JPH04170534A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photosensitive material excellent in a high sensitive quick process aptitude in a high illumination short time exposure by setting a gelatine quantity at 2.5g/m<2> or less in a side having a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a base material, containing an iron compound wherein silver halide particles are 10<-3>mol or less with respect to silver, and adding a sensitizing pigment before chemical sensitization of the silver halide particles. CONSTITUTION:A gelatine quantity is 2.5g/m<2> or less in a side having a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a base material, an iron compound wherein silver halide particles are 10<-3>mol or less with respect to silver is contained, and a sensitizing pigment is added before chemical sensitization of the silver halide particles. Accordingly, a photosensitive material highly sensitive in a high illumination exposure, suitable for a quick process and excellent in pressure property is obtained, and also a photosensitive material having a spectrum sensitivity suitable for respective scanner light sources is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic material that has high sensitivity and excellent suitability for rapid processing in high-intensity, short-time exposure. It relates to photosensitive materials.

(Prior Art) In recent years, single-scanner systems have been widely used in the field of printing plate making. There are various types of recording apparatuses that use image forming methods using a scanner, and the light sources for recording in these scanner-only recording apparatuses include glow lamps, xenon lamps, tungsten lamps, LEDs, or He-He.
There are lasers, argon lasers, semiconductor lasers, etc.

The photosensitive materials used in these scanners are required to have various properties, but in particular, they are exposed for a short time of 10-3 to 10-7 seconds, so even under such conditions, they have high sensitivity and high contrast. It is an essential condition. Especially in the field of facsimile, in order to emphasize promptness,
It is important to have excellent suitability for rapid processing, and in the future it will be desirable to increase the number of lines and narrow the light beam in order to speed up scanning and improve image quality. There has been a strong desire to develop a photosensitive material that has the following characteristics.

Rapid development processing is the time it takes for the leading edge of the film to pass through the developing tank, transfer section, fixing tank, transfer section, washing tank, and drying section after the leading edge of the film is inserted into the automatic developing machine and comes out of the drying section. refers to a process in which the duration is 20 to 60 seconds.

If the transport speed of an automatic developing machine is increased in order to shorten these processes, problems such as (1) poor fixing, (2) poor washing, and (3) poor drying occur. In order to solve these problems, it is effective to reduce the amount of ceratin in the silver halide photosensitive material and the amount of coated silver as described in Japanese Patent Application No. 124727/1994. In this case, (a) the lower black density decreases, (
Problems arise such as b) deterioration of graininess and (c) deterioration of pressure property.

In order to solve the above problems (a) and (b), it is necessary to reduce the grain size in the silver halide emulsion, and for this purpose, it is necessary to increase the sensitivity of the silver halide emulsion. This problem can be solved by containing Fe salt as described in Japanese Patent Application No. 1-124726. However, the problem of deterioration of pressure properties was not resolved, and it became necessary to solve this problem.

(Objective of the Invention) Therefore, the first object of the present invention is to provide a photosensitive material that is highly sensitive during high-intensity exposure, is suitable for rapid processing, and has excellent pressure resistance. The object of the present invention is to provide a photosensitive material having a spectral sensitivity suitable for each scanner light source.

(Structure of the Invention) The first object of the present invention is to provide a silver halide photograph having at least one light-sensitive silver halide emulsion layer and at least one light-insensitive hydrophilic colloid layer on the same side of a support. In the photosensitive material, the amount of seratin on the side having the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer on the support is 2. 5g/m? or less, and the silver halide grains contain 10 −1 mol or less of an iron compound relative to silver,
This was also achieved by adding a sensitizing dye to the silver halide grains before chemical sensitization.

The second object was achieved by spectrally sensitizing the silver halide grains of the light-sensitive material using at least one of the sensitizing dyes represented by formulas 1 to V below.

(Specific structure of the invention) A specific configuration of the present invention will be explained in detail.

In the silver halide photographic emulsion according to the present invention, the silver halide may be any of silver chloride, silver bromide, silver chlorobromide, silver chloroiodobromide, and silver iodobromide, but the silver chloride content is 30 mol%. It is preferably at least 50 mol%, and more preferably at least 50 mol%. Further, the silver iodide content is preferably 5 mol% or less, more preferably 2 mol% or less.

The shape of the silver halide grains may be cubic, tetradecahedral, octahedral, amorphous, or plate-like, but cubic or plate-like is preferable. The average particle size of silver halide particles is 0.01 μm
It is preferably 1 μm or less, more preferably 0.64 μm or less, ((standard deviation of particle size)/(average particle size) l
It is preferable to have a narrow particle size distribution with a coefficient of variation expressed by 100 of 15% or less, more preferably 10% or less.

The silver halide grains may consist of a uniform phase in the interior and the surface, or may consist of different phases.

The photographic emulsion used in the present invention is P, Glafkid
Chimie et Physique Pho by es
tograhique (published by Pau1Monte1,
(1967), G., F. Duffin, Pho.
tographic Emulsion Chemi
stry (The Focal Press, 196
6 years), V. L., Zelikman et al. Making and Coating Photog
rapic Emulsion (The Foca
1 Press, 1964).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the formation of the reaction between the soluble silver salt and the soluble halogen salt may be performed using any of the one-sided mixing method, simultaneous mixing method, and a combination thereof. good.

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 form of the 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, a so-called Chondrald or double jet method can also be used.

According to this method, a silver halide emulsion with regular crystalline shape and nearly uniform grain size can be obtained.

In addition, in order to make the particle size uniform, British patent 1,
No. 535,016, Special Publication No. 4 B-36890, No. 52
As described in No. 16364, there is a method of changing the addition rate of silver nitrate or alkali halide depending on the grain growth rate, and as described in British Patent No. 4,242,445 and Japanese Patent Application Laid-open No. 158124/1983. It is preferable to use a method of changing the concentration of an aqueous solution as shown in the figure below to grow rapidly within a range that does not exceed the critical saturation level.

Grain formation of the silver halide emulsion of the present invention is preferably carried out in the presence of a silver halide solvent such as a tetrasubstituted thiourea or an organic thioether compound.

Preferred tetrasubstituted thiourea/S silver halide solvents used in the present invention include JP-A-53-82408 and JP-A-55-777.
It is a compound represented by the following general formula described in No. 37, etc.

In the formula, R, R2, R3 and R4 represent a substituted or unsubstituted alkyl group, an alkenyl group (such as an allyl group), or a substituted or unsubstituted aryl, and these may be the same or different from each other, The total number of carbon atoms in R1 to R4 is preferably 30 or less. Also, R1 and R2, R2 and R
3, or R3 and R4 can be combined to form a 5- to 6-membered heterocyclic imidazolidinethione, piperidine, morpholine, etc. Both straight chain and branched alkyl groups are used as the alkyl group.

As a substituent for an alkyl group, for example, a hydroxy group (-
0H), a carboxy group, a sulfonic acid group, an amino group, an alkyl residue having 1 to 5 carbon atoms (0-alkyl), a phenyl group, or a 5- to 6-membered heterocycle (furan, etc.) . The substituent for the aryl group is a hydroxy group, a carboxy group or a sulfonic acid group.

Here, particularly preferably, R1 to R4 have three or more alkyl groups, each alkyl group has 1 to 5 carbon atoms, the aryl group is a phenyl group, and the total number of carbon atoms in R1 to R4 is 20 or less. It is.

Examples of compounds that can be used in the present invention include the following.

OHOH I Sl 0HOH The organic thioether silver halide solvent preferably used in the present invention is a solvent in which an oxygen atom and a sulfur atom are separated by ethylene, as described in, for example, Japanese Patent Publication No. 47-11386 (U.S. Pat. group (e.g. -O
A compound containing at least one CR2CH2S), disclosed in JP-A-54-155828 (US Pat.
It is a chain thioether compound having an alkyl group at both ends (each alkyl group has at least two substituents selected from hydroxy, amine, carboxy, amide, or sulfone) described in No. 4). Specifically, the following examples can be given.

HOCHzCHz S C) IzCHt S
CH2CHt○HHOCH, CH2CH2-S -CH
2CH2-S -CH2CHICH20HHOCH2C
HCH,S CH2CH2S CHz CHCH20H
I3 0H0H HOOCCH2CHCH2-S -CH2CH2-5-
C) lICHCH2COOH0H0H 1 (QCH2CHCH2S CH2CH20CH2CH
! S CH2CHCH20H1] OHO) (The amount of the silver halide solvent added varies depending on the type of compound used, the intended grain size, the halogen composition, etc., but is preferably 10-5 to 10-2 mol per 1 mol of silver halide.

If the grain size exceeds the desired size due to the use of a silver halide solvent, the desired grain size can be achieved by changing the temperature during grain formation, the addition time of the silver salt solution, the halide salt solution, etc.

The iron compound used in the present invention is a divalent or trivalent iron ion-containing compound, preferably an iron salt or iron complex salt that is water-soluble within the concentration range used in the present invention. Specifically, ferrous arsenate ferrous bromide ferrous carbonate ferrous chloride ferrous citrate ferrous fluoride ferrous formate ferrous gluconate ferrous hydroxide ferrous iodide - Ferrous lactate Ferrous oxalate Ferrous phosphate Ferrous succinate Ferrous sulfate Ferrous thiocyanate Ferrous nitrate Ferrous nitrate Ammonium basic Ferric acetate Ferric albumate Ferric acetate Ammonium Bromide Ferric chloride Ferric chlorate Ferric citrate Ferric fluoride Ferric formate Glycero phosphate Ferric hydroxide Ferric acid phosphate Ferric Nitrate Ferric Phosphate Ferric Pyrophosphate Ferric Pyrophosphate Sodium Thiocyanide Ferric Sulfate Ferric Ammonium Sulfate Ferric Sulfate Guanidine Ferric Ammonium Citrate Hexane Cyanoferrous (II) potassium pentacyanoammine ferrous potassium ethylene dinitrilotetraacetic acid ferric sodium hexacyanoferric (I [[) acid potassium tris(dipyridyl) ferric pentacyanonitrosyl ferric potassium chloride diiron, especially hexacyanoferrate (n), hexacyanoferrate (II)
[) Acid salts, ferric thiocyanate salts and ferric thiocyanate salts exhibit remarkable effects.

These iron compounds are used after being dissolved in water or a suitable solvent. Instead of using water-soluble iron, it is also possible to add and dissolve other silver halide grains doped with iron in advance during the preparation of silver halide grains.

The total amount of iron compounds used in the present invention ranges from lXl0-' to lXl0- per mole of silver halide finally formed.
"Mole is suitable, preferably 5 x 104 to lXl0
−'Mole.

These compounds can be added as appropriate during the production of the silver halide emulsion and at each stage before coating the emulsion, but in particular, they can be added during grain formation and incorporated into the silver halide grains. preferable.

The addition position may be uniformly distributed in the particles, or localized at the early, middle, or late stages of particle formation.
It is preferable to add at a later stage of particle formation, ie after 50%, more preferably 80% of the final particle size has been formed.

In the present invention, other metals included in group (1), such as cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, may be used in combination. In particular, the combined use with iridium salts such as hexachloroiridium, hexaammineiridium, trioxalatoiridium, and hexacyanoiridium is advantageous because emulsions with high sensitivity and high contrast can be obtained. Further, the combined use with rhodium salts such as rhodium chloride and ammonium hexachlororhodate (I[I) acid is advantageous because a high-contrast emulsion can be obtained.

The light-sensitive silver halide emulsion of the present invention is spectrally sensitized with a sensitizing dye before chemical sensitization. The timing of adding the sensitizing dye is before chemical sensitization, before grain formation of the silver halide emulsion;
Any time after particle formation, before the water washing step, or after the water washing step is acceptable, but
The most preferable step is after the water washing step and before chemical sensitization.

As the sensitizing dye used in the present invention, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used.

Useful sensitizing dyes for use in the present invention include, for example, RESEA
RCHDISCLOSURRI tem 17643
Section N-A (December 1978, p. 23), 1 t
em1831X (August 1979 p. 437) or in the literature cited.

In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected.

For argon laser light sources, JP-A-60-162
No. 247, JP 2-48653, U.S. Patent No. 2,16
1,331 and West German Patent No. 936°071, for simple melon anine and helium-neon laser light sources, Japanese Patent Application Laid-open Nos. 50-62425 and 54-18726
For the trinuclear cyan dyes shown in No. 59-102229, Japanese Patent Publication No. 4B-42172 for LDE light sources,
To No. 51-9609 and No. 55-39818, JP-A No. 6
For thiacarbocyanines described in No. 2-284343 and semiconductor laser light sources, Japanese Patent Application Laid-Open No. 59-1910
Trivalent orbocyanines described in No. 32, JP-A No. 60-80841, and dicarbocyanines containing a 4-quinoline nucleus described in JP-A-59-192242 are advantageously selected.

Among the above-mentioned sensitizing dyes, it is particularly preferable to use dyes represented by the following general formulas (I) to (V) from the viewpoint of sensitizing properties and residual color properties.

(I) Z.

,・−”゛°゛−−−−°−゛−”′−−12. ---
゛R, -NfCH=CH, , C=CQ.

Zl is a nonmetallic atomic group necessary to form a 5-membered or 6-membered double ring, and examples of the heterocycle include a thiazole ring, a selenazole ring, an oxazole ring, a benzothiazole ring, a benzoselenazole ring, Examples include a benzoxazole ring, a naphthothiazole ring, a naphthoselenazole ring, a naphthoxazole ring, a pyridine ring, a quinoline ring, etc. Furthermore, these heterocycles may have a substituent, and examples of these substituents include Halogen atoms (e.g. chlorine atom, bromine atom), e.g. alkyl groups, preferably alkyl groups having 1 to 4 carbon atoms (e.g. methyl, ethyl, n-propyl), halogenated alkyl groups (e.g. trifluoromethyl) , an alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, n-propyloxy group), a hydroxy group, and an aryl group (eg, phenyl group).

Q represents a nonmetallic atomic group necessary to form a 5-membered heterocycle. Examples of this heterocycle include rhodanine ring, thiohydantoin ring, thioxazolidinedione ring, thioselenazolidinedione ring, etc. These heterocycles may have a substituent, and these substituents Preferably, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, a 2-hydroxyethyl group, a 2-hydroxyethyloxyethyl group, a 2-methoxyethyl group, a 2-acetoxyethyl group, Carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, benzyl group, phenethyl group, n -butyl group), aryl group (e.g. phenyl group, p-sulfophenyl group) or pyridyl group (e.g. 2-pyridyl group, 3-
pyridyl group, methyl-2-pyridyl group).

R1 represents an alkyl group or a substituted alkyl group, for example,
1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 7 carbon atoms
4 alkyl groups (e.g. methyl, ethyl, propyl,
isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups such as aralkyl groups (e.g. benzyl, 2-phenylethyl), hydroxyalkyl groups (e.g. 2-hydroxyethyl, 3-hydroxypropyl), carboxy Alkyl groups (e.g. 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl),
Alkoxyalkyl groups (e.g. 2-methoxyethyl,
2-(2-methoxyethoxy)ethyl)sulfoalkyl group (e.g. 2-sulfoethyl, 3-sulfopropyl,
3-sulfobutyl, 4-sulfobutyl, 2-(3-sulfopropoxy)ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl groups (e.g. 3-sulfatopropyl, 4 -sulfatobutyl), heterocyclic-substituted alkyl groups (e.g. 2-(pyrrolidin-2-one-1-yl)ethyl,
(tetrahydrofurfuryl), 2-acetoxyethyl, carbomethoxymethyl, 2=methanesulfonylaminoethyl, allyl group, etc.

Next, specific examples of the compound represented by the above general formula (I) used in the silver halide photographic material of the present invention will be shown.

However, as a matter of course, the compounds used in the present invention are not limited to these.

Representative example of sensitizing dye represented by general formula (I) C00H SO+KjU CHI CH=CH.

CH. CH. OH CH. CH2So. K (I[) Z2 and Z each represent a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle.

Examples of the above heterocycles include thiazole rings (e.g., thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-di-phenylthiazole, etc.), benzothiazole rings (e.g., benzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-methylbenzothiazole,
6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole,
6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole,
5-Hydroxybenzothiazole, 5-carboxybenzothiazole, 5-fluorobenzothiazole, 5-dimethylaminobenzothiazole, 5-acetylaminobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5 -Hydroxy-6-methylbenzothiazole, 5-ethoxy-6-
methylbenzothiazole, tetrahydrobenzothiazole, etc.), naphthothiazole rings (e.g. naph1-[2
, t-a) Thiazole, Naphtho[1,2-d)thiazole, Naphtho[2゜3-d]thiazole, 5-methoxynaphtho[1゜2-d]thiazole, 7-nitoxynaphtho[
2゜1-d] Thiazole, 8-methoxynaphtho [2゜1
-cll Thiazole, 5-methoxynaphtho [2゜3-
d] Thiazole, etc.), selenazole rings (e.g. 4-methylselenazole, 4-phenylselenazole), benzoselenazole rings (e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-phenylbenzoselenazole, 5-methoxy benzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, etc.), naphthoselenazole rings (e.g. naphtho[2,1
-d) selenazole, naphthol: 1. 2-d] selenazole), oxazole ring (e.g. oxazole, 4-
Methyloxazole, 5-methyloxazole, 4,5
-dimethyloxazole), benzoxazole rings (e.g. benzoxazole, 5-fluorobenzoxazole, 5-chlorobenzoxazole, 5-bromobenzoxazole, 5-trifluoromethylbenzoxazole, 5-methylbenzoxazole, 5-methyl-
6-phenylbenzoxazole, 5.6-dimethylbenzoxazole, 5-methoxybenzoxazole,
5,6-Simethoxybenzoxazole, 5-phenylbenzoxazole, 5-carboxybenzoxazole, 5-methoxycarbonylbenzoxazole, 5-
acetylbenzoxazole, 5-hydroxybenzoxazole, etc.), naphthoxazole rings (e.g. naphthoC2,l-c!Eoxazole, naphtho[1°2-d
]oxazole, naphthoC2,3-d)oxazole, etc.), 2-quinoline ring, imidazole ring, benzimidazole ring, 3,3'-dialkylindolenine ring, 2-
Examples include a pyridine ring and a thiazoline ring. Particularly preferably, at least one of Z2 and Z3 is a thiazole ring, thiazoline ring, oxazole ring, or benzoxazole ring.

In the above general formula, the alkyl group represented by R2 or R8 is an alkyl group having 5 or less carbon atoms (e.g., methyl group, ethyl group, n-propyl group, n-butyl group), and the substituted alkyl group is an alkyl radical. Substituted alkyl groups having 5 or less carbon atoms (e.g. hydroxyalkyl groups (e.g. 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group), carboxyalkyl groups (e.g. carboxymethyl group, 2-carboxyethyl group) , 3-carboxypropyl group, 4-carboxybutyl group, 2-(2-carboxyethoxy)ethyl group, etc.),
Sulfoalkyl groups (e.g. 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroquine-3-sulfopropyl group, 2-(
3-sulfopropoxy)ethyl group, 2-acetoxy-3
-Sulfopropyl group, 3-methoxy-2-(3-sulfopropoxy)propyl group, 2-[3-sulfopropoxy)ethoxy]ethyl group, 2-hydroxy-3-(3'-
sulfopropoxy)propyl group), an aralkyl group (the number of carbon atoms in the alkyl radical is preferably 1 to 5, and the aryl group is preferably a phenyl group, such as a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group,
p-t-lylpropyl group, p-methoxyphenethyl group,
p-chlorphenethyl group, p-carboxybenzyl group,
p-sulfophenethyl group, p-sulfobenzyl group), aryloxyalkyl group (alkyl radical has 1 carbon number
-5 are preferred, and the aryl group of the aryloxy group is preferably a phenyl group, such as phenoxyethyl group, phenoxypropyl group, phenoxybutyl group, p-methylphenoxyethyl group, p-methoxyphenoxypropyl group, etc.), vinylmethyl Examples of the aryl group include a phenyl group. L, , R2, and LJ represent a methine group or a substituted methine group =C-. R' is an alkyl group (e.g. methyl group, ethyl group), substituted alkyl group (
Examples include alkoxyalkyl groups (e.g., 2-ethoxyethyl group, etc.), carboxyalkyl groups (e.g., 2-carboxyethyl group, etc.), alkoxycarbonylalkyl groups (e.g., 2-methoxycarbonylethyl group), aralkyl groups (e.g., benzyl group, phenethyl group, etc.). L represents an aryl group (e.g., phenyl group, p-methoxyphenyl group, p-chlorophenyl group, O-carboxyphenyl group, etc.).Also, Ll and R2, and L3 and R3 are each bonded by a methine chain to form a nitrogen-containing May form a heterocycle.Q
Examples of the substituent attached to the nitrogen atom at the 3-position of the thiazolinone ring or imidazolinone ring formed by 2 and Q include an alkyl group (preferably having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group), Allyl group, aralkyl group (alkyl group radical preferably has 1 to 5 carbon atoms, e.g. benzyl group, p-carboxyphenylmethyl group),
Aryl group (total number of carbon atoms is preferably 6 to 9, e.g. phenyl group, p-carboxyphenyl group), hydroxyalkyl group (alkyl radical preferably has 1 to 5 carbon atoms, e.g. 2-hydroquinethyl group), carboxy Alkyl group (preferably the alkyl radical has 1 to 5 carbon atoms, for example, carboxymethyl group), alkoxycarbonyl alkyl group (the alkyl radical in the alkoxy moiety preferably has 1 to 3 carbon atoms, and the alkyl moiety has 1 to 3 carbon atoms)
5 is preferable, and examples thereof include methoxycarbonylethyl group).

Examples of anions represented by Xl include halokene ions (iodine ions, bromide ions, chloride ions, etc.), perchlorate ions, thiocyanate ions, pensene sulfonate ions, p-1-luenesulfonate ions, and methyl sulfate. ion, ethyl sulfate ion, etc.

Typical examples of the sensitizing dye represented by the general formula (n) are as follows.

(In) [In the formula, Y1 and Y2 each represent a group of nonmetallic atoms necessary to form a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring, or a quinoline ring, and these heterocycles is lower alkyl group (e.g. methyl group, ethyl group), alkoxy group (e.g. methoxy group, ethoxy group) 1, hydroxy group, aryl group (
For example, phenyl group), alkoxycarbonyl group (for example, methoxycarbonyl group), halogen atom (for example, chlorine atom, bromine atom), etc. may be substituted. R,,R,respectively represent a lower alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group), an alkyl group having a sulfo group (
For example, β-sulfoethyl group, γ-sulfopropyl group, γ
-Sulfobutyl group, δ-sulfobutyl group, sulfoalkoxyalkyl group (e.g. sulfoethoxyethyl group, sulfoethoxyethyl group), alkyl group having a carboxy group (e.g. β-carboxyethyl group, γ-carboxypropyl group, γ- carboxybutyl group, δ-carboxybutyl group).

R6 represents a methyl group, an ethyl group, or a propyl group.

X2 represents an anion commonly used in cyanine dyes (eg, halogen ion, pensene sulfonate ion, p-h luenesulfonate ion, etc.).

nt and ni represent 1 or 2. m represents 0 or 1, and when it is an inner salt, m=o.

Specific examples of compounds of (I) CH, So, H(CH2)2So,.

― (CH,), So,.

(CHI), So, H(CHt)t So,.

R and R3 may each be the same or different,
Each represents an alkyl group (including substituted alkyl groups). Preferably 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl.

Examples of substituents include carboxyl group, sulfo group, cyano group, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom), hydroxyl group, alkoxycarbonyl group (
Preferably, the number of carbon atoms is 8 or less, e.g. methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), the alkoxy group (preferably the number of carbon atoms is 7 or less, e.g. methoxy, ethoxy, propoxy, butoxy, benzyloxy), aryloxy group (e.g. phenoxy, p
-tolyloxy), acyloxy groups (preferably up to 3 carbon atoms, e.g. acetyloxy, probionyloxy), acyl groups (preferably up to 8 carbon atoms, e.g. acetyl, propionyl, benzoyl, mesyl), carbamoyl groups (e.g. carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl groups (e.g. sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl), aryl groups (e.g. phenyl, p-hydroxyphenyl, p- Examples include alkyl groups substituted with carboxyphenyl, p-sulfophenyl, α-naphthyl, etc. (preferably the alkyl moiety has 6 or less carbon atoms). However, two or more of these substituents may be substituted with an alkyl group in combination.

R* and Rlo each independently represent a hydrogen atom, a lower alkyl group (preferably 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl, butyl), a lower alkoxy group (preferably 1 to 4 carbon atoms, e.g. methoxy , nidoxy, propoxy, butoxy), phenyl group, benzyl group or phenethyl group.

In particular, lower alkyl groups and benzyl groups are advantageously used.

Rl l and R1° each represent a hydrogen atom, or Rli and R1° are linked to form a divalent alkylene group (eg, ethylene or trimethylene).

The alkylene group may contain one, two or more suitable groups, such as alkyl groups (preferably 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, butyl), halogen atoms (e.g. chlorine, bromine, etc.). atoms), or alkoxy groups (preferably 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy,
butoxy), etc.

R13 is a hydrogen atom, a lower alkyl group (preferably 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl), a lower alkoxy group (preferably 1 to 4 carbon atoms, e.g. methoxy, ethoxy, propoxy, butoxy), phenyl , a benzyl group, or independently an alkyl group (including substituted alkyl groups. Preferably, the alkyl moiety has 1 to 18 carbon atoms)
, more preferably 1 to 4, such as methyl, ethyl, propyl, butyl, benzyl, phenylethyl), or an aryl group (including substituted phenyl groups, such as phenyl, naphthyl, tolyl, p-chlorophenyl), and Wl and W2 and can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. However, R1 and R+i or R1
° and Rli are connected to form a divalent alkylene group (the above R1
(synonymous with a divalent alkylene group formed by linking 1 and R+2).

Z4 and Z5 represent a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as a thiazole nucleus [
For example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzo Thiazole, 6
-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethquinbenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5 −
Phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5
, 6-dimethylbenzothiazole, 5-hydroxy-6
-Methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphthoC2,1
-d'l thiazole, naphtho[1°2-d]thiazole, naphtho(2,3-d]thiazole, 5-methoxynaphtho[:1.2-d)thiazole, 7-nitoxynaphthoC
2,1-dlthiazole, 8-methoxynaphthoC2,1
-d] Thiazole, 5-methoxynaphtho[2,3-d)
thiazole], selenazole core [e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5
-Hydroxybenzoselenazole, naphtho[2,1-d
) selenazole, naphtho [1°2-d] selenazole]
, oxazole nucleus [benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5
-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6- Chlorbenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphthoC2,1-dloxazole, Tef1 −
(1,2-dl oxazole, naphtho[2,3d]oxazole], quinoline nucleus [e.g. 2-quinoline, 3-
Methyl-2-quinoline, 5-ethyl-2-quinoline, 6
-Methyl-2-quinoline, 8-fluoro-2-quinoline, 6-medoxy-2-quinoline, 6-hydroxy-2-
Quinoline, 8-chloro-2-quinoline, 8-fluoro-
4-quinoline), 3,3-dialkylindolenine nucleus (
For example, 3,3-dimethylindolenine, 3゜3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5- Methylindolenine, 3,
3-dimethyl-5-chloroindolenine), imidazole core (e.g. 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1- Methyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-methoxybenzimidazole, ■
-Methyl-5-cyanobenzimidazole, ■-Ethyl-5-cyanobenzimidazole, 1-methyl-5-fluorobenzimidazole, ■-Ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1 -Allyl-5,6-dichlorobenzimidazole, ■-Allyl-5-chlorobenzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-5
-trifluoromethylbenzimidazole, l-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho[1,2-d:limidazole), pyridine nucleus (e.g. pyridine, 5-methyl-2-pyridine, 3
-methyl-4-pyridine). Among these, thiazole nuclei and oxazole nuclei are preferably used. More preferably a benzothiazole nucleus,
A naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is advantageously used.

X is an acid anion (e.g. chloride, bromide, iosite, tetrafluoroborate, hexafluorophosphate, methylsulfate, ethylsulfate, benzenesulfonate, 4-methylbenzenesulfonate,
4-chlorobenzenesulfonate, 4-nitrobenzenesulfonate, trifluoromethanesulfonate, perchlorate).

m3 represents 0 or 1, and when it is an inner salt, m=o.

Specific examples of compounds of (IV) C2H, c, H5 V-3 IV-6 re ■0 IV-8 IV-9 I ]C
2H5C,H.

(Xρ). 4 R11 and RI5 may be the same or different, and each represents an alkyl group (including a substituted alkyl group). Specific examples thereof are the same as those described for R7 and R1 in general formula (IV).

R1 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group, or a phenethyl group. Specific examples of Rl 1 are R9, R+o in general formula (IV)
This is the same as described in .

(2) is a hydrogen atom, a lower alkyl group (preferably 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl), an alkoxy group (preferably 1 to 4 carbon atoms, e.g. methoxy,
nidoxy, butoxy), a halogen atom (e.g. fluorine atom, chlorine atom), a substituted alkyl group (preferably having 1 to 4 carbon atoms, e.g. trifluoromethyl, carboxymethyl).

Z represents a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, and specific examples of the 5- or 6-membered nitrogen-containing heterocycle are 24 and Z5 of general formula (IV). This is the same as the ring described in .

X represents an acid anion, and a specific example of X4 is represented by the general formula (I
It is the same as the acid anion described in X3 of V).

m4 represents 0 or 1, and in the case of an inner salt, m=0. ng and p each independently represent 1 or 2.

Specific examples of compounds (V) C2H, I- C, H, I- V-3 C2Hi ■0 2 H5 Cj20. ○ 2H5 Book (CH2) 20H re These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are disclosed in Research Disclosure (Res.
176 Volume 17
643 (published December 1978), page 23, item 5.

The silver halide emulsion used in the present invention is usually chemically sensitized. Chemical sensitization methods include sulfur sensitization, reduction sensitization,
Known methods such as noble metal sensitization methods can be used, used alone or in combination.

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 iridium.

As the sulfur sensitizer, in addition to the sulfur compounds contained in Seratin, various sulfur compounds such as thiosulfates, thioureas, thiosoles, rhodanines, etc. can be used.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

The silver halide emulsion in the present invention has the following general formula (1-
It may contain compounds represented by a), (1-b), and (1-c).

(1-a) Z-SO2・S-M (1-b) 6.・Par-゛-゛゛ ・′°゛-゛y
c-so, ・s-c y□1. Brim□
0.1,5pa(1-c) y c-so2・5-(CI-1,), -3-3O2
-p YZ represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heterocyclic group. Y represents an atomic group necessary to form an aromatic ring or a heterocycle having 6 to 18 carbon atoms. M represents a metal atom or an organic cation. n represents an integer from 2 to IO. Furthermore, the alkyl group, aryl group, heterocyclic group, aromatic ring, and heterocyclic ring represented by Z and Y may be substituted.

Examples of substituents include lower alkyl groups such as methyl groups and ethyl groups, aryl groups such as phenyl groups, alkoxyl groups having 1 to 8 carbon atoms, halogen atoms such as chlorine, nitro groups, amino groups, carboxyl groups, etc. be able to.

The heterocycle represented by Z and Y includes thiazole,
Mention may be made of benzthiazole, imidazole, benzimidazole, and oxazole rings.

The metal atom represented by M is preferably a metal atom such as a potassium ion or potassium ion, and the organic cation is preferably an ammonium ion or a guanidine group.

Specific examples include the following.

The amount of the compound represented by the general formulas (1-a), (1-b), and (1-c) added is 0.001 per mole of silver halide.
-1 g, especially 0.01-0.2 g is preferred. The addition time may be any time from during grain formation of the silver decagenide emulsion to immediately before coating, preferably during grain formation or during chemical sensitization.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthion; niazaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy substituted (1,3,3a,7) tetrazaindenes); ), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.

In particular, polyhydroxybenzene compounds are preferred because they improve pressure resistance without impairing sensitivity.

The polyhydroxybenzene compound is preferably a compound having one of the following structures.

CH X and Y are respectively -H1-CH, nor\rogen atom -OM
(M is an alkali metal ion), -alkyl group, phenyl group, amino group, carbonyl group, sulfone group, sulfonated phenyl group, sulfonated alkyl group, sulfonated amino group, sulfonated carbonyl group, carboxyphenyl group,
Carboxyalkyl group, carboxyamino group, hydroxyphenyl group, hydroxyalkyl group, alkyl ether group, alkylphenyl group, alkylthioether group,
or a phenylthioether group.

More preferably, -Hl-OH, -C1, -Br, -
COOH, -CH, CH, C00H1-CH,, -CH
I GH,, -CH(CH3),, -C(CH3),
, -0CH,, -CHolSOsNa, -8○,H, -
8CH. X and Y may be the same or different.

Particularly preferable representative compound examples are E-(1) E-42) E-(3
)CH E-(4) E-(5) E-(6)
E-(7) E-(8) E-(9
)OHOH E-(10) E-(11)
The E-10 polyhydroxybenzene compound may be added to the emulsion layer of the sensitive material, or may be added to a layer other than the emulsion layer. The amount added is preferably in the range of 10-5 to 1 mol, particularly in the range of 10-'' mol to 10-1 mol.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
It may also contain developing agents such as urea derivatives, imidazole derivatives, 3-pyrazolidones and aminophenols.

Among them, 3-pyrazolidones (1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, etc.) are preferred, and usually 5
g/rr? It is used below, and 0.01 to 0.2 g/ba is more preferable.

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

For example, the active vinyl compounds (1,3,5-triacryloyl-hexahydro-3-)riazine, bis(vinylsulfonyl)methyl ether, N,N-methylenebis-[β
-(vinylsulfonyl)propionamide], etc.), active halogen compounds (such as 2゜4-dichloro-6-hydroxy-s-triazine), mucohalogen acids (such as mucochloric acid), N-carbamoylpyridinium salts ((1
-molpoly)carbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium salts (1-(l-chloro-1-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) can be used alone or in combination. Among them, JP-A-53-41220,
53-57257, 59-162546, 60-
80846 and U.S. Pat.
, 325.287 are preferred.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention can be used to aid coating, prevent static electricity, improve slipperiness, emulsification and dispersion, prevent adhesion, and improve photographic properties (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, 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 glycols Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfonate Carboxy groups, such as alkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino acids;
Ampholytic surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides, alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, complex compounds such as pyridinium, imidazolium, etc. Cationic surfactants such as ring quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

Further, in order to prevent static electricity, it is preferable to use a fluorine-containing surfactant described in JP-A-60-80849.

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-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example, alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate glycidyl (meth)
For acrylate alone or in combination, or in combination with acrylic acid, methacrylic acid, etc., a polymer containing monomer components can be used.

The silver halide emulsion layer used in the present invention can contain a polymer latex such as an alkyl acrylate.

There are no particular restrictions on the developing agent used in the developer used in the present invention, but it preferably contains dihydroxybenzenes, and dihydroxybenzenes and 1-phenyl-3- Combinations of pyrazolidones or dihydroxybenzenes and p-amine phenols may also be used.

Hydroquinone, the dihydroxybenzene developing agent used in the present invention, is preferred.

Examples of the developing agent for l-phenyl-3-pyrazolidone or its derivatives used in the present invention include 1-phenyl-3-pyrazolidone and -phenyl-4,4-dimethyl-3-pyrazolidone.

As the p-aminophenol developing agent used in the present invention, N-methyl-p-aminophenol is preferred.

The developing agent is preferably used in an amount of usually 0.05 mol/l to 0.8 mol/l. In addition, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols, the former is 0.
05 mol/1-0.5 mol/l, the latter 0.06 mol/l
I! It is preferable to use the following amounts. Furthermore, JP-A-56
- Amino compound described in No. 106244, Japanese Patent Publication No. 48-
The imidazole compound described in No. 35493 can be used.

The developer used in the present invention contains a compound described in JP-A-56-24347 as a silver stain preventive agent, a compound described in JP-A-62-212,651 as a development unevenness preventive agent, and a dissolving agent. As the agent, compounds described in JP-A-61-267759 can be used.

Furthermore, regarding the development processing method of the photosensitive material of the present invention, please refer to the description in JP-A No. 2-103536, pages 19 to 20, the description in JP-A No. 2-55349, pages 13 to 16, and JP-A No. 2-103037. The descriptions on pages 16 to 19 of the publication can be referred to.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 [11] Preparation of emulsion Preparation of emulsion A - Riichitaba water 1.01 Gelatin 20 g Sodium chloride 20 gl, 3-dimethylimidazo 20 ■Lysine-2-thionebenzenethiosulfonate 8 ■Liumata-Tabi Water 40011T
l Silver nitrate 100 g Main liquid water 40 - Sodium chloride 30.5 g Potassium bromide
14, Og hexachloroiridium (
Potassium III) acid (0,001% aqueous solution) Ammonium 15-hexabromorodium (DI) acid (0,001% aqueous solution) 1.5J38°C,
The 2nd and 3rd solutions were simultaneously added to the 1st solution maintained at pH 4.5 over a period of 10 minutes with stirring to form core particles of 0.16 μm. Subsequently, the following liquids 4 and 5 were added over 10 minutes. Furthermore, 0.15 g of potassium iodide was added to complete particle formation.

Soil - Shikasui 400 - Silver nitrate 100g Dan - Shikasui 400 - Sodium chloride 30.5g Potassium bromide
14. After that, it was washed with water by the flocculation method according to a conventional method, and gelatin was added.

The pH was adjusted to 5, L pAg 7.5, and chemical sensitization was performed at 65°C by adding 8 μ of sodium thiosulfate and 12 μ of chloroauric acid to obtain 1, 3.3a, and 1,3.3a as stabilizers.
200 μl of 7-chitraazaindene and phenoxyethanol were added as a preservative. Finally 80 mol% silver chloride
A silver iodochlorobromide cubic grain emulsion having an average grain size of 0.20 μm was obtained. (Coefficient of variation 9%) Furthermore, 1100p of phenoxyethanol is added as a preservative.
p was added.

Preparation of Emulsion B After washing with water and adding gelatin in the same manner as Emulsion A, the ortho-sensitizing dyes shown in Table 1 were added to ortho-sensitize. Furthermore, for supersensitization and stabilization, 4,4'-
Bis-(4,6-dinaphthoxypyrimicin-2-ylamino)-stilbendisulfonic acid sodium salt with silver 1
300 μm was added per mole. Other than this, the procedure was exactly the same as that of emulsion A, and the final product contained 80 mol% of silver chloride with an average grain size of 0.
A silver iodochlorobromide cubic emulsion of 20 μm was obtained (coefficient of variation 9%).Other than adding potassium hexacyanoferrate(n) (0.1%) to the preparation solution 5 of emulsion C in the amount shown in Table 1. was prepared in exactly the same manner as emulsion A, and the final product contained 80 mol% of silver chloride and had an average grain size of 0.
．． A 20 μm silver iodochlorobromide cubic emulsion was obtained (coefficient of variation 8%) Preparation of emulsion After washing with water and adding ceratin, the ortho-sensitizing dyes shown in Table 1 were added and ortho-sensitized. I gave it a feeling. Further, for supersensitization and stabilization, 4,4'-bis-(4,6-dinaphthoxypyrimidin-2-ylamino)-stilbenedisulfonic acid sodium salt was added at an amount of 300 μm per mole of silver. Other than these, the process was exactly the same as Emulsion C, and the final product contained 80 mol% of silver chloride with an average grain size of 0.
A 20 μm silver iodochlorobromide cubic emulsion was obtained (coefficient of variation 9
%) 2. Preparation of coating samples Of the emulsions A-D prepared in this way, the ortho-sensitizing dyes shown in Table 1 were added to A and C, which had not yet been ortho-sensitized, to ortho-sensitize them. . Further, for supersensitization and stabilization, 4,4'-bis-(4,6-dinaphthoxypyrimidin-2-ylamino)-stilbenedisulfonic acid disodium salt was added at 300 μm per mole. .

Hydroquinone 100 was then added to all emulsions A-D.
■/rd, polyethyl allylate latex with gelatin binder ratio of 25%, 2-bis(vinylsulfonylacetamido)ethane as a hardening agent added to 86■/rd,
Coating samples 1 to 20 were coated on a polyester support by adding gelatin to the amount of gelatin coated as shown in Table 1. At this time, gelatin was added on the upper side of the emulsion layer as a protective layer.
゜5 g/rd, dye of the following structural formula ■20■/rr?
As a matting agent, polymethyl methacrylate with a particle size of 2.5 μm was added at 60 μm/r+ (, colloidal silica with a particle size of 10 μm at 70 μm/r+), and as a coating aid, dodecylbenzenesulfonic acid sodium salt and the following structural formula The fluorine-containing surfactant was coated simultaneously with the emulsion layer.

■　C,F,,5o2N-CH2COOKC,H.

OHON HCHgSOJa The amount of gelatin listed in Table 1 is 0.0% of the seratin in the protective layer.
It represents the sum of 5 g/rrr and the seratin in the emulsion layer.

The sample support used in this example had a back layer and a back protective layer having the following compositions.

[Back layer]

Gelatin 2, Og/rd sodium dotesylbensene sulfonate 80 ■/d dye ■
70■/% dye ■
70■/d dye ■
90■/d1.3-Divinylsulfone-2-propertool 60■/d [Back protective layer] Seratin 0.5g/Polymethyl methacrylate resistant (particle size 4.7 μm) 30mg/% Sodium dodecylbenzenesulfonate 20■ / Fluorine-resistant surfactant (■ above) 2■ /d Silicone oil
100■/rr? ■ (CH2), SO; (CH2), 5OaK
So, K So, ■ [3] Evaluation of sample i) Evaluation of photographic performance The obtained sample was subjected to an interference filter with a peak at 488 nm and a continuous wedge, and the emission time was 10'se.
The film was exposed to xenon Fluorescent light (e), and sensitometry was performed at the temperature and time shown below using an automatic processor FG-71ONH manufactured by Fuji Photo Film Co., Ltd.

However, as the developer and fixer, developer solution (2) and fixer solution (2) were used, respectively.

Development 38°C 14 seconds Fixation 37°C 9.7 seconds Washing 26°0 9 seconds Squeeze 2.4 seconds Drying 55°C 8.3 seconds Total 43.4 seconds Logarithm of exposure to give density 3.0 The sensitivity is shown in Table 1 as a relative sensitivity of 0. Table 1 also shows the slope of the straight line connecting the points of density 0.1 and 3.0 on the characteristic curve as the gradation.

*For each dye, the Gel coating amount was 1.0 g/r&, no iron was contained, and the sensitivity was 100 when the dye was added immediately before coating.

ii) Evaluation of suitability for rapid processing Sensitization was carried out in the same manner as in i) except that the line speed of the FG-71ONH automatic processor was lowered and the time from development to drying was increased by 1.7 times for a total of 73.8 seconds. The suitability for rapid processing was evaluated based on the sensitivity and gradation difference from i).

1ii) Evaluation of pressure resistance (scratch) The untreated coated sample was tested at 0, 1 mm and 0.0
After passing under a 1 mm sapphire needle, processing from development to drying was performed under the same conditions as in the evaluation of photographic performance.

Visually evaluate the degree of blackening of the part of the sample rubbed with the needle,
Ranked from 5 (good) to 1 (bad).

Developer - ■ Hydroquinone 25.0g 4-Methyl-4-hydroxyntyl-1-phenyl-3-pyrazolidone 0.5g Potassium sulfite 90.0g Disodium ethylenediaminetetraacetate 2.0g Potassium bromide 5.0g 5-methylbenzotriazole 0.2g 2-mercaptobenzimidazole-5-sulfonic acid 0.3g sodium carbonate 20g Add water
If (add sodium hydroxide to adjust pH to 10.6) Fixer - ■ Ammonium thiosulfate 210g Sodium sulfite (anhydrous) 20g Disodium ethylenediaminetetraacetic acid 0.1g Glacial acetic acid
Add 15g water
1β (pH 4.0 with ammonia water)
8) Washing water Tap water sensitivity difference is 73.8 seconds Sensitivity of processing -43, Sensitivity gradation difference of 4 seconds is 〃 gradation - ノ! Represents gradation. That is, the smaller the sensitivity difference and gradation difference, the more suitable for rapid processing.

As is clear from Table 1, in order to achieve high sensitivity, excellent suitability for rapid processing, and good pressure resistance, it is necessary to apply a small amount of ceratin, contain an iron compound, and chemically sensitize the sensitizing dye. It turns out that it is necessary to add it beforehand.

Example 2 [1] Preparation of emulsion Preparation of emulsion E In the same manner as emulsion A used in Example I, after washing with water and adding gelatin, panchromatic sensitization was carried out by adding the panchromatic sensitizing dyes shown in Table 2. .

Furthermore, for supersensitization and stabilization, 300 μm of 4,4'-bis(4,6-dinaphthoxypyrimidin-2-ylamino)-stilbenedisulfonic acid disodium salt was added per mole of silver. Ta.

Other than this, the procedure was exactly the same as emulsion A, and finally silver chloride was added to 8
A silver iodochlorobromide cubic emulsion containing 0 mol % and an average grain size of 0.20 μm was obtained (coefficient of variation 9%). Preparation of emulsion F. The procedure was the same as that of emulsion C used in Example I, up to the addition of ceratin after washing with water. After this, panchromatic sensitization was carried out by adding the panchromatic sensitizing dyes shown in Table 2.

Furthermore, for supersensitization and stabilization, 4,4'-bis(4,6-dinaphthoxypyrimidin-2-ylamino)-stilhendisulfonic acid disodium salt was added at a concentration of 300 μm per mole of silver. added.

Other than this, a silver iodochlorobromide cubic emulsion containing 80 mol% of silver chloride and an average grain size of 0.20 μm was obtained in the same manner as Emulsion C (coefficient of variation 9%) [2] Coated sample Preparation Emulsions A and C prepared in Example I were subjected to panchromatic sensitization by adding the panchromatic sensitizing dyes shown in Table 2.

Furthermore, for supersensitization and stabilization, 300 μm of 4,4'-bis(4,6-dinaphthoquine-pyrimidin-2-ylamino)-stilbenedisulfonic acid disodium salt was added per mole of silver. Ta.

Thereafter, emulsions A, C, E, and F were coated in the same manner as in Example 1 to prepare coated samples 1 to 9.

[3] Evaluation of Samples i) Evaluation of Photographic Performance Evaluations were made in the same manner as in Examples ~l. However, exposure was performed with xenon flash light of 10''-8 seconds through an interference filter having a peak at 633 nm.

However, for each dye, the Gel coating amount was 1.0 g/distance, no iron was contained, and the sensitivity was 100 when the dye was added immediately before coating.

Both ii) and 1Li) were evaluated in the same manner as in Example 1.

As is clear from Table 2, in order to achieve high sensitivity, excellent suitability for rapid processing, and good pressure resistance not only for the ortho dye of general formula (1) but also for the panchromatic dye of general formula (I[), Contains iron compounds with a small amount of gelatin applied,
It can be seen that it is necessary to add the sensitizing dye before chemical sensitization.

Example 3 [1] Preparation of emulsion Preparation of emulsion G In the same manner as in emulsion A used in Example 2, the steps up to the addition of ceratin after washing with water were carried out, and then the panchromatic dyes shown in Table 3 were added for panchromatic sensitization.

Other than this, a silver iodochlorobromide cubic emulsion containing 80 mol% of silver chloride and having an average grain size of 0.20 μm was obtained in the same manner as in Emulsion A (coefficient of variation 9%). Preparation Example of Emulsion H After washing with water and adding seratin in the same manner as Emulsion C used in Example I, the panchromatic dyes shown in Table 3 were added for panchromatic sensitization.

Other than this, the procedure was exactly the same as Emulsion C, and finally silver chloride was added to 8
A silver iodochlorobromide cubic emulsion containing 0 mol % and an average grain size of 0.20 μm was obtained (coefficient of variation 9%) [2] Preparation of coating samples Emulsions A and C prepared in Example I were mixed with the panchromatic emulsions shown in Table 3. Panchromatic sensitization was performed by adding a dye.

Thereafter, emulsions A, C, G, and H were coated in the same manner as in Example 1 to prepare coated samples 1 to 9.

[3] Evaluation of Sample i) Evaluation of Photographic Performance Evaluation was made in the same manner as in Example-1. However, it was exposed to xenon flash light for 10-'sec through an interference filter having a peak at 670 nm. However, for each dye, G
The et coating amount was 1°0 g/rd, no iron was contained, and the sensitivity was 100 when the dye was added immediately before coating.

ii) Evaluation of suitability for rapid processing 11i) Evaluation of pressure resistance (scratch) ii) and 1ii) were all evaluated in the same manner as in Example 1.

/ / As is clear from Table 3, the panchromatic dye of general formula (I [I) also has high sensitivity and excellent suitability for rapid processing,
It can also be seen that in order to improve the pressure resistance, it is necessary to contain an iron compound with a small amount of gelatin coated and to add a sensitizing dye before chemical sensitization.

Example 4 [1] Preparation of emulsion Preparation of emulsion I In the same manner as emulsion A used in Example 2, after washing with water and adding gelatin, the infrared sensitizing dyes shown in Table 4 were added and infrared sensitized. I felt it.

Furthermore, for supersensitization and stabilization, 2.5
-Dimethyl-3-allyl-benzothiazole iodo salts were added at 300 and 450 cm, respectively, per mole of silver.

Other than this, the procedure was exactly the same as emulsion A, and finally silver chloride was added to 8
A silver iodochlorobromide cubic emulsion containing 0 mol % and an average grain size of 0.20 μm was obtained (coefficient of variation 9%). Preparation of emulsion J. Addition of ceratin after washing with water in the same manner as emulsion C used in Example I. After carrying out the above steps, infrared sensitization was carried out by adding the infrared sensitizing dyes shown in Table 4.

Furthermore, for supersensitization and stabilization, 2,5
-Dimethyl-3-allyl-benzothiazole iodo salts were added at 300 and 450 cm, respectively, per mole of silver.

Other than this, a silver iodochlorobromide cubic emulsion containing 80 mol% of silver chloride and an average grain size of 0.20 μm was obtained in the same manner as Emulsion C (coefficient of variation 9X) [2] Coated sample Preparation Emulsions A and C prepared in Example I were subjected to infrared sensitization by adding the infrared sensitizing dyes shown in Table 4.

Furthermore, for supersensitization and stabilization, 4,4'-bis(4,6-dinaphthoxypyrimicin-2-ylamino)-stilbene disulfonic acid disodium salt
-Dimethyl-3-allyl-benzothiazole iodo salts were added at 300 and 450 cm, respectively, per mole of silver.

Thereafter, emulsions A, C, I, and J were coated in the same manner as in Example 1 to prepare coated samples 1 to 9.

[3] Evaluation of Samples i) Koizumi Satokuma Omega Sato Evaluation was carried out in the same manner as in Example-1. However, exposure was performed using a 10-'see xenon flash light through an interference filter having a peak at 780 nm. However, for each dye, G
et coating amount l.

Og/rrr, iron-free, sensitivity added just before dye to 10
It was set to 0.

Both ii) and ii) were evaluated in the same manner as in Example 1.

As is clear from Table 4, in order for the infrared dye of general formula (IV) to have high sensitivity, excellent suitability for rapid processing, and good pressure resistance, it is necessary to contain an iron compound with a small amount of Seratin applied. , and that it is necessary to add a sensitizing dye before chemical sensitization.

Example 5 [1] Preparation of emulsion Preparation of emulsion After washing with water and adding ceratin in the same manner as in Emulsion A used in Example 2, the infrared sensitizing dye shown in Table 5 was added to infrared sensitize. I felt it.

Furthermore, for supersensitization and stabilization, 2,5
-Dimethyl-3-allyl-benzothiazole iodo salts were added at 300 and 450 cm, respectively, per mole of silver.

Other than this, the procedure was exactly the same as emulsion A, and finally silver chloride was added to 8
Preparation of an emulsion to obtain a silver iodochlorobromide cubic emulsion containing 0 mol% and an average grain size of 0.20 μm (coefficient of variation 9%) Addition of ceratin after washing with water in the same manner as Emulsion C used in Example I. After carrying out the above steps, the infrared sensitizing dyes shown in Table 5 were added to carry out infrared sensitization.

Furthermore, for supersensitization and stabilization, 4,4'-bis(4,6-dinaphthoxypyrimicin-2-ylamino)-stilbene disulfonic acid disodium salt
-Dimethyl-3-allyl-hendithiazole iodo salts were added at 300 and 450 cm, respectively, per mole of silver.

Other than this, a silver iodochlorobromide cubic emulsion containing 80 mol% of silver chloride and an average grain size of 0.20 μm was obtained in the same manner as Emulsion C (coefficient of variation 9%) [2] Coated sample Preparation of Emulsions A and C prepared in Example I were subjected to infrared sensitization by adding the infrared sensitizing dyes shown in Table 5.

Furthermore, for supersensitization and stabilization, 4,4'-bis(4,6-dinaphthoxypyrimicin-2-ylamino)-stilbene disulfonic acid disodium salt
-Dimethyl-3-allyl-hendithiazole iodo salts were added at 300 and 450 cm, respectively, per mole of silver.

Thereafter, emulsions A, C, K, and L were coated in the same manner as in Example 1 to prepare coated samples 1 to 9.

[3] Evaluation of Sample 1) Erosion Dwarf 2 Seal Evaluation was carried out in the same manner as in Example-1. However, exposure was performed using a 10-'see xenon flash light through an interference filter having a peak at 780 nm. However, for each dye,
Gel application amount 1.0g/rr? , no iron was added, and the sensitivity was set at 100 when the dye was added immediately before coating.

ii) and 5) were evaluated in the same manner as in Example 1.

In order to have high sensitivity and excellent suitability for rapid processing for dyes, and to improve pressure resistance, it is necessary to contain iron compounds with a small amount of Seratin applied, and to add sensitizing dyes before chemical sensitization. It turns out that it is necessary.

Example 6 [l] Preparation of emulsion Preparation of emulsion M The procedure was exactly the same as emulsion A except that the iron compound shown in Table 6 was added to the 5 liquid of Example 1, and silver chloride was finally added to 80 mol%.
A silver iodochlorobromide cubic emulsion with an average grain size of 0°20 μm was obtained (coefficient of variation 8%). Preparation of emulsion N. After washing with water and adding gelatin in the same manner as in emulsion M, the ortho-sensitizing dyes shown in Table 6 were prepared. was added for ortho sensitization.

Furthermore, for supersensitization and stabilization, 4,4'-bis-
(4,6-dinaphthoxypyrimidin-2-ylamino)-stilbenedisulfonic acid sodium salt was added at an amount of 300 μm per mole of silver. Other than these, the final product was exactly the same as Emulsion M, containing 80 moles of silver chloride, and having an average grain size of 0.2.
A silver iodochlorobromide cubic emulsion of 0 μm was obtained (coefficient of variation 9%).
) [2] Preparation of coating sample Emulsion prepared in this manner ~1. Ortho sensitization was performed by adding the ortho sensitizing dyes shown in Table 1 to M of N. Furthermore, for supersensitization and stabilization, 4,4'-bis-(4,
300 μm of 6-dinaphthoxypyrimicin-2-ylamino-stilbendisulfonic acid sodium salt was added per mole of silver.

Thereafter, emulsions M and N were coated in the same manner as in Example 1 to prepare coated samples.

[3] Sample evaluation Evaluation was made in the same manner as in Example 1.

As is clear from Table 6, various iron compounds can be used in the present invention.

Example 7 [1] Preparation of emulsions Emulsions P, Q, R, and S Emulsion A was used except that sodium chloride and potassium bromide of Example 1 were changed to 20.2 g and 35°1 g, respectively.
A silver iodochlorobromide cubic grain emulsion containing 50 mol % of silver chloride and having an average grain size of 0.19 μm was finally obtained in exactly the same manner as , B, C, and D.

Preparation of Emulsions T, U, V, and W Emulsions A, except that the sodium chloride and potassium bromide of 3iζ5M in Example 1 were changed to 9.9 g and 56 g, respectively.
Silver iodochlorobromide cubic particles containing 50 mol % of silver chloride and having an average particle diameter of 0.19 μm were obtained in exactly the same manner as B, C, and D.

[2] Preparation of coating sample Of emulsion P-W, P is not spectrally sensitized.

R, T, and V were spectrally sensitized in the same manner as in Example 1.

Thereafter, emulsion P-W was coated in the same manner as in Example 1 to prepare a coated sample.

[Evaluation of 3″J sample Evaluation was made in the same manner as in Example 1.

From Table 7, the effect of the present invention is recognized even if the halogen composition is changed.

/ / / /′ 7・′ / /′

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on the same side of the support, the photosensitive halogen on the support is The amount of gelatin on the side having the silveride emulsion layer and the non-photosensitive hydrophilic colloid layer is 2.5 g/m^2
or less, and the silver halide grains are 1
1. A silver halide photographic material containing 0^-^3 moles or less of an iron compound, and characterized in that a sensitizing dye is added before chemical sensitization of silver halide grains. (2) The silver halide emulsion layer has the following general formula (I)
The silver halide photosensitive material according to claim 1, which contains at least one of the sensitizing dyes listed in (V). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Z_1 represents a group of nonmetallic atoms necessary to form a 5- to 6-membered heterocycle, and Q_1 represents a group of nonmetallic atoms necessary to form a 5-membered nitrogen-containing heterocycle. Represents a group of nonmetallic atoms necessary for R_1 represents an alkyl group or substituted alkyl. n_1 represents 1 or 2. (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Z_2 and Z_3 each represent a group of nonmetallic atoms necessary to complete a 5-membered or 6-membered nitrogen-containing heterocyclic nucleus. R_
2 and R_3 each represent an alkyl group, a substituted alkyl group, or an aryl group. Q_2 and Q_3 together represent 4-thiazolidinone, 5-thiazolidinone, or
Represents a group of nonmetallic atoms necessary to complete the 4-imidazolidinone nucleus. L_1, L_2, L_3 are each methine group,
Or represents a substituted methine group. n_2 and n_3 are each 1
or 2. X_1 represents an anion. m_1
represents 0 or 1, and when forming an inner salt, m=
It is 0. (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Y_1 and Y_2 each form a heterocyclic ring such as a benzothiazole ring, benzoselenazole ring, naphthothiazole ring, naphthoselenazole ring, or quinoline ring. Represents a necessary group of nonmetallic atoms, and these heterocycles include lower alkyl groups, alkoxy groups, hydroxy groups, aryl groups,
May be substituted with an alkoxycarbonyl group or a halogen atom. R_4 and R_5 each represent a lower alkyl group, a sulfo group, or an alkyl group having a carboxy group. R_6 represents a lower alkyl group. X_2 represents an anion. n_4 and n_5 represent 1 or 2. m_2
represents 0 or 1, and when it is an inner salt, m=0. (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R_7 and R_8 each represent an alkyl group or a substituted alkyl group. R_9 and R_1_0 each independently represent a hydrogen atom lower alkyl group, lower alkoxy group, phenyl group, benzyl group or phenethyl group. R_1_1, R_1
_2 each represents a hydrogen atom, or R_1_1 and R_
1_2 are connected to form a divalent alkylene group. R
_1_3 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group, or ▲a mathematical formula, a chemical formula, a table, etc.▼. However, here W_1 and W_
2 each independently represents an alkyl group or an aryl group,
W_1 and W_2 can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. Also, R_9 and R_
1_3 or R_1_0 and R_1_3 can also be connected to form a divalent alkylene group. Z_4 and Z_5 each independently represent a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. X_3
represents an acid anion. m represents 0 or 1, and m_3=0 when forming an inner salt. (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R_1_4 and R_1_5 represent an alkyl group and a substituted alkyl group, respectively. R_1_6 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. V is a hydrogen atom, a lower alkyl group,
Represents an alkoxy group, a halogen atom, or a substituted alkyl group. Z_5 represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. X_4 represents an acid anion. n_6 represents 1 or 2. m_4 represents 0 or 1, and in the case of an inner salt, m_4=0. p represents 1 or 2.