3,
4-Thiatrizol-5-ylamino) benzamide]
-1,2,3,4-Tetrahydroacridinium perchlorate (NI-14) 7- (3-cyclohexylmethoxythiocarbonylaminobenzamide) -10-propargyl-
1,2,3,4-Tetrahydroacridinium trifluoromethanesulfonate (NI-15) 7- (3-ethoxythiocarbonylaminobenzamide) -10-propargyl-1,2,3,4-tetrahydroacridi Aluminum trifluoromethanesulfonate (NI-16) 7- [3- (3-ethoxythiocarbonylaminophenyl) ureido] -10-propargyl-1,
2,3,4-Tetrahydroacridinium trifluoromethanesulfonate (NI-17) 7- (3-ethoxythiocarbonylaminobenzenesulfonamide) -10-propargyl-1,2,
3,4-Tetrahydroacridinium trifluoromethanesulfonate (NI-18) 7- [3- {3- [3- (5-mercaptotetrazol-1-yl) phenyl] ureido} benzamide] -10-propargyl -1,2,3,4-Tetrahydroacridinium trifluoromethanesulfonate (NI-19) 7- [3- (5-mercapto-1,3,4-
Thiadiazol-1-ylamino) benzamide] -10
-Propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (N-I-20) 7- [3- (3-butylthioureido)
Benzamide] -10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate General formula [N-II] (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 aral 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, a hydrazone structure (NN = C) may be formed in a form including G, R ²² , R ²⁴ and hydrazine nitrogen.
Further, the above-mentioned groups may be substituted with a substituent when possible. ) Next, specific examples of the compound represented by the general formula [N-II] are shown.

(N-II-1) 1-formyl-2- {4- [3- (2-
Methoxysuenyl) ureido] -phenyl} hydrazine (N-II-2) 1-formyl-2- {4- [3- {3-
[3- (2,4-Di-tert-pentylphenoxy) propyl] ureido} phenylsulfonylamino] -phenyl} hydrazine (N-II-3) 1-formyl-2- {4- [3- ( 5-
Mercaptotetrazol-1-yl) benzamido] phenyl} hydrazine (N-II-4) 1-formyl-2- [4- {3- [3-
(5-Mercaptotetrazol-1-yl) phenyl]
Ureido} phenyl] hydrazine (N-II-5) 1-formyl-2- [4- {3- [N-
(5-Mercapto-4-methyl-1,2,4-triazol-3-yl) carbamoyl] propanamide} phenyl] hydrazine (N-II-6) 1-formyl-2- [4- [3- {N −
[4- (3-mercapto-1,2,4-triazole-4-
Iyl) phenyl] carbamoyl] propanamide] phenyl} hydrazine (N-II-7) 1-formyl-2- [4- {3- [N-
(5-Mercapto-1,3,4-thiadiazol-2-yl) carbamoyl] propanamide} phenyl] -hydrazine (N-II-8) 2- [4- (benzotriazole-5-
Carboxamido) phenyl] -1-formylhydrazine (N-II-9) 2- [4- {3- [N- (benzotriazole-5-carboxysamide) carbamoyl] propanamide} phenyl] -1-formylhydrazine ( N-II-10) 1-formyl-2- {4- (N-phenylcarbamoyl) thiosemicarbazide] phenyl} hydrazine (N-II-11) 1-formyl-2- {4- [3- (3-
Phenylthioureido) benzamide] phenyl} hydrazine (N-II-12) 1-formyl-2- [4- (3-hexylureido) phenyl] hydrazine (N-II-13) 1-formyl-2- {4 -[3- (5-
(Mercaptotetrazol-1-yl) benzenesulfonamide] phenyl} hydrazine (N-II-14) 1-formyl-2- {4- [3- {3-
[3- (5-Mercaptotetrazol-1-yl) phenyl] ureido} benzenesulfonamide] phenyl}
Hydrazine (N-II-15) 1-formyl-2- [4- {3- [3-
(2,4-Di-tert-pentylphenoxy) propyl] ureido} phenyl] hydrazine The nucleating agent used in the present invention can be contained in the photosensitive material or in the processing liquid of the photosensitive material, and preferably the photosensitive material. It can be contained inside.

When the nucleating agent is incorporated in the light-sensitive material, it is preferably added to the inner latent silver halide emulsion layer. For example, it may be added to the intermediate layer, the undercoat layer or the 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.

When a nucleating agent is contained in the light-sensitive material, the amount used is preferably 10 ^-8 to 10 ^-2 mol, and more preferably 10 ^-7 to 10 ^-3 mol, per mol of silver halide.

When a nucleating agent is added to the processing solution, the amount used is
It is preferably 10 ^-5 to 10 ^-1 mol, more preferably 10 ^-5 mol per ¹ mol.
^-4 to 10 ^-2 mol.

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-
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline, 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-
Examples include 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 wapper), the application, 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 water volume in the multi-stage countercurrent system 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, P248-253 (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, etc .; aminophenols such as p-aminophenol, N-methyl-
p-aminophenol, 2,4-diaminophenol and the like;
3-pyrazolidones, for example 1-phenyl-3-pyrazolidones, 1-phenyl, 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, alone or in combination. In addition, JP-A-58-55
The developing solution described in No. 928 can also be used.

For detailed examples of developers, preservatives, buffers and developing methods for black-and-white photosensitive materials and their use, refer to Research Disclosure No.17643 (1978
Published in December) XIX ~ X ||

(Examples) 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
(0 micron), the following 1st to 14th layers were multilayer-coated, and the 15th to 16th layers were coated on the back side to prepare a color photographic light-sensitive material. The polyethylene on the side coated with the first layer contains titanium oxide as a white pigment and a trace amount of ultramarine as a bluing dye (the chromaticity of the surface of the support is 8 ^* for L ^* , a ^* , b ^* systems,
-0.20 and -0.75. ).

(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 emulsion for the 14th layer, a Lippmann emulsion which was not surface-sensitized was used.

1st layer (antihalation layer) Black colloidal silver …… 0.10 Gelatin …… 0.70 2nd layer (intermediate layer) Gelatin …… 0.7 3rd layer (low sensitivity red sensitive layer) Red sensitizing dye (ExS-1,2, Silver bromide spectrally sensitized by 3) (average grain size 0.25μ, size distribution [variation coefficient] 8
%, Octahedron) ...... 0.04 Silver chlorobromide spectrally sensitized with red sensitizing dye (ExS-1,2,3) (5 mol% silver chloride, average grain size 0.40μ, size distribution 10%, octane) Hedron) …… 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 equivalent) …… 0.18 Stain prevention Agent (Cpd-5) …… 0.003 Coupler dispersion medium (Cpd-6) …… 0.03 Coupler solvent (Solv-1,2,3 equivalent) …… 0.12 4th layer (high sensitivity red sensitive layer) Red sensitizing dye (ExS-1,2,3) spectrally sensitized silver bromide (average grain 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-fade agent (Cpd-1,2,3,4 equivalent) …… 0.18 Coupler dispersion medium (Cpd -6) …… 0.03 Coupler solvent (Solv-1,2,3 equivalent) …… 0.12 Fifth layer (intermediate layer) Gelatin …… 1.00 Anti-fading agent (Cpd-7) ・ ・ ・ 0.08 Anti-solvent solvent (Solv -4,5 equivalent) ...... 0.16 Polymer latex (Cpd-8) ...... 0.10 6th layer (low sensitivity green sensitive layer) Silver bromide spectrally sensitized with green sensitizing dye (ExS-4) (average) Grain size 0.25μ, size distribution 8%, octahedron) ...
… 0.04 Silver chlorobromide spectrally sensitized with a green sensitizing dye (ExS-4) (5 mol% silver chloride, average grain size 0.40μ, size distribution)
10%, octahedron) …… 0.06 Gelatin …… 0.80 Magenta coupler (ExM-1,2,3 equivalent) …… 0.11 Anti-fading agent (equal to Cpd-9,26) …… 0.15 Anti-stain agent (Cpd) −10,11,12,13 in 10: 7: 7: 1 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 sensitization with green sensitizing dye (ExS-4) Sensitive silver bromide (average grain size 0.65μ, size distribution 16%, octahedron) ...
… 0.10 Gelatin …… 0.80 Magenta coupler (ExM-1,2,3 equivalent) …… 0.11 Anti-fading agent (Cpd-9,26 equivalent) …… 0.15 Anti-staining agent (Cpd-10,11,12, 13 to 10: 7: 7: 1 ratio)
…… 0.025 Coupler dispersion medium (Cpd-6) …… 0.05 Coupler solvent (Solv-4,6 equivalents) …… 0.15 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow filter layer) Yellow colloid Silver: 0.12 Gelatin: 0.07 Anti-fading agent (Cpd-7): 0.03 Anti-color mixing agent solvent (Solv-4,5 equivalent): 0.10 Polymer latex (Cpd-8): 0.07 10th layer (intermediate) Layer) Same as 5th layer 11th layer (low sensitivity blue sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.40μ, size distribution 8%, 8% (Face piece) ...
… 0.07 Silver chlorobromide spectrally sensitized with blue sensitizing dye (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 equivalent) ...... 0.35 Anti-fading agent (Cpd-14) ...... 0.10 Anti-staining agent (Cpd-5,15 1: 0.007 Coupler dispersion medium (Cpd-6) …… 0.05 Coupler solvent (Solv-2) …… 0.10 12th layer (high sensitivity blue sensitive layer) Blue sensitizing dye (ExS-5,6) Spectral sensitized silver bromide (average grain size 0.85μ, size distribution 18%, octahedron) ...
… 0.15 Gelatin …… 0.60 Yellow coupler (ExY-1,2 equivalent) …… 0.30 Anti-fading agent (Cpd-14) …… 0.10 Anti-staining agent (Cpd-5,15 in 1: 5 ratio) …… 0.007 Coupler dispersion medium (Cpd-6) …… 0.05 Coupler solvent (Solv-2) …… 0.10 13th layer (UV absorbing layer) Gelatin …… 1.00 UV absorber (Cpd-2,4,16 equivalents) …… 0.50 Anti-fading agent (Cpd-7,17 equivalents) ...... 0.03 Dispersion medium (Cpd-6) ...... 0.02 UV absorber solvent (Solv-2,7 equivalents) ...... 0.08 Anti-irradiation dye (Cpd-18, 19,20,21,27 to 1
0: 10: 13: 15: 20 ratio) ...... 0.05 14th layer (protective layer) Fine grain silver chlorobromide (97 mol% silver chloride, average size 0.1)
μ) …… 0.03 Acrylic modified copolymer of polyvinyl alcohol …… 0.
01 Polymethylmethacrylate 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 Absorbent (Cpd-2,4,16 equivalents) …… 0.50 Dye (Cpd18,19,20,21,27 equivalents) …… 0.06 16th layer (backside protective layer) Polymethylmethacrylate particles (average particle size) 2.4
μ) and silicon oxide (average particle size 5μ) Equivalent …… 0.05 Gelatin …… 2.00 Gelatin hardening agent (H-1, H-2 equivalent) …… 0.14 How to make emulsion EM-1 Of potassium bromide and silver nitrate The aqueous solution was added to gelatin with vigorous stirring at 75 ° C for 15 minutes at the same time to obtain octahedral silver bromide grains having an average grain size of 0.40μ. 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-mole per mol of silver was added to this emulsion.
Thion, 6 mg sodium thiosulfate and 7 mg chloroauric acid (4
Chemical sensitization treatment was carried out by sequentially adding water salt) and heating at 75 ° C. for 80 minutes. With the particles thus obtained as the core,
Further growth was performed in the same precipitation environment as in the first time, and finally an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.7 μ was obtained. The coefficient of variation of particle size was about 10%. To this emulsion 1.5 mg sodium thiosulfate per mole silver and 1.5
Chloroauric acid (tetrahydrate) was added to the mixture and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

In each photosensitive layer, ExZK-1 and ExZK-2 were used as nucleating agents in an amount of 10 ^-3 and 10 ^-2 % by weight, respectively, based on silver halide. Further, each layer has an alkanol XC (Dupon
Co., Ltd.) and sodium alkylbenzenesulfonate, and succinic acid ester and Magefac F-120 (Dainippon Ink Co., Ltd.) were used as coating aids. (Cpd-23, 24, 25) was used as a stabilizer in the layer containing silver halide and colloidal silver.

 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 tricresyl phosphate Solv-5 dibutyl phthalate Solv-6 trioctyl phosphate Solv-7 di ( 2-Ethylhexyl) phthalate H-1 1,2-bis (vinylsulfonylacetamide)
Ethane H-2 4,6-Dichloro-2-hydroxy-1,3,5-triazine Na salt ExZK-17 7- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-10-propargyl-1,2, 3,
4-Tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5- {3-
[2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenylcarbamoyl] -4-hydroxy-1-naphthylthio} tetrazol-1-yl]
Phenyl} ureido] benzenesulfonamide} phenyl] -1-formylhydrazine Treatment step A Treatment step Time Temperature Color development 135 seconds 38 ° C Bleach fixing 40〃 33〃 Water wash (1) 40〃 33〃 Water wash (2) 40〃 33〃 Dry 30 ~ 80〃 The composition of each processing solution was as follows.

Color developer Mother liquor D-sorbit 0.15g Sodium naphthalene sulfonate 0.15g Formalin condensate Ethylenediaminetetrakis 1.5g Methylenephosphonic acid Diethylene glycol 12.0ml Benzyl alcohol 13.5ml Potassium bromide 0.80g Benzotriazole 0.003g Sodium sulfite 2.4g N, N-bis (Carboxymethyl) 6.0 g Hydrazine D-Glucose 2.0 g Triethanolamine 6.0 g N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulphate Potassium carbonate 30.0 g Optical brightener (Dianostilbene type) 1.0g Add water 1000ml pH (25 ℃) 10.25 Drift and fixer mother liquor Ethylenediamide tetraacetic acid ・ 2 sodium ・ dihydrate 4.0g Ethylenediamide tetraacetic acid ・ Fe (III) ・ Ammonium ・ 2water Salt 70.0g Ammonium thiosulfate (700g / l) 180ml p-Toluenesulfi Sodium acid salt 20.0g Sodium bisulfite 20.0g 5-Mercapto-1,3,4-triazole 0.5g Ammonium nitrate 10.0g Add water to produce progeny 1000ml pH (25 ℃) 6.20 Rinse water Tap water 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) are passed through a mixed bed type column, and calcium and magnesium ion concentration is 3 mg / l or less. Was added, followed by the addition of 20 mg / l sodium isocyanurate dichloride. The pH of this solution is 6.5-
It was in the range of 7.5.

A light-sensitive material is prepared as described above, and the color light-sensitive material N
oA. Sample Nos. 1 to 9 were prepared in the same manner as Sample No. A except that the fog-releasing compound and the nucleation accelerator were used in each photosensitive layer as shown in Table 1. These samples were subjected to wedge exposure (3200 k, 0.1 second, 100 CMS) before and after incubation (45 ° C., 80% RH, 2 days), and then subjected to processing step A. The obtained color image density was measured, and the magenta density values are shown in Table 1.

Sample No. 1,2,4,5,7,8 using the irritation agent-releasing compound of the present invention and the nucleation accelerator has a higher Dmax than Comparative Examples No. 3,6,9, A. And Dmin was low and I liked it. Moreover, the effect was more remarkable after the incubation.

Similar results were obtained for yellow and cyan densities.

Example-2 Example-1 was repeated except that 1-1, 1-3, 1-4, 1-7, 1-2 were used in place of 1-24, and similar results were obtained.

Example-3 Example-3 except that 2-1 and 2-2 were used instead of 2-4.
1 was repeated and similar results were obtained.

Example-4 Example-1 was repeated except that 3-5,3-8,3-9,3-10 was used instead of 3-1 and similar results were obtained.

〔The invention's effect〕

According to the present invention, an image having a high maximum image density Dmax can be obtained without increasing the minimum image density Dmin, and such an image can be obtained even if a rapid development process is performed. In addition, the minimum image density Dmin does not increase even after long-term storage, and the maximum image density Dmax
It is possible to suppress these fluctuations with a small decrease.
In the present invention, as seen in Table 1 of Example 1, the decrease in the maximum image density Dmax after incubation (corresponding to long-term storage) is very small, and the minimum image density Dmin
Does not increase at all. This effect is not exhibited by using the stimulant-releasing compound alone, but is exhibited only when used in combination with a specific nucleation accelerator.

Claims (1)

(57) [Claims] 1. A photographic light-sensitive material having at least one non-pre-fogged internal latent image type silver halide emulsion layer on a support, and a coupling reaction with an oxidized product of a developing agent and / or a redox reaction during development. At least one compound capable of releasing a rash agent represented by the following general formula [M] under alkaline conditions and a nucleation accelerator represented by the following general formula [AI] and / or [A-II] A direct positive photographic light-sensitive material characterized by containing. General formula [M] In the formula, R ^m1 represents a divalent aromatic group, R ^m2 is a hydrogen atom,
Represents an alkyl group, an aralkyl group, 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 (NH = C <), and R ^m3
And R ^m4 both represent a hydrogen atom or one of them represents a hydrogen atom and the other represents one of an alkylsulfonyl group, an arylsulfonyl group and an acyl group. A represents a group that promotes adsorption to silver halide, and L represents a divalent continuous group. n represents 0 or 1. General formula [AI] General formula [A-II]