JPS6315237A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain an image having ultra-high contrast and high resolving power by incorporating a hydrazine deriv. into a silver halide emulsion layer or other hydrophilic colloidal layer and incorporating a quinone scavenger into the silver halide emulsion layer or other hydrophilic colloidal layer which does not contain the hydrazine deriv. CONSTITUTION:At least two layers of the silver halide emulsion layers are provided on a base. The hydrazine deriv. is incorporated into at least one layer of the silver halide emulsion layer or the other hydrophilic colloidal layer and the quinone scavenger is incorporated into the silver halide emulsion layer or the other hydrophilic colloidal layer which contains substantially no hydrazine deriv. The quinone scavenger acts to prevent the contamination between the high-contrast emulsion layer contg. the hydrazine deriv. and the low-contrast emulsion layer which does not contain the hydrazine deriv. so that the layers does not affect each other. Narrowing of an exposing latitude is prevented by using the quinone scavenger to trap quinones in the intermediate layer or the low-contrast emulsion layer.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application) The present invention relates to a silver halide photosensitive material, and more specifically, to a silver halide photosensitive material that provides ultra-high contrast and high resolution and is used in the field of photolithography. It is.

BACKGROUND OF THE INVENTION It is known that certain e-+ halides can be used to form extremely high contrast photographic images, and methods for forming such images are used in the field of photolithography.

For example, silver chloride bromide (at least the silver chloride content is j0
Image areas and non-image areas can be clearly distinguished by processing a lithium-type halogenated complex photosensitive material consisting of 4 or more with a hydroquinone developer containing an extremely low effective concentration of sulfite ions (usually 0.1 mol/or less). It was differentiated into Methods of obtaining line drawings or halftone dot images with high contrast and high blackening density are known. However, with this method, the concentration of sulfite in the developer is low, making the development extremely unstable against air oxidation.Currently, various efforts and innovations have been made to keep the solution activity stable. Met.

For this reason, the above development method (lith development system)
There is a need for an image forming system that eliminates the instability of image formation caused by K, develops with a processing solution that has good storage stability, and obtains ultra-high contrast photographic characteristics, and U.S. Patent No./47.7
≠λ issue, same≠, /A! , No. 977, μ, ssi, ♂j
No. 7, same g.

Coco≠, ≠O1 No., same gu, 2μ3.739, same≠, 2
No. 72,406, same≠,,? //, as seen in 7-layer No. 1, surface latent image type silver halide photographic light-sensitive material added with a specific acylhydrazine compound to -1) H/8 ~ 7
2.3 with sulfite preservative O0/! mol / or more and has good storage stability, and γ is 10 f.
A system for forming negative images with ultra-high contrast has been proposed.

This new image forming system has the feature that it can also use silver iodobromide and silver chloroiodobromide, whereas conventional ultra-high contrast image formation could only use silver chlorobromide with a high tin chloride content. There is.

However, in both cases, should the γ value exceed IO? ii!
Although it is possible to obtain a reasonable contrast, on the other hand, because the characteristic curve has a good sharpness, it has the disadvantage that it is difficult to see fine lines when the exposure amount is lowered. For example, when photographing a text document using a discontinued camera, if the photosensitive material is underexposed, the character fif will suddenly drop and the text will become illegible. Therefore, such a high-contrast photosensitive material has a disadvantage in that the latitude with respect to variations in exposure amount is narrowed.

These drawbacks can be improved by using a relatively soft i-sensitive material with a γ value smaller than IO. However, with soft light-sensitive materials, the character density will not drop suddenly when the exposure amount is lowered, and even if the exposure amount is lowered, the density will remain high enough to be used in the next reversal process. This allows you to obtain images that can be used as text. As described above, a light-sensitive material having a soft contrast has the advantage that the latitude expands toward the low exposure amount side, but conversely, it has the disadvantage that it is difficult to produce a background density (Dmax) due to the soft contrast. In other words, the density of the white part of the original (solid black on negative film) is the density of the characteristic curve =
/, j, the higher the γ value of the high density part, the higher the Dmax.In line drawing photography, which has the disadvantage of a low Dmax due to the low Nrn on the high density side of soft light-sensitive materials, there are no characters in the original. A mixture of documents with high density, low contrast with low density per character, Mincho typeface (thin line width), Gothic typeface (thick line width), manuscripts with colored backgrounds, etc. These various types of originals have different optimal exposure amounts.

When trying to capture the image of a plate made by combining originals with different optimum exposure amounts - it is extremely difficult to select exposure conditions for light-sensitive materials with a narrow exposure latitude, and sometimes all of the original is Sometimes it was not possible to photograph certain parts of the document with good reproducibility, and parts of the original were separated by changing the exposure conditions.

In other words, I was trying to reproduce the thin black lines in the manuscript.

When the exposure amount is lowered, the background density (corresponding to the solid black area on a negative film, expressed as Dmax) increases.
There is a problem that the density of thin white lines (white lines on a black background) on the original is low and the density of the white lines on the original is low and the density of the white lines on the original is low, and on the other hand, when the exposure level is increased, the fine black lines on the original are crushed. - The exposure latitude in such line drawing I# is wide and the back ground mK (
A photosensitive material with a high Dmax) has been desired.

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

Another object of the present invention is to provide a method for forming an ultra-high contrast image that can reproduce line drawings well and has a high background density W (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, and at least one of the silver halide emulsion layers or other hydrophilic colloid layers. This can be achieved by using a halogenated photosensitive material that contains a hydrazine derivative in one layer and a quinone scavenger in a silver halide emulsion layer or another hydrophilic colloid layer that does not substantially contain a hydrazine derivative. did it.

Here, "containing substantially no hydrazine derivative" means
This means that it may be contained to the extent that the above-mentioned purpose is not impaired.

In the present invention, it is presumed that the action of the quinone scavenger is to prevent contagion between the high contrast emulsion layer containing the hydrazine derivative and the soft emulsion layer not containing the hydrazine derivative so that they do not influence each other. be done.

In other words, a soft emulsion has gradations below D=/,j 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. . Quinone reacts with hydrazine derivatives to create an active form of contagious development that causes high contrast development. Further, this quinone diffuses from the soft emulsion layer to the high contrast emulsion layer containing the hydrazine derivative.

Therefore, it is thought that high-contrast development occurs from the foot portion of the characteristic curve, a desirable characteristic curve shape cannot be obtained, and the exposure latitude of the line drawing becomes narrow.

However, it is presumed that by using a quinone scavenger that traps quinone in the intermediate layer or soft emulsion layer, the above-mentioned problems can be solved and a sensitive material with a wide exposure latitude as in the present invention can be obtained.

Quinone scavenger is a compound that reacts with quinone and reduces quinone.1.夛）Royance is a compound that adds to quinone.

When the photosensitive material (photosensitive material) in the present invention is subjected to current X, ff processing, the obtained characteristic curve D (1 degree) -0,3 to D=
It is preferable that the γ (gamma) I value of the part /, s is 70 or less, and the γ value of the part D=3.0 from D=/, J is 70 or more. More specifically, the development process here refers to, for example, the process described in Examples.

Hereinafter, the former γ value will be abbreviated as 11 value, and the latter γ value will be abbreviated as γ1° value.

In the present invention, γ and γ can be determined more specifically by the method described below. That is, the density -o on the characteristic curve obtained by the development process.

The slope of the straight line connecting the two points 3 and concentration -/, J is 9, and the slope of the straight line connecting the point density = /, j and concentration = 3.0 is T.
I (closed.

That is, in the present invention, the γ1 value is preferably 70 or less [
2~g, more preferably ≠~g.

Further, the γ□ value is 10 or more, preferably 72 or more, and more preferably 72 to jO.

It is sufficient that the light-sensitive material used in the present invention has at least two silver halide emulsion layers (more specifically, a silver halide emulsion layer that substantially contributes to image formation).
In addition to '@, three layers, an lIt layer, may be provided.

When the silver halide emulsion layer of the sensitive material used in the present invention has two layers, these layers include an emulsion layer that provides a hard gradation (high contrast emulsion layer) and an emulsion layer that provides a soft gradation (soft contrast emulsion layer). Emulsion layer) is preferred.

Here, the former mainly deals with the gradation in the area above D=i,s, and the latter mainly deals with the gradation in the area below D-7,j.

The former hard emulsion layer preferably has a γ value of 10 or more, and the latter soft emulsion Igi preferably has a γ value of 70.
It is preferable that it is less than

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

Examples of the quinone scavenger used in the present invention include reducing substances such as dihydroxybenzene derivatives, sulfites, organic sulfinic acids, he-substituted hydroxydiamines, ascorbic acid or erythorbic acid and their derivatives, and diol compounds and their derivatives. Can be done.

These quinone scavengers are preferably localized in specific layers of the silver halide photosensitive material, and from this point of view, it is preferable to introduce a diffusion-resistant group into the quinone scavengers in order to suppress their free movement between layers. Preferably, it is preferable to introduce a group that promotes adsorption to silver halide grains and use the silver halide grains in a state of adsorption. Here, the diffusion-resistant group is preferably an organic residue having 7 or more carbon atoms (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 detailed below.

Among dihydroxybenzenes, preferred are compounds represented by the following general formula (+).

General formula (1) [In the formula, at least one of G1 and 02 represents a hydroxy group, and the other is selected from the groups having the same meaning as the following 几1 to R4. 'FL or R4 independently represent a hydrogen atom,
Hydroxy group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted alkylthio group, halogen atom, /, λ, tertiary amine group, substituted or unsubstituted carbonamide group, substituted or unsubstituted sulfonamide group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted at least 7 Contains N, 0, S atoms! or a 6-membered heterocyclic group, a formyl group, a t-group, a sulfonic acid group, a carboxylic acid group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted alkylsulfonyl group.

However, the sum of the carbon atoms of R1 to R4 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. ) Among these preferred dihydroxybenzenes, particularly preferred are / to tt-substituted catechol or hydroquinone, in which the sum of Hammett's sigma values of two substituents other than hydroxyl groups is -/, 2 to 17.2. , particularly preferably within the range of -i, o to +0.3.

Specific examples of these compounds include, for example, U.S. Pat.
72g, No. 44, JP-A No. 10632, etc., U.S. Patent J, 700, No. 33, West German Patent Publication f'q
'i, 2. /1I-7, 7F7, Japanese Patent Application Publication No. 1963-/! 6
, ≠ 3g issue, and the monobranched alkyl hydroquinones described in the same Geter issue 10632, US patent!
, 72g, No. 639, λ, No. 732.300, British Patent 7! , 2/Hiroshi No. 6, same/, No. 016,201, Chemical Abstracts Magazine Vol. 3 A3A7h, etc., dilinear alkyl hydroquinones, U.S. Patent 3
, 700, No. 1-33, No. 2.732.300, British Patent No. 1011p20r, Japanese Patent Application Publication No. 1973-/Jls
1AJg No. 1sO-33337, Tokuko Akira! 0-2
/24t issue, same! It is described in 6-410♂/g issue, Michal Abstracts magazine, volume j AjA7h, etc.

Di-branched alkylhydroquinones, JP-A-Sho J1. -10
Ri3hiro≠, 37-22.237, same! Tar202≠A
j, same j♂-/71A3/, JP Sho J Tar 8072, JP Sho J Tar 37≠Tough, dihydroxybenzene derivatives described in U.S. Patent No. 3,227,332, etc., JP 37
Examples include polymers having a dihydroxybenzene skeleton as described in -/7 Rihiro 7, etc.
The scope of the present invention is not limited thereto. These compounds may be used as a mixture of 2m or more.

The synthesis of these compounds is described in French Painting Patent No. 1.1A96.36.
No. 2, West German Patent No. 1, IIO.

This can be easily carried out by the method described in No. 327 or similar methods.

Examples of dihydroxybenzene f=j conductors with reduced diffusivity are shown below, but the scope of the present invention is not limited thereto.

H ]-j 1 -dH H H 1-/ ≠ 1-/J H ]-/ ♂ H Among organic sulfinic acids or salts thereof, preferred are:
It is a compound represented by the following general formula (n).

General formula (II) 几-8O□N1 (wherein, M represents a hydrogen atom, an alkali metal atom, unsubstituted or / or substituted ammonium, and 几 is a substituted or unsubstituted ammonium having 7 to 30 carbon atoms. alkyl group having 7 to 30 carbon atoms, substituted phenyl group having 7 to 30 carbon atoms, IO
Represents 30 to 30 substituted or unsubstituted naphthyl groups.

Preferred M in formula (II) is a hydrogen atom or an alkali metal atom (Li, ha, K, Cs), and preferred substituents for the group represented by R include the following. That is, a straight chain, branched, or cyclic alkyl group (preferably a carbon atom number/to one!);
O), aralkyl group (preferably monocyclic or cocyclic, the number of carbon atoms in the alkyl moiety is / to 3), alkoxy group,
(Preferably an alkyl group, an acyl group, an alkyl group, or a haarylnulfonyl group having a carbon atom number of 1 to 2 o) or a 2-substituted amino group (preferably a carbon atom number of 1 to 2 o), in the case of a 2-substituted The total number of carbon atoms in the substituents is 20 or less), / to 3-substituted or unsubstituted Waleido group (preferably those with 7 or 20 carbon atoms), substituted or unsubstituted an aryl group (preferably a bicyclic one having 2 to λ carbon atoms), a substituted or unsubstituted ruthio group (preferably a carbon atom number 6 to λ);
death! ), substituted or unsubstituted alkylthio group (preferably number of carbon atoms / to λ), substituted or unsubstituted alkylsulfonyl group (preferably number of carbon atoms / to 2)
, a substituted or unsubstituted lunulfoxy group (preferably one having 6 to 2 carbon atoms and a monocyclic or ! ring), a substituted or unsubstituted alkylsulfonyl group (preferably one to one carbon atom) , a substituted or unsubstituted ori-ru sulponyl group (preferably having 6 to λ carbon atoms, monocyclic or bicyclic), or a substituted or unsubstituted ori-ruoki group (preferably having 6 to 2 carbon atoms, monocyclic or bicyclic), carbamoyl group (preferably number of carbon atoms), sulfamoyl group (preferably number of carbon atoms), hydroxy group, halogen atom (e.g. F1a, Br, I)
, a sulfonic acid group, or a carboxylic acid group. Among these substituents, those that can have further substituents may have the following substituents, namely, alkyl groups (number of carbon atoms / to !0), aryl groups (number of carbon atoms / to !0), !00 monocyclic or bicyclic), alkoxy group (number of carbon atoms / to 20), aryloxy group (number of carbon atoms / to 20), alkylthio group (number of carbon atoms / to 20), arylthio group (carbon Atomic number 2 to 20
), alkylsulfonyl group (number of carbon atoms/~λ0)
, arylsulfonyl group (6 to 20 carbon atoms)
, carbonamide group (number of carbon atoms/to 10), sulfonamide group (number of carbon atoms 0 to 20), carbamoyl group (number of carbon atoms 7 to !0), sulfamoyl group (1y,/ to 20 carbon atoms), Alkyl sulfoxy group (number of carbon atoms/to 20), Ririichi Rusulfoxy i'G (number of atoms/to jo), ester group (number of carbon atoms - 20), hydroxy group, - C00M2 is -S02 M (M'd water RIW
.

or alkali Kanagawa atom, substituted or unsubstituted monomonium), or halogen atom (F, ci, Br%
I). These groups may be linked to each other to form a ring. These groups may also be part of a pomopolymer or fuborimer chain.

Examples of common sulfinic acids are shown below, but the scope of the present invention is not limited thereto.

■-6 ool +1- C41-19 io n-C3H1□So□Nax/y=7
° 3 Synthesis methods for these compounds are described, for example, by Rin, B.

Syntheti by Wagner, HoD, Zook
rQrganiCCchemistry, pza07~
5'101 John Wiley & 5ons, In
r,, New York.

It is described along with other compound examples in the 3rd annual edition of RIJ.

Among the N[substituted human O xylamines, preferred is a compound represented by the following general formula (1).

General formula (1) % formula % (where m represents 0 or /, Q is a hydrogen atom, an acyl group with a carbon number of / to 0, or a substituted or unsubstituted acyl group with a carbon number of / to 10) R represents a 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 1 to 30 carbon atoms.However, at least one of Q or 7 has 7 carbon atoms. (30 to 30 organic groups) Among the compounds represented by the general formula ([), preferred are m representing O or /, and Q representing a hydrogen atom. Preferred substituents for the alkyl group or phenyl group represented by 几 are as follows. That is, a linear, branched, or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or λ ring,
The number of carbon atoms in the alkyl moiety is / to 3), an alkoxy group (preferably, the number of carbon atoms is / to 20), or 2
tl-substituted amino group (preferably an alkyl group, acyl group, alkyl or arylsulfonyl group having 7 to 20 carbon atoms; when 2 is substituted, the total number of carbon atoms in the substituent is 20 or less) , / to jfl-substituted or unsubstituted ureido group (preferably one having a carbon atom number of / to one), a substituted or unsubstituted ryol group (preferably one having a 7 or ! ring having 6 to 2 carbon atoms) ), substituted or unsubstituted arylthio group (preferably 6 to λ carbon atoms), substituted or unsubstituted alkylthio group (preferably 7 to 2 carbon atoms), substituted or unsubstituted alkylsulfoxy group ( Preferably the number of carbon atoms / or λ)
, substituted or unsubstituted aryl nulphoxy group (preferably monocyclic or bicyclic with 6 to 2 carbon atoms), substituted or unsubstituted alkylsulfonyl group (preferably 1 to 2 carbon atoms) , a substituted or unsubstituted arylsulfonyl group (preferably having 1 to 2 carbon atoms, monocyclic or bicyclic), aryloxy group (preferably having 6 to λ carbon atoms, monocyclic or bicyclic), 2-ring), carbamoyl group (preferably number of carbon atoms/silicon 2), sulfamoyl group (preferably number of carbon atoms 7 to 2)
, hydroxy group, 710 gene atoms (e.g. F1a, Br
, I), a sulfonic acid group, or a carboxylic acid group.

Among these substituents, those that can have further substituents may have the following substituents; namely, alkyl groups (having 6 to 20 carbon atoms), oryl groups (having 6 carbon atoms), to 20 monocyclic or λ ring), alkoxy group (number of carbon atoms) to 20), iri-ruoxy group (number of carbon atoms 6 to 20), alkylthio group (number of carbon atoms / to 20), arylthio group (having 6 to 20 carbon atoms), alkylsulfonyl group (having 6 to 20 carbon atoms),
0), arylsulfonyl group (having 6 to 20 carbon atoms)
), carbonamide group (number of carbon atoms/to 20),
Sulfonamide group (number of carbon atoms 0 to 20), carbamoyl group (number of carbon atoms / to 20), sulfamoyl group (number of carbon atoms / to 20), alkylsulfoxy group (number of carbon atoms / to 20), aryl Nulphoxy group (number of carbon atoms/to 20), ester group (number of carbon atoms/to 20), hydroxy group, -COOM or -80
2M (M represents a hydrogen atom or an alkali metal atom, substituted or unsubstituted ammonium), or a halogen atom (F
%, Br, I). Specific examples of these compounds include, for example, R.B. Wagner, ) (D. Zook, S.
ynthetiCQrganiC(:'hemistr
y, p J j is, p! 76, etc., along with the synthesis method.

Specific examples of these monosubstituted hydroxyfluamines are listed below, but the scope of the present invention is not limited only to these.
H1-, 2n-C'15H3, C0NHOH1-J
n-C1゜H25NHOH1-tt n-C
17H34CONHOHt 05H1, U5M11 ■-70 Other reducing substances include, for example, nucorbic acid,
Erythorbic acid and derivatives thereof or the diol compounds described in British Patent No. 22jjtO can be used. Specific examples of these are shown below, but the scope of the present invention is not limited thereto.

N-2H2O(CH2)6 C-OH CH3(CH2)s COH IV-4' CH3(CH2)7Co CH-
(CH2)7COOHOH In the photosensitive material of the present invention, the quinone scavenger does not need to be in the same layer as the hydrazine derivative.

When a quinone scavenger is included in a silver halide emulsion layer containing a hydrazine derivative, it is not preferable because it inhibits the contrast enhancement effect based on the hydrazine derivative.

The quinone scavenger used in the present invention is contained in hydrophilic colloid layers such as interlayers, filter layers, protective layers, and undercoat layers in addition to silver halide emulsion layers that do not contain hydrazine derivatives.

Preferably, it is a silver halide emulsion layer not containing a hydrazine derivative (for example, a soft emulsion layer) or an intermediate layer between silver halide emulsion layers (for example, between a soft emulsion layer and a hard emulsion layer containing a hydrazine derivative). , especially the latter is preferred.

The amount of quinone scavenger added is O1θ0/~
/, OP/m" is preferable, 0.0/~0, j
j'/m'' is more preferable.

The intermediate layer may or may not be present, but when an intermediate layer is provided, its thickness is preferably O1/~3.0μ, and 0. ．． 2
~, 2.0μ is more preferable.

The high contrast emulsion layer and the soft contrast emulsion layer may be arranged in any order with respect to the support.

That is, the 0 layer (the emulsion layer farther from the support) may be a high contrast emulsion layer, and the 0 layer (the emulsion layer closer to the support) may be a soft contrast emulsion layer.

Further, as for the sensitivity values of the 0 layer and the 0 layer, the 0 layer may be more sensitive, or the U/if may be more sensitive.

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

Either the sensitivity (SH) of the high contrast emulsion layer or the sensitivity (SS) of the soft emulsion layer used in the present invention may be higher, but it is preferable that the following relationship be satisfied.

0<1sHssl<0. Niko's SH%Ss is the value obtained when a sample coated with each emulsion in a single layer was prepared and subjected to sensitometry.

More specifically, the density of the characteristic curve obtained by exposing tungsten light through an optical wedge for sensitometry and then developing with the developer described in Examples below.

! It is expressed as the logarithm (logE) of the exposure amount that gives .

Also, especially 0, /<1SH-8sI(o,! More preferably.

Here SS sI (> 0, 6 tona 64 go Kl"
This is not preferable because the t and Dmax become << and the cutting becomes poor.

On the other hand, when 5H-ss>0, A, the reproducibility of thin lines becomes poor and the exposure latitude becomes narrow, which is not preferable.

Further, when the 0 layer is a high contrast emulsion layer and the U layer is a soft contrast emulsion layer, it is preferable that the relationship between the sensitivities of the two is as follows.

o<83-sH<o, b Also, especially 0, /<89-8H<0,3 It is more preferable that

Next, when the 0 layer is a soft emulsion layer and the U layer is a high contrast emulsion layer, it is preferable that the relationship between the illuminances of the two is as follows.

-o, g<s8-sH(.

In addition, it is particularly preferable that o, j< S S S H < o, /.

Regarding the relationship between SH and Ss, it is preferable that the above-mentioned relational expression be satisfied, but the specific value of the emulsion layer to be used depends on the halogen composition, grain size, and gradation of the silver halide emulsion used. It varies depending on etc. Moreover, those skilled in the art can easily provide an emulsion layer having such a relationship.

The coating silver amount of the photosensitive material used in the present invention is preferably 2,3-A,Oy)7m'', more preferably 3,0-J,Ojl7m''.

There is no particular restriction on the ratio of the amount of coated silver in each silver halide emulsion layer. However, when there are two emulsion layers, the ratio (molar ratio) of the amount of coated silver in both layers is preferably layer far from the body)/lower layer (layer close to the support) = 2/♂~g/2
, more preferably 3/7 to 7/3.

The total thickness of the silver halide emulsion layer is /, 3~! , O
pm is preferred, and 2.0-IA, Opm is more preferred.

It is preferable that the high contrast emulsion layer contains a sufficient amount of a hydrazine derivative to increase the contrast. The soft emulsion layer may or may not contain a hydrazine derivative, and if it does, it is necessary that the amount is such that the contrast does not become higher than that of the hard emulsion layer.

Examples of hydrazine derivatives used in the present invention include aryl hydrazides in which a sulfinic acid residue is bonded to a hydrazo moiety as described in U.S. Pat. Examples include compounds represented by:

General formula (IV) R1-NHNH-G-2 In the formula, R2 represents an aliphatic group or an aromatic group, R2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, It represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryloxy group, and G represents a carbonyl group, a sulfonyl group, a nulphoxy group, a phosphoryl group, or a substituted or unsubstituted iminomethylene group.

In general formula (1v), the aliphatic group represented by R1 preferably has carbon atoms/~30, particularly carbon atoms/
~20 straight chain, branched or cyclic alkyl groups. Does the branched alkyl group have 7 or more heteroatoms in it? It may be cyclized to form a heterocycle containing fJj1. Further, this alkyl group may have a t substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

The aromatic group represented by R1 in formula (IV) is a monocyclic or bicyclic ring group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group is monocyclic or! It may be condensed with the aryl group of the ring to form a heteroaryl group.

Reportedly, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Examples include inquinoline ring, benzimidazole ring, thiazole ring, and benzothiazole ring, among which those containing all be/zene rings are preferred.

Particularly preferred as R1 is a aryl group.

The aryl group or unsaturated heterocyclic group of R1 may be substituted, and typical f substituents include linear, branched or cyclic alkyl groups (F or those having carbon number/~20) , an aralkyl group (preferably a monocyclic or l-ring alkyl moiety having / to 3 carbon atoms), an alkoxy group (preferably a carbon number of 7 to θ), g! Replaced amino group (preferably f
or amino group substituted with an alkyl group having carbon number/-, 20), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably carbon number/-
30), ureido group (preferably carbon number/~
30).

In the general formula (IV), the alkyl group represented by R2 is preferably an alkyl group having carbon number/~V, which is substituted with a halogen atom, a cyano group, a carboxy group, a nulpho group, an alkoxy group, a phenyl group, etc. It may have a group.

In the general formula (IV), the optionally substituted aryl group of the group represented by 'Cs R2 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 nulfo group, or the like.

Among the groups represented by 2 in general formula (fY), the optionally substituted alkoxy group is an alkoxy group having carbon number/~g, even if it is substituted with a halogen atom, an aryl group, etc. good.

Among the groups represented by R2 in general formula 1), the optionally substituted ryolyloki7 group is preferably a monocyclic one, and examples of the substituent include a halogen atom.

Among the groups represented by R2, when G is a carbonyl group, preferred are a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, and a substituted or unsubstituted phenyl group, with a hydrogen atom being particularly preferred.

When G is a sulfonyl group, R2 is preferably a methyl group, an ethyl group, a phenyl group or a ≠-methylphenyl group, with a methyl group being particularly preferred.

When G is a phosphoryl group, s''2 is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, or a phenyl group, with a phenoxy group being particularly preferred.

When G is a sulfo group, preferable R2 is a cyanobenzyl group, methylthiobenzyl group, etc., and when G is a monosubstituted or unsubstituted iminomethylene group, preferable R2 is a methyl group, an ethyl group, a substituted or unsubstituted is a phenyl group.

R1− in general formula (1■)! A ballast group commonly used in immobile photographic additives such as couplers may be incorporated into the bamboo R2 structure.

The ballast group is a group having a carbon number of ♂ or more and is relatively inert to the developing solution, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. Be able to do that.

R1 or 2 in the general formula (IV) may have a group incorporated therein to enhance adsorption to the surface of the 710 silver germide grain. Such adsorption groups include thiourea group,
U.S. Patent No. ≠ for heterocyclic thiolamide groups, merkabuto-bicyclic groups, triazole groups, etc.

31! , 10! Examples include the groups listed in No.

G in general formula (IV) is most preferably a carbonyl group.

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.

In addition, the fact that the hydrazine derivative represented by general formula (1v) itself is diffusion resistant means that it prevents diffusion to other emulsion layers.
This is preferable from the viewpoint of obtaining the desired gradation.

Y-f ■-10 ■-/3 ■-77 IV-/♂ rV-/ri ■-20 ■-27 ■-22 ■-23 TV-2≠ V-23 ■-26 ■-27 Bar, 2♂ ■-2ri■ CH2Cl1□S)1 ■-30 ff -j / ■-32 In the present invention, hydrazine derivatives are used in silver halide emulsion layers and/or other hydrophilic colloid layers, but preferably halogenated This is a silver emulsion layer. In particular, when using a diffusion-resistant hydrazine derivative, it is effective to use it in the silver halide emulsion layer.

In the present invention, the hydrazine derivative is contained in an amount of /x10-6 mole per mole of halogenated bale! It is preferable to contain x10-2 mol, especially /x10-5 mol to 2X/θ
A preferable addition amount is in the range of -2 moles.

In the present invention, when the hydrazine derivative is contained in a photographic light-sensitive material, it is used as an aqueous solution if it is water-soluble, or as an alcohol M (for example, methanol, ethanol) if it is water-insoluble.
It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as ester, ester (eg, ethyl acetate), or carbon (eg, acetone).

A hydrazine derivative may be used alone in the present invention,
Two or more types may be used in combination.

Next, the emulsions used in the high contrast emulsion layer and the soft contrast emulsion layer used in the present invention will be explained.

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, silver iodobromide, etc.

The silver halide emulsion may or may not be chemically sensitized. Sulfur sensitization, reduction sensitization and noble metal sensitization are known as chemical sensitization methods, and any of these may be used alone or in combination. A preferred chemical sensitization method is sulfur sensitization, and examples of the sulfur sensitizer include sulfur compounds contained in gelatin, as well as natural sulfur compounds, such as
Thiosulfates, thioureas, rhodanine, etc. can be used. A specific example is US Pat. No. 37≠.

ri≠≠No., same, 2, 27F, ri≠No.7, same, 2. Hiro 10.6g No. 2, 721, 41, 3゜3
0/, 3/3 issue, same 3, A! is described in Ri J, No. 2.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and rhodium. A specific example is U.S. Patent 2, 444J'
, No. 07,0, British Patent 67r.

It is described in No. 061, etc.

As the reduction sensitizer, soot salts, amines, formamidine-nulfinic acid, silane compounds, etc. can be used. Specific examples of these are U.S. Patent No. 7,130,
2. J/1,67g issue! .

It is described in Ri♂3,60 Ri No., Ko, Ri No. 13.610, 2゜Otorihiro, No. 637.

The average grain size of the silver halide is preferably 0.7 .mu.m or less, preferably 0.13 .mu.m to 0.1 .mu.m. Average grain size is a term commonly used and easily understood by those skilled in the field of silver halide photographic science. Particle size means the particle diameter in the case of particles that are spherical or can be approximated to a sphere. If the particle is cubic, the edge length
J″'
The 7 Autograph Process [C, E, Me e
The theory by S. and T.H. James
of the photographer.

proCessJ) + 3rd edition, 31. ~143 pages (
1966, (Macmillan [MCm1 l 1 anJ
Please refer to the company publication).

There are no limitations on the shape of the silver halide grains, and they may be tabular, spherical, cubic, ltA-hedral, regular octahedral, rhombohedral, or any other shape. The narrower the grain size distribution, the more preferable it is, and particularly preferred is a so-called monodisperse emulsion in which 0%, preferably 3% of the total grains fall within a grain size range of ±tA0 of the average grain size.

In the silver halide emulsion used in the present invention, (d) cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. may coexist.

For example, iridium salt or its complex salt is preferably silver 1
By using θ ~10 moles per mole,
Photographic characteristics with higher sensitivity and higher gamma can be obtained. Specific examples used here include iridium trichloride, iridium tetrachloride, potassium hexachloroiridate (I[), potassium hexachloroiridate (IY), hexachloroiridate (1)! Ammonium etc.

In addition, rhodium salt or its complex salt is preferably used in an amount of 10-8 to 10-4 mol per mol of silver, more preferably 3 x 10
-7~! By using 10-5 mol of silver halide emulsion, the contrast can be increased and the image quality can be improved. Specific examples used here include rhodium dichloride, rhodium trichloride, potassium rhodium(1) hexachloride, and ammonium rhodium(1) hexachloride.

In the present invention, the soluble silver salt and the soluble silver salt may be reacted by any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrald double jet method. According to this method, the crystal form is regular. A silver halide emulsion with nearly uniform grain size can be obtained.

For more information on silver halide emulsions and their preparation methods, see RESEA 几CHDISCLOTJRg/7
Volume 6, ■tem/7 Otsu IA3 P, 22-P, 23
It is described in the literature described or cited in (/7f/, February).

Next, the light-sensitive material used in the present invention can contain various compounds for the purpose of preventing capri or stabilizing the photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material.

Namely, the compounds such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, aO benzimidazoles, bromobenzimidazole, mercaptothiazoles, mercaptobenzimidazole, mercaptobenzimidazoles, mercaptothiadiazole mercaptopyrimidines: mercaptotriazines; Compounds; azaindenes, such as triazaindenes, tetrazaindenes (Hydroxy-substituted (i, 3, 3a + 7) tetrazaindenes), pentaazaindene U, etc.; benzentiosulfonic acid, benzenesulfinic acid, Many compounds known as antifoggants or stabilizers can be added, such as penscensulfonic acid amide and the like.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners.

For example, alum salts (alum alum, chromium acetate, etc.), aldehydes @ (formaldehyde, glyoxal, glitaraldehyde, etc.), hemenalol compounds (dimethylol urea, methylol dimethylhydantoin, etc.)
, dioxane derivatives (2゜3-dihydroxydioxane, etc.), active vinyl compounds (/, 3.!;-triacryloyl-hexahytrose-t-IJ T'), bis(vinylsulfonyl) methyl ether, N, N' -methylenebis-[β-(vinylsulfonyl)fluorhionamide], etc.), active halogen compounds (2, Guzik a
(6-hydroxy-7-S-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), inoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, etc.
They can be used alone or in combination. Among them, JP-A-33-IAI22/, 433-372! ;7, same j
Preferred are the active vinyl compounds described in U.S. Pat.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, 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; cellulone derivatives such as hydroxyethyl cellulose, carboxydimethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl Use of a wide variety of synthetic hydrophilic polymeric materials such as single or copolymers of alcohol partial acetals, polyhevinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Be able to do it.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

The photographic emulsion layer or other hydrophilic colloid layer of the optical material made using the present invention contains coating aids, 11° prevention, slip property improvement, emulsification dispersion, contact radius prevention, and thickness property improvement (e.g., development Various surfactants may be included for various purposes such as enhancement, contrast enhancement, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene Non-ionic substances such as glycolalkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. arnylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants: Alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfuric ester acids, alkyl phosphoric esters, heacyl-alkyltaurines, sulfosuccinates, sulfonate Carboxy groups, such as alkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactant containing acidic groups such as sulfo group, phospho group, sulfate ester group, phosphate ester group; amino acid M
, aminoalkyl sulfone l! l! amphoteric surfactants such as aminoalkyl sulfates or phosphates, alkyl betaias, and amine oxides; amphoteric surfactants such as alkylamine salts, aliphatic or aromatic ammonium salts, and heterocyclic surfactants such as pyridinium and imidazolium. Cationic surfactants such as ammonium salts, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in Japanese Patent Publication No. 72. When used as an antistatic agent here, a surfactant containing a fluorine tube is particularly preferred.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, polymethyl methacrylate, etc. in the photographic emulsion layer and other hydrophilic colloid layers 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) acrylates, alkyl dialkyl (meth) acrylates, glycidyl (meth) acrylates, (meth) acrylamides, etc. alone or in combination, or combinations of these with acrylic acid, methacrylic acid, etc. A polymer as a monomer component can be used.

It is preferable that the silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Examples of compounds having acid groups include organic acids such as salicylic acid, acetic acid, and ascorbic acid, and polymers or copolymers having acid groups such as acrylic acid, maleic acid, and phthalic acid as repeating units. Regarding these compounds, patent application No. 1.0-66/7, same bo
-6♂za No. 73, 60-163131. No., l” same 1
．． The description in the specification of No. 0-/9slsj can be referred to. Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and acid monomers such as acrylic acid and crosslinkable monomers having two or more unsaturated groups such as divinylbenzene as high molecular compounds.
It is a water-dispersible latex of copolymer consisting of

The silver halide emulsion of the present invention can be ortho- or panchromatically sensitized or superchromatically sensitized by using cyanine colors such as cyanine, merocyanine, and carpositin, singly or in combination, or by using them in combination with nutyryl dye, etc. You can feel the sensation. Among them, Tokukai Shoj/-taja 36, 5i
-ir3i/ and U.S. Patent j, , 567, ≠jg
The sensitizing dyes described in this issue are preferably used. Also, the above-mentioned RESEARCHDI8CLOUR, E Item
/761A3 It is also possible to use those disclosed in the publications disclosed or cited in Section (2).

Various other additives are used in the silver halide photographic material used in the present invention. For example, desensitizers, plasticizers, slip agents, development accelerators, oils, dyes, etc.

These additives and the additives mentioned above are specifically described in Research Disclosure.
1) isr, 1osure) No. 176, pages 22-3/(RD-/76413) (Der,,,/97
r) etc. can be used.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on one or both sides of a flexible support commonly used in photographic materials. Useful flexible supports include films of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, and polyethylene terephthalate.

Known processing solutions such as developing solutions can be used in the present invention.

For more information on the development method used, please see ESEARC.
HDISCLOURE / Volume 76 Item/76
Hiroshi J Section XIX, Section XX, Section XXI P, 2-P, 30
C/Z7Lr, December).

In order to obtain photographic characteristics of ultra-high contrast and high sensitivity using the silver halide photosensitive material of the present invention, it is necessary to use conventional infectious developing solutions or US Pat. It is not necessary to use a highly alkaline developer with a pH close to 3 as described in ≠/RI, No. 7j, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains 0.7 j mol/2 or more of sulfite ions as a preservative, and has a pH of
Sufficiently ultra-high contrast negative images can be obtained with a developer having a pH of 10.3 to 3, particularly pH 0 to 2.0.

There is no particular restriction on the developing agent used in the developer used in the present invention, but it is preferable that it contains dihydroxybenzenes, since it is easy to obtain good halftone dot quality. Combinations of 3-pyrazolidones or combinations of dihydroxybenzenes and p-aminephenols may also be used.

The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,3-
Dichlorohydroquinone, 2.3-dibromohydroquino/, 2. Examples include j-dimethylhydroquinone, and hydroquinone is particularly preferred.

The developing agents for /-phenyl-3-pyrazolidone or its derivatives that can be used in the present invention include /-phenyl-3-pyrazolidone, l-phenyl-≠, Hiro-dimethyl-3-pyrazolidone, /-phenyl-≠-methyl-≠- Hydroxymethyl-3-virazolito/, /-phenyl-≠, Hiro-dihydroxymethyl-3-vira y! Jton, /-phenyl-j-methyl-3-pyrazolidone, /-p-aminophenyl-≠, ≠-dimethyl-3-pyrazolidone, /-p-
Examples include trilu≠, 4L-dimethyl-3-pyrazolidone, and the like.

Examples of the p-aminophenol developing agent used in the present invention include hemomethyl-p-aminophenol, p-aminephenol, N-(β-hydroxyethyl/l/)-p-aminophenol, and N-(≠-hydroxyphenyl)chrysin. , 2-methyl-p-reminophenol, p-benzylaminophenol, etc. Among them, he-methyl-p-
-Aminophenol is preferred.

The developing agent is usually 0. It is preferably used in an amount of OJ mol/2 to Q0 g mol/It. In addition, when using a combination of dihydroxybenzenes and/-phenyl-3-pyrazolidones or p-amino-phenols, the former is reduced to 0.
．． OJ mol/11 to 0°j mol/2, preferably the latter in an amount of 0.01 mol/2 or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The sulfite is preferably 0.1/L mol/2 or more, particularly 0.3 mol/2 or more. Also, the upper limit is 2. J mole/2=! It is preferable to do so.

The alkaline agents used for setting p)I include pH adjusting agents and buffers such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

Additives used in addition to the above components include compounds such as boric acid and borax; development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosol; Organic solvents such as hexylene glycol, ethanol, and methanol: Mercato-based compounds such as /-7enyl-j-mercaptotetrazole, 2-mercaptobenzimidazole-j-sulfonic acid sodium salt, and indazole-based compounds such as j-nitroindazole. , a capri-preventing agent such as a benztriazole-based compound such as j-methylbenztriazole, or a black pepper preventive agent.
It may also contain a water softener, a hardening agent, an amino compound described in JP-A No. 36-10 Otsu λ4L, and the like.

The developing temperature is preferably 7 g°C to 30°C, and the opening time during development is preferably 73 to 60 seconds.

After development processing, the characteristic curves of the samples exposed stepwise were determined, and the sensitivity (H8-j processing of film /16/ was set as 100) was determined from the exposure amount of density 7.3, and 0.
The gammas from 3 to /, J and from /, j to 3.0 were determined (details are given below). On the other hand, the line drawing exposure latitude and practical Dm of the samples subjected to line drawing practical exposure were evaluated by the following methods.

Method for Measuring 0γ (Gamma) Value The sample described in the Example was exposed to tungsten light having a color temperature of 3200° for 3 seconds through a sensitometry wedge, and then developed as described in the Example.

The slope of the straight line connecting the two points of density=0°3 and density=/,j on the characteristic curve thus obtained is γ.

The slope of the straight line connecting the two points of density=/, j and a degree=3.0 was assumed to be γ□, and γ1 and γ□ were calculated, respectively, using the above-mentioned calculation formula.

Method for evaluating O line drawing exposure latitude For manual phototypesetting, a document containing white lines and black lines with a line width of 100 μm was prepared using Par PL-10OWP (manufactured by Fuji Photo Film ■). A white line is a solid black line with a white line inside a black background, and a black line is a line with a white background and a black line inside. The line widths of these black lines and white lines are determined by scanning the original in the line width direction with a reflection type microdensitometer, and the optical density is set to 0.
It was confirmed that the line width at ゜6 was 100μ. The manual phototypesetting with white lines and black lines obtained in this way is done by copying the manuscripts -, e- with reflective plate-making cameras D and 5.
The samples described in Examples were photographed using C-jJ/ (manufactured by Inu Nippon Screen ■) and then developed. Exposure was performed by changing the exposure speed of the plate-making camera, and the critical exposure amount for white line reproduction and the boundary exposure amount for black line reproduction were determined, and the difference between the two was taken as exposure latitude. In other words, if you lower the exposure, the black lines on the original (which will become white lines on negative film) will be reproduced, but the white lines on the original (which will become dotted lines on negative film) will be reproduced.
The line width becomes thinner and the density becomes lower, and a lower limit exposure amount is found at which the white line cannot be reproduced with an exposure amount below this value. Similarly, if you increase the exposure amount, you will find an upper limit exposure amount where Haraori's whiteness is good, but the dotted line becomes blurred.

The exposure amount difference between the upper limit and lower limit determined in this way (Δ1
ogE) was taken as the line drawing exposure latitude. The larger the value of this exposure amount difference, the wider the latitude. The limit point for white lines and black lines is that the line width determined by scanning the developed negative film in the line width direction with a transmission microdensitometer at optical density = /, j is less than IOμ (cannot be used for the next process). The width of the line is as follows.

Line drawing exposure latitude = log (upper limit exposure amount) - 1o
It can be expressed as g (lower limit exposure area). The value of line exposure latitude evaluated by this method is preferably 00 g or more.

O Practical Dmax Evaluation Method It is preferable that the solid black portion on the developed negative film has a higher density. The density of this solid black area becomes a problem on the low exposure side, and the limit exposure f for reproducing white lines on the original is
Measure the transmission density of the black solid area at (lower limit exposure f) with a Macbeth densitometer TD-30≠, and calculate this value as the practical Dmax.
And so.

Practical skill Dmax is preferably ≠, θ or more.

(Example) Next, the present invention will be specifically explained using examples.

Example-l A silver chloroiodobromide emulsion (silver iodide 0.00.
1 mol of silver bromide, 30 mol of silver bromide) was prepared. This silver chloroiodobromide emulsion contains (NH4) 3 R as a rhodium salt.
hC26f/X/0 mol/A g 1
moles, 3Irα6 as iridium salt ≠×70−7
A rhodium salt and an iridium salt were added to the halogen solution so as to contain 1 mol/Ag, and the halogen aqueous solution and silver nitrate aqueous solution were mixed at 30° C. for 60 minutes to form particles. This silver chloroiodobromide emulsion (average grain size 0830 μm, cubic, monodispersed) was washed with water, desalted, gold-sulfur sensitized, and dimethine merocyania dye (1) was added to increase the spectral amplification by 1. , as a stabilizer, 2-methyl-≠-
Hydroxy7-1.3,3a,7-titraza(7f: / and, /,≠-Dispersion of dihydrox7benzene and polyethyl acrylate, /,3-vinylnurfol-2-
Emulsion Ai*4 was prepared by adding propatool.

Dimethine merocyanine dye (1) Further, compound 1-7 was added to this emulsion A in the form of 7 jars of quinone to give o, i or 0.397 m' to form emulsions B and C, respectively.

In addition, compound 1-/
7 was added to give emulsions of 0.7 or 0.3 y/i to give emulsions E and E, respectively. These are all emulsions for the 0 layer.

Next, in the same manner as emulsion A, rhodium salt (NH4)3
Rh (76f3; After washing and desalting with water in the same manner as emulsion A, gold-sulfur sensitization was performed, and dimethine merocyanine dye (1) was added for spectral sensitization. As a stabilizer, !-Methyl≠-Hydroxy/,
3゜3a, 7-chitrazaindene and/, ≠-dihydroquibenzene and polyethyl acrylate dispersion,
/ , 3-vinylsulfonyl-,2-furopanol was added, and ■-72 was added as a hydrazine compound.
/ 0-4 mol 1 mol kg Processed emulsion F.

Next, a nitrate aqueous solution, potassium iodide, and a potassium bromide aqueous solution were added to a gelatin aqueous solution kept at 30°C in the presence of 1 and a half moles of A g, Hiro x 70-7 moles of iridium (1) potassium hexachloride, and ammonia. By adding at the same time for 60 minutes and keeping the pAg at 70g during that time, the average particle size was 0.20.
μ, cubic monodisperse emulsion with average silver iodide content of 1 molt'
T? I got Aa.

This emulsion was subjected to sulfur sensitization using sodium thiosulfate, and then a sensitizing dye (j,j'-dichloro-3,3'-di(
3-sulfopropyl)-terethyl-oxacarbocyanine sodium salt) x 10 per mole of silver, respectively.
Spectral sensitization was performed by adding molar amount. Furthermore, as a stabilizer ≠−
Hydroxy-6-methyl-7,3,3a,7-chitrazaindene was added.

Furthermore, as a surfactant, an alkylbenzene sulfonate, as a hardening agent, 3-vinylsulfonyl-2-furopanol, and a hydrazine compound, and 1v-72! ;
Emulsion-G was prepared by adding 1 mol of X70-3 Ag and a dispersion of hypopolyethyl acrylate.

These emulsions F and G are both emulsions for the U layer.

Next, polyvinylbenzene sulfonate as an anionic surfactant and sodium dodecylbenzenesulfonate as a thickener was added to an aqueous gelatin solution as an intermediate layer to prepare an intermediate layer coating solution-A. Additionally, compound 1-7 was added to this coating solution as a quinone scavenger.
．． The intermediate layer coating solution was prepared by adding the solution at a concentration of / or 0°3/mK, respectively. Similarly, Compound 1-/7 was added as a quinone scavenger to the coating solution A to give O1/or o, 3y/rl to prepare intermediate layer coating solution A and E.

These emulsions F%G are used as the U layer, intermediate layer coating liquid Il-2 is used as the intermediate layer, emulsions A-E are used as the 0 layer, and the U layer and the 0 layer are coated with Ag.
The amount is /, 71/ze (0 layer + U layer = 3.≠y/ze) The intermediate layer is coated as gelatin so that it becomes Z, Jf/rl, and on top of that, gelatin /, Of/ is applied as a protective layer.
The samples shown in Table 1 were prepared by coating the film on a polyethylene terephthalate support with a film thickness of 100 μm so that the film thickness was 1rjK.

Each of these samples was exposed through a sensitometric optical wedge to tungsten light at 32,000 °C for 3 seconds, and then treated with a developer having the following composition: f °Cj Develop for 0 seconds,
Fixed, washed with water, and dried. (For the development process, an automatic processor FG-61, OF manufactured by Fuji Photo Film Co., Ltd. was used.) (Developer formulation) Hydroquinone 3J, Ophemethyl-p-amino 0.♂yphenol//2m salt sodium hydroxide Ta ,OF tribasic potassium phosphate 7≠,OF potassium sulfite
Tao,oy ethylenediaminetetraacetic acid No,Op disodium chloride potassium bromide 3.0riJ-Methylbenzotriazole o,tsy3-diethylamino-/
-/J, Of Add prononol water 12 (pH=11
．． x) Determine the characteristic curve from the sample after development processing and calculate the density/.

Sensitivity from the exposure amount giving 3 (sensitivity of sample /I6/ to 10
θ) and rco, 3~/, j), r(/.

j~3.0) was determined. In addition, line drawings were photographed and developed in the same manner as sensitometry, and then the line drawing exposure latitude and practical Dmax were evaluated by the method described below.

From Table 1, it can be seen that the sample layer /~≠ that does not use a quinone scavenger has a narrow (impossible) line drawing exposure latitude, but the sample A j = 21 of the present invention is good.The line drawing exposure latitude is o, It is preferable that it is more than g.

Sample 4/-≠ has a high γ, C0,3~/, and this is the cause of worsening the line exposure latitude. It can be seen that the line exposure latitude is improved by using the quinone scavenger.

γ, if the value is 7 or more, the line image quality is good;
There is no problem with either sample. In addition, the sensitivity and practical Dmax of the sample of the present invention were good and there were no problems, and the line drawing exposure latitude was improved.

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

Example 2 Compound ■-6 or ■-g as a quinone carbavenger was added to the intermediate layer coating solution A in the same manner as in Example-2. A coating solution was prepared in which the following amounts were added, and each solution was added to an intermediate layer coating solution.

Similarly, compound ■-≠, IV-j is added to intermediate layer coating liquid-A.
0. /11/m were prepared and used as intermediate layer coating solutions.

In the same manner as in Example-/, emulsion F or G is used as a U layer, the intermediate layer coating liquid is used as an intermediate layer, and emulsion A is used as a 0 layer, and a protective layer is formed thereon in the same manner as in Example-/. Coated sample/I6-! I created 3-3.

These samples were exposed and developed in the same manner as in Example-/, and the sensitivity, γ, exposure latitude of line drawing, and practical Dmax were evaluated.

Procedural amendment 1. Display of incident Showa Otsu/Year Patent Application No. 1t0306
No. 2, Title of the invention Silver halide photosensitive material 3, Relationship with the case of the person making the amendment Patent applicant 43 Subject of the amendment Column 5 of “Detailed description of the invention” in the specification, “Invention” in the description of the contents of the amendment Please refer to the section “Detailed explanation” below.
to correct.

1) On page 73, line 7, after “may be part of”, rRx to R4 are connected to each other! , z or a 7-membered ring. The ring is preferably a substituted or unsubstituted benzene ring. Insert J.

2) Page 27, line r "7 to 30J ``/ or 3 oj and correct it.

3) Page 27/3rd line "l to 20" [Otsu to 20J and correct it.

4) Page 27/! row "l or ko 0" "Otsunaishiko O" and correct it.

5) Page 73/line 1 "Nitrate" "silver nitrate" and correct it.

Claims (1)

[Claims] A halogenated material having at least two silver halide emulsion layers on a support, containing a hydrazine derivative in at least one of the silver halide emulsion layers or other hydrophilic colloid layers, and containing substantially no hydrazine derivative. A silver halide photosensitive material characterized by containing a quinone scavenger in a silver emulsion layer or other hydrophilic colloid layer.