JPH0812394B2 - Silver halide photosensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide light-sensitive material, and more specifically to a super-high contrast and high-resolution silver halide light-sensitive material used in the field of photoengraving. Is.

(Prior Art) It is known that a photographic image having an extremely high contrast can be formed by using a certain type of silver halide, and such a photographic image forming method is used in the field of photolithography.

For example, silver chlorobromide (with a silver chloride content of at least 50
%), The effective concentration of sulfite ion was made extremely low (usually 0.1 mol / mol).
l or less) By treating with a hydroquinone developer,
There is known a method of obtaining a line drawing or a halftone dot image having a high contrast and a high blackening density in which an image portion and a non-image portion are clearly distinguished. However, in this method, since the concentration of sulfurous acid in the developer is low, the development is extremely unstable against air oxidation, and various efforts and ingenuities are being used to keep the solution activity stable. It was.

Therefore, an image forming system that eliminates the instability of image formation due to the above-described developing method (lith development system) and develops with a processing solution having good storage stability to obtain super-high contrast photographic characteristics is provided. Required, US Patent 4,166,742
No., 4,168,977, 4,221,857, 4,224,401,
No. 4,243,739, No. 4,272,606, No. 4,311,781, a surface latent image type silver halide photographic light-sensitive material containing a specific acylhydrazine compound is added at pH 11.0 to 12.3.
It has been proposed that a system containing a sulfurous acid preservative in an amount of 0.15 mol / l or more and having a good storage stability is processed to form a super-high contrast negative image having a γ of more than 10. This new image forming system can only use silver chlorobromide with a high content of silver chloride in conventional super-high contrast image formation, whereas it can also be used with silver iodobromide and silver chloroiodobromide. There is.

However, in both cases, it is possible to obtain ultra-high contrast where the γ value exceeds 10, but on the other hand, because the characteristic curve is well cut off, there is the drawback that it is difficult to attach fine lines when the exposure amount is lowered. Occurs. For example, when a character original is photographed using a plate-making camera, if a super-high-contrast photosensitive material with good cut-out is used and underexposure is performed, the character density is sharply lowered and the character cannot be read. Therefore, such a high-sensitivity light-sensitive material has a drawback that the latitude with respect to variations in exposure amount becomes narrow.

Use of a relatively soft photosensitive material having a γ value of less than 10 can remedy such a defect. In other words, in a soft photosensitive material, the character density does not drop sharply when the exposure amount is lowered, and even if the exposure amount is lowered, it has a density that can be used in the next returning step, An image usable as characters can be obtained. As described above, a soft-sensitive light-sensitive material has an advantage that the latitude spreads to the low-exposure amount side, but on the contrary, it has a drawback that the background density (Dmax) is hard to appear due to the soft-tone. In other words, the density of the white background of the document (black on the negative film) is the density of the characteristic curve = 1.5.
Therefore, the higher the γ value in the high-density portion, the higher the Dmax, and in soft-sensitive photosensitive materials, the γ value on the high-density side is low, so the Dmax is low. High-quality, low-contrast, low-contrast, Mincho-type (thin linewidth), Gothic-type (thick linewidth), or original with colored background However, these various originals have different optimum exposure amounts.

When trying to shoot a block made of a combination of these originals with different optimal exposures, it is extremely difficult to select the exposure conditions with a photosensitive material with a narrow exposure latitude.
Occasionally, it was not possible to capture all parts of a document with good reproducibility in one shot, and the documents were separated by changing the exposure conditions partially.

In other words, if the exposure amount is reduced in an attempt to reproduce the black thin lines of the original, the background density (corresponding to the black solid portion on the negative film, represented as Dmax) becomes low, and the white thin lines (black background of the original) (White line inside the line) has a low density and is crushed, and conversely, when the exposure amount is increased, a black thin line of the document is crushed, which causes a wide exposure latitude in line drawing. Further, a photosensitive material having a high background density (Dmax) has been desired.

(Problems to be Solved by the Invention) Accordingly, an object of the present invention is to provide an image forming method having a wide exposure latitude in line drawing, a super-high contrast, and a high resolution.

Another object of the present invention is to provide a super-high contrast image forming method which reproduces a line drawing well and has a high background density (Dmax).

(Means for Solving the Problems) The above object of the present invention is to have at least two silver halide emulsion layers on a support, the silver halide emulsion layers or other hydrophilic colloid layers. A silver halide light-sensitive material characterized by containing a hydrazine derivative in at least one layer and substantially containing no hydrazine derivative in a silver halide emulsion layer or another hydrophilic colloid layer containing a quinone scavenger. Could be achieved by

Here, substantially not containing the hydrazine derivative means that the hydrazine derivative may be contained to such an extent that the above-mentioned purpose is not impaired.

In the present invention, the action of the quinone scavenger is presumed to prevent the transmission between the hard emulsion layer containing the hydrazine derivative and the soft emulsion layer not containing the hydrazine derivative so as not to affect each other. To be done.

That is, the soft-tone emulsion takes charge of the gradation of D = 1.5 or less on the characteristic curve, but when development occurs at the foot of this characteristic curve, quinone is generated as an oxidation product of the developing agent. Quinones react with hydrazine derivatives to produce active species for infectious development that cause high contrast development. Further, this quinone diffuses from the soft emulsion layer to the hard emulsion layer containing the hydrazine derivative. Therefore, it is considered that a high-contrast development occurs from the foot portion of the characteristic curve, the desired characteristic curve shape cannot be obtained, and the exposure latitude of the line drawing becomes narrow.

However, it is presumed that the use of a quinone scavenger for trapping quinone in the intermediate layer or the soft emulsion layer solves the above-mentioned problems, and that a light-sensitive material having a wide exposure latitude as in the present invention can be obtained.

The quinone scavenger is a compound capable of reacting with quinone and reducing quinone, or a compound adding to quinone.

When the photosensitive material (sensitive material) of the present invention is developed, the γ (gamma) value in the portion of D (density) = 0.3 to D = 1.5 of the characteristic curve obtained is 10 or less, and D = 1.5 to D. It is preferable that the γ value in the portion of = 3.0 is 10 or more. More specifically, the development processing here refers to, for example, the processing described in Example 1.

Here, the former γ value is abbreviated as a γ _L value, and the latter γ value is abbreviated as a γ _H value.

In the present invention, γ _H and γ _L can be more specifically determined by the following method. That is, the slope of the straight line connecting the two points of density = 0.3 and density = 1.5 on the characteristic curve obtained by the development processing is γ _L , and the density = 1.5 and density = 3.0
The slope of the straight line connecting the points was defined as γ _H.

That is Can be expressed as

In the present invention, the γ _L value is 10 or less, preferably 2 to 9, and more preferably 4 to 8.

The γ _H value is 10 or more, preferably 12 or more, more preferably 12 to 50.

The silver halide emulsion layer (more specifically, the silver halide emulsion layer that can substantially contribute to image formation) of the light-sensitive material used in the present invention may be at least two layers. It may be provided with four layers.

When the silver halide emulsion layer of the light-sensitive material used in the present invention is composed of two layers, these layers are an emulsion layer giving a hard gradation (hard emulsion layer) and an emulsion layer giving a soft gradation (soft gradation). And an emulsion layer).

The former mainly receives the gradation in the region of D = 1.5 or more, and the latter mainly receives the gradation in the region of D = 1.5 or less.

Further, the former hard-tone emulsion layer preferably has a γ value of 10 or more, and the latter soft-tone emulsion layer preferably has a γ value of less than 10.

Next, the quinone scavenger used in the present invention will be described in detail.

The quinone scavenger used in the present invention includes
Examples thereof include dihydroxybenzene derivatives, sulfites, organic sulfinic acids, N-substituted hydroxyamines, ascorbic acid or erythorbic acid and their derivatives, and diol compounds and their derivatives.

These quinone scavengers are preferably localized in a specific layer of the silver halide light-sensitive material. From this point, the quinone scavenger introduces a diffusion resistant group in order to suppress free movement between layers. Preferably, or introducing a group that promotes adsorption to silver halide grains,
It is preferably used as adsorbed on silver halide grains. Here, the diffusion resistant group is preferably an organic residue having a carbon number of 7 or more (preferably 20 or less), and the adsorption group is preferably a group having a mercapto group, a thiocarbonyl group, a benzotriazole skeleton or an indazole skeleton.

 These compounds will be described in detail below.

Preferred among the dihydroxybenzenes are the compounds represented by the following general formula (I).

General formula (I) [In the formula, at least one of G ₁ and G ₂ represents a hydroxy group, and the other is selected from the groups synonymous with R ₁ to R ₄ below.
R ₁ to R ₄ are each independently a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a halogen atom 1, 2, 3
Primary amino group, substituted or unsubstituted carbonamido group, substituted or unsubstituted sulfonamide group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted at least one N 5 or 6 containing an O, S or S atom
Membered heterocyclic group, formyl group, keto group, sulfonic acid group,
It represents a carboxylic acid group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group.
However, the sum of the number of carbon atoms of R ₁ to R ₄ is 7 or more, and these groups may be part of a polymer chain having a number average degree of polymerization of 3 or more. R ₁ to R ₄ are linked together to form 5, 6 or 7
You may form a member ring. As the ring, a substituted or unsubstituted benzene ring is preferable. Among these preferred dihydroxybenzenes, 1 to 4 substituted catechol or hydroquinone is particularly preferable, and the sum of the sigma values of the hamet of the substituents other than the two hydroxyl groups is -1.2 to +1.2, and particularly preferable. Is within the range of -1.0 to +0.5.

Specific examples of these compounds include, for example, US Pat.
728,659, mono-linear alkylhydroquinones described in JP-A-49-106329, U.S. Pat.
No. 2, West German Patent Publication 2,149,789, JP-A-50-156,438,
Mono-branched alkyl hydroquinones described in JP-A-49-106329, US Patents 2,728,659 and 2,732,300
No. 3, British Patent Nos. 752146, 1,086,208, di-linear alkylhydroquinones described in Chemical Abstracts, Vol. 5, 6367h, US Pat. No. 3,700,453,
No. 2,732,300, British Patent No. 1086208, Japanese Patent Laid-Open No. 50-156438
No. 60-55339, No. 50-21249, 56-40818,
It is described in Chemical Abstracts, Vol. 5, 6367h, etc. Di-branched alkyl hydroquinones, JP-A-56-1
09344, 57-22237, 59-202465, 58-17431, Shoko Sho
59-35012, Japanese Examined Patent Publication No. 59-37497, U.S. Pat. No. 3,227,552, and the like, and dihydroxybenzene derivatives described in JP-A-57-17949.
Examples thereof include polymers having a dihydroxybenzene skeleton, but the scope of the present invention is not limited thereto. You may use these compounds as a mixture of 2 or more types. The synthesis of these compounds is described in French Patent No. 1,496,562 and West German Patent No. 2,110,5.
It can be easily carried out by the methods described in No. 21 and the like, and methods analogous thereto.

Examples of dihydroxybenzene derivatives having reduced diffusibility are shown below, but the scope of the present invention is not limited to these.

Preferred among the organic sulfinic acids or salts thereof are compounds represented by the following general formula (II).

General formula (II) R-SO ₂ M (In the formula, M represents a hydrogen atom, an alkali metal atom, unsubstituted or 1 to 4 substituted ammonium, and R represents a substituted or unsubstituted C 1 to 30 carbon atom. It represents an alkyl group, a substituted phenyl group having 7 to 30 carbon atoms, and a substituted or unsubstituted naphthyl group having 10 to 30 carbon atoms.

Preferred as M in the general formula (II) is a hydrogen atom or an alkali metal atom (Li, Na, K, Cs), and R
Preferred examples of the substituent of the group represented by are the following: a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably monocyclic or Bicyclic, alkyl moiety having 1 to 3 carbon atoms, alkoxy group, (preferably 1 to 20 carbon atoms), 1- or 2-substituted amino group (preferably alkyl group having 1 to 20 carbon atoms, acyl A group, an alkyl or arylsulfonyl group, and in the case of 2-substituted, the total number of carbon atoms in the substituent is 20 or less), 1 to 3 substituted or unsubstituted ureido group (preferably having 1 carbon atom) To 20), a substituted or unsubstituted aryl group (preferably one or two rings having 6 to 29 carbon atoms), a substituted or unsubstituted arylthio group (preferably having 6 carbon atoms). 29), a substituted or unsubstituted alkylthio group (preferably having 1 to 29 carbon atoms), a substituted or unsubstituted alkylsulfoxy group (preferably having 1 to 29 carbon atoms), a substituted or unsubstituted arylsulfoxy group A group (preferably having 6 to 29 carbon atoms, monocyclic or 2
Ring), a substituted or unsubstituted alkylsulfonyl group (preferably having 1 to 29 carbon atoms), a substituted or unsubstituted arylsulfonyl group (preferably having 6 to 29 carbon atoms, monocyclic or bicyclic) ), An aryloxy group (preferably having 6 to 29 carbon atoms, monocyclic or bicyclic), a carbamoyl group (preferably having 1 to 9 carbon atoms).
29), sulfamoyl groups (preferably having 1 to 29 carbon atoms), hydroxy groups, halogen atoms (eg F, Cl,
Br, I), a sulfonic acid group, or a carboxylic acid group. Among these substituents, those which may have further substituents may have the following substituents: an alkyl group (having 1 to 20 carbon atoms), an aryl group (having 6 to 20 carbon atoms). Monocyclic or bicyclic), alkoxy group (having 1 to 20 carbon atoms), aryloxy group (having 6 to 20 carbon atoms), alkylthio group (having 1 to 20 carbon atoms), arylthio group (having 6 carbon atoms) To 20), alkylsulfonyl group (1 to 20 carbon atoms), arylsulfonyl group (6 to 20 carbon atoms), carbonamido group (1 to 20 carbon atoms), sulfonamide group (0 to 20 carbon atoms) ), Carbamoyl group (1 to 20 carbon atoms), sulfamoyl group (1 to 20 carbon atoms), alkylsulfoxy group (1 to 2 carbon atoms)
0), arylsulfoxy groups (1 to 2 carbon atoms
0), an ester group (having 2 to 20 carbon atoms), a hydroxy group, -COOM or -SO ₂ M (M represents a hydrogen atom or an alkali metal atom, a substituted or unsubstituted ammonium), or a halogen atom (F, Cl, Br, I). These groups may be linked to each other to form a ring. These groups may also be part of a homopolymer or copolymer chain.

Examples of organic sulfinic acids are shown below, but the scope of the present invention is not limited to these.

10 n-C ₈ H ₁₇ SO ₂ Na Synthetic methods for these compounds are, for example, RBWagner, HDZ
ook by Synthetic Organic Chemistry, p807-810, John
Wiley & Sons, Inc, New York, 1953, etc. are described together with other compound examples.

Preferred among the N-substituted hydroxylamines are compounds represented by the following general formula (III).

General formula (III) (In the formula, m represents 0 or 1, Q represents a hydrogen atom, an acyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms.
20 represents a substituted or unsubstituted phenyl group, and R represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted phenyl group having 6 to 30 carbon atoms. However, at least one of Q and R is an organic group having 7 to 30 carbon atoms. Of the compounds represented by the general formula (III), m is 0 or 1, and Q is a hydrogen atom.
The preferred substituents for the alkyl group or phenyl group represented by R are as follows. That is, a straight chain,
A branched or cyclic alkyl group (preferably having 1 carbon atom)
To 20), an aralkyl group (preferably monocyclic or bicyclic, the alkyl moiety has 1 to 3 carbon atoms), an alkoxy group, (preferably 1 to 20 carbon atoms), a mono- or di-substituted amino group (preferably Is an alkyl group having 1 to 20 carbon atoms, an acyl group, an alkyl or arylsulfonyl group, and in the case of 2-substituted, the total number of carbon atoms in the substituent is 20 or less), 1 to 3 substituted, or Unsubstituted ureido group (preferably having 1 to 29 carbon atoms), substituted or unsubstituted aryl group (preferably 1 or 2 ring having 6 to 29 carbon atoms), substituted or unsubstituted arylthio group (Preferably having 6 to 2 carbon atoms
9), a substituted or unsubstituted alkylthio group (preferably having 1 to 29 carbon atoms), a substituted or unsubstituted alkylsulfoxy group (preferably having 1 to 29 carbon atoms), a substituted or unsubstituted arylsulfoxy group (Preferably having 6 to 29 carbon atoms, monocyclic or bicyclic), substituted or unsubstituted alkylsulfonyl group (preferably having 1 to 29 carbon atoms), substituted or unsubstituted arylsulfonyl group (preferably carbon) Mono- or bicyclic C6-C29 aryloxy group (preferably C6-C29 mono- or bicyclic) carbamoyl group (preferably C1-C29) ), A sulfamoyl group (preferably having 1 to 29 carbon atoms), a hydroxy group, a halogen atom (for example, F, Cl, Br, I), a sulfonic acid group, or a carboxylic acid group. Of these substituents, those which may have a substituent may have the following substituents; that is, an alkyl group (having 1 to 2 carbon atoms).
0), aryl groups (monocycles having 6 to 20 carbon atoms or 2
A ring), an alkoxy group (having 1 to 20 carbon atoms),
Aryloxy group (6 to 20 carbon atoms), alkylthio group (1 to 20 carbon atoms), arylthio group (6 to 20 carbon atoms), alkylsulfonyl group (1 to 20 carbon atoms), arylsulfonyl group ( 6 to 20 carbon atoms, carbonamido group (1 to 10 carbon atoms)
20), sulfonamide groups (having 0 to 20 carbon atoms), carbamoyl groups (having 1 to 20 carbon atoms), sulfamoyl groups (having 1 to 20 carbon atoms), alkylsulfoxy groups (having 1 to 20 carbon atoms), Aryl sulfoxy group (1 to 20 carbon atoms), ester group (2 to 20 carbon atoms), hydroxy group, -COOM or -SO ₂ M (M is hydrogen atom or alkali metal atom, substituted or unsubstituted ammonium) Or a halogen atom (F, Cl, Br, I). Specific examples of these compounds are, for example, RB Wagner, H.
It is described in D. Zook, Synthetic Organic Chemistry, p556, p576, etc. together with the synthesis method.

Specific examples of these N-substituted hydroxylamines will be given below, but the scope of the present invention is not limited thereto.

III-1 CH ₃ (CH ₂ ) ₁₀ CONHOH III-2 nC ₁₅ H ₃₁ CONHOH III-3 nC ₁₂ H ₂₅ NHOH III-4 nC ₁₇ H ₃₄ CONHOH As the above other reducing substances, for example, ascorbic acid, erythorbic acid and their derivatives, or the diol compounds described in British Patent No. 922550 can be used. Specific examples of these are shown below, but the scope of the present invention is not limited thereto.

In the light-sensitive material of the present invention, the quinone scavenger need not be in the same layer as the hydrazine derivative. When quinone scavenger is contained in the silver halide emulsion layer containing a hydrazine derivative, the hardening effect based on the hydrazine derivative is hindered, which is not preferable.

The quinone scavenger used in the present invention is contained in a hydrophilic colloid layer such as an intermediate layer, a filter layer, a protective layer and an undercoat layer in addition to the silver halide emulsion layer containing no hydrazine derivative. Preferably, a silver halide emulsion layer containing no hydrazine derivative (eg, a soft-tone emulsion layer), an intermediate layer of the silver halide emulsion layer (eg, between the soft-tone emulsion layer and a hard-tone emulsion layer containing a hydrazine derivative).
And the latter is particularly preferable.

The amount of quinone scavenger added is 0.001 to 1.0
preferably g / m ^2, and more preferably 0.01 to 0.5 g / m ^2.

Although the intermediate layer may or may not be present, when the intermediate layer is provided, its thickness is preferably 0.1 to 3.0 μ, more preferably 0.2 to 2.0 μ.

The hard emulsion layer and the soft emulsion layer may be arranged on the support in any order.

That is, the O layer (the emulsion layer farther from the support) may be the hard emulsion layer and the U layer (the emulsion layer closer to the support) may be the soft emulsion layer.

As for the sensitivity values of the O layer and the U layer, the O layer may have higher sensitivity or the U layer may have higher sensitivity.

Further, the high-contrast emulsion layer may be composed of not only one layer but also two or more layers. The soft emulsion layer may be composed of not only one layer but also two or more layers.

The sensitivity of the sensitivity (S _H) and the soft emulsion layer of high contrast emulsion layer used in the present invention (S _S) may be filed either high feeling,
It is preferable that the following relationships are satisfied.

Here, S _H and S _S are values obtained by preparing a sample in which each emulsion is coated in a single layer and performing sensitometry.
More specifically, an exposure amount that gives a density = 1.5 of a characteristic curve obtained by exposing with tungsten light through an optical wedge for sensitometry and then developing with a developer described in Example 1 below. Expressed as the logarithm of (logE).

Also especially Is more preferable.

Here, when S _S −S _H > 0.6, Dmax is difficult to be obtained and the cutting becomes poor, which is not preferable.

On the other hand, if S _H −S _S > 0.6, the reproducibility of the fine line becomes poor and the exposure latitude becomes narrow, which is not preferable.

When the O layer is a hard emulsion layer and the U layer is a soft emulsion layer, it is preferable that the sensitivities of the two layers are as follows.

Also especially It is more preferable that

Next, when the O layer is a soft-tone emulsion layer and the U layer is a hard-tone emulsion layer, it is preferable that the relationship between the two sensitivities is as follows.

Also especially It is more preferable that

Regarding the relationship between S _H and S _S , it is preferable that the above-mentioned relational expression is satisfied, but the specific values of the emulsion layers used depend on the halogen composition of the silver halide emulsion used, the grain size, It varies depending on the gradation. Further, those skilled in the art can easily provide the emulsion layer having such a relationship.

The coated silver amount of the photosensitive material used in the present invention is preferably 2.5 to 6.0 g / m ² , and more preferably 3.0 to 5.0 g / m ² .

There is no particular limitation on the ratio of the coated silver amount in each silver halide emulsion layer.

However, in the case of two emulsion layers, the ratio (molar ratio) of the coated silver amount of both layers is preferably upper layer (farther from the support) / lower layer (closer to the support) = 2 / 8- 8/2, more preferably 3/7 to 7/3.

The total thickness of the silver halide emulsion layer is 1.5 to 5.0 μm.
Is preferable, and 2.0 to 4.0 μm is more preferable.

It is preferable that the high-contrast emulsion layer contains a sufficient amount of hydrazine derivative for high-contrast. The soft emulsion layer may or may not contain a hydrazine derivative, and in the case of containing it, it is necessary that the contrast is not higher than that of the hard emulsion layer.

Examples of the hydrazine derivative used in the present invention include aryl hydrazides having a sulfinic acid residue bonded to a hydrazo moiety described in U.S. Pat.No. 4,478,928, and compounds represented by the following general formula (IV). Can be mentioned.

In formula (IV) R ₁ -NHNH-G-R ₂ , R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl Represents a group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryloxy group, and G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an N substituted or unsubstituted iminomethylene group.

In the general formula (IV), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms.
Is a linear, branched or cyclic alkyl group. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, a carbonamide group or the like.

The aromatic group represented by R ₁ in the general formula (IV) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.
Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, and among others, a ring containing a benzene ring is preferable.

Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical examples of the substituent include a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 20), an aralkyl group. (Preferably an alkyl moiety having 1 to 3 carbon atoms having 1 to 3 rings), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably having 1 to 20 carbon atoms) Substituted amino group), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms) Things to have) and so on.

As the alkyl group represented by R ₂ in the general formula (IV),
Preferably, it is an alkyl group having 1 to 4 carbon atoms and may have a substituent such as a halogen atom, a cyano group, a carboxy group, a sulfo group, an alkoxy group and a phenyl group.

In the general formula (IV), the aryl group which may be substituted among the groups represented by R ₂ is a monocyclic or bicyclic aryl group, and includes, for example, a benzene ring. This aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group or the like.

The alkoxy group which may be substituted in the group represented by R ₂ in the general formula (IV) is an alkoxy group having 1 to 8 carbon atoms, which may be substituted with a halogen atom, an aryl group or the like.

Of the groups represented by R ₂ in the general formula (IV), the optionally substituted aryloxy group is preferably a monocyclic group, and the substituent includes a halogen atom and the like.

Of the groups represented by R ₂ , when G is a carbonyl group, preferred is a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, or a substituted or unsubstituted phenyl group, and a hydrogen atom is particularly preferred.

When G is a sulfonyl group, R ₂ is preferably a methyl group, an ethyl group, a phenyl group or a 4-methylphenyl group, and particularly preferably a methyl group.

When G is a phosphonyl group, R ₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group or a phenyl group, and particularly preferably a phenoxy group.

When G is a sulfoxy group, preferred R ₂ is a cyanobenzyl group or a methylthiobenzyl group, and when G is an N-substituted or unsubstituted iminomethylene group, preferred R ₂ is a methyl group, an ethyl group, a substituted or unsubstituted group. Is a phenyl group.

R ₁ or R _{2 in} the general formula (IV) may have a ballast group incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more and relatively inactive with respect to a developing solution, and examples thereof include an alkyl group, an alkoxy group, a phenyl group,
It can be selected from an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like.

R ₁ or R _{2 in} the general formula (IV) may be one in which a group that enhances adsorption on the surface of the silver halide grain is incorporated. Examples of the adsorptive group include groups described in US Pat. No. 4,385,108 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group and triazole group.

A carbonyl group is most preferable as G in the general formula (IV).

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

Further, the fact that the hydrazine derivative represented by the general formula (IV) itself is diffusion resistant prevents diffusion into other emulsion layers,
It is preferable from the viewpoint of obtaining the target gradation.

In the present invention, the hydrazine derivative is used in the silver halide emulsion layer and / or other hydrophilic colloid layer, but is preferably the silver halide emulsion layer. In particular, when a diffusion-resistant hydrazine derivative is used, it is effective to use it in the silver halide emulsion layer.

In the present invention, the hydrazine derivative is preferably contained in an amount of 1 × 10 ^-6 mol to 5 × 10 ^-2 mol, and particularly 1 × 10 ^-5 mol to 2 × 10 ^-2 mol per mol of silver halide. It is a preferable addition amount.

When the hydrazine derivative of the present invention is contained in a photographic light-sensitive material, it is an aqueous solution when it is water-soluble, and alcohols (for example methanol, ethanol), esters (for example ethyl acetate), ketones (for example, water-insoluble). A solution of an organic solvent miscible with water such as acetone) may be added to the silver halide emulsion solution or the hydrophilic colloid solution.

In the present invention, the hydrazine derivative may be used alone or in combination of two or more kinds.

Next, the emulsions used in the hard-tone emulsion layer and the soft-tone emulsion layer used in the present invention will be described.

The silver halide in the silver halide photographic emulsion is not particularly limited and may have any halogen composition such as silver chloride, silver chlorobromide and silver iodobromide.

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, reduction sensitization and noble metal sensitization methods are known, and any of these may be used alone or in combination. The preferred chemical sensitization method is sulfur sensitization. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanins, etc. can be used in addition to the sulfur compounds contained in gelatin. . As a specific example, U.S. Pat.No. 1,574,944,
2,278,947, 2,410,689, 2,728,668, 3,5
No. 01,313 and No. 3,656,952.

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 618,061.

As the reduction sensitizer, a primary tin salt, amines, formamidine sulfinic acid, a silane compound or the like can be used. Examples of these are U.S. Pat.Nos. 2,487,850, 2,518,
698, 2,983,609, 2,983,610, 2,694,637.

The average grain size of silver halide is preferably 0.7 μm or less, and particularly preferably 0.5 μm to 0.1 μm. The average grain size is a term commonly used and easily understood by experts in the field of silver halide photographic science. The particle size means a particle diameter when the particles are spherical or can be approximated to a sphere. If the particle is a cube Is the particle size. It is determined by algebraic average or geometric average based on the average grain projected area. For more information on how to determine the average particle size, see “Meese James The Theory of the Photographic Process“ CE Mees
TH James: The theory of the photographic proces
s "), 3rd edition, pp. 36-43 (1966, (Macmillan" Mcm
illan ”company))).

The shape of the silver halide grains is not limited and may be any of tabular, spherical, cubic, tetradecahedral, regular octahedral, rhombohedral and other shapes. Further, the grain size distribution is preferably narrow, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total grain number falls within the grain size range of ± 40% of the average grain size is particularly preferable.

The silver halide emulsion used in the present invention contains 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, or the like in the process of formation of silver halide grains or physical ripening. May coexist.

For example, by using an iridium salt or a complex salt thereof, preferably 10 ⁻⁸ to 10 ⁻⁵ mol per mol of silver, higher sensitivity and high gamma photographic characteristics can be obtained. Specific examples used here include iridium trichloride, iridium tetrachloride, potassium hexachloroiridium (II) acid, potassium hexachloroiridium (IV) acid, ammonium hexachloroiridium (III) acid, and the like.

Further, the rhodium salt or its complex salt is preferably 10 ⁻⁸ to 10 ⁻⁴ mol, and more preferably 5 × 10 ^{−7 to} 5 ×, per mol of silver.
By using 10 ^-5 mol, the silver halide emulsion can have a high contrast and the image quality can be improved. Specific examples used here include rhodium dichloride, rhodium trichloride, potassium hexachloride rhodium (III) acid, and rhodium hexachloride (III).
Ammonium acid and the like.

In the present invention, the method of reacting the soluble silver salt with the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PA in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
A method of keeping g constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

For details on silver halide emulsions and their preparation methods, see RESEARCH DISCLOURE Volume 176, Item 17643 P.22-
P.23 (December 1978) or cited.

Next, the light-sensitive material used in 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, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1
-Phenyl-5-mercaptotetrazole) and the like; 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. Can be added.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitalaldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N′-methylenebis- [β- (vinylsulfonyl) propionamide], etc.), active Halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycyclo acid, etc.) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazine Azinylated gelatin, etc. They can be used alone or in combination. Among them, JP-A-53-41221, JP-A-53-57257, and JP-A-59-162
Active vinyl compounds described in 546 and 60-80846 and active halides described in US Pat. No. 3,325,287 are preferable.

Gelatin is advantageously used as a binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example gelatin derivatives,
Graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives; various kinds such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Synthetic hydrophilic polymeric substances can be used.

As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained.

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Non-ionic interfaces such as alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglycerides, alkyl phenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salt, alkyl naphthalene sulfonate, alkyl sulfate ester acid, alkyl phosphate ester, N-acyl-N-alkyl taurine, sulfosuccinate ester, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene Anionic surfactants containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfuric acid ester group, a phosphoric acid ester group such as an alkyl phosphoric acid ester; an amino acid, an aminoalkyl sulfonic acid, an aminoalkyl sulfuric acid Or amphoteric surfactants such as phosphoric acid esters, alkylbetaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and fats Ho containing a group or heterocycle It can be used cationic surfactants such as Honiumu or sulfonium salts. Particularly, the surfactant preferably used in the present invention has a molecular weight of 6 described in JP-B-58-9412.
It is a polyalkylene oxide of 00 or more. When used as an antistatic agent, a fluorine-containing surfactant is 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 light-sensitive material used in the present invention may contain a dispersion of a water-soluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate,
Glycidyl (meth) acrylate, (meth) acrylamide, etc., alone or in combination, or a polymer containing these and acrylic acid, methacrylic acid, etc. as a monomer component can be used.

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.

The silver halide emulsion of the present invention, by using cyanine dyes such as cyanine, merocyanine and carbocyanine alone or in combination, or by using them in combination with a styryl dye or the like, spectral or supersensitization to ortho or panchromatic. You can do it. Among them, the sensitizing dyes described in JP-A-51-95836, JP-A-52-18311 and US Pat. No. 3,567,458 are preferably used. In addition, the above-mentioned RESEARCH DISCLOURE Item 17643
Those disclosed in the literature disclosed in Section IV or cited can also be used.

The silver halide photographic light-sensitive material used in the present invention includes
Various other additives are used. For example, desensitizer,
Plasticizers, slip agents, development accelerators, oils, dyes, etc.

Regarding these additives and the above-mentioned additives, specifically, Research Disclosure (Research Disclosur
e) No. 176, pages 22 to 31 (RD-17643) (Dec., 1978) and the like can be used.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for photographic light-sensitive materials. Useful as the flexible support is a film made of a synthetic polymer such as cellulose acetate, cellulose acetate butyrate, polystyrene or polyethylene terephthalate.

As the processing solution such as the developing solution used in the present invention, a known processing solution is used.

RESEARCH DISCLOURE Volume 176 Item 17643 XIX Section, XX
Section, XXI section P.28-P.30 (December 1978).

In order to obtain photographic characteristics of ultrahigh contrast and high sensitivity using the silver halide light-sensitive material of the present invention, it is necessary to use a conventional infectious developer or a highly alkaline developer having a pH value close to pH 13 described in U.S. Pat.No. 2,419,975. Instead, a stable developer 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 to 10.
With a developer having a pH of 12.3, particularly 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.

Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
There are 2,5-dimethylhydroquinone and the like, but hydroquinone is particularly preferable.

Examples of the developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4. -Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-
Methyl-3-pyrazolidone, 1-p-aminophenyl-
4,4-Dimethyl-3-pyrazolidone, 1-p-tolyl-
4,4-dimethyl-3-pyrazolidone and the like.

Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol and N- (4-hydroxyphenyl). Glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, etc. are available, but among them N-methyl-p
-Aminophenol is preferred.

The developing agent is preferably used usually in an amount of 0.05 mol / l to 0.8 mol / l. In addition, dihydroxybenzenes and 1-
When the combination with phenyl-3-pyrazolidones or p-amino-phenols is used, the former is 0.05 mol / l
It is preferable to use 0.5 mol / l and the latter in an amount of 0.06 mol / l or less.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
Sulfite is preferably 0.4 mol / l or more, particularly preferably 0.5 mol / l or more. The upper limit is preferably 2.5 mol / l.

Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate, etc.
Contains pH regulators and buffers.

As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve , Organic solvents such as hexylene glycol, ethanol, methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-mercapto compounds such as sodium salt of sulfonic acid, indazole compounds such as 5-nitroindazole, An antifoggant or a black pepper inhibitor such as a benztriazole compound such as 5-methylbenztriazole may be contained, and if necessary, a toning agent, a surfactant, a defoaming agent, a water softener. , Hardener, JP-A-56-106244 Such amino compounds may contain.

The developing temperature is preferably 18 to 50 ° C, and the developing time is preferably 15 to 60 seconds.

After development processing, among the samples
Obtain the characteristic curve and change the sensitivity (film N
The gamma values of 0.3 to 1.5 and 1.5 to 3.0 were determined (specifically, by the following method). On the other hand, the sample that has been subjected to line drawing practical exposure is subjected to line drawing exposure latitude and practical Dm by the following method.
Was evaluated.

Method for measuring γ (gamma) value The sample described in the example was exposed to a tungsten light having a color temperature of 3200 ° K for 5 seconds through an optical wedge for sensitometry, and then the development process described in the example was performed.

The slope of the straight line connecting the two points of density = 0.3 and density = 1.5 on the characteristic curve thus obtained is γ _L density = 1.5 and density =
Γ _L and γ _H were obtained by the above-described calculation formulas, with the gradient of the straight line connecting the two points of 3.0 being γ _H.

○ Evaluation method for line drawing exposure latitude Manual typesetting paper PL-100WP (Fuji Photo Film Co., Ltd.)
The original with white lines and black lines with a line width of 100 μ was prepared by using. A white line is a solid black area with white lines in a black background, and a black line is a white background with a black line inside. The line widths of these black lines and white lines were confirmed by scanning the document in the line width direction with a reflection type microdensitometer and confirming that the line widths at optical density = 0.6 were 100 μm.
The manuscript of the manual typesetting paper with white and black lines thus obtained was photographed on the sample described in Example using a reflection type plate-making camera DSC-351 (manufactured by Dainippon Screen Co., Ltd.) and then developed. Processed. Exposure was carried out by changing the exposure seconds of the plate-making camera, and the limit exposure amount for white line reproduction and the actual exposure amount for black line reproduction were obtained, and the difference between the two was used as the exposure latitude. In other words, if the exposure amount is decreased, the black line of the original (white line on the negative film) will be reproduced, but the white line of the original (black line on the negative film) will have a thin line width and low density. Therefore, the lower limit of the exposure amount is found so that the white line cannot be reproduced with the exposure amount less than this. Similarly, when the exposure amount is increased, the upper white exposure amount is found to be good while the original white line is good, but the black line is crushed. The exposure dose difference (ΔlogE) between the upper limit and the lower limit determined in this way was used as the line drawing exposure latitude. The larger the exposure amount difference, the wider the latitude, which is preferable. The white line and the black line have a critical point that the negative line after development is scanned in the line width direction with a transmission type microdensitometer and the line width obtained at an optical density of 1.5 is 10 μm or less. Line width).

It can be expressed as line drawing exposure latitude = log (upper limit exposure amount) −log (lower limit exposure amount). The value of the line drawing exposure latitude evaluated by this method is preferably 0.8 or more.

○ Practical technique Evaluation method of Dmax It is preferable that the solid black portion on the developed negative film has a high density. The density of this solid black area is a problem on the low exposure side, and the transmission density of the solid black area at the exposure limit (lower limit exposure amount) that reproduces the white line of the original is measured with the Macbeth densitometer TD-504. However, this value was set as the practical skill Dmax.

 The practical skill Dmax is preferably 4.0 or more.

(Examples) Next, the present invention will be specifically described with reference to Examples.

Example 1 A silver chloroiodobromide emulsion (silver iodide 0.
1 mol% and silver bromide 30 mol%) were prepared. To this silver chloroiodobromide emulsion, 1 × 10 ⁻⁶ of (NH ₄ ) ₃ RhCl ₆ was used as a rhodium salt.
Mol / Ag 1 mol, K ₃ IrCl ₆ as iridium salt 4 × 10 ⁻⁷
A rhodium salt and an iridium salt were added to the halogen solution so as to contain 1 mol of Ag / Ag, and the halogen aqueous solution and the silver nitrate aqueous solution were mixed at 50 ° C. for 60 minutes to form particles. This silver chloroiodobromide emulsion (average grain size 0.30μ,
(Cube, monodisperse) was desalted with water, subjected to gold-sulfur sensitization, and then spectrally sensitized by adding dimethine merocyanine dye (I). As a stabilizer, 2-methyl-4-hydroxy-1, 3,
Emulsion A was prepared by adding 3a, 7-tetrazaindene and a dispersion of 1,4-dihydroxybenzene and polyethyl acrylate, 1,3-vinylsulphonyl-2-propanol.

Dimethine merocyanine dye (I) Further, Compound I-7 as a quinone scavenger was added to Emulsion A to a concentration of 0.1 or 0.3 g / m ² to obtain Emulsions B and C, respectively. Further, Compound I-17 as a quinone scavenger was added to Emulsion A at 0.1 or 0.3 g / m ² to obtain Emulsions D and E, respectively. These are all emulsions for the O layer.

Then, in the same manner as in Emulsion A, rhodium salt (NH ₄ ) ₃ RhCl
₆ × 5 × 10 ^-6 mol / Ag 1 mol A silver chloroiodobromide emulsion with an average grain size of 0.19 μ (silver iodide 0.1 mol%, bromide) Silver 30 mol%) was prepared. This was washed with water and desalted in the same manner as in Emulsion A, subjected to gold-sulfur sensitization, and then spectrally sensitized by adding dimethine merocyanine dye (I). As a stabilizer, 2-methyl-4-hydroxy- 1,3,3a, 7-tetrazaindene, and a dispersion of 1,4-dihydroxybenzene and polyethyl acrylate, 1,3-vinylsulphonyl-2-propanol was added, and IV-12 was further added as a hydrazine compound. Emulsion F was prepared by adding 6 × 10 ⁻⁴ mol / mol Ag.

Next, in 1 mol of Ag in a gelatin aqueous solution kept at 50 ° C,
In the presence of 4 × 10 ^-7 mol of potassium iridium (III) hexachloride and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide are added simultaneously for 60 minutes, and the pAg between them is adjusted.
By keeping it at 7.8, a cubic monodisperse emulsion having an average grain size of 0.20 μm and an average silver iodide content of 1 mol% was prepared.

This emulsion was subjected to sulfur sensitization with sodium thiosulfate and then sensitized dye (5,5'-dichloro-3,3'-di (3-
(Sulfopropyl) -9-ethyl-oxacarbocyanine sodium salt) was spectrally sensitized by adding 6 × 10 ^-4 mol per mol of silver. Furthermore, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer.

Further, a dispersion of alkylbenzene sulfonate as a surfactant, 1,3-vinylsulfonyl-2-propanol as a hardener, 5 × 10 ^-3 mol / mol Ag of IV-12 as a hydrazine compound, and polyethyl acrylate. To give Emulsion-G.

 Both of these emulsions F and G are emulsions for the U layer.

Then, an aqueous solution of gelatin for the intermediate layer was added with polypotassium p-vinylbenzene sulfonate as a thickening agent of sodium dodecylbenzenesulfonate as an anionic surfactant to prepare an intermediate layer coating solution-a. Further, Compound I-7 as a quinone scavenger was added to this coating liquid (i).
Intermediate layer coating solutions B and C were prepared by adding 0.1 or 0.3 g / m ² respectively. Similarly, the compound I-17 as a quinone scavenger was added to the coating solution I at 0.1 or 0.3 g / m ² to prepare intermediate layer coating solutions D and E.

Emulsions F and G are U layers, intermediate layer coating liquids I to D are intermediate layers, and emulsions A to E are O layers. U and O layers are coated Ag.
The amount is 1.7g / m ² (O layer + U layer = 3.4g / m ²
Coating with gelatin as 1.5 g / m ² and then as a protective layer with gelatin as 1.0 g / m ² film thickness 100 μm
It is coated on the polyethylene terephthalate support of
One sample was prepared.

Each of these samples was exposed to 3200 ° K tungsten light through an optical wedge for sensitometry for 5 seconds,
It was developed with a developer having the following composition for 30 seconds at 38 ° C., fixed, washed with water and dried. (The automatic processing machine FG-660F manufactured by Fuji Photo Film Co., Ltd. was used for the development processing.) [Developer formulation] Hydroquinone 35.0 g N-methyl-p-amino 0.8 g Phenols 1/2 sulfate sodium hydroxide 9.0 g Potassium triphosphate 74.0 g Potassium sulfite 90.0 g Ethylenediaminetetraacetic acid 1.0 g Disodium salt Potassium bromide 3.0 g 5-Methylbenzotriazole 0.6 g 3-Diethylamino-1- 15.0 g Propanol Add water 1 (pH = 11.6) The characteristic curve was obtained from the sample after development processing, and the sensitivity (from sample No. 1 was set to 100) and γ
(0.3 to 1.5) and γ (1.5 to 3.0) were obtained. In addition, a line drawing was photographed and developed in the same manner as in the sensitometry, and then the line drawing exposure latitude and the practical skill Dmax were evaluated by the above-mentioned method.

From Table-1, sample without quinone scavenger
No. 1 to 4 have a narrow line image exposure latitude, which is impossible,
It can be seen that Sample Nos. 5 to 28 of the present invention are good. The line drawing exposure latitude is preferably 0.8 or more.

Sample Nos. 1 to 4 have high γ _L (0.3 to 1.5),
This is the cause of worsening the line drawing exposure latitude. It can be seen that the line drawing exposure latitude is improved by using the quinone scavenger.

If the γ _L value is 7 or more, the line drawing image quality is good, and any sample has no problem. The sample of the present invention had good sensitivity and practical Dmax, and there was no problem, and the line image exposure latitude was improved.

Even if there is no intermediate layer, the line drawing exposure latitude is good if the soft emulsion layer contains quinone scavenger, and it is more preferable if the intermediate layer has an intermediate layer and quinone scavenger is contained in the intermediate layer. I understand.

Example-2 Compound II-6 or II-8 as a quinone scavenger was added to Intermediate Layer Coating Solution-a in the same manner as in Example-1, respectively.
A coating liquid added so as to be 0.1 g / m ² was prepared and used as a coating liquid for the intermediate layer.

Similarly, coating solutions were prepared by adding Compounds III-4 and IV-5 to 0.1 g / m ^{2 of the} intermediate layer coating solution-a and designated as intermediate layer coating solutions C and H, respectively.

In the same manner as in Example-1, the emulsion F or G was used as a U layer, the intermediate layer coating solution was used as an intermediate layer, and the emulsion A was used as an O layer. Application was performed to prepare sample Nos. 29 to 36. These samples are from Example-1.
Exposure, development were carried out in the same manner as in, and the sensitivity, γ, exposure latitude of line drawing, and practical skill Dmax were evaluated.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-56-153336 (JP, A) JP-A-61-145546 (JP, A)

Claims (1)

[Claims] 1. A support having at least two silver halide emulsion layers, wherein the silver halide emulsion layer or at least one of the other hydrophilic colloid layers contains a hydrazine derivative and contains a hydrazine derivative. A silver halide light-sensitive material characterized by containing a quinone scavenger in a silver halide emulsion layer or other hydrophilic colloid layer which is not substantially contained.