JPH0339731A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain high covering power as well as satisfactory suitability to writing by regulating the average roughness of the surface of a support coated with a photographic emulsion layer along the center line to >=0.15mum and incorporating a specified compd. into the emulsion layer or a layer adjacent to the emulsion layer. CONSTITUTION:The average roughness of the surface of a support coated with a photographic emulsion layer along the center line is regulated to >=0.15mum and at least one of compds. represented by formulae I-III is incorporated into the emulsion layer or a layer adjacent to the emulsion layer. In the formula I, each of R1 and R2 is aryl or a heterocyclic group, R is an org. bonding group, n is 0-6, m is 0 or 1, and when n is >=2, R's may be different from each other. In the formula II, R21 is an aliphat., arom. or heterocyclic group, R22 is H, optionally substd. alkoxy, heterocyclic oxy, etc., and each of P1 and P2 is H, acyl, etc. In the formula III, Ar is aryl contg. at least one diffusion resistant group or group accelerating the adsorption of silver halide and R31 is substd. alkyl. A photographic sensitive material having high covering power as well as satisfactory suitability to writing is 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 matte film.

[Background of the invention]

As is well known, matte film is used for reproducing mechanical and architectural drawings and maps, enlarging aerial photographs using screens, and making synthetic leather. A matte film is a film made opaque by adding a large amount of matting agent into the film. The reason why a large amount of matting agent is added to the film to make the film matte is that by matting, it is possible to make additions and corrections with pencil or ink after exposure and processing. This is done so that the drawing can be erased with an eraser, allowing the drawing to be corrected and written on.

Therefore, after exposure and processing, matte film has the above-mentioned additions,
It is used to correct and write on drawings by erasing them, and is also used to perform diazo removal and make copies.

However, if a large amount of matting agent is added to the film, there is a problem that the covering power decreases and the concentration decreases.

Covering power here refers to the ability of a silver image to block light, and the diffusion density (D) of the silver image based on the amount of silver per unit area (M) D/
M is the hail value. As a technique for preventing this reduction in covering power, for example, Japanese Patent Application Laid-Open No. 57-82832
As described in the above issue, a method is known in which a matting agent is basically added only to the protective layer without adding it to the emulsion layer. However, this technique has a problem in that it is difficult to obtain sufficient writability because the amount of matting agent that can be added is limited.

Furthermore, methods of increasing the covering power by adding a tetrazolium compound to the hydrophilic colloid layer are disclosed in JP-A No. 64-59346, and a method of increasing the covering power by adding a hydrazine compound to the hydrophilic colloid layer in JP-A No. 64-13137, but these methods are still insufficient. This is not possible.

[Purpose of the invention]

In view of the above-mentioned problems, an object of the present invention is to provide a silver halide photographic light-sensitive material which has high covering power while having sufficient addability.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, in which the center line average roughness of the surface on which the photographic emulsion layer is coated is 0.15μ or more, and the following formulas (1), [2], [3] are present in the emulsion layer or adjacent layer:
This is achieved by a silver halide photographic material containing at least one compound represented by:

- Formula (1) (wherein R3 and R3 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n represents O to 6, m represents 0 or l, and n is 2 or more (In the formula, Rt+ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R2M represents a hydrogen atom, a substituted an alkoxy group that may be
Represents a heterocyclic oxy group, amino group, or aryloxy group, %Pl and P! represents a hydrogen atom, an acyl group, or a sulfinic acid group. ) - Formula [3] Ar-NHNH-CRst (In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and Rmt represents a substituted alkyl group.) Hereinafter, the present invention This will be explained in detail.

The center line average roughness (Ra) in the present invention is determined by the method described in Japanese Industrial Standard JISB-α601.

In the present invention, it is necessary that the Ra value is 0.15 μs or more, which is a necessary condition for obtaining good writability. More preferably, the Ra value is 0.3 to 0.8μ.
It is preferably in the range of m. When the Ra value is 0.3μ or more, the density of the ink or pencil is sufficient. Also, Ra
If the value exceeds 0.8μ, the writing will feel rough and the fatigue level of the worker will increase.

As a method for adjusting the Ra value, there is a method of adding a matting agent into the hydrophilic colloid layer. Hydrophilic colloid layers to which matting agents are added include emulsion layers, protective layers, interlayers, undercoat layers, etc., and it is possible to add them to multiple layers, and it is also possible to use two or more types of matting agents together. is also possible. The average particle size of the matting agent is 0.3μm to 8.0μm
- is preferably in the range.

The amount of the matting agent added is such that the total amount of the matting agent contained in the hydrophilic colloid layer on the side where the emulsion layer is coated is 0.1 to
It is preferably in the range of 3.0 g/m'', more preferably 0.3 to 2.0 g/+m''. Examples of organic matting agents include, in the case of water-dispersible vinyl polymers, polymethyl methacrylate, polyacrylonitrile, acryl nitrile-1 methylstyrene copolymer, polystyrene, styrene-divinylbenzene copolymer, polyvinyl acetate, Examples of cellulose derivatives include methyl cellulose, ethyl cellulose, cellulose acetate, and cellulose acetate propionate, such as polyethylene carbonate and polytetrafluoroethylene; examples of starch derivatives include carboxy starch, carboxy nitrophenyl starch, and urea-formaldehyde-starch reactants; Gelatin hardened with a known hardening agent and hardened gelatin hardened with coacervate to form microcapsule hollow particles can be preferably used. Preferred examples of the inorganic matting agent include silicon dioxide, titanium dioxide, isimaginium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, and diatomaceous earth. Can be used. The above-mentioned matting agents can be used by mixing different types of substances as necessary.

Below, Equations (1), (2), and [3] will be specifically explained.

General formula (1) In the formula, R1 and R1 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 l.

Here, examples of the aryl group represented by R1 and R2 include a phenyl group, a naphthyl group, etc., and examples of the heterocyclic group include a pyridyl group, a benzothiazolyl group, a quinolyl group, a thienyl group, etc., but preferred as R1 and R1. is an aryl group.

Various substituents can be introduced into the aryl group or heterocyclic group represented by R1 and R2. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., tomoxy, ethoxy, impropoxy, butoxy, octyloxy, dodecyl oxine, etc.), acylamino groups ( For example, acetylamino, pivalylamino, benzoylamino, tetradecanoylamino, a-<2.
4-di-t-amylphenoxy)butyrylamino, etc.)
Sulfonylamino groups (e.g. methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, benzenesulfonylamino, etc.), urea groups (e.g.
phenylurea, ethylurea, etc.), thiourea group (
For example, 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. R
Examples of divalent organic groups represented by include alkylene groups (e.g., methylene, ethylene, tolyltylene, tetramethylene, etc.), terrylene groups (e.g., phenylene, naphthylene, etc.), aralkylene groups, etc. It may contain an oxy group, a thio group, a seleno group, a carboxyl group, an -N- group (R3 represents a hydrogen atom, an alkyl group, or an aryl group), or a sulfonyl group. R
Various substitutions can be introduced into the group represented by.

Examples of substituents include C0NHN41Ra (R4
has the same meaning as R1 and R described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxy group, an acyl group, an aryl group, and the like.

R is preferably an alkylene group.

- Of the compounds represented by formula (1), preferably R1
and R2 is a substituted or unsubstituted phenyl group, and n=
This is a compound in which m-1''t'R represents an alkylene group.

Representative compound represented by the above formula (1) Specific compound 3 4 -6 7 10 11 12 13 -14 15 17 18 19 20 21 22 25 26 =27 29 30 31 32 33 34 35 36 ■ 37 38! 40 41 42 43 44 5 tC@Ht+ -46 7 = 48 50 51 52 54 Next, the aliphatic group represented by Ro, which will be explained about general formula [2], preferably has 6 or more carbon atoms, In particular, it is 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 heralo atoms 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 RlI 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 virolazole 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 R11 is an aryl group.

The aryl group or unsaturated heterocyclic group of R□ may be substituted, and representative substituents include linear, branched, or t;
is a cyclic alkyl group (preferably a monocyclic or bicyclic alkyl portion having 1 to 20 carbon atoms), an alkoxy group (
(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)
30), a ureido group (preferably a carbon number of 1 to
30).

R1 of general formula [2]! Among the groups represented by the above, 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 R, in general formula [2], the optionally substituted aryloxy group or heterocyclic oxy group is preferably a monocyclic group, and the substituent is a halogen atom alkyl group, an alkoxy Among the groups represented by R22, which include a cyano group and the like, preferred are an optionally substituted alkoxy group or an amino group.

A may be an optionally substituted alkyl group, an alkoxy group, or a cyclic structure containing a 10--5--N- group bond. However, Ro is never a hydrazino group.

R11 or Ro in general formula (1) may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.

The ballast group is a relatively inert group with respect to photography and has 8 or more carbon atoms, 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.

Ro or R1 in the general formula [2] may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include the groups described in US Pat. No. 4,355,105, such as thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups. -Among the compounds represented by the formula [2], the compound represented by the following formula (2-a) is particularly preferred.

General formula (2-a) In the above formula (2-a), Rts and Ro are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxypropyl group) , 2-cyanoethyl group,
2-chloroethyl group), an optionally substituted phenyl group,
Naphthyl group, cyclohexyl group, p-methylphenyl group, naphthyl group, a-hydroxynaphthyl group, cyclohexyl group, p-methylcyclohexyl group, pyridyl group, 4
-propyl-2-pyridyl group, pyrrolidyl group, 4-methyl-2-pyrrolidyl group), and R□ represents a hydrogen atom or an optionally substituted benzyl group, alkoxy group, or alkyl group (e.g. benzyl group, p-methyl benzyl group, methoxy group, ethoxy group, ethyl group,
butyl group), R2 and Rly represent a divalent aromatic group (for example, a phenylene group or a naphthylene group), and Y
represents a sulfur atom or an oxygen atom, and L represents a divalent bonding group (e.g. -5OICH, CH2NH-SO2NH, -O
CH, SO, NH, -0--CH-N-), R11 represents -N R/R// or -R1, R
', R'' and Rts are a hydrogen atom, an optionally substituted alkyl group (e.g. methyl group, ethyl group, dodecyl group), a phenyl group (e.g. phenyl' group, p-methylphenyl group, p-methoxyphenyl group), Represents a naphthyl heterocyclic group (e.g., an unsaturated heterocyclic group such as pyridine, thiophene, furan, or a saturated heterocyclic group such as tetrahydro7rane, sulfolane), and R/ and R no/ represent the ring together with the nitrogen atom. (eg, piperidine, piperazine, morpholine, etc.).

m and n represent 0 or l. When Ro represents OR2, Y preferably represents a sulfur atom.

Above - Algebraic formulas represented by formula [2] and (2-a) [
2] Specific example-2 3 0 0 0 -6 7 8 0 0 10 11 12 2-13 0 units.

14 15 16 1 *-NHNECOCHsCToSO*CToCToOH
S*NHNHCCOCH*CHxSC1l*CH*O
H18 20 21 22 HS 23 -24 -25 -26 -27 28 0 -29 30 31 32 0 0 0 0 3 34 35 36 37 -38 0 1 42 43 H.

4 45 46 -47 2 =48 49 50 51 * -NHNWANEr*Hts 52 6 57 -58 -59 -60 Next, taking Compound 22-47 among the above-mentioned specific compounds as an example, its synthesis method will be described.

Synthetic synthetic leather scheme of compound 2-45 (A) (B) Compound 4-nitrophenylhydrazine 153g and 500g
Mix mQ of diethyl oxalate and reflux for 1 hour. Ethanol is removed as the reaction progresses, and finally it is cooled to precipitate crystals. Filter, wash several times with petroleum ether and recrystallize. Next, 50 of the obtained crystals (A)
9 was heated and dissolved in 1000 m12 of methanol, and pd/
Compound (B) is obtained by reduction under a C (palladium/carbon) catalyst in a H2 atmosphere pressurized at 50 Psi.

This compound (B) 229 was dissolved in a solution of 200 mQ of acetonitrile and 16 g of pyridine, and the compound (C) 24 was heated at room temperature.
g of acetonitrile solution was added dropwise. After filtering out insoluble matter,
The filtrate was concentrated and purified by recrystallization to obtain Compound (D) 319.

Compound (D) 309 was hydrogenated in the same manner as above to obtain compound (
E) 209 was obtained.

Compound (E) 109 was dissolved in 100 ml of acetonitrile, 3.0 g of ethyl inthiocyanate was added, and the mixture was refluxed for 1 hour. After distilling off the solvent, the compound (F) 7 was purified by recrystallization.
．． Obtained 0g. Compound (F) 5.09 methanol 50
After dissolving in Peng Q, methylamine (40% aqueous solution 8 days 0) was added and stirred. After slightly concentrating methanol, the precipitated solid was taken out and purified by recrystallization to obtain Compound 2-45.

Synthetic leather of compound 2-47 Synthetic leather scheme (B) tr) (D) (E) Compound 2-47 Dissolve compound (B) 229 in pyridine 200- and add p-nitrobenzenesulfonyl chloride 22 into a stirring vessel.
g was added. The reaction mixture was poured into water, and the precipitated solid was taken out to obtain compound (C). Compound 2-47 was obtained by reacting this compound (C) in the same manner as compound 2-45 according to the synthetic leather scheme.

Next, general formula [3] will be explained.

-Math [3]　　　　　.

Ar-NHNH-C-Rsl In the general formula [3], Ar represents an aryl group containing at least one diffusion-resistant group or /10 silver-genide adsorption-promoting group, but the diffusion-resistant group is an immobile group such as a coupler. Ballast groups commonly used in photographic additives are preferred. 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.

R31 represents a substituted alkyl group, and the alkyl group represents a linear, branched, or cyclic alkyl group, such as methyl, ethyl, globyl, 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, pyri, midylthio, 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. Eva, N-methylcarbamoyl, N, N
-dimethylcarbamoylcarbamoyl, 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, etc.) ), sulfo, sulfamoyl, alkylsulfamoyl (eg, methylsulfamoyl, etc.), arylsulfamoyl (eg, phenylsulfamoyl, etc.).

Even if the hydrogen atom of hydrazine is substituted with a substituent such as a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl, etc.), an acyl group (e.g., acetyl, trifluoroacetyl, etc.), an oxalyl group (e.g., ethoxalyl, etc.), good.

As a representative compound represented by the above formula [3],
There are the following.

−! -2 = 3 6 7 -8 = 9 =10 -11 12 3 14 15 16 17 18 19 =20 21 22 23 4 25 -26 *-NHNHCCHtOC)lzcHtOcLcl(*
OH-27 28 29 -30 31 -32 33 =34 3235 6 37 8 39 -40 41 -42 43 -44 -45 46 47 8 49 -50 Next, a synthesis example of compound 3-5 will be described.

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

The general formula (
The amounts of the compounds 1), C2), and (3) are determined according to 7・a of the present invention.
It is preferably in the range of 5 x 10-' to 5 x 10-' mol, more preferably in the range of 5 x 10-' to 1 be.

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 hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer, or a backing layer may be provided between the silver halide emulsion layer and the protective layer.

The compounds represented by formulas (1), (2), and (3) are added to 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. Next, the silver halide used in the silver halide photographic material of the present invention will be explained. Silver halide of 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.
0.05 to 0.5 μ- is preferably used, but the range of 0.05 to 0.5 μ is preferably used. 10~0.40μ- 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 the edge length in the case of cubic grains, and is expressed by the edge length for 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 grains having a multilayer structure of at least two layers can be used, for example, silver iodobromide in the core and bromide in the shell. It is possible to use grains made from silver iodobromide grains, which are silver. 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 formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salts containing), rhodium salt, Metal ions can be added using at least one selected from salts (complex salts containing) and iron salts (complex salts containing) to contain these metal elements inside the particles and/or on the particle surfaces, and By placing the particles in a suitable reducing atmosphere, reduction sensitization can be imparted to the inside and/or the surface of the particles.

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, Mltin chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-ourosulfobenzothiazole methyl chloride, Various noble metal sensitizers represented by ammonium chloroparatate, potassium chloroaurate, sodium chlorovaradite, etc. 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 (l-7enyl-5-mercaptotetrazole, 2
-Mercaptobenzthiazole), benzotriazoles (5-brombenzotriazole-5-methylbenzotriazole), benzimidazoles (6-nidropenzimidazole), and the like can be used to stabilize or suppress fog.

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.
Compounds described in Section XXI B-D of No. 17463 can be added.

Preferably, it is a compound represented by the following formula [4].

General formula [4] Rl-0+CH, CH, 0+-n H [In the formula, R represents a hydrogen atom or an unsubstituted or substituted aromatic ring, and n represents an integer from 1O to 200. ] Specific examples more preferable than the compound represented by the general formula [4] will be given, but the invention is not limited thereto.

4 1 HO(CB ! CHz O)n H
n = 104 2 HO (CH! CH!
O)n Hn = 304 3 HO(CHt
CH20)n Hn =504-4 HO(
CH2CHzO)nHn=704 5 HO(
C)ItCH*0)nHn”1504 6H
O(CHt CH! O)n Hn = 200 or less ♂
Tsutada (4-7) (4-8) (4-9) (4-10) (4-11) (4-12) (4-13) (4-14) (4 15) (4 16) (4-17) These compounds are commercially available and can be easily obtained. These compounds have 0 to 11 moles of halogenation.
．． It is preferable to add 0.01 to 4.0 moles, and 0.02 to 4.0 moles.
2 mol is more preferred.

In addition, two or more types of compounds having different values of n may be included.

The silver halide emulsion used in the present invention contains a J-sensitive dye,
Plasticizers, antistatic agents, surfactants, hardening agents, etc. can also be added. Pattern holes (1), (2), (
When adding the compound (3) to hydrophilic colloid J, gelatin is suitable as the binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin J can also be used. These hydrophilic binders are preferably coated on both sides of the support at an amount of 10 g/m 2 or less.

Supports that can be used in the practice of the invention include, for example, 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 examples of 1(0 (CH-CB)n-OH type developing agents include hydroquinone, and others include catechol and pyrogallol.

In addition, typical l(O- (CH- CH)n- NHz type developers include ortho and rose aminophenols or aminopyrazolones, and N-methyl-p-
Aminophenol, N-β-hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid,
2-aminonaphthol and the like.

As a heterocyclic developer, l-7x-nyl-3
-pyrazolidone, l-phenyl-4,4-dimethyl-3
-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l-phenyl-4-
Examples include 3-pyrazolidones such as methyl-4-hydroxymethyl-3-pyrazolidone.

Others: The Theory Op, by T. H. James
The Photographic Process 4th Edition (The Theo
ry of the Photographic Pr
ocess.

Fourth Edition) pages 291-334 and Journal of the American Chemical Society (Journal of the American Chemical Society)
rican Chess+1cal greedy
) Vol. 73, p. 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, adjustment of pi-1 and buffer function with caustic alkali, alkali carbonate, or amine used in general black and white developers, inorganic development inhibitors such as brompotali, and 5-methylbenzotriazole, 5-methylbenzoyl Mitasor,
Organic development inhibitors such as 5-nitroindazole, adenine, guanine, l-phenyl-5-mercaptotetrazole, metal ion scavengers such as ethylenediaminetetraacetic acid,
Development accelerators such as methanol, ethanol, and benzyl alcohol kylene oxide; surfactants such as sodium alkylarylsulfonate; natural saponins; saccharides and alkyl esters of the aforementioned compounds; hardeners such as glutaraldehyde, formalin, and glyoxal; It is optional to add an ionic strength adjusting agent such as sodium sulfate.

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. Furthermore, alkylamino alcohols such as diethylamino-1.2 propanediol and butylaminopropanol can be particularly preferably used.

〔Example〕

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

Example 1 (Preparation of Silver Halide 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, the temperature reached 21rC (1
．． was added at 6×1 G-' moles per mole of silver.

The obtained emulsion was an emulsion consisting of cubic grains with an average grain size of 0.20 Itm. This emulsion was washed with water and desalted according to a conventional method, and the pAg at 40°C was adjusted to 8.80 with an aqueous potassium iodide solution. Furthermore, during redispersion, a mixture of the following compounds (A), (B), and [C] (A) CB) (C) (Preparation of silver halide photographic material) A 0.1 μ thick undercoat layer ( Japanese Patent Publication No. 59-1994
A silver halide emulsion layer having the following formulation (1) with a gelatin amount of 2.0 was applied on one undercoat layer of a 100 μm thick polyethylene tereftate film coated with a polyethylene tereftate film (see Example 1 of No. 1).
g/l, silver amount is 3.5 g/l, and on top of that, a protective layer of the following formulation (2) is applied with a gelatin amount of 1.5 g/l.
g/+", and on the other undercoat layer on the opposite side, apply a backing layer according to the following recipe (3) so that the amount of gelatin is 2.7 g/m". On top of that, a protective layer of the following formulation (4) is applied with a gelatin amount of 1.0 g.
/a'' to obtain sample No. 1=16.

Prescription (1) (Silver halide emulsion layer composition) Gelatin
2.0g/m" Silver halide emulsion A Silver amount 3.5g/m" Antifoggant: 5-
Ditroindazole stabilizer 4-methyl-6-hydroxy-1,3,3a,7-chitrazaindene surfactant: sabonin promoter) 10(CHxCHtO)y*OH (Exemplary compound 4-4
) Latex polymer: 3 mg/30*g/m 0-1 g/- 00 mg1 0.5 g/m Compound according to the present invention or comparative compound (- Formula (1)
, [2], [3]) Amounts shown in Tables 1 and 2 Sensitizing dye 8 mg/m" Prescription (2) [Emulsion protective layer composition] Gelatin 1.5 g/- Matting agent: Amount of average particle size 3.5 μm of silica in the amount shown in the table!Surfactant S2CH*COOCHx(C00CHx(Chardening agent2(CH1CH5O*CHt)0 0, IOg/san2 Formula (3) (Backing layer composition) Gelatin 2.7g /m"Surfactant: Saponin 0.1g/m"Hardening agent: Glyoxal 0.1g/m"Dodecylbenzenesulfone 0.01g/m"Prescription (4) [Backing protective layer m] Gelatin Ig/m" Matting agent: Polymethyl metal with an average particle size of 3.0 to 5.0μ.
Tarrito 0.05
g/m" Surfactant S: 0.01 g/s" Hardening agent: Glyoxal 0.01 g/m"
One sample was developed using an automatic developing machine for rapid processing using the following developer and fixer.

g Sodium sulfite 60g Hydroquinone 35g 5-amino-l
-Pentanol 50g Potassium bromide 5-methylbenzotriazole 1-phenyl-3-pyrazolotone Add water to make 1Q, and adjust sodium hydroxide to 11.5.

Fixer formulation (set fRA) Ammonium thiosulfate (72.5% V/V2, 5g 0, 3g 0, 2g pH in ram aqueous solution) 240mffi 7g 6, 5g g g Sodium sulfite Sodium acetate trihydrate Borate Sodium citrate・Dihydrate salt (composition B) Pure water (ion exchange water) Sulfuric acid (50% w/w aqueous solution) Aluminum sulfate (A (21O, converted content g.t% v/w) aqueous solution) 1
7 Peng A 4.7 g 26.5 g When using the fixer, 500 ml of water was used (dissolved in the order of Toki Aino A and lees in 1 and finished to 1 I2. The PU of this fixer was adjusted to 6 with acetic acid) .

(Development processing conditions) (Process) (@ degrees) (Time) Development
Fix at 40℃ for 15 seconds
35 °0 15 Sand water washing
Dry at 30°C for 10 seconds 500
10 seconds The comparative compounds added to the silver halide emulsion layer in formulation (1) were as follows:
Compounds A), (B), and (C) were used.

(A) (B) (C) The results of the above examples are shown in Table 1.

Here, the sensitivity is a relative value of the reciprocal of the exposure amount required to obtain a density of 3.0, and the sensitivity of sample 1 was assumed to be 100.

(Measurement of center line average roughness) After developing the unexposed sample in the same manner as in the evaluation of photographic performance,
It was measured using the rS5P type.

(Evaluation of retouchability) After the unexposed sample was subjected to the same process as in the evaluation of photographic performance, the retouchability was evaluated using a drafting pencil and a Rotring pen for drafting. The evaluation was performed visually using a 10x magnifying glass, with emphasis on line density, density uniformity, and line width stability.

Here, superiority is expressed by ranks 1 to 5, and rank 5 indicates samples 16 to 19, in which the hydrazine compound of the present invention was added to samples 13 to 19, which have a center line average roughness of 0.15 μm or more, compared to comparative samples 13 to 15. It can be seen that the maximum concentration is high and the covering power is improved. Improving covering power is
The larger the center line average roughness is, the more noticeable it is. Note that the covering power is the ratio of the density to the amount of silver, and when the amount of silver is constant, the higher the density, the higher the covering power.

The retouchability was measured for samples 7 to 12 with a center line average roughness of 0.1 μm.
is rank 2 and not at a level that can be commercialized, o, igμ
It can be seen that samples 13 to 18 of m are ranked 4 and are at a level that can be commercialized sufficiently.

Example 2 The same procedure as in Example 1 was carried out except that the silver halide emulsion was changed to emulsion B below and processing was performed using a developer having the following formulation. The results are shown in Table 2.

(Preparation of Silver Halide Emulsion B) A silver iodobromide emulsion (0.5 mol % of silver iodide per mol of silver) was prepared by a simultaneous mixing method. During this mixing, 1rC
Q, is added at 6X 10-' moles per mole of silver.

The resulting emulsion consisted of cubic grains with an average grain size of 0.15 .mu.m. Wash this emulsion with water according to the usual method.
After desalting, sulfur sensitization was carried out at 62°C for 90 minutes, and I) Ag at 40°C was reduced to 7.90 using a potassium iodide aqueous solution.
75.0g Sodium hydroxide
7.9g trisodium phosphate (decahydrate)
75.0g5-methylbenzotriazole
0.25g N,N-diethylethanolamine
12. Add 51Q water to adjust to ta and adjust pH to 11.
Adjusted to 6.

From the results in Table 2, samples 35 to 38, in which the hydrazine compound of the present invention was added to samples 32 to 38 with a center line average roughness of 0.15 μm or more, had a higher maximum concentration and covering power than comparative samples 32 to 34. I can see that it's improving. The improvement in covering power is more remarkable as the center line average roughness increases.

The retouchability was measured for samples 26 to 3 with a center line average roughness of 0.1 μm.
1 is rank 2 and is not at a level that can be commercialized, 0.1
It can be seen that samples 32 to 37 with a size of 8 μm are ranked 4 and are at a level that can be commercialized sufficiently.

〔Effect of the invention〕

According to the present invention, it was possible to provide a 7\silver halide photographic light-sensitive material that has sufficient addibility and high covering power.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, wherein the centerline average roughness of the surface on which the photographic emulsion layer is coated is 0. ．．
A silver halide photographic material having a diameter of 15 μm or more and containing at least one compound represented by the following general formulas [1], [2], and [3] in the emulsion layer or an adjacent layer. General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n is 0 to 6, m is 0
or 1, and when n is 2 or more, each R may be the same or different. ) General formula [2] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R_2_1 is an aliphatic group, aromatic group, or heterocyclic group, R_2_2 is a hydrogen atom, an optionally substituted alkoxy group, or a heterocyclic group) Represents an oxy group, an amino group, or an aryloxy group, and P_1 and P_2 represent a hydrogen atom, an acyl group, or a sulfinic acid group.) General formula [3] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and R_3_1 represents a substituted alkyl group.)