JPH0451142A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obviate the sticking of films and to obtain high-contrast images having good haze and excellent sharpness by incorporating an acidic polymer into emulsion layers and specifying the center line average roughness on the surface on the side where the emulsion layers are provided. CONSTITUTION:The silver halide photographic sensitive material which has at least one layer of the silver halide emulsion layers on a base and contains a hydrazine deriv. into the emulsion layers or the adjacent layers has the acidic polymer in the emulsion layers and the center line average roughness on the surface on the side where the emulsion layers are provided is >=0.05mum and <0.20mum. The acidic polymer is the polymer which contains an acidic group of <=9 pKa value and has monomer components having preferably a carboxyl group, sulfoxyl group or phosphoric acid group. Particularly the use of this polymer in the form of an aq. polymer latex is more preferable as the formation of flocs and precipitate by interaction with gelatin hardly arises. The sticking of the films is obviated in this way and the high-contrast images having the good haze and the excellent sharpness are obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a silver halide photographic material, and more particularly to a high contrast silver halide photographic material.

[Prior Art] In recent years, in the field of printing photolithography, printed matter has become increasingly colored and complex. For this reason, demands for improved and stable quality of silver halide photographic materials for printing (hereinafter referred to as printing materials), which are intermediate media for printing, are increasing year by year. Conventionally, in order to achieve high quality, ``Funatsuri'' printing sensitive materials have been given suitability for so-called "lith development" processing.

However, in "Lith development," it is mechanically impossible to contain high concentrations of sulfite ions, which are preservatives, in the developing solution, and as a result, the stability of the developing solution is extremely poor. is a well-known fact among those skilled in the art.

As techniques for eliminating the instability of "lithographic development" and obtaining high-contrast images comparable to the "lithographic developing" process, several attempts can be found in patent documents. For example, techniques for obtaining high-contrast images using hydrazine compounds are disclosed in JP-A-53-16623 and JP-A-53-20921.
No. 53-20922, No. 53-49429, No. 53
-66731, 53-66732, 53-77
No. 616, No. 53-84714, No. 53-13713
No. 3, No. 54-37732, No. 54-40629,
No. 55-52050, No. 55-90940, No. 56
-67843 etc. In the processing method of the image forming method using these hydrazine compounds,
In order to obtain high-contrast images, it is necessary that the pH value of the developer containing a hydrazine compound or the OpH value of the processing developer for photographic light-sensitive materials containing a hydrazine compound be at a relatively high level. However, this high pH value had the disadvantage that it reduced the useful life of the developer.

On the other hand, in JP-A-56-106244, a high-contrast image is formed at a relatively low pH (11 to 11.5) by containing a hydrazine compound and a development-promoting amount of an amino compound during image formation. He says it can be done.

Image forming methods using these hydrazine compounds can provide very high contrast images.

On the other hand, in order to improve physical properties such as curl characteristics, dimensional characteristics, and coating properties of the film, latex is generally incorporated into the emulsion layer and other hydrophilic colloid layers.

5. Problems to be Solved by the Invention] However, the inclusion of latex in the hydrophilic colloid layer is one of the causes of poor film adhesion.
For this purpose, a large amount of matting agent must be added. Addition of a large amount of matting agent causes deterioration of haze and further deterioration of edge sharpness.

The present invention was made in view of such conventional problems,
To provide a silver halide photographic material which improves film adhesion and provides high-contrast images with good haze and excellent edge sharpness.

[Means for Solving the Problems] In order to achieve the above object, the present invention has at least one silver halide emulsion layer on a support, and contains a hydrazine derivative in the emulsion layer or an adjacent layer. In a silver halide photographic light-sensitive material, the emulsion layer contains an acidic polymer, and the center line average roughness of the surface on which the emulsion layer is coated is 0.05 μm or more and less than 0.20 μm. It is characterized by

The present invention will be explained in detail below.

The acidic polymer used in the present invention is a polymer having a monomer component having an acidic group having a pKa value of 9 or less, preferably a carboxyl group, a sulfoxyl group, or a phosphoric acid group, particularly in the form of an aqueous polymer latex. It is preferable to use it because it interacts with gelatin and does not easily cause aggregation or precipitation.

The acidic polymer latex preferably used in the present invention and its manufacturing method will be explained in more detail below. First, regarding monomers, examples of copolymerizable ethylenically unsaturated monomers containing at least one acid group include carboxylic acid monomers represented by general formula (M). In the R1° formula, R1° represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L represents a divalent, trivalent or tetravalent linking group. r is 0 or 1, and m is 1°2 or 3.

R. Examples include a hydrogen atom, an unsubstituted alkyl group such as a methyl group, an ethyl group, and an n-propyl group, and a substituted alkyl group such as a carboxymethyl group.

Among these, a hydrogen atom, a methyl group, or a carboxymethyl group is preferred.

L is a divalent, trivalent or tetravalent linking group, and in the case of a divalent linking group, it is a group in the case of a 10-13 valent linking group, examples of which are alkylene groups (e.g. methylene group, ethylene group,
trimethylene group), arylene group (e.g. phenylene group), -C-O-X- (where X has 1 to about 6 carbon atoms)
represents an alkylene group or an arylene group. Same below) CH2COOH CH, = C OOH CH, = C -C-NH-X-〇-C- (For example, 1r r is O or 1.

m is 1.2 or 3.

Preferred examples of the copolymerizable ethylenically unsaturated monomer represented by general formula (M) include the following, but examples of ethylenically unsaturated monomers having at least one acid group are not necessarily limited to these: In addition, monomers such as carboxylic acid anhydrides and lactone rings that form carboxylic acid groups when in contact with the developer, monomers having phenolic hydroxyl groups, and monomers having phosphoric acid groups as disclosed in JP-A-54-128335, etc. Examples include monomers and monomers having a sulfonic acid group.

In addition to the above monomers having acid groups, the monomers constituting the acidic polymer latex preferably used in the present invention include crosslinkable monomers containing at least two or more copolymerizable ethylenically unsaturated groups. (hereinafter referred to as "crosslinkable monomer") is preferably used. Examples of crosslinking monomers include the following.

Divinylbenzene, ethylene glycol acrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate,
Triethylene glycol dimethacrylate, trivinylcyclohexane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritolte)/lamethaflylate. Among these, ethylene glycol dimethacrylate, divinylbenzene, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate are particularly preferred, but are not particularly limited thereto.

The copolymerization ratio of the acidic polymer of the present invention is such that the monomer (A) having an acid group is 20 to 90 mol percent, particularly 50 to 9 mol percent.
It is preferred that the amount of the crosslinking monomer (B) is 1 to 50 mol percent, especially 10 to 30 mol percent.

In order for the acidic polymer of the present invention to exhibit multiple functions,
It may also contain a monomer unit copolymerized with a third copolymerizable ethylenically unsaturated monomer unit. Examples of such copolymerizable ethylenically unsaturated monomers include ethylene, propylene, 1-butene, isobutyne, styrene, alpha-methylstyrene, vinyltoluene, ethylenically unsaturated esters of fatty acids (e.g. vinyl acetate, acetic acid allyl), esters of ethylenically unsaturated carboxylic acids (e.g. methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, n-hexyl acrylate, 2- Examples include, but are not limited to, monoethylenically unsaturated compounds (eg, acrylonitrile, methacrylate), dienes (eg, butadiene, isoprene), and the like. The copolymerization ratio of these third monomer units is 0 to 50 mole percent, preferably 0 to 20
It is a mole percent.

Next, the polymerization initiator will be described. As a polymerization initiator, it is possible to use a polymerization initiator that is known from the fundamentals of polymer synthesis, such as those known in "Experimental Methods of Polymer Synthesis" (Kagaku Doujin) co-authored by Yoroyuki Otsu and Masayoshi Kinoshita. Water-soluble polymerization initiators are preferred for the production method of the present invention. Persulfates and azo-based initiators are known as water-soluble polymerization initiators, but persulfates such as potassium persulfate give particularly good results in the production method of the present invention. The amount of polymerization initiator used is 0.05 to 5 weight percent, preferably 0.1 to 10 weight percent, based on the monomer.

The acidic polymers produced have a load and exist relatively stably dispersed in water, so it is often not necessary to add a surfactant to the water, but it is necessary to add a surfactant to the polymer. It is also possible to stabilize the state of dispersion in water. Examples of surfactants that can be used in the present invention are listed below, but the surfactants that can be used are limited to these 7 (1 "t, t,: (!: i1 word 61 also 4
Pa・ Two or less・Remainder=4 1 and 11 Di So, Na 5O, Na C+ z H2S OS O3N a CH6H330COCH2 C1-H-s OCOCHS Os NaC2Hs 2Hs The acidic polymer latex preferably used in the present invention is dissolved in heated water. It is obtained by simultaneously adding a monomer and a polymerization initiator to.

Polymerization temperature is one of the most important production conditions in the production method of the present invention.
It is one. The polymerization temperature is usually 50 to 80°C. In the production method of the present invention, it is also possible to polymerize at 50 to 80°C, but under such conditions, water,
Since a large amount of aggregates that are not dispersed or dissolved in the organic solvent are generated, it is impossible to form a coated product with a good surface condition unless these are completely removed. It is easy to imagine that removal of these aggregates would result in an increase in the price of the crosslinked polymer due to removal costs and reduced yield.

In the present invention, higher polymerization temperatures are preferred.

However, due to the constraints of polymerization in water, it is usually preferable to carry out polymerization at 90 to 98°C, but it is also possible to carry out polymerization at higher temperatures by devising polymerization equipment. After the polymerization reaction, the acidic polymer of the present invention is preferably partially neutralized using an alkali.

The degree of neutralization is 0 to 30 mol% in the polymer, especially 3
A range of ˜20 mol % salt is preferred.

When the acidic polymer of the present invention is used in a silver halide photographic light-sensitive material containing a hydrazine derivative, the polymer is used in the form of a polymer latex, and an alkali is added to the polymer latex to adjust the pH of the polymer latex.
is preferably adjusted to a range of 3.5 to 5.0.

The acidic polymer latex of the present invention is disclosed in Japanese Unexamined Patent Publication No. 54-10
It can also be produced by a reverse-phase emulsion polymerization method, as started in No. 9831, or by a method in which acid groups are created by hydrolyzing with acid or alkali after the polymerization reaction.

Specific examples of the acidic polymer of the present invention are shown below, but the invention is not limited thereto. Incidentally, the copolymerization ratios described in the polymer examples represent mole percentages.

τpu τ1 11 - Mi or less thin - white;, Base 0° Construction soil Q x:y:z=60:40: 1.58 ○ x:y:z=64:11:25 (mol%) (mol% ) u,','r --4- The silver halide photographic light-sensitive material of the present invention has a center line average roughness of 0.05 μm or more on the surface on which the photographic emulsion layer containing a hydrazine derivative is coated. It is less than 0.020 μm, preferably 0.007 μm or more and less than 0.15 μm.

The center line average roughness is specified in detail in JISBO601.

The silver halide photographic material of the present invention may contain a matting agent. As a matting agent, silica (Sin2
) particles and other inorganic fine particles and resin fine particles are used. In the present invention, the particle size of the matting agent is preferably 0.3 μm.
~8.0μm, and the amount of matting agent added is 1~30μm.
The range is preferably 0 mg/rIi', more preferably 3
~50rng/rr? It is.

Preferred compounds as hydrazine derivatives used in the present invention are compounds represented by the following general formulas [1], [2], and [3].

General formula [1] In the formula, R1 and R2 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n represents O to 6, m represents O or 1, and when n is 2 or more , each R may be the same or different.

General formula [2] In the formula, R21 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R2□ represents a hydrogen atom, a substituted or unsubstituted alkoxy group, a heterocyclic oxy group, an amino group, or an aryloxy group. , and P and R2 each represent a hydrogen atom, an acyl group, or a sulfinic acid group.

General formula [3CoA r-NHNH-C-Rsr In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and Ral represents a substituted alkyl group.

The general formulas [1], [2], and [3] will be specifically explained below.

General formula [1] In the formula, R and R3 represent an aryl group or a heterocyclic group, R represents a divalent organic group, n is 0 to 6, and m is 0
Or represents 1.

Here, the aryl group represented by R4 and R8 includes phenyl group, naphthyl group, etc., and the heterocyclic group includes pyridyl group, benzothiazolyl group, quinolyl group, thienyl group, etc., but as R1 and R2 Preferred is an aryl group.

Various substituents can be introduced into the aryl group or heterocyclic group represented by R1 and R3. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, isopropoxy, butoxy, octyloxy, dodecyloxy, etc.), and acylamino groups. (e.g. acetylamino, bivalylamino, benzoylamino, tetradecanoylamino, α-(2,
4-di-t-amylphenoxy)butyrylamino, etc.)
, sulfonylamino groups (e.g., methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, pencenesulfonylamino, etc.), urea groups (e.g., phenylurea, ethylurea, etc.), thiourea groups (e.g., phenylthiourea, ethylthiourea, etc.) , a hydroxy group, an amino group, an alkylamino group (eg, methylamino, dimethylamino, etc.), a carboxy group, an alkoxycarbonyl group (eg, ethoxycarbonyl), a carbamoyl group, a sulfo group, and the like. Examples of the divalent organic group represented by R include alkylene groups (e.g., methylene, ethylene, tolyltylene,
tetramethylene, etc.), arylene groups (e.g., phenylene, naphthylene, etc.), aralkylene groups, etc. Aralkylene groups include oxy groups, thio groups, R8 seleno groups, carbonyl groups, -N- groups (R3 is hydrogen), etc. atom,
(representing an alkyl group, an aryl group), a sulfonyl group, etc. Various substitutions can be introduced into the group represented by R.

Examples of the substituent include -CONHNHR4 (R represents the same meaning as R and R3 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxy group, an acyl group, an aryl group, etc. .

R is preferably an alkylene group.

Of the compounds represented by the general formula [1], preferably R and R2 are substituted or unsubstituted phenyl groups, and n=
A compound in which m=1 and R represents an alkylene group.

Typical long compound represented by the above general formula [1] Next, general formula [2] will be explained. The aliphatic group represented by R21 preferably has 6 carbon atoms.
Among the above, it is particularly a straight chain, branched or cyclic alkyl group having 8 to 50 carbon atoms. The branched alkyl group herein 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, or a sulfoxy group.

The aromatic group represented by R21 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.

Examples include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrorazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R2 is an aryl group.

The aryl group or unsaturated heterocyclic group of Rtl may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably a monocyclic alkyl group having 1 to 20 carbon atoms). or two rings), alkoxy groups (
(preferably one having 1 to 20 carbon atoms), substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), acylamino group (preferably one having 2 to 30 carbon atoms), sulfonamide Group (preferably 1 to 1 carbon atoms)
3o), ureido group (preferably one or more carbon atoms)
30).

Among the groups represented by R22 in general formula [2], the optionally substituted alkoxy group has 1 to 20 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

Among the groups represented by R22 in the general formula , cyano group, etc.

Among the groups represented by R22, preferred are an optionally substituted alkoxy group or an amino group.

A2 may be an optionally substituted alkyl group, an alkoxy group, or a cyclic structure containing a 10--3--N- group bond. However, R22 is never a hydrazino group.

R21 or R2□ in the general formula [2] may have a ballast group, which is commonly used in immobile photographic additives such as cuffler, incorporated therein.

The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
It can be selected from alkylphenoxy groups, etc.

R2 or R22 in general formula [2] may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Such adsorption groups include thiourea group,
Examples include groups described in US Pat. No. 4,355.105, such as a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group. Among the compounds represented by the general formula [2], the compounds represented by the following general formula [2-a] are particularly preferred.

General formula [2-a] In the above general formula [2-a, R≧3 and R24 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxy propyl group, 2-cyanoethyl group, 2-chloroethyl group), optionally substituted phenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (e.g. phenyl group, p-methylphenyl group, naphthyl group, α-hydroxy naphthyl group, cyclohexyl group, p-methylcyclohexyl group, pyridyl group, 4-propyl-2-pyridyl group, pyrrolidyl group, 4-methyl-
2-pyrrolidyl group), and R21l represents a hydrogen atom or an optionally substituted benzyl group, alkoxy group, or alkyl group (e.g. benzyl group, p
- methylbenzyl group, methoxy group, ethoxy group, ethyl group, butyl group), 'Rzs and lRt represent a divalent aromatic group (e.g. phenylene group or naphthylene group), and Y represents a sulfur atom or an oxygen atom. , L represents a divalent bonding group (e.g. -SO2CH2CH2N HSO
2NH.

-0CH2SO2NH, -0--CH=N-), R2, represents -NR'R' or -0Rse, R'
R' and R2 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, dodecyl group), phenyl groups (e.g. phenyl group, p-methylphenyl group,
p-methoxyphenyl group), naphthyl group (e.g. α-naphthyl group, β-naphthyl group), or heterocyclic group (e.g.
unsaturated heterocyclic groups such as pyridine, thiophene, and furan;
Alternatively, it represents a saturated heterocyclic group such as tetrahydrofuran or sulfolane), and R' and R' may form a ring (eg, piperidine, piperazine, morpholine, etc.) together with the nitrogen atom.

m and n represent 0 or 1. When R21 represents 0Rto, Y preferably represents a sulfur atom.

Representative general formulas [2] and [2-a] represented by the above general formulas [
2] Specific example 1 2 = d CF.

Oh.

○O OH CH.

Next, among the above specific compounds, compound 2-452-47
Taking as an example, we will show how to synthesize it.

Synthesis of Compound 2-45 (A) (B) C2Hs Compound 2-45 was dissolved in 50 ml of alcohol, and methylamine (40% aqueous solution 8 ml, 9) was added and stirred. After slightly concentrating methanol,
The precipitated solid was taken out and purified by recrystallization to obtain compound 2-45.
I got it.

Synthesis of Compound 2-47 (C) (D) (E) Compound 2-47 Compound 4-2L Lophenylhydrazine 153g and 50
Mix 0ml (l) of diethyl oxalate and reflux for 1 hour. Ethanol is removed as the reaction progresses, and finally cooled to precipitate crystals. Filtered, washed several times with petroleum ether, and recrystallized. Next, 50g of the obtained crystals (A) was heated and dissolved in 1000+J methanol, and pd
/C (palladium on carbon) catalyst in a pressurized H2 atmosphere of 50 Psi.

Compound (B) is obtained.

22g of this compound (B) was dissolved in a solution of 200m2 of acetonitrile and 16g of pyridine, and 24g of compound (C) was dissolved at room temperature.
An acetonitrile solution of was added dropwise.

After filtering off insoluble matter, the filtrate is concentrated and recrystallized to obtain the compound (
D) 31 g was obtained.

30 g of compound (D) was hydrogenated in the same manner as above to obtain compound (
E) 20g was obtained.

Compound (E) Log was dissolved in 100 mL of acetonitrile, 30 g of ethyl inthiocyanate was added, and the mixture was refluxed for 1 hour. After distilling off the solvent, the compound (F) was purified by crystallization.
7.0g was obtained. 5.0 g of compound (F) was mixed with meta compound (
B) 22g to 200ml of pyridine. p-Nitrobenzenesulfonyl chloride 22
g was added. The reaction mixture was poured with water, and the precipitated solid was taken out to obtain compound (C).

This compound (C) was synthesized into compound 2-4 according to the synthesis scheme.
Compound 2-47 was obtained by the same reaction as in 5.

Next, the general formula [3 will be explained.

General formula [3] %Formula% In the general formula [3], Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group,
The diffusion-resistant group is preferably a ballast group commonly used in immobile photographic additives such as couplers. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, and may be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. I can do it.

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385.108, such as a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.

R81 represents a substituted alkyl group, and the alkyl group represents a linear, branched, or cyclic alkyl group, such as methyl, ethyl, propyl, butyl, isopropyl, pentyl, cyclohexyl, and the like.

Substituents introduced into these alkyl groups include alkoxy (e.g., methoxy, ethoxy, etc.), aryloxy (e.g., phenoxy, p-chlorophenoxy, etc.), heterocyclic oxy (e.g., pyridyloxy, etc.), mercapto, alkylthio (methylthio), etc. , ethylthio, etc.), arylthio (e.g., phenylthio, p-chlorophenylthio, etc.), heterocyclic thio (e.g., pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), alkylsulfonyl (e.g., methanesulfonyl, butanesulfonyl, etc.),
arylsulfonyl (e.g. benzenesulfonyl etc.),
Heterocyclic sulfonyl (e.g. pyridylsulfonyl, morpholinosulfonyl, etc.), acyl (e.g. acetyl, benzoyl, etc.), cyano, chloro, bromine, alkoxycarbonyl (e.g. ethoxycarbonyl, methoxycarbonyl, etc.), aryloxycarbonyl (e.g. phenoxycarbonyl, etc.), Carboxy, carbamoyl, alkylcarbamoyl (e.g., N-methylcarbamoyl, N,N
-dimethylcarbamoyl, etc.), arylcarbamoyl (
(e.g., N-phenylcarbamoyl, etc.), amino, alkylamino (e.g., methylamino, N,N-dimethylamino, etc.), arylamino (e.g., phenylamino, naphthylamino, etc.), acylamino (e.g., acetylamino, benzoylamino, etc.) ), alkoxycarbonylamino (e.g., ethoxycarbonylamino, etc.), aryloxycarbonylamino (e.g., phenoxycarbonylamino, etc.), acyloxy (e.g., acetyloxy, benzoyloxy, etc.), alkylaminocarbonyloxy (e.g., methylaminocarbonyloxy, etc.) ),
Arylaminocarbonyloxy (e.g., phenylaminocarbonyloxy), sulfo, sulfamoyl,
Examples include multiple groups such as alkylsulfamoyl (eg, methylsulfamoyl, etc.), arylsulfamoyl (eg, phenylsulfamoyl, etc.).

The hydrogen atom of hydrazine may be substituted with a substituent such as a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.), an acyl group (eg, acetyl, trifluoroacetyl, etc.), an oxalyl group (eg, ethoxalyl, etc.).

Typical compounds represented by the above general formula [3] Ct Hs Kyoto -NHNHCOCH,CH,C00C,H.

C2Hs Next, a synthesis example of compound 3-5 will be described.

Synthesis of Compound 3-5 Synthesis Scheme Compound 2-45. Compound 3-5 was obtained according to the synthesis method.

General formula [
The amount of the compounds 1], [2], and [3] is preferably from 5 x 10-' to 5 x 10-1 mol per 1 mol of silver halide contained in the silver halide photographic material of the present invention. More preferably 5 x 10-6 to lXl
It is in the range of 0-'' moles.

The silver halide photographic material of the present invention has at least one silver halide emulsion layer. That is, at least one silver halide emulsion layer may be provided on one side of the support, or at least one silver halide emulsion layer may be provided on both sides of the support.

Then, this silver halide emulsion can be coated directly on the support, or it can be coated via another layer such as a hydrophilic colloid layer that does not contain the silver halide emulsion.
Furthermore, a hydrophilic colloid layer as a protective layer may be coated on the silver halide emulsion layer. Further, the silver halide emulsion layer may be coated separately into silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between each silver halide emulsion layer.

That is, an intermediate layer made of hydrophilic colloid may be provided if necessary. Further, a non-photosensitive appearance aqueous colloid layer such as an intermediate layer, a protective layer, an antihalation layer, a backing layer, etc. may be provided between the silver halide emulsion layer and the protective layer.

The compounds represented by general formulas [1], [2], and [3] can be used in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer in the silver halide photographic light-sensitive material of the present invention. Contain in

Next, the silver halide used in the silver halide photographic material of the present invention will be explained. /'% silver halide,
Any composition can be used. Examples include silver chloride, silver chlorobromide, silver chloroiodobromide, pure silver bromide, and silver iodobromide. The average diameter of the silver halide particles is 0.05 to 0.5 μm
Among them, those in the range of 0, 1 are preferably used.
A thickness of 0 to 0.40 μm is suitable.

Although the particle size distribution of the silver halide grains used in the present invention is arbitrary, it is preferably adjusted so that the monodispersity value defined below is in the range of 1 to 30, more preferably in the range of 5 to 20.

Here, the monodispersity is defined as the value obtained by dividing the standard deviation of particle diameter by the average particle diameter times 100. For convenience, the grain size of silver halide grains is expressed by principal in the case of cubic grains, and other grains (octahedral, tetradecahedral, etc.)
is calculated by the square root of the projected area.

When carrying out the present invention, for example, silver halide particles and
In 7, a type having a multilayered structure of at least two layers can be used, for example, a type consisting of silver iodobromide grains in which the core part is silver iodobromide and the shell part is silver bromide. Can be used. At this time, iodine can be contained in any layer within 5 mol%.

The /'% silver halide grains used in the silver halide emulsion of the present invention are prepared using complex salts (including cadmium salts, zinc salts, lead salts, thallium salts, iridium salts) during the process of grain formation and/or grain growth. ), rhodium salts (complex salts containing), and iron salts (complex salts containing) to add metal ions to contain these metal elements inside the particles and/or on the particle surfaces. Furthermore, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Furthermore, silver halide can be sensitized by various chemical sensitizers. As the sensitizer, for example, activated gelatin, sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacinate, etc.),
Selenium sensitizer (N.

N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, silver 1 tin chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-ourosulfobenzothiazole methyl chloride , ammonium chloroparadate, potassium chlorooleate, sodium chloroparadite, and the like can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

The silver halide grains used in the present invention can be preferably applied to grains whose surface sensitivity is higher than their internal sensitivity, so-called silver halide grains that give negative images. can be increased.

Further, the silver halide emulsion used in the present invention includes mercapto compounds (1-phenyl-5-mercaptotetrazole, 2
-Mercaptobenzthiazole), benzotriazoles (5-brobenzotriazole-5-methylbenzotriazole), benzimidazoles (6-nitropenzimidazole), indazoles (5-nitroindazole), etc. for stabilization or fogging. can be suppressed.

The photosensitive silver halide emulsion layer or its adjacent layer may contain research disclosure materials for the purpose of increasing sensitivity, increasing contrast, or promoting development.
(Usure) Compounds described in Section XXI B-D of No. 17643 can be added.

The silver halide emulsion used in the present invention includes a sensitizing dye,
Plasticizers, antistatic agents, surfactants, hardeners, etc. can also be added.

When the compound of the general formula according to the present invention is added to a hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin can also be used. These hydrophilic binders are preferably coated on both sides of the support in an amount of 10 g or less, 7 m or less each.

Examples of supports that can be used in carrying out the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

For developing the silver halide photographic material of the present invention, the following developing agents are used, for example.

Typical HO-(CH=CH)n-OH type developing agents include hydroquinone, and others such as catechol and pyrogallol.

In addition, typical HO(CH=CH) n N Hz type developers include ortho and rose aminophenols or aminopyrazolones, N-methyl-p-aminophenol, N-β-hydroxyethyl-p -aminophenol, p-hydroxyphenylaminoacetic acid, 2
-Aminonaphthol etc.

Examples of the heterogeneous developer include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and 1-phenyl-4-dimethyl-3-pyrazolidone. -4-methyl-
3- such as 4-hydroxymethyl-3-virapriton
Examples include pyrazolidones and the like.

Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ory of the Photographic P
rocess.

Fourth Edition, pages 291-334 and Journal of the American Chemical Society.
an Chemical 5ociety) Volume 73,
Developers such as those described on page 3, 100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material of the invention, the effects of the invention will not be impaired. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, adjusting the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers and providing a buffer function, and inorganic development inhibitors such as bromokali, 5-methylbenzotriazole, 5-methylbenzimidazole, 5-methylbenzotriazole, 5-methylbenzimidazole, -nitroindazole, adenine, guanine, l-phenyl-5-
Organic development inhibitors such as mercaptotetrazole, metal ion scavengers such as ethylenediaminetetraacetic acid, methanol,
Development accelerators such as ethanol, benzyl alcohol, polyalkylene oxide, sodium alkylarylsulfonate, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, glutaraldehyde,
It is optional to add hardening agents such as formalin and glyoxal, ionic strength regulators such as sodium sulfate, and the like.

The developer used in the present invention may contain alkanolamines such as jetanolamine and triethanolamine, and glycols such as diethylene glycol and triethylene glycol as organic solvents. In addition, alkylamino alcohols such as diethylamino-1°2-propanediol and butylamitubrobanol can be particularly preferably used.

[Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

(Preparation of Silver Halide Photographic Emulsion A) A silver iodobromide emulsion (2 mol % of silver iodide per 1 mol of silver) was prepared using a simultaneous mixing method. During this mixing, 21rC1m
was added at 8X10-7 moles per mole of silver. The obtained emulsion was an emulsion consisting of cubic grains with an average grain size of 0.24 μm. This emulsion contains 6.5 cc of 1 per mole of silver.
% potassium iodide aqueous solution was added, modified gelatin (exemplified compound G-8 of Japanese Patent Application No. 1-180787) was added,
It was washed with water and desalted in the same manner as in Example 1 of Japanese Patent Application No. 1-180787. The pAg at 40°C after desalting was 8.0. Further, during redispersion, the lower compounds [A], [B], [C]
A mixture of was added.

[A] [B] [
C] Prescription (1) (Silver halide emulsion layer composition) Gelatin
2.0 g/m Silver halide emulsion A Silver fi 3.2 g/m Sensitizing dye:
8 mg/bo (Preparation of silver halide photographic light-sensitive material) Undercoat layer with a thickness of 0.1 μm on both sides (JP-A-59-1994
A silver halide emulsion layer having the following formulation (1) was applied on one undercoat layer of a 100 μm thick polyethylene terephthalate film coated with a polyethylene terephthalate film having a gelatin content of 2.
0g/r/, and silver amount was 3.2g/rrr, and furthermore, an emulsion protective layer of the following formulation (2) was coated thereon so that the gelatin amount was 1.0g/rrr. Moreover, on the other undercoat layer on the opposite side, a backing layer of the following formulation (3) is coated so that the amount of gelatin is 2.4 g/m, and on top of that, a backing retention layer of the following formulation (4) is applied. Sample No.
1 to 16 were obtained.

Stabilizer: 4-methyl-6-hy3a,7-chitrazaindene Capric inhibitor: adenine surfactant; saponin droxy-1,3 30mg/rd 10mg/resistant 0.1g/bo 8mg/hydrazine-resistant derivative ( Exemplary compound 3-39) 2X 10-
'mol/Agmol Latex polymer according to the invention The amounts shown in Table 1 of polyethylene glycol molecules I! 40000.1g/
A Hardener H-1: 60mg/rrf
Prescription (3) (Buffing layer composition) Prescription (2) (Emulsion protective layer composition) Gelatin surfactant S-2: 0.9 g/m 10 mg/CH, C00CH, (C,H,)C,H.

C Summer (COOCH, CH (C2H,) C, H.

03Nm Matting agent: Silica with an average particle size of 3.5μm The amount shown in Table 1 Hardener: Formalin 30mg/gelatin resistance 2.4g/m Surfactant;
Saponin 0.1g/BO: S-16mg/resistant (Backing protective layer composition) Prescription (4) Gelatin matting agent: Average particle size 3 Polymethyl methacrylate surfactant: S-2 Hardener: Glyoxal: H-1 In addition, the latex po used for comparison is shown.

0 to 5.0μm 1g/50mg/10mg/25mg/35mg/rn” rimmer as below (sharpness evaluation) Add a screen with a halftone dot area of 50% (150 lines/inch) to the step wedge. A sample was attached to the sample and exposed for 5 seconds using a xenon light source, and then the sample was developed under the following conditions in an automatic rapid processing machine equipped with the following developer and fixer. The dot quality of the sample was evaluated.The evaluation was based on the fringe (blur) that occurs around the halftone dots.
Observe with a 100x magnifying glass, and those with high dot quality are ranked as "5", and are ranked as "4", "3", "2",
There were 5 ranks up to "1". Note that a rank of "1" is extremely poor, and a rank of less than "3" is generally at a practically unfavorable level.

Developer recipe Ethylenediaminetetraacetic acid sodium salt 1g Sodium sulfite 60g Trisodium phosphate (decahydrate) 75g Hydroquinone
225g sodium hydroxide
8g 3-(dimethylamino)-1,2-propanediol N,N-diethylethanolamine 15 g Sodium bromide 3g 5-methylbenzotriazole 0.25 gl-Phenyl-5-
Mercaptotetrazole 08g 1-phenyl-44-dimethyl-3-virazolidonemethol 0.25g phenylpicolinium bromide Add water 11pH 11,
7 Fixer formulation (composition A) Ammonium thiosulfate (725% W/V aqueous solution) 240
m, 9 7 g Trihydrate 6.5g g ・Dihydrate 2g Sodium sulfite Sodium acetate Sodium borate citrate (composition) Pure water (ion exchange water) 17ml Sulfuric acid (50% W/V (7) aqueous solution ) 47g
Aqueous solution with aluminum sulfate CA1xOs equivalent content of 8.1%%'/V) 6
When using a 5g fixer, the above composition A was dissolved in 500J of water in that order, and the final composition was used. The pH of this fixer
was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development
Fixing at 40°C for 15 seconds, washing at 35°C for 15 seconds, drying at 306C for 10 seconds, and drying at 50°C for 10 seconds (evaluation of haze) The unexposed sample was processed in the same manner as when evaluating sharpness, and haze was evaluated. Evaluation was performed visually by shining transmitted light onto the sample. Good haze was ranked as "5", and the following five ranks were given as "4", "3", "2", and "1".

Incidentally, rank "1" is extremely bad<, and if it is lower than r3J, it is generally at a practically unfavorable level.

(Evaluation of Adhesiveness) To check the adhesiveness of the above sample, 23°C and 80% relative humidity were used.
After adjusting the humidity at 10%, stack 10 sheets of the same sample and
While applying a pressure of
Heat treatment was performed in a constant temperature bath at °C. Adhesiveness (sticking): 5
A graded evaluation was performed. 5 is the best, 1-2 are unusable,
A score of 3 or above was considered a usable level.

(Measurement of center line average roughness) After developing the unexposed sample in the same manner as when evaluating sharpness,
It was measured using hometer S5Pq.

As is clear from the results in Table 1, the samples of the present invention are found to have good edge sharpness, haze, and adhesion.

[Effects of the Invention] As explained in detail above, the present invention uses an acidic polymer to improve film adhesion, thereby making it possible to reduce the amount of matting agent, resulting in good haze and edge sharpness. It is possible to provide a silver halide photographic material from which excellent high-contrast images can be obtained.

Claims (1)

[Claims] A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the emulsion layer or an adjacent layer, the emulsion layer containing an acidic polymer; Center line average roughness of the surface on which the emulsion layer is coated is 0.05 μm or more and 0.20 μm
A silver halide photographic light-sensitive material characterized in that the silver halide photosensitive material is less than m.