JPH0778603B2 - Silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention forms an extremely hard negative image, a highly sensitive negative image, a silver halide photographic light-sensitive material giving a good halftone dot image, or a direct positive photographic image. And a photographic light-sensitive material containing a novel compound as a nucleating agent for silver halide.

(Prior Art) Addition of a hydrazine compound to a silver halide photographic emulsion or a developing solution is carried out according to US Pat. Nos. 3,730,727 (developing solution combining ascorbic acid and hydrazine) and 3,227,552 (to obtain a direct positive color image). No. 3,386,831 (containing β-mono-phenylhydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitizers), No. 2,419,975, and Mess (Mess)
The Theory of Photographic Process 3rd edition (1966)
Year) pp. 281 etc.

Among these, in particular, U.S. Pat. No. 2,419,975 discloses that addition of a hydrazine compound gives a negative tone image with high contrast.

In the patent specification, when a hydrazine compound is added to a silver chlorobromide emulsion and development is performed with a developer having a high pH of 12.8,
It is described that extremely hard photographic characteristics having a gamma (γ) of more than 10 can be obtained. However, a strong alkaline developer having a pH close to 13 is easily oxidized by air and is unstable, and cannot withstand long-term storage and use.

The ultra-high contrast photographic characteristics with a gamma of more than 10 are useful for printing plate making, whether it is a negative image or a positive image.
It is very useful for photographic reproduction of continuous-tone images or reproduction of line drawings. For this purpose, the conventional content of silver chloride is 50 mol%, preferably 75 mol%.
A method of using a silver chlorobromide photographic emulsion having a particle size of more than 5,000 and developing with a hydroquinone developer having an extremely low effective concentration of sulfite ion (usually 0.1 mol / l or less) has been generally used. However, in this method, since the concentration of sulfite ion in the developer is low, the developer is extremely unstable and cannot be stored for more than 3 days.

Furthermore, since none of these methods requires the use of a silver chlorobromide emulsion having a relatively high silver chloride content, high sensitivity cannot be obtained. Therefore, there has been a strong demand for obtaining super-high contrast photographic characteristics useful for reproducing halftone images and line images by using a high-sensitivity emulsion and a stable developing solution.

The present inventors U.S. Pat.Nos. 4,224,401 and 4,168,977,
No. 4,243,739, No. 4,272,614, No. 4,323,643, etc., disclosed a silver halide photographic emulsion which gives a very hard negative photographic property by using a stable developing solution.
It has been found that the acylhydrazine compounds used in them have several drawbacks.

That is, it is known that these conventional hydrazines generate nitrogen gas during the development processing, and these gases collect in the film and become bubbles to impair the photographic image. The fact that it leaks into the liquid adversely affects other photographic light-sensitive materials.

In addition, when a large amount of these conventional hydrazines are required for sensitizing and hardening, or when high sensitivity is required for the performance of the photosensitive material, other sensitization techniques (for example, chemical sensitization) are used. To increase the particle size, increase the particle size, add a compound that promotes sensitization such as described in U.S. Pat.Nos. 4,272,606 and 4,241,164), and generally sensitize over time during storage and Increased fog may occur.

Therefore, a compound which can reduce the generation of such bubbles and the outflow to the developing solution, has no problem in the stability over time, and can obtain extremely hard photographic characteristics with the addition of an extremely small amount is desired. Was there.

Also, U.S. Pat.Nos. 4,385,108, 4,269,929, and 4,24
No. 3,739 describes that hydrazines having substituents that are easily adsorbed to silver halide grains can be used to obtain extremely hard negative tone gradation photographic properties. Among the hydrazine compounds, those specifically mentioned in the above-mentioned known examples have a problem that they cause desensitization with time during storage. Therefore, it was necessary to select a compound that does not cause such a problem.

On the other hand, although there are various direct positive photography methods, there is a method in which a silver halide grain which has been fogged in advance is exposed in the presence of a desensitizer and then developed, and a method in which a silver halide grain having a photosensitive nucleus is mainly used. The most useful method is to develop a silver emulsion in the presence of a nucleating agent after exposure. The present invention relates to the latter. A silver halide emulsion having a photosensitive nucleus mainly inside the silver halide grain and forming a latent image mainly inside the grain is said to be an internal latent image type silver halide emulsion and is mainly formed on the surface of the grain. It can be distinguished from the image forming silver halide grains.

A method for directly obtaining a positive image by surface-developing an internal latent image type silver halide photographic emulsion in the presence of a nucleating agent and a photographic emulsion or a light-sensitive material used in such a method are known.

In the above method for obtaining a direct positive image, the nucleating agent may be added to the developing solution, but the nucleating agent is added to the photographic emulsion layer of the light-sensitive material or other appropriate layer so as to be adsorbed on the silver halide grain surface. Sometimes better inversion characteristics can be obtained.

As the nucleating agent used in the method for obtaining the above direct positive image, U.S. Pat.Nos. 2,563,785 and 2,588,982, hydrazines, and U.S. Pat.No. 3,227,552, hydrazides and hydrazine compounds described in U.S. Pat. Patents 3,615,615, 3,719,494, 3,734,738,
4,094,683 and 4,115,122, British Patent 1,283,
835, the heterocyclic quaternary salt compounds described in JP-A Nos. 52-3426 and 52-69613, U.S. Pat. Nos. 4,030,925 and 4,03
1,127, 4,139,387, 4,245,037, 4,255,511
No. and 4,276,364, thiourea-bonded acylphenylhydrazine compounds described in British Patent No. 2,012,443, compounds having a heterocyclic thioamide described in U.S. Patent No. 4,080,207 as an adsorption group, British Patent No. 2,011. ,
Phenylacylhydrazine compound having a heterocyclic group having a mercapto group as an adsorption type described in 397B, a sensitizing dye having a nucleating substituent in the molecular structure described in U.S. Pat.No. 3,718,470, Kaisho 59-200, 230, 59
-212,828 and 59-212,829, and the hydrazine compounds described in Research Disclosure No. 23510 (November 1953) are known. However, all of these nucleating agents for obtaining a high-tone negative image or positive image have insufficient activity as a nucleating agent, and those with high activity have insufficient storage stability, or emulsions. It has been found that there are drawbacks such that the activity fluctuates by the time of application after the addition to the above, and the film quality deteriorates when more types are added.

For the purpose of solving these drawbacks, JP-A-60-179,734,
61-170,733, 61-270,744, 62-65,034, 62-
No. 948, Japanese Patent Application No. 62-58,513, No. 62-67,508, No. 62-67,5
09, 62-67,510, 62-166,117, 62-143,469
Although the nucleating agent described in No. 1 is proposed, it is desired to lower the pH of the processing solution in order to improve the stability of the processing solution (that is, prevent the deterioration of the developing agent), or shorten the processing time of development. In view of the desire to do so or to reduce the dependency of changes in developer composition (for example, pH, sodium sulfite, etc.), a higher nucleating activity has been desired.

(Problems to be Solved by the Invention) Accordingly, the first object of the present invention is, firstly, a halogen capable of obtaining a very hard negative tone photographic characteristic with a gamma of more than 10 by using a stable developing solution. A silver halide photographic light-sensitive material is provided.

Secondly, the object of the present invention is to provide novel highly active hydrazines which can impart desired extremely hard negative tone photographic characteristics with a small addition amount even at a low addition amount without adversely affecting photographic characteristics. It is to provide a negative silver halide photographic light-sensitive material containing the same.

Thirdly, an object of the present invention is to provide a direct positive type silver halide photographic light-sensitive material containing a novel highly active hydrazine which can give excellent reversal characteristics even in a low pH developer.

A fourth object of the present invention is to provide a silver halide photographic light-sensitive material containing novel highly active hydrazines which are easy to synthesize and have excellent storage stability and which are stable with time.

(Means for Solving Problems) An object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer, the photographic emulsion layer or at least one hydrophilic colloid layer having the following: This has been achieved by including the compound represented by the general formula (I).

General formula (I) In the formula, A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other represents a sulfonyl group, or an acyl group, G ₁ is a carbonyl group, a sulfonyl group, a sulfoxy group, Or represents an imino methylene group, L ₁ represents a divalent linking group, R ₁ and R ₂ represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, R ₃ is a hydrogen atom, an alkyl group, Aryl group, alkoxy group, aralkyl group, aryloxy group,
Alternatively, it represents an amino group, and R ₄ represents a hydrogen atom, an alkyl group or an aryl group.

INDUSTRIAL APPLICABILITY The present invention has the following formula (I) It was possible to find highly active hydrazines that could not be predicted from the conventional knowledge by introducing.

Next, the general formula (I) will be described in detail.

In the general formula (I), A ₁ and A ₂ are each a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a hamet having a sum of substituent constants of −0.5 or more). A substituted phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or the sum of the substituent constants of a hamet is −0.
5 or more substituted benzoyl group), or a linear or branched or cyclic unsubstituted and substituted aliphatic acyl group (as a substituent, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, A hydroxyl group, a carboxy group, and a sulfonic acid group.),
Most preferably, both A ₁ and A ₂ are hydrogen atoms.

The aliphatic group represented by R ₁ and R ₂ is a linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group, preferably having 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms. belongs to. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein.

For example, methyl group, t-butyl group, n-octyl group, t-
Examples thereof include an octyl group, a cyclohexyl group, a hexenyl group, a pyrrolidyl group, a tetrahydrofuryl group and an n-dodecyl group.

The aromatic group is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.

The heterocyclic group is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O or S atoms, which may be a single ring or a condensed ring with another aromatic ring or heterocyclic ring. May be formed. Preferred as a heterocycle is a 5- or 6-membered aromatic heterocycle,
For example, pyridine ring, imidazolyl group, quinolinyl group,
Benzimidazolyl group, pyrimidyl group, pyrazolyl group,
Examples thereof include an isoquinolinyl group, a benzthiazolyl group and a thiazolyl group.

R ₁ and R ₂ may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted.

For example, alkyl group, aralkyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group,
Examples thereof include a sulfamoyl group, a carbamoyl group, an aryl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group and a carboxyl group.

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

R ₁ and R ₂ may combine with L ₁ to form a ring. Also, R ₁ and R
₂ may be linked to form a ring, which is cyclized to form a heterocycle containing one or more heteroatoms (eg oxygen atom, sulfur atom, nitrogen atom, etc.) It may be, for example, a pyrrolidine ring, a piperidine ring, a morphono group and the like.

The divalent organic group represented by L ₁ is an atom or atomic group containing at least one of C, N, S and O, and specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group. , A heteroarylene group (these groups may have a substituent) or a combination thereof, and an arylene group is preferable. The arylene group specifically represents a phenylene group or a naphthylene group, and may be substituted with a substituent. As the substituent, an alkyl group, an aralkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group,
Halogen atom, cyano group, acyl group, nitro group and And so on.

G _1, R ₃ is when G ₁ is a carbonyl group R ₃ is a hydrogen atom, an alkyl group (e.g. methyl group, a trifluoromethyl group, 3
-Hydroxypropyl group, 3-methanesulfonamidopropyl group etc.), aralkyl group (eg o-hydroxybenzyl group etc.), aryl group (eg phenyl group, 3,
5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, etc.) are preferable. When G ₁ is a sulfonyl group, R ₃ is an alkyl group (eg, methyl group) or an aralkyl group (eg, o).
-Hydroxyphenylmethyl group etc.), aryl group (eg phenyl group etc.) or substituted amino group (eg dimethylamino group etc.) and the like are preferable.

When G ₁ is a sulfoxy group, R ₃ is preferably a cyanobenzyl group or a methylthiobenzyl group, and G ₁ is In the case of, R ₃ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group or a phenyl group.

When G ₁ is an N-substituted or unsubstituted iminomethylene group, R ₃ is a methyl group, an ethyl group or a substituted or unsubstituted phenyl group.

Here, examples of the substituent of R ₃ include the following. These groups may be further substituted.

For example, alkyl group, aralkyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group,
Sulfamoyl group, carbamoyl group, alkylthio group,
Examples thereof include an arylthio group, a sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, an acyloxy group, an acyl group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, and a nitro group.

Also, if possible, these groups may form a ring linked to each other.

Here, a carbonyl group is particularly preferable as G ₁ , and a hydrogen atom or a group represented by the general formula (a) is preferable as R ₃ .

In the general formula (a) -L ₂ -Z ₁ formula, Z ₁ is a group capable of splitting the G ₁ -L ₂ -Z ₁ moiety nucleophilically attacks against G ₁ from the remainder molecule, L ₂ is Z ₁ is a divalent organic group capable of nucleophilically attacking G ₁ to form a cyclic structure with G ₁ , L ₂ and Z ₁ .

More specifically, Z ₁ is a hydrazine compound represented by the general formula (I) when oxidized by Easily nucleophilically attacks G ₁ when generating Is a group capable of splitting from G ₁ , specifically OH, SH or
NHR ₅ (R ₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, -COR ₆ or -SO ₂ R ₆ , and R ₆ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.) , CO
It may be a functional group which directly reacts with G ₁ such as OH (wherein OH, SH, NHR ₅ and --COOH are temporarily used to generate these groups by hydrolysis of alkali etc.). May be protected) or (R ₇ and R ₈ represent hydrogen atom, alkyl group, alkenyl group, aryl group or heterocyclic group) and react with G ₁ by reacting with nucleophile such as hydroxide ion or sulfite ion It may be a functional group that enables

The divalent organic group represented by L ₂ is an atom or atomic group containing at least one of C, N, S and O, and specific examples thereof include an alkylene group, an alkenylene group, an alkynylene group and an arylene group. Group, a heteroarylene group (these groups may have a substituent), -O-, -S-, (R ₉ represents a hydrogen atom, an alkyl group or an aryl group)-
N =, —CO—, —SO ₂ — and the like or a combination thereof, and preferably the ring formed by G ₁ , Z ₁ and L ₂ is a 5-membered or 6-membered ring.

Among those represented by the general formula (a), preferred are those represented by the general formula (b) and the general formula (c).

General formula (b) In the formula, R _b ^{1 to} R _b ⁴ are hydrogen atoms, alkyl groups, (preferably having 1 to 12 carbon atoms) alkenyl groups (preferably having 2 to 12 carbon atoms) aryl groups (preferably having 6 to 12 carbon atoms) 12 items) etc., and may be the same or different. B is an atom necessary for completing a 5-membered ring or 6-membered ring which may have a substituent, m and n are 0 or 1, and (n +
m) is 0 or 1 when Z ₁ is a COOH group, Z is OH,
It is 1 or 2 for SH and NHR ₄ .

The 5- or 6-membered ring formed by B is, for example, a cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring or a quinoline ring, and Z ₁ has the same meaning as in formula (a).

Of the general formula (b), preferred are those in which m = 0 and n = 1, and particularly preferred is that the ring formed by B is a benzene ring.

General formula (c) In the formula, R _c ¹ and R _c ² represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a halogen atom, and may be the same or different.

R _c ³ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. p represents 0, 1 or 2 and q represents 1
Represents ~ 4.

R _c ¹ , R _c ² and R _c ³ may combine with each other to form a ring as long as Z ₁ can undergo an intramolecular nucleophilic attack on G ₁ .

R _c ¹ and R _c ² are preferably a hydrogen atom, a halogen atom or an alkyl group, and R _c ³ is preferably an alkyl group or an aryl group.

q is preferably 1 to 3, when q is 1, p is 1 or 2, when q is 2, p is 0 or 1, and when q is 3, p is 0 or 1, and q is 2 Or when 3 CR _c ¹
R _c ² may be the same or different.

Z ₁ has the same meaning as in formula (a).

R ₄ represents a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, a methoxymethyl group or the like) or an aryl group (for example, a phenyl group or the like), and a hydrogen atom is preferable.

Next, R ₁ , R ₂ , L ₁ or R ₃ , and especially R ₁ and R ₂ are preferably those containing a diffusion resistant group such as a coupler, that is, a so-called ballast group. This ballast group has 8 or more carbon atoms and is an alkyl group, a phenyl group, an ether group, an amide group, a ureido group,
It is composed of one or more combinations of urethane group, sulfonamide group, thioether group and the like.

Further, R ₁ , R ₂ , L ₁ or R ₃ is preferably a compound represented by the general formula (I) having an adsorption promoting group Y ₁ L _{3 l} on the surface of silver halide.

Y ₁ is an adsorption promoting group to silver halide, and L ₃ is a divalent linking group. l is 0 or 1. Preferred examples of the adsorption accelerating group represented by Y ₁ on silver halide include a thioamide group, a mercapto group, a group having a disulphide bond or a 5- or 6-membered nitrogen-containing heterocyclic group.

The thioamide adsorption promoting group represented by Y ₁ is Is a divalent group represented by, and may be a part of the ring structure, or may be an acyclic thioamide group. Useful thioamide adsorption promoting groups are described, for example, in U.S. Pat.
No. 4,031,127, 4,080,207, 4,245,037,
No. 4,255,511, No. 4,266,013, and No. 4,276,364,
And "Research Disclosure" (Resear
ch Disclosure) Volume 151 No. 15162 (November 1976) and Volume 176 No. 17626 (December 1978).

Specific examples of the acyclic thioamide group include, for example, thioureido group, thiourethane group, dithiocarbamic acid ester group and the like, and specific examples of the cyclic thioamide group include, for example, 4-thiazoline-2-thione, 4-imidazoline- group.
2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-
Triazoline-3-thione, 1,3,4-thiadiazoline-
2-thione, 1,3,4-oxadiazoline-2-thione,
Examples thereof include benzimidazoline-2-thione, benzoxazoline-2-thione and benzothiazoline-2-thione, which may be further substituted.

The mercapto group of Y ₂ is an aliphatic mercapto group, an aromatic mercapto group or a heterocyclic mercapto group (when the carbon atom to which the --SH group is bonded is a nitrogen atom next to it, a cyclic thioamide having a tautomeric relationship with this) Synonymous with the group, and specific examples of this group are the same as those listed above).

Examples of the 5-membered to 6-membered nitrogen-containing heterocyclic group represented by Y ₁ include 5-membered to 6-membered nitrogen-containing heterocycles consisting of a combination of nitrogen, oxygen, sulfur and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine and the like.
These may be further substituted with appropriate substituents.

Examples of the substituent include those mentioned as the substituents of R ₁ and R ₂ .

Among those represented by Y ₁ , preferred are cyclic thioamide groups (that is, mercapto group-containing nitrogen-containing heterocycles,
For example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.), Alternatively, it is the case of a nitrogen-containing heterocyclic group (for example, a benzotriazole group, a benzimidazole group, an indazole group, etc.).

Two or more Y ₁ L _{3 l} groups may be substituted and may be the same or different.

Examples of the divalent linking group represented by L ₃ include C, N, S and O.
An atom or atomic group containing at least one of the above. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, -NH-,
-N =, - CO -, - SO 2 - ( these groups may also have with substituent) is made of a single or combination of such.

Specific examples include -CONH -, - NHCONH -, - SO 2 NH-, -COO -, - NHCOO-, -CH ₂ -, CH _{2 2,} NHCONHCH ₂ CH ₂ CONH-, -CH ₂ CH ₂ SO ₂ NH-, -CH ₂ CH ₂ CONH- General formula (II) In the formula, R ₁₀ has the same meaning as the substituent of R ₁ and R _{2 in} the general formula (I), and k represents 0, 1 or 2.

R ₁ , R ₂ , R ₃ , A ₁ , A ₂ and G ₁ have the same meanings as described in formula (I), Is preferably a hydrazino group substituted at the o-position or the p-position.

Specific examples of the compound represented by formula (I) are shown below. However, the present invention is not limited to the following inventions.

A typical example of the method for synthesizing the compound represented by formula (I) will be described with reference to synthetic examples.

Synthesis Example 1 Synthesis of Exemplified Compound I-2 2- (4-aminophenyl) -1-formylhydrazine
15.1 g (0.1 mol) was dissolved in a mixed solvent of 50 ml of dimethylacetamide and 50 ml of acetonitrile, 10.1 g (0.1 mol) of triethylamine was added to the mixture while stirring well under a nitrogen atmosphere, and then the reaction temperature was cooled to about 0 ° C. -(N-
20 g (0.1 mol) of propyl) aminosulfonyl chloride was slowly added dropwise over about 1 hour. After the addition, the reaction temperature was returned to about 20 ° C and stirred for 30 minutes. The reaction solution was poured into water of 1 and extracted with ethyl acetate 1. After drying over sodium sulfate, ethyl acetate was distilled off. The residual oily substance was isolated and purified by silica gel column chromatography to obtain Exemplified Compound I-2 as an oily substance.
17.6 g (56.2%) was obtained.

Synthesis Example 2 Synthesis of Exemplified Compound I-3 2- (4-aminophenyl) -1-formylhydrazine
15.1 g (0.1 mol) was dissolved in a mixed solvent of 50 ml of dimethylacetamide and 50 ml of acetonitrile, 10.1 g (0.1 mol) of triethylamine was added with stirring under a nitrogen atmosphere, and then the reaction temperature was cooled to about 0 ° C. 29.6 g (0.1 mol) of dibenzylaminosulfonyl chloride was slowly added dropwise over about 1 hour. After the addition, the reaction temperature was returned to about 20 ° C. and the mixture was stirred for 30 minutes. The reaction solution was poured into water of 1 and ethyl acetate 1 was added. It was extracted and dried over sodium sulfate, and ethyl acetate was distilled off.

The residual oily substance was isolated and purified by silica gel column chromatography to obtain 26.0 g (63.3 g) of Exemplified Compound I-3 as an oily substance.
%)Obtained.

When the compound of the present invention is incorporated into the photographic emulsion layer or the hydrophilic colloid layer, the compound of the present invention is dissolved in water or a water-miscible organic solvent (if necessary, alkali hydroxide or ternary). A secondary amine may be added to form a salt to dissolve it), a hydrophilic colloid solution (for example, a silver halide emulsion,
Gelatin aqueous solution, etc.) (at this time, the pH may be adjusted by adding acid or alkali, if necessary).

The compounds of the present invention may be used alone or in combination of two or more kinds. The addition amount of the compound of the present invention is preferably 1 × 10 ^{−5 to} 5 × 10 ⁻² mol, and more preferably 2 × 10 ⁻⁵ mol to 1 × 10 ⁻² mol, per 1 mol of silver halide, and they are combined. An appropriate value can be selected according to the properties of the silver halide emulsion.

The compound represented by formula (I) of the present invention can form a negative image with high contrast when used in combination with a negative emulsion. On the other hand, it can also be used in combination with an internal latent image type silver halide emulsion. The compound represented by formula (I) of the present invention is preferably used in combination with a negative emulsion to form a negative image having high contrast.

When used for forming a negative image with high contrast, the average grain size of silver halide used is preferably fine grains (for example, 0.7 μ or less), and particularly preferably 0.5 μ or less. The particle size distribution is basically not limited, but it is preferably monodisperse. The term "monodisperse" as used herein means that at least 95% by weight or number of particles is ± 40 of the average particle size
It is composed of particle groups having a size within%.

The silver halide grains in the photographic emulsion are cubic, octahedral, and rhombo 12
Those with regular (regular) crystals such as tetrahedrons and tetradecahedrons, and those with irregular (irregular) crystals such as spheres and flat plates, or composite forms of these crystal forms You may have one.

The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, etc. are allowed to coexist in the process of formation or physical ripening of silver halide grains. Good.

The silver halide used in the present invention is 10 ^-8 to 10 per mol of silver.
It is a halosilver iodide prepared in the presence of ^-5 mol of an iridium salt or a complex salt thereof and having a silver iodide content on the grain surface higher than the average silver iodide content of the grain. When an emulsion containing such a silver haloiodide is used, higher sensitivity and high gamma photographic characteristics can be obtained.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. Good.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, rhodium, etc. may be contained. Specific examples thereof are described in US Pat. No. 2,448,060 and British Patent 618,016. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanins and the like can be used in addition to the sulfur compounds contained in gelatin.

In the above, it is preferable to use an iridium salt or a rhodium salt before the physical ripening in the production process of the silver halide emulsion, especially at the time of grain formation.

In the present invention, the silver halide emulsion layer is provided in Japanese Patent Application No. 60-64199.
Japanese Patent Application No. 60-232086, it is preferable to include two kinds of monodisperse emulsions having different average grain sizes from the viewpoint of increasing the maximum density (Dmax). The chemical sensitization method is most preferably sulfur sensitization. The large size monodisperse emulsion may not be chemically sensitized, but may be chemically sensitized. Large-sized monodisperse particles generally do not easily undergo black sensitization and therefore are not chemically sensitized. However, when chemical sensitization is performed, it is particularly preferable to apply shallowly so as not to generate black pits. Here, "shallowing" means that the chemical sensitization is performed for a shorter time than the chemical sensitization of small-sized grains, the temperature is lowered, and the addition amount of the chemical sensitizer is suppressed. The difference in sensitivity between the large size monodisperse emulsion and the small size monodisperse emulsion is not particularly limited, but ΔlogE is 0.1 to 1.0, more preferably 0.2 to 0.7, and the large size monodisperse emulsion is preferably high. Here, the sensitivity of each emulsion was such that a hydrazine derivative was included and coated on a support, and sulfite ion was added at 0.15 mol / l.
It is obtained when processed using a developer having a pH of 10.5 to 12.3 containing the above. The average particle size of the small size monodisperse grains is 90% or less, preferably 80% or less of the average size of the large size silver halide monodisperse grains. The average grain size of the silver halide emulsion grains is preferably 0.02
It is preferable that the average particle size of large-sized and small-sized monodisperse particles be included in this range from 0.1 to 0.5 μ, more preferably from 0.1 to 0.5 μ.

When two or more kinds of emulsions having different sizes are used in the present invention, the coating amount of the small size monodisperse emulsion is preferably 40 to 90 wt%, more preferably the total coating amount of silver.
50-80 wt%.

In the present invention, monodisperse emulsions having different grain sizes may be introduced into the same emulsion or may be introduced into different layers. When they are incorporated in separate layers, it is preferred that the large emulsion is the upper layer and the small emulsion is the lower layer.

As the total amount of coated ^{silver, 1g / m 2 ~8g / m} 2 is preferred.

The sensitizing dyes described in JP-A-55-52050, pages 45 to 53 (for example, cyanine dyes and merocyanine dyes) may be added to the light-sensitive material used in the present invention. it can. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.
A dye that does not have a spectral sensitizing effect by itself, or a substance that does not substantially absorb visible light, together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Discloser (Research Discloser).
Closure) Volume 176 17643 (issued in December 1978) Page 23, IV, J
It is described in the section.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, Etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes) ), Pentaazaindenes, etc .; many compounds known as antifoggants or stabilizers such as benzenethiosulphonic acid, benzenesulphonic acid, benzenesulphonic acid amide, etc. are added. Rukoto can. Among these, preferred are benzotriazoles (eg 5-methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.

Suitable development accelerators or accelerators for nucleating infectious development used in the present invention include JP-A Nos. 53-77616 and 54-37732.
No. 53, No. 53-137133, No. 60-140340, No. 60-14959, No. 61
In addition to the compounds disclosed in Nos. -165752 and 63-106748, various compounds containing N or S atoms are effective.

These accelerators, the optimal addition amount varies depending on the type of compound, 1.0 × 10 ^-3 ~ 0.5 g / m ² , preferably 5.0 × 10 ^-3 ~
It is desirable to use in the range of 0.1 g / m ² .

The light-sensitive material of the present invention may contain a desensitizer in the photographic emulsion layer and other hydrophilic colloid layers.

The organic desensitizer used in the present invention is defined by its polarographic half-wave potential, that is, the redox potential determined by polarography, and the sum of the polaro anode potential and the cathode potential is positive. The polarographic redox potential measurement method is described, for example, in US Pat. No. 3,501,307. The organic desensitizer preferably contains at least one water-soluble group, specifically, a sulfonic acid group,
Carboxylic acid groups, sulfonic acid groups, etc. may be mentioned, and these groups form salts with organic bases (eg, ammonia, pyridine, triethylamine, piperidine, morpholine, etc.) or alkali metals (eg, sodium, potassium, etc.). Good.

As organic desensitizers, Japanese Patent Application No. 61-280998, pages 55 to 7 can be used.
Those represented by the general formulas (III) to (V) described on page 2 are preferably used.

The organic desensitizer in the present invention is 1.
0 × 10 ^{-8 to} 1.0 × 10 ^-4 mol / m ² , especially 1.0 × 10 ^{-7 to} 1.0 × 10
^-5 mol / m ² is preferably present.

The emulsion layer of the present invention or the other hydrophilic colloid layer may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. As a filter dye, a dye for further reducing photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity range of silver halide, and safety against safelight light when handled as a light-sensitive room light-sensitive material A dye having substantial light absorption mainly in the range of 380 nm to 600 nm is used to enhance the light emission.

These dyes are added to the emulsion layer depending on the purpose, or added together with a mordant to the upper portion of the silver halide emulsion layer, that is, to the non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with respect to the support. It is preferable to fix it before use.

It depends on the molar extinction coefficient of the UV absorber, but usually 10 ^-2
It is added in a range of ^{g / m 2 ~1g / m 2} . Preferably 50 mg to 500
It is mg / m ² .

The ultraviolet absorber can be added to the coating solution by dissolving it in an appropriate solvent [eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof].

As the ultraviolet absorber, for example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used.

Specific examples of the ultraviolet absorber, U.S. Patent No. 3,533,794, the same 3,3
14,794, 3,352,681, JP-A-46-2784, U.S. Patent
3,705,805, 3,707,375, 4,045,229, 3,70
0,455, 3,499,762, West German patent application publication 1,547,863
No. etc.

Filter dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cytanine dyes and azo dyes. A dye that is water-soluble or that is decolorized by alkali or sulfite ion is preferable from the viewpoint of reducing the residual color after the development treatment.

Specifically, for example, pyrazolone oxonol dyes described in U.S. Patent No. 2,274,782, diarylazo dyes described in U.S. Patent No. 2,956,879, U.S. Patent No. 3,423,207,
No. 3,384,487 styryl dyes and butadienyl dyes, merocyanine dyes described in U.S. Pat.No. 2,527,583, U.S. Pat.Nos. 3,486,897, 3,652,284, and 3,
718,472 merocyanine dyes and oxonol dyes, U.S. Pat.No. 3,976,661 enaminohemioxonol dyes and British Patents 584,609, 1,177,429
No. 48-85130, No. 49-99620, No. 49-114420
U.S. Pat.Nos. 2,533,472, 3,148,187, and 3,
No. 177,078, No. 3,247,127, No. 3,540,887, No. 3
The dyes described in 3,575,704 and 3,653,905 are used.

The dye is a suitable solvent [eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone,
It is dissolved in methyl cellosolve or the like or a mixed solvent thereof and added to the coating liquid for the non-photosensitive hydrophilic colloid layer of the present invention.

The amount of the specific dye is generally ^{10 -3 g / m 2 ~1g /} m 2, it is possible to find the preferred amount ranges particularly ^{10 -3 g / m 2 ~0.5g /} m 2.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.
For example, chromium salts, aldehydes, (formaldehyde,
Glutaraldehyde etc.), N-methylol compounds (dimethylol urea etc.), active vinyl compounds (1,3,5
-Triacryloyl-hexahydro-s-triazine,
1,3-vinylsulfonyl-2-propanol, etc., active halogen compounds (2,4-dichloro-6-hydroxy-)
s-triazine and the like), mucohalogen acids and the like can be used alone or in combination.

For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example,
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization. In particular, the surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412. When used as an antistatic agent here, a surfactant containing fluorine (see, for example, U.S. Pat. No. 4,201,586).
And JP-A-60-80849 and 59-74554) are particularly preferable.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide or polymethylmethacrylate in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of preventing adhesion.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, a polymer having a monomer component of alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, or a combination thereof, or a combination thereof with acrylic acid, methacrylic acid, or the like is used. be able to.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention preferably contain a compound having an acid group. Examples of the compound having an acid group include salicylic acid, acetic acid, organic acids such as ascorbic acid and acrylic acid, maleic acid,
Mention may be made of polymers or copolymers having repeating units of acid monomers such as phthalic acid. Regarding these compounds, Japanese Patent Application Nos. 60-66179 and 60-68873,
Reference can be made to the descriptions in the specifications of No. 60-163856 and No. 60-195655. Of these compounds, ascorbic acid is particularly preferable as the low molecular weight compound, and an acid monomer such as acrylic acid is used as the high molecular weight compound and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene is used. It is a water dispersible latex of the copolymer.

In order to obtain super-high contrast and high-sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, the conventional infectious developer or US Pat.
It is not necessary to use the highly alkaline developing solution close to pH 13 described in 2,419,975, and a stable developing solution can be used.

That is, the silver halide light-sensitive material of the present invention contains sulfite ion as a preservative in an amount of 0.15 mol / l or more and has a pH of 10.5-1.
With a developer having a pH of 2.3, especially pH 11.0 to 12.0, a sufficiently high-contrast negative image can be obtained.

There is no particular limitation on the developing agent used in the developing solution used in the present invention, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl-3- A combination of pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used. The developing agent is preferably used usually in an amount of 0.05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols is used, the former is 0.05 mol / l to 0.5 mol / l and the latter is 0.06 mol / l.
It is preferably used in an amount of less than mol / l.

As a preservative of sulfite used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Formaldehyde sodium bisulfite and the like. Sulfite is preferably 0.4 mol / l or more, and particularly preferably 0.5 mol / l or more.

In the developer of the present invention, a silver stain preventing agent is disclosed in JP-A-56-24,34.
The compounds described in No. 7 can be used. The compounds described in Japanese Patent Application No. 60-109,743 can be used as a dissolution aid added to the developing solution. Further, as the pH buffer used in the developing solution, the compounds described in JP-A-60-93,433 or the compounds described in Japanese Patent Application No. 61-28,708 can be used.

The compound represented by the general formula (I) can be used in combination with a negative-working emulsion as described above for a high-contrast light-sensitive material, and can also be used in combination with an internal latent-image-type silver halide emulsion. Describe. In this case, the general formula (I)
The compound represented by is preferably contained in the internal latent image type silver halide emulsion layer, but may be contained in the hydrophilic colloid layer adjacent to the internal latent image type silver halide emulsion layer.
Such a layer may be any layer having any function, such as a color material layer, an intermediate layer, a filter layer, a protective layer and an antihalation layer, as long as it does not prevent the nucleating agent from diffusing into the silver halide grains. May be.

The content of the compound represented by the general formula (I) in the layer is such that an internal latent image type emulsion gives a sufficient maximum density (for example, 1.0 or more in silver density) when developed with a surface developer. Is desirable. In practice, the appropriate content may vary over a wide range as it depends on the properties of the silver halide emulsion used, the chemical structure of the nucleating agent and the development conditions, but internal latent image type halogenation About 0 per mole of silver in the silver emulsion.
A range of 005 mg to 500 mg is practically useful, with about 0.01 mg to about 100 mg per silver mole being preferred. When it is contained in the hydrophilic colloid layer adjacent to the emulsion layer, the same amount as the above may be contained with respect to the amount of silver contained in the same area of the internal latent image type emulsion layer. The definition of the internal latent image type silver halide emulsion is described in JP-A-61-170733, page 10, upper column and British Patent 2,089,057, page 18 to page 20.

Preferred internal latent image type emulsions that can be used in the present invention are
From Japanese Patent Application No. 61-253716, page 28, line 14 to page 31, line 2, the preferred silver halide grains are described in the same specification, No. 31.
It is described on page 3, line 3 to page 32, line 11.

In the light-sensitive material of the present invention, the internal latent image type emulsion may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by using a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used. These sensitizing dyes include, for example, JP-A-59-40,
The cyanine dyes and merocyanine dyes described in Nos. 638, 59-40,636 and 59-38,739 are included.

The light-sensitive material of the present invention may contain a color image-forming coupler as a coloring material. Alternatively, it can be developed with a developing solution containing a color image forming coupler.

Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17643 (December 1978) Item VII-D and 18717 (1).
(November 979).

It is also possible to use a coupler in which the color-forming dye has an appropriate diffusibility, a non-color-forming coupler, or a DIR coupler which releases a development inhibitor with a coupling reaction or a coupler which releases a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler.

In the present invention, it is preferable to use a two-equivalent yellow coupler, and a representative example thereof is an oxygen atom-releasing type yellow coupler or a nitrogen atom-releasing type yellow coupler. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Examples of the magenta coupler that can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye.

As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole coupler, U.S. Pat.
Pyrazolobenzimidazoles described in 9,899, preferably pyrazolo [5,1] described in U.S. Patent No. 3,725,067.
-C] [1,2,4] triazoles, pyrazolotetrazoles described in Research Disclosure 24220 (June 1984) and Research Disclosure 24230.
(June 1984), and pyrazolopyrazoles. The imidazo compound described in European Patent 119,741 [1,2-
b] Pyrazoles are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in EP 119,860 are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.No. 4,052,212.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of phenol-based couplers include U.S. Pat. Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. Cyan couplers that are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Cyan couplers, 2,5-diacylamino-substituted phenol couplers, and phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

In order to correct the unnecessary absorption in the short wavelength region which the dyes formed from the magenta and cyan couplers have, it is preferable to use a colored coupler together with the color photosensitive material for photographing.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Patent No. 4,366,237 and British Patent No. 2,1.
Specific examples of magenta couplers are described in 25,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and West German Patent Application Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

Various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the photosensitive layer in order to satisfy the properties required for the light-sensitive material, or two or more layers in which the same compound is different. Can also be introduced.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler, and 0.003 to 0.3 mol for the cyan coupler. It is 0.002 to 0.3 mol.

In the present invention, a developing agent such as hydroxybenzenes (for example, hydroquinones), aminophenols, 3-pyrazolidones and the like may be contained in the emulsion or the light-sensitive material.

The photographic emulsion used in the present invention is combined with a dye image-providing compound (coloring material) for a color diffusion transfer method capable of releasing a diffusible dye in response to the development of silver halide, and subjected to an appropriate development treatment. After that, it can be used to obtain a desired transferred image on the image receiving layer. A large number of such color materials for color diffusion transfer method are known, and among them, although they are initially non-diffusive, they are formed by a redox reaction with an oxidation product of a developing agent (or an electron transfer agent). It is preferable to use a coloring material of a type that cleaves to release a diffusible dye (hereinafter abbreviated as DRR compound). Of these, a DRR compound having an N-substituted sulfamoyl group is preferable. Particularly preferred in combination with the nucleating agent of the present invention, U.S. Pat.Nos. 4,055,428, 4,053,312 and
DRR compounds having an o-hydroxyarylsulfamoyl group as described in US Pat.
A DRR compound having a redox nucleus as described in 3-149,328. When used in combination with such a DRR compound, the temperature dependence during treatment is remarkably small.

Specific examples of the DRR compound include those described in the above patent specifications, and as the magenta dye image-forming substance, 1-
Hydroxy-2-tetramethylene sulfamoyl-4-
[3'-methyl-4 '-(2 "-hydroxy-4" -methyl-5 "-hexadecyloxyphenylsulfamoyl) -phenylazo] -naphthalene, 1-phenyl-3 as a yellow dye image-forming substance -Cyano-4- (2
, 4-di-tert-pentylphenoxyacetamino)
-Phenylsulfamoyl] phenylazo) -5-pyrazolone and the like.

Details of the color couplers which can be preferably used in the present invention are described on page 33, line 18 to page 40, last line of the same specification.

After imagewise exposure using the light-sensitive material of the present invention, after or while being subjected to fogging treatment with light or a nucleating agent, a surface developer having a pH of 11.5 or less containing an aromatic primary amine color developing agent. It is preferable to directly form a positive color image by performing color development, bleaching, and fixing processing in 1. The pH of this developer is 1
More preferably, it is in the range of 1.0 to 10.0.

The fogging treatment in the present invention is a so-called "light fogging method".
Either of the method of subjecting the entire surface of the photosensitive layer to this exposure and the method of developing in the presence of a nucleating agent, which is called "chemical fogging method", may be used. You may develop in the presence of a nucleating agent and fog light. Further, a light-sensitive material containing a nucleating agent may be fog-exposed.

The light fogging method is described in the above-mentioned Japanese Patent Application No. 61-253716, p. 47, line 4 to p. 49, line 5, and regarding the nucleating agent usable in the invention, p. 49, 6 of the same specification. Lines to page 67, line 2, particularly the general formulas [N-1] and [N-2].
The use of a compound represented by Specific examples thereof include [NI-1] described on pages 56 to 58 of the same specification.
~ [NI-10] and [N-II-] described on pages 63 to 66 of the same specification.
The use of 1] to [N-II-12] is preferable.

Regarding the nucleation accelerator that can be used in the present invention, see No. 68 of the same specification.
See page 11, line 71 to page 71, line 3, and as specific examples thereof, use of (A-1) to (A-13) described on pages 69 to 70 is preferable.

The color developing solution used for the development processing of the light-sensitive material of the present invention is described in the same specification, page 71, line 4 to page 72, line 9, and particularly, aromatic primary amine color developing agents. As a specific example, a p-phenylenediamine compound is preferable, and a typical example thereof is 3-methyl-4-amino-N.
-Ethyl-N- (β-methanesulfonamidoethyl) aniline, 3-methyl-4-amino-N-ethyl-N-
(Β-hydroxyethyl) aniline, 3-methyl-4-
Examples thereof include amino-N-ethyl-N-methoxyethylaniline and salts thereof such as sulfate and hydrochloride.

In order to directly form a positive color image by the color diffusion transfer method using the light-sensitive material of the present invention, a black-and-white developing agent such as a phenidone derivative can be used in addition to the above color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be carried out simultaneously with the fixing process by one-bath bleach-fixing process or separately. Further, in order to speed up the processing, a processing method of performing bleach-fixing processing after bleaching processing or a method of performing bleach-fixing processing after fixing processing may be used. Aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent in the bleaching solution or the bleach-fixing solution of the present invention. As the additive used in the bleaching solution or the bleach-fixing solution of the present invention,
Various compounds described on pages 22 to 30 of Japanese Patent Application No. 61-32462 can be used. After the desilvering process (bleach-fixing or fixing), a treatment such as washing with water and / or stabilization is performed. It is preferable to use softened water as the washing water or the stabilizing solution. Examples of the water softening method include a method using an ion exchange resin or a reverse osmosis device described in Japanese Patent Application No. 61-131632. As a concrete method of these, it is preferable to carry out the method described in Japanese Patent Application No. 61-131632.

Further, as the additive used in the washing and stabilizing steps, various compounds described in detail in Japanese Patent Application No. 61-32462, pp. 30-36 can be used.

It is preferable that the amount of replenisher in each processing step is small. The amount of the replenisher is preferably 0.1 to 50 times, more preferably 3 to 30 times the carry-in amount of the pre-bath per unit area of the light-sensitive material.
Double.

Example 1 An aqueous solution of silver nitrate, an aqueous solution of potassium iodide and an aqueous solution of potassium bromide were simultaneously added to an aqueous gelatin solution kept at 50 ° C. for 60 minutes in the presence of 4 × 10 ⁻⁷ mol of potassium iridium (III) hexachloride and ammonia per mol of silver. And the pAg during that period was kept at 7.8 to give an average grain size of 0.25μ and an average silver iodide content of 1 mol%.
A cubic monodisperse emulsion of was prepared. Chemical sensitization never happened. These silver iodobromide emulsions contained 5,5'-
Sodium salt of dichloro-9-ethyl-3,3'-bis (3-sulfopropyl) oxacarbocyanine, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer, poly A dispersion of ethyl acrylate, polyethylene glycol, 1,3-vinylsulfonyl-2-propanol and the compound of the present invention shown in Table 1 were added, and the amount of silver was 3.4 g / m 2 on a polyethylene terephthalate base.
Application was performed as it became ² . Gelatin was 1.8 g / m ² .

As a protective layer, a layer containing gelatin 1.5 g / m ² , polymethylmethacrylate particles (average particle size 2.5 μm) 0.3 g / m ² , and the following surfactant was applied thereon.

As comparative examples, samples were prepared using compounds A and B instead of the compound of the present invention. Examples of these compounds are shown in Table 1.

These samples were exposed to tungsten light of 3200 ° K through an optical wedge, developed with the following developer for 30 seconds at 34 ° C, and fixed.
It was washed with water and dried.

The photographic properties obtained are shown in Table 1. When the compound of the present invention was used, high sensitivity, high contrast and halftone dot quality were obtained for Comparative Compound-C. It was also found to give higher Dmax compared to comparative compounds A and B.

[Developer]

Hydroquinone 50.0 g N-methyl-p-aminophenol 0.3 g 4-methyl-4-hydroxymethyl-1-phenyl-3
-Pyrazolidone-Sodium hydroxide 18.0 g Boric acid 54.0 g Potassium sulfite 110.0 g Ethylenediaminetetraacetic acid disodium 1.0 g Potassium bromide 10.0 g 5-Methylbenzotriazole 0.4 g 2-Mercaptobenzimidazole-5-sulfonic acid 0.
3g Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2g N-n-butyldiethanolamine 15.0g Sodium toluenesulfonate 8.0g Add water 11 Adjust pH to 11.6 (add potassium hydroxide) pH 11. 6 Example 2 5.0 × 10 ⁻⁶ per mol of silver in a gelatin aqueous solution kept at 40 ° C.
Simultaneously mixing an aqueous solution of silver nitrate and an aqueous solution of sodium chloride in the presence of a molar amount of (NH ₄ ) ₃ RhCl ₆ , after removing soluble salts by a method well known in the art, gelatin is added and chemically aged. However, 2-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was added as a stabilizer.
This emulsion was a cubic monodisperse emulsion having an average grain size of 0.12 μm.

In this emulsion, the hydrazine compound and polyethyl acrylate latex shown in Table 2 were added to the solid content of 30 wt% of gelatin.
Added, as a hardener, 1,3-vinylsulfonyl-2-
Propanol was added and 3.8 g / m ² on the polyester support.
Was applied so that the amount of Ag would be. Gelatin was 1.8 g / m ² . A 1.5 g / m ² layer of gelatin was applied as a protective layer thereon.

To this sample, a step wedge and a halftone dot document having a halftone dot area of 50% were brought into close contact with each other, and FPA-80 manufactured by Fuji Photo Film Co., Ltd.
It was exposed by a 0 type printer, developed with the developer of Example 1 for 20 seconds at 38 ° C., fixed, washed with water and dried. Further, the exposure and the development were similarly performed through only the step wedge.

The obtained photographic results are shown in Table 2.

Next, Table 2 shows the photographic performance of the exposed sample of about 61 cm × 51 cm, which was processed 0 times or 40 times each day by using 20 l of the developer, after 2 weeks.

From the results shown in Table 2, it is understood that the samples of the present invention have small fluctuations in sensitivity and fluctuations in the percentage of returned halftone dots when the development processing is running. In particular, the comparative compounds -A and -B are characterized by small fluctuations in the liquid that was run without treatment, and the comparative compound -C was 40 sheets / day.
It is noted that the fluctuations in the liquid running while processing are small.

Example 3 On a paper support laminated on both sides with polyethylene, a multilayer color light-sensitive material No. A having the following layer constitution was prepared.

(Layer constitution) The composition of each layer is shown below. The number is the amount applied per m ² in g
Express with. The silver halide emulsion and colloidal silver are expressed in terms of silver, and the spectral sensitizing dye is expressed in terms of mol per mol of silver halide.

Support Polyethylene laminated paper [Polyethylene on the E1 layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] E1 layer Silver halide emulsion A 0.26 Spectral sensitizing dye (ExSS-1) 1.0 × 10 ^-4 Spectral sensitizing dye (ExSS-2) 6.1 × 10 ^-5 Gelatin 1.11 Cyan coupler (ExCC-1) 0.21 Cyan coupler (ExCC-2) 0.26 UV absorber (ExUV-1) 0.17 Solvent (ExS-1) 0.23 Development control agent (ExGC-1) 0.02 Stabilizer (ExA-1) 0.006 Nucleation accelerator (ExZS-1) 3.0 × 10 ^-4 Nucleation agent (ExZK-1) 8.0 × 10 ^-5 Layer E2 Gelatin 1.41 Mixed color Inhibitor (ExKB-1) 0.09 Solvent (ExS-1) 0.10 Solvent (ExS-2) 0.10 E3 layer Silver halide emulsion A 0.23 Spectral sensitizing dye (ExSS-3) 3.0 × 10 ^-4 Gelatin 1.05 Magenta coupler ( ExMC-1) 0.16 Color image stabilizer (ExSA-1) 0.20 Solvent (ExS-3) 0.25 Development modifier (ExGC-1) 0.02 Stabilizer (ExA-1) 0.006 Nucleation accelerator (ExZS-1) 2.7 × 10 ^-4 Nucleating agent (ExZK- 1) 1.4 × 10 ^-4 E4 layer gelatin 0.47 Anti-color mixture (ExKB-1) 0.03 Solvent (ExS-1) 0.03 Solvent (ExS-2) 0.03 E5 layer Colloidal silver 0.09 Gelatin 0.49 Anti-color mixture (ExKB-1) ) 0.03 Solvent (ExS-1) 0.03 Solvent (ExS-2) 0.03 E6 layer Same as E4 layer E7 layer Silver halide emulsion A 0.40 Spectral sensitizing dye (ExSS-4) 4.2 × 10 ^-4 Gelatin 2.17 Yellow Coupler (ExYC-1) 0.51 Solvent (ExS-2) 0.20 Solvent (ExS-4) 0.20 Development regulator (ExGC-1) 0.06 Stabilizer (ExA-1) 0.001 Nucleation accelerator (ExZS-1) 5.0 × 10 ^-4 Nucleating agent (ExZK-1) 1.2 × 10 ^-5 E8 layer gelatin 0.54 UV absorber (ExUV-2) 0.21 Solvent (ExS-4) 0.08 E9 layer gelatin 1.28 Acrylic modified copolymer of polyvinyl alcohol ( Degree of modification 17%) 0.17 Fluid paraffin 0.03 Polymethylmethacrylate latex particles (average particle size 2.8 μm) 0.05 Layer B1 gelatin 8.70 Layer B2 Same as layer E9 Other compositions were added a gelatin hardening agent ExGK-1 and surfactant.

Silver halide emulsion A Gelatin prepared by adding 0.5 g of 3,4-dimethyl-1,3-thiazoline-2-thione and 0.3 g of lead acetate to a mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate per 1 mol of Ag. While stirring vigorously in the aqueous solution, it was added simultaneously at 55 ° C over about 5 minutes, and the average particle size was about 0.2 µm (silver bromide content 40%).
(Mol%) of monodispersed silver chlorobromide emulsion was obtained. To this emulsion were added 35 mg of sodium thiosulfate and 20 mg of chloroauric acid (tetrahydrate) per mol of silver, and the mixture was heated at 55 ° C. for 60 minutes for chemical sensitization.

The silver chlorobromide grains thus obtained were used as cores for further growth by treatment for 40 minutes in the same precipitation environment as the first time, and finally a monodisperse core / shell silver chlorobromide emulsion having an average grain size of 0.4 μm. Got The coefficient of variation of particle size is about
It was 10%.

To this emulsion, 3 mg of sodium thiosulfate and 3.5 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, and internal latent image type halogenation was carried out. A silver emulsion A was obtained.

Compound used to make the sample (1): (2): (3) 5: 8: 9 mixture (weight ratio) (ExUV-2) UV absorber (1): (2): (3) 2: 9: 8 mixture ( Weight ratio) (ExA-1) Stabilizer 4-Hydroxy-5,6-trimethylene-1,3,3a, 7-tetrazaindene (ExZS-1) Nucleation accelerator 2- (3-Dimethylaminopropylthio) -5- Mercapto-1,3,4-thiadiazole hydrochloride (ExGK-1) Gelatin hardening agent 1-oxy-3,5-dichloro-S-triazine sodium salt The replenishing method of the washing water was a so-called countercurrent replenishing method in which the washing water was replenished and the overflow solution of the washing bath was introduced into the washing bath.

[Color developer] Mother liquor Diethylenetriaminepentaacetic acid 0.5 g 1-Hydroxyethylidene-0.5 g 1,1-Diphosphonic acid diethylene glycol 8.0 g Benzyl alcohol 10.0 g Sodium bromide 0.5 g Sodium chloride 0.7 g Sodium sulfite 2.0 g N, N-diethylhydroxyl Amine 3.5 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline 6.0 g Potassium carbonate 30.0 g Fluorescent brightener (stilbene type) 1.0 g Pure water added 1000 ml pH 10.50 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fixing solution] Mother liquor Ammonium thiosulfate 100 g Sodium hydrogen sulfite 10 g Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate 40 g Ethylenediaminetetraacetic acid disodium dihydrate 5 g 2-Mercapto-1,3,4-triazole 0.5 g Pure Water was added to 1000 ml pH 7.0 pH was adjusted with aqueous ammonia or hydrochloric acid.

[Wash water]

 Pure water was used.

Here, the pure water is the one in which the concentration of all cations other than hydrogen ions and all anions other than hydroxide ions in tap water is removed to 1 ppm or less by ion exchange treatment.

In the same manner as in Sample No. A except that the compounds shown in Table 3 were used instead of the nucleating agent (ExZK-1), multilayer color light-sensitive materials No. 1 to
3 was produced.

The sample prepared in this manner was wet exposed (1 /
After 10 seconds and 10 CMS), processing step A was performed to measure the cyan color image density. The results obtained are shown in Table 3.

The amount of the compound of the present invention added was equivalent to ExZK-1.

Samples Nos. 1 to 3 using the compound of the present invention had a high maximum concentration (Dmax) and were preferable as compared with No. A to which the comparative compound ExZK-1 was added. Similar results were obtained for magenta and yellow densities.

Example 4 Photosensitive elements Nos. 1 to 6 were prepared by coating respective layers on a polyethylene terephthalate transparent support in the following order.

(1) A copolymer described in U.S. Pat. No. 3,898,088 containing the following repeating units in the following ratio (3.0 g
/ m ² ) And a mordant layer containing gelatin (3.0 g / m ² ).

(2) Titanium oxide 20 g / m ² and the white reflective layer containing gelatin 2.0 g / m ^2.

(3) Carbon black 2.70g / m ² and gelatin 2.70g / m ²
Light-shielding layer containing m ² .

(4) Magenta DRR compound of the following (0.45 g / m ^2), diethyllaurylamide (0.10g / m ^2), 2,5- di -t- butyl hydroquinone (0.0074 g / m ^2), and gelatin (0.76
g / m ² ) containing layer.

(5) Nucleating agent and 5-pentadecyl-hydroquinone-2-sulfone shown in Table 4 containing an internal latent image type emulsion (1.4 g / m ² in silver amount), a green sensitizing dye (1.9 mg / m ² ). A green-sensitive internal latent image type direct positive silver iodobromide emulsion (2 mol% silver iodide) layer containing sodium acidate (0.11 g / m ² ).

(6) A layer containing gelatin (0.94 g / m ² ).

Processing was carried out by combining the above-mentioned photosensitive elements Nos. 1 to 6 and the following respective elements.

Processing liquid A container that can be ruptured under pressure by 0.8 g each of the treatment liquid of the above composition
Filled.

Cover sheet Polyacrylic acid (neutralization layer) of polyacrylic acid (viscosity of about 1,000 cp in 10% by weight aqueous solution) 15 g / m ² on the polyethylene terephthalate support, and acetyl cellulose (100 g of acetyl of 100 g acetyl) as the neutralization timing layer. 3.8 g / m ² of styrene and maleic anhydride (composition (molar) ratio, styrene: maleic anhydride = about 60:40, molecular weight about 50,000) A cover sheet coated with 0.2 g / m ² was prepared.

Forced deterioration conditions Two sets of the above-mentioned photosensitive elements No. 1 to 6 are prepared, and one set is a refrigerator (5
C.) and the other set was left for 4 days at a temperature of 35.degree. C. and a relative humidity of 80%.

Processing step The cover sheet and the photosensitive sheet are overlaid, and after exposing the color test chart from the cover sheet side, the processing solution is spread between both sheets so as to have a thickness of 75 μ I went with the help of a roller). The treatment was carried out at 25 ° C. After the processing, the green density of the image formed on the image-receiving layer was measured by a Macbeth reflection densitometer one hour after the processing through the transparent support of the photosensitive sheet. The results are shown in Table 4.

Comparative compound D D ^F _max: maximum concentration S ^F of positive image of refrigerator storage goods: relative sensitivity of the concentration 0.5 positive image of refrigerator storage goods (when set to 100 to S ^F of the photosensitive element 1) S ^W: 35 ℃ relative sensitivity 80% for 4 days was left unattended and the relative sensitivity of the concentration 0.5 positive image of the sample (the S ^F of the photosensitive element 1 when set to 100) as clear from the above results, the photosensitive element was added nucleating agent of the present invention Nos. 3 to 6 were more likely to produce Dmax with the same addition amount than the photosensitive element 1 produced by the conventional method, and the photosensitive elements 3 to 6
2 indicates that there is less change in sensitivity when the photosensitive material is aged.

Example 5 In carrying out the present invention, the following emulsion X was prepared.

Emulsion X 20 mg of thioether (1,8-dihydroxy-3,6-dithiaoctane) was added to each of the silver nitrate aqueous solution and the potassium bromide aqueous solution at a constant rate while maintaining the silver electrode potential at a potential for growth of octahedral grains. 1/8 mol of silver nitrate corresponding to 1/8 mol of silver nitrate was added to the contained gelatin aqueous solution (pH = 5.5) at 75 ° C. for 5 minutes to obtain spherical AgBr monodisperse particles having an average particle diameter of about 0.14 μm. 20 mg of sodium thiosulfate and 20 mg of chloroauric acid (4 mol / mol of silver halide were added to this emulsion).
Hydrochloric acid salt) was added to adjust the pH to 7.5, and the mixture was chemically sensitized at 75 ° C. for 80 minutes with good stirring to obtain a core emulsion. Next, at the same temperature, a silver nitrate aqueous solution (containing 7/8 mol of silver nitrate) and a potassium bromide aqueous solution were continuously stirred under a well-stirred condition for 40 minutes while maintaining the silver electrode potential at which the octahedral grains grow. At the same time, they were simultaneously added to cause the shell to grow, and a monodisperse octahedral core-shell emulsion having an average grain size of about 0.3 μm was obtained. This emulsion was washed with water and desalted in a conventional manner, heated and dissolved, and then the pH was adjusted to 6.5, and 5 mg of sodium thiosulfate and 5 mg of chloroauric acid (tetrahydrate) were added per mol of silver halide. Each of them was added and ripened at 75 ° C. for 60 minutes to chemically sensitize the shell surface, and finally an internal latent image type monodisperse octahedral core shell emulsion (Emulsion X) was obtained. As a result of measuring the grain size distribution of this emulsion from an electron micrograph, the average grain size was 0.30 μm and the coefficient of variation (average grain size × 100 / standard deviation) was 10%.

The above emulsion X was mixed with panchromatic sensitizing dye 3,3'-diethyl-9-
Methyl thiocarbocyanine per mol of silver halide
After adding 5 mg, the exemplified compound (I-
7) (I-8) and ExZK-1 as a comparative compound, and the addition amount shown in Table 5 and compound-a as a nucleation accelerator 1
X 10 ^-3 mol and 1 mol of silver halide were added per mol of silver halide to obtain a polyethylene terephthalate support having a silver content of
A direct positive photographic light-sensitive material sensitive to red light was prepared by simultaneously coating with a protective layer consisting of gelatin and a hardener at 2.8 g / m ² so as to coat it.

1Kw tungsten lamp (color temperature 2854 ° K)
The sensitometer exposed for 0.1 second through a step wedge.

Next, Kod with an automatic processor (Kodak Proster I Processor)
38 using ak Proster Plus processing solution (developing solution pH 10.7)
Development was performed at 18 ° C. for 18 seconds, followed by subsequent washing with water, fixing, washing with water and drying.

The maximum density (Dma
x), minimum density (Dmin) and relative sensitivity were measured, and the results shown in Table 5 were obtained.

As is clear from the results in Table 5, the exemplified compound (I-
7) It is understood that (I-8) not only exhibits reversal characteristics superior to the control nucleating agent at a 1/10 addition amount of the control ExZK-1, but also has high sensitivity. That is, it is understood that the novel nucleating agent of the exemplified compound has extremely high nucleating activity.

Further, when the developer pH was adjusted to pH 10.0 with an acid, and when these samples were similarly developed, it was found that the same excellent reversal characteristics were exhibited.

Claims (1)

[Claims] 1. A photographic emulsion layer having at least one silver halide photographic emulsion layer, and the photographic emulsion layer or at least one other hydrophilic colloid layer containing a compound represented by the following general formula (I). A silver halide photographic light-sensitive material. General formula (I) In the formula, A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other represents a sulfonyl group, or an acyl group, G ₁ is a carbonyl group, a sulfonyl group, a sulfoxy group, Or represents an imino methylene group, L ₁ represents a divalent linking group, R ₁ and R ₂ represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, R ₃ is a hydrogen atom, an alkyl group, Aryl group, alkoxy group, aralkyl group, aryloxy group,
Or represents an amino group, R ₄ is a hydrogen atom, an alkyl group,
Alternatively, it represents an aryl group.