JPH0419733A - Silver halide photographic sensitive material and method for developing same - Google Patents

Abstract

PURPOSE:To form a photosensitive material high in sensitivity at the time of exposure to high illumination by incorporating a specified amount of silver chloride in silver halide and a specified amount of iridium compound and one of iron, rhenium, osmium, and ruthenium compounds, and one of specified compounds in silver. CONSTITUTION:The silver halide grains comprise >=30mol% silver chloride grains and contain, per mol of the silver halide, the <=10<-6>mol iridium compound, at least one of the iron, rhenium, ruthenium, and osmium compounds in an amount <=10<-3>mol, and at least one of the compounds represented by formulae I - III in which Z is 1 - 18C alkyl, 6 - 18 C aryl, or a heterocyclic group; Y is an aromatic group necessary to form a 6 - 18 C aromatic ring or a hetero ring; M is a metal atom or an organic cation; and (n) is an integer of 2 - 10, thus permitting high sensitivity at the time of short-time exposure to high illumi nation and rapid processing aptitude to be obtained.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic material having a high window ratio and excellent suitability for rapid processing in high-intensity short-time exposure. This invention relates to a silver photographic material and a developing method thereof.

[Prior art]

In recent years, single-scanner systems have been widely used in the printing plate-making field. 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, because they are exposed for a short time of 104 to 10-7 seconds, they have high sensitivity and high contrast even under such conditions. This is a necessary condition. Particularly in the field of facsimile, it is important to have excellent suitability for rapid processing to emphasize speedy reporting, and in the future, it will be necessary to increase the number of lines and narrow the light beam to achieve faster scanning and higher image quality. Garbage is desired;
There has been a strong desire to develop photosensitive materials with high sensitivity and high contrast.

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 processor is increased to shorten these processes, (1) decrease in contrast, (2) poor fixing, and (3)
Problems such as poor washing and (4) poor drying occur.

Generally, in order to solve the above problems (1) and (2), it is advantageous to increase the silver chloride content of the silver halide emulsion, but this has the disadvantage of low sensitivity. Also (2), (3
) and (4), it is effective to reduce the amount of coated silver and gelatin in the silver halide photosensitive material. It is necessary to reduce the grain size in the emulsion, and from this point of view as well, there has been a desire to develop a photosensitive material containing a silver halide grain emulsion with a high silver chloride content and having even higher sensitivity.

[Purpose 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, and the second object is to provide a processing method suitable for rapid development processing.

[Structure of the invention]

An object of the present invention is to provide a silver halide photographic material having at least one light-sensitive emulsion layer containing silver halide grains on a support, wherein the silver halide grains contain 30 mol % or more of silver chloride. At least one of an iridium compound in an amount of 10-' mol % or less and an iron, rhenium, ruthenium, or osmium compound in an amount of 10-' mol or less relative to silver.
Contains a species, and further contains the following general formulas (1-a) and (1-b)
This was achieved by a silver halide photographic material containing at least one of the compounds represented by (1-c) and (1-c).

(1-a) Z-SO 6 to 18), or atomic group M necessary to form a heterocycle; metal atom or organic cation n; integer from 2 to 10 (specific configuration of the invention) The specific configuration of the present invention will be described in detail.

The silver halide photographic emulsion according to the present invention contains silver chloride, silver chlorobromide or silver chloroiodobromide as silver decagenide. At this time, silver chloride is contained in an amount of 30 mol % or more, more preferably 60 mol % or more. Also, the silver iodide content is 5 mol%
The content is 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 grain size of silver halide grains is 0.01 μm
~1 μm is preferable, but more preferably 0.4 μm or less, ((standard deviation of particle size)/(average particle size))×10
It is preferable to have a narrow particle size distribution with a coefficient of variation represented by 0 of 15% or less, more preferably 10% or less.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

The photographic emulsion used in the present invention is P, Glafkid
Chimie et Physique by es
Photographique (Pau1Mon
TE1 Publishing, 1967), Photographic Emulison Che by G. F. Duffin
mistry (The Focal Press, 1
966), V.L., Zelilvan et a.
Making and Coating Photo
graphic E+gulsion(The Fo
Cal 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 having a regular crystal shape and a 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. 4B-36890, No. 52-
As described in No. 16364, a method of changing the addition rate of silver nitrate or alkali halide depending on the grain growth rate, British Patent No. 4,242,445, Japanese Patent Application Laid-open No. 5
It is preferable to use a method of varying the concentration of an aqueous solution as described in Japanese Patent No. 5-158124 to grow rapidly within a range that does not exceed the critical saturation level.

The grain formation of the silver halide emulsion of the present invention is carried out using tetrasubstituted thioureas, halogenated compounds such as thioether compounds! ! Preferably, this is carried out in the presence of a solvent.

Preferred tetrasubstituted thiourea silver halide solvents used in the present invention include JP-A-53-82408 and JP-A-55-7773.
It is a compound represented by the following general formula described in No. 7, etc.

In the formula, R, Rt, R2 and R4 represent a substituted or unsubstituted alkyl group, an alkenyl group (such as an allyl group), or a substituted or unsubstituted aryl group, and these may be the same or different from each other. , the total number of carbon atoms of R1-R4 is preferably 30 or less. Furthermore, 5- to 6-membered heterocyclic rings such as imidapridinethione, piperidine, and morpholine can be produced by combining R1 and R2, R, and R5, or R and R4. 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 (-
〇H), carboxy group, sulfonic acid group, amino group, alkoxy group in which the alkyl residue has 1 to 5 carbon atoms (
Examples of the substituent of the aryl group which is a phenyl group or a 5- to 6-membered heterocycle (such as furan) include a hydroxy group, a carboxy group, or a sulfone group.

Here, it is particularly preferable that R1 to R1 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. It is as follows.

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

11) (-1) 0 ■ H Kensi The organic thioether silver halide solvent preferably used in the present invention is a solvent containing an oxygen atom and Compounds containing at least one group in which a sulfur atom is separated by ethylene (e.g. -0 CHt CHg -5-), JP-A-54-155828 (U.S. Pat. No. 4,277)
A chain thioether having an alkyl group at both ends (each alkyl group has at least two substituents selected from hydroxy, amino, carboxy, amide, or sulfone) listed in No. 6.374) It is a compound. Specifically, the following examples can be given.

HOCII□CHz S CHzCtlt S
C1l□CH,0H1(OCIhCIIzCL S
CHzCIIz S CHzCIhCl(zO
HHOCIIzCIICI(zscTocHzscLc
HcH20tlOf(01l II00CCII *CIICII□-3CIIxCI
Ig 5-C11ICIIICIIICOO11110
c11IC11C11!5CIIICII□0CII□
C1hSCIIzCIICIIz011OH011 The talking power n amount of the silver halide solvent varies depending on the type of compound used, the intended grain size, the halogen composition, etc., but is 10-s to 10-! per mole of silver halide!
Moles are preferred.

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.

Silver halide used in the present invention A water-soluble iridium compound can be used as the iridium compound used in the present invention.

For example, halogenated iridium (II[) compounds, halogenated iridium (IV) compounds, and iridium complex salts having halogens, amines, oxalates, etc. as ligands, such as hexachloroiridium (I[[) or (IV)]. complex salt, hexaammineiridium (I[[
) or (IV) complex salt, trioxalatoiridium (
III) or (rV) complex salts. In the present invention, among these compounds, those with a valence of
It is possible to use them in any combination of values. These iridium compounds are used after being dissolved in water or an appropriate solvent, but methods commonly used to stabilize solutions of iridium compounds include aqueous hydrogen halide solutions (e.g., hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.). , or alkali halides (e.g. KCl, NaCl, KBr, Na
Br, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve other silver halide grains doped with iridium in advance during the preparation of silver halide grains.

The total amount of iridium compound added according to the present invention is the final amount of halogenated i! IX 10- per mole
”-I X 10-S mol is suitable, preferably 5
X10-B to 5X10-6 moles.

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.

Specific compounds include iridium chloride (■), iridium bromide (■), iridium chloride (■),
Sodium hexachloroiridate(III), hexachloroiridium (I[l) salt, hexamine iridium (TV) salt, trioxalatoiridium (Ill)
Salts, halogen amines such as trioxalatoiridium (TV) salts, and oxalato complex salts are preferred.

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 ferric thiocyanide Ferric sulfate Ferric ammonium sulfate Ferric sulfate Guanidine Ferric ammonium citrate Ferric hexane cyanoferrate (II) potassium pentacyanoammine ferrous potassium ethylene dinitrilotetraacetic acid ferric sodium hexacyanoferric (I [[) acid potassium tris(dipyridyl) ferric pentacyanonitrosyl ferric potassium chloride diiron, especially hexacyanoferrate (■), hexacyanoferrate (II)
I) Acid salts, ferric thiocyanate and ferric thiocyanate exhibit remarkable effects.

The rhenium, ruthenium, and osmium compounds used in the present invention are disclosed in European Publication Patent (EP) 0336689.
No. A, No. 0336427A1, No. 0336425A1
The aquatic coordination complexes described in No. 0336426A1 are preferred, and those containing at least 41 cyanide ligands are particularly preferred. In preferred embodiments, these compounds can be represented by the following formulas.

(M (CN)!-9Ly)" where M is rhenium, ruthenium, osmium, L is a catenary ligand, y is an integer 0, 1, or 2, and n is 2, -3 Or -4.

A specific example is (Re(CN)s) −' (Ru(CN)
s ) (Os(CN)s ) −' [ReF
(CN)s) (RuF (CN)s) −'
(OsF(CN)s)(ReC1(CN)s
) −' CRuC](CN)s :](Os
C1(CN)s ) −(ReBr(CN)s )(R
uBr(CN)s ) −' (OsBr(CN)
s ) (Rel(CN)s) −(Rut(CN)s)
[0sl(CN)s) −(ReF2(CN)4)(
RuFz(CM)s ) -COsFz(CM)s ]
(ReC1z(CN)a) −' (RuC1z
(CN)4](OsC1z(CN)a:] −(RuB
rz(CN)al(OsBrz(CN)n)-'
[ReBrx(CN)n)(Rulz(CN)4)
-(Os,Iz(CN)s) -'[Ru(CN
) s (QCS) ) −(Os (CN)s(OC
N)) -a(Ru(CN)s(SCN)) -'
(Os(CN)s(SCN)) −'(Ru(CN
)s (N3)) −(Os(CN)s (Ni))
(Ru(CN)s(HzO)) −(Os(CN)s
(HzO)) - is mentioned.

The above iron, rhenium, ruthenium, and osmium compounds are preferably added during the formation of silver halide grains.

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. The amount added is 10-3 mol or less, preferably 10-6 to 10-4 mol, per 1 mol of silver.

In the present invention, other metals included in Group (1), such as cobalt, nickel, rhodium, palladium, and platinum, may be used in combination. In particular, the combination with rhodium salts such as rhodium chloride and ammonium hexachlororhodium (I[[)ate) is advantageous in that a high-contrast emulsion can be obtained.

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 gelatin, various yellow-yellow compounds such as thiosulfates, thioureas, thiosoles, and rhodanines can be used.

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

General formulas (1-a), (1-b), (1-
The alkyl group, aryl group, heterocyclic group, aromatic ring and heterocyclic ring represented by Z and Y in the compound represented by c) may be substituted.

Examples of substituents include lower alkyl groups such as a methyl group and ethyl group, an alkyl group such as a phenyl group, an alkoxyl group having 1 to 8 carbon atoms, a halogen atom such as chlorine, a nitro group, an amino group, and a carboxyl group. etc. can be mentioned.

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

The metal atoms represented by M include sodium ions,
Preferred examples include metal atoms such as potassium ions, and ammonium ions and guanidine groups as organic cations.

Specific examples include the following.

H3C-SOz ・SNa 1-cystine disulfoxide CH3SOz'5Na C+Jzs SOz'5Na Compounds included in general formulas (1-a), (1-b), and (1-C) can generally be prepared by well-known methods. It can be synthesized.

For example, it can be synthesized by reacting the corresponding sulfonyl fluoride with sodium sulfide, or by reacting the corresponding sodium sulfinate with sulfur. On the other hand, these compounds can also be easily obtained as commercial products.

General formulas (1-a), (1-b), (1-
The amount of the compound represented by C) added is 0.001 to 1 g, particularly 0.001 to 1 g per mole of silver halide. 01-0.2g is preferred. The addition time may be any time from during grain formation of the silver halide emulsion to just before coating, but preferably during grain formation or during chemical aggravation.

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopholarianine 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
RCHDISCLO3URE Item 1
7 6 4 3 Section W-A (December 1978 p. 2
3), 1te+m1831X section (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 example, for A) argon laser light source, JP-A-60-1
No. 62247, JP-A No. 2-48653, U.S. Patent No. 2,
Simple merocyanine described in No. 161.331 and West German Patent No. 936071! , 'B) For helium-neon laser light sources, see Japanese Patent Application Laid-open Nos. 50-62425 and 54-1.
No. 8726, trinuclear cyan dyes shown in No. 59-102229, C) For LDE light sources,
No. 2172, No. 51-9609, No. 55-39818
thiacarbocyanines described in JP-A No. 62-284343; and D) thiacarbocyanines described in JP-A-59-191032 and JP-A-60-80841 for semiconductor laser light sources. , Japanese Patent Publication No. 59-19
Dicarbocyanines containing a 4-quinoline nucleus, such as those described in No. 2242, are advantageously selected.

Representative compounds of those sensitizing dyes are shown below.

Specific compound example A-5 of B) Specific compound example e of B) Js tHs Specific compound of C) General formula (I) [In the formula, Y1 and Yt are respectively a benzothiazole ring, a henzoselenazole ring, and a naphthothiazole ring. Represents a group of nonmetallic atoms necessary to form a heterocyclic ring such as a ring, a naphthoselenazole ring, or a quinoline ring, and these heterocycles are lower alkyl groups, alkoxy groups, hydroxy groups, awar groups,
May be substituted with an alkoxycarbonyl group or a halogen atom.

R,, R, each represents an alkyl group having a lower alkyl group, a sulfo group, or a carboxy group.

Represents a lower alkyl group.

Anion represents.

0. represents 1 or 2.

represents 1 or 0, When it is an inner salt, =○ represents.

] Specifically, (C1h) SO, ++ (C1h) 3s (h O C-5 (Cllx) 5s (hll (C1h) COSO, ) asO: +1l (CHz) 4sO3e (CHz) 3503 Specific Compounds of G zHs D) C!L ■ Particularly, the combination with the sensitizing dye of mI C) is preferable because it enables a high frequency range.

These enhancing 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 exacerbating dyes, combinations of supersensitizing dyes, and substances showing supersensitization Search Disclosure
176 volume 176
43 (published December 1979), page 23, section 5.

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 oxazolinthione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted (1,3,3a,7) tetrazaindenes); A number of compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, henzenesulfonic acid amide, etc.), pentaazaindenes, 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.

X and Y are respectively -H, -ON, halogen 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 -I-1, -0Hl-CC.

-Br, -COOHl-CIl, CHI C0OH.

-CH5, -CH-CH3, CH(CHs)z
,C(CHI3)! , -0CI+3, -CH
olSOsNa.

It may be.

Particularly preferred representative compound examples include E-Tl) E-(2) E-(31 E-(4) E-(5) E-(6) O1+ (+N E -(22) E-(22) ft The polyhydroxybenzene compound may be added to the emulsion layer of the sensitive material or to a layer other than the emulsion layer, and the amount added is 1 mol. A range of 10-s to 1 mole is useful, and a range of io" to 10"8 mole is particularly useful.

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: Included are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among these, oxonol dyes, hemioxonol dyes, and merocyanine dyes are useful.

The photographic hole 7FI layer of the photographic light-sensitive material of the present invention has increased sensitivity,
For the purpose of increasing contrast or accelerating development, for example, polyalkylene derivatives such as polyalkylene derivatives or their ethenobe esters, amines, thionithyl compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, A developing agent such as 3-pyrazolidones, amine phenols, etc. may also be included.

Among them, 3-pyrazolidones (1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-hyperazolidone) are preferred, and usually 5
Used below g/nr, 0.01-0.2 g
/+rr is more preferable.

The photographic emulsion and photosensitive hydrophilic colloid of the present invention include inorganic or fa W! It may contain a film forming agent.

For example, the active vinyl compounds (1,3,5-)lyacryloyl-hexahydro-5-triazine, bis(vinylsulfonyl)methyl ether, N,N-methylenebis-[β
-(vinylsulfonyl)propionamide], etc.), active halogen compounds (2゜4-dichloro-6-hydroxy-5-1-riazine, etc.), mucohalogen acids (mucochloric acid, etc.), N-carbamoyl tridinium salts 1 ( (
1-molpoly)carbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium salts (1(1-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 may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for the purpose of promoting development, increasing contrast, exacerbation, etc.

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 alkyl ethers, polyalkylene glycols) Alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), BJm acid esters of polyhydric alcohols, 17
Nonionic surfactants such as alkyl esters of: alkyl carboxylates, alkyl sulfone M salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphate esters, N-acyl-N - Carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as alkylclarins, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides, etc.; amphoteric surfactants such as alkylamine salts, aliphatic or aromatic Cationic surfactants such as group quaternary ammonium salts, heterocyclic cylindrical quaternary ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

Further, it is preferable to use a fluorine-containing surfactant described in JP-A No. 60-80849 and the like for the antistatic barrel.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magsium oxide, or polymethyl methacrylate 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, a polymer containing as a monomer component alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. is used. be able to.

Gelatin is advantageously used as the condensing agent or TW-preserving colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives,
Graft polymers of gelatin and other cylindrical molecules, proteins such as albumin and casein, droxyethyl cellulose,
Carboxymethylcellulose, cellulose derivatives such as cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, A wide variety of synthetic hydrophilic polymeric materials can be used, such as polyvinylpyrazoles, single or copolymers of polyvinylpyrazoles, and the like.

As the gelatin, in addition to coal-treated gelatin, acid-treated gelatin may be used, and gelatin enzymatic decomposition products and gelatin enzymatic decomposition products can also be used.

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

Supports for the fluorescent material of the present invention include cellulose triacetate, cellulose diacetate, nitrocellulose,
Polystyrene, polyethylene terephthalate paper, baryta-coated paper, polyolefin-coated paper, etc. can be used.

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- A combination of pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may also be used.

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone, with hydroquinone being particularly preferred.

As the developing agent for 1-phenyl-3-pyrazolidone or its derivative used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5
-Methyl-3-pyrazolidone, 1-P-aminophenyl 4,4-dimethyl-3-pyrazolidone, 1-P-tolyl-4,4-dimethyl-3-pyrazolidone, 1-P-tolyl-4-methyl-4 -Hydroxymethyl-3-virapritone and the like.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminephenol, N-(β-hydroxyedyl)-p-aminephenol, and N-(4-hydroxyphenyl). glycine,
There are 2-methyl-p-7 minophenol, P-benzylaminophenol, etc., among which N-methyl-p-aminophenol is preferred.

The amount of developing agent is usually 0.05 mol/! Preferably, it is used in an amount of ~0.8 mol/1. In addition, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or P-amino-phenols, the former is
OS mol/l - 0.5 mol/l.

0.06 mol/j of the latter! It is preferable to use the following amounts.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium lithium nitrate, sodium bisulfite, potassium bisulfite, and sodium formaldehyde sulfite.

Sulfite is preferably 0.3 mol/l or more, particularly 0.4 mol/l or more, and the upper limit is up to 2.5 mol/l, especially,
It is preferable to set it up to 1.2.

Alkaline agents used to set pH include pH4Ig moderating agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate, sodium silicate, and potassium silicate. and buffering agents.

Additives used in addition to the above components include compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methyl cellosolve. , organic solvents such as hexylene glycol, ethanol, and methanol; mercapto compounds such as 1-phenyl-5-mercaptotetrazole and 2-mercaptobenzimidazole-5-sulfonic acid sodium salt; indazole compounds such as 5-nitroindazole; It may contain an antifoggant such as a penztriazole compound such as 5-methylbenztriazole, and may further contain a color III agent, a surfactant, an antifoaming agent, a water softener, a film hardening agent, etc. as necessary. In particular, the amino compounds described in JP-A-56-106244 and the imidazole compounds described in JP-B-4B-35493 are preferred from the viewpoint of accelerating development or increasing sensitivity.

The developer used in the present invention includes 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 Japanese Patent Application No. 109743/1988 can be used.

The fixing solution is an aqueous solution containing, in addition to the fixing agent, a hardening agent (for example, a water-soluble aluminum compound), acetic acid, and a dibasic acid (for example, tartaric acid, citric acid, or a salt thereof) as necessary;
Preferably pH 3.8 or higher, more preferably 4.0~
5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, with ammonium thiosulfate being particularly preferred from the viewpoint of fixing speed.The amount of the fixing agent used can be changed as appropriate, and is generally about 0.1 to about 5 mol/l. be.

The water-soluble aluminum salt used mainly as a hardening agent in the fixing solution is a compound generally known as a hardening agent for acidic hardening fixing solutions, such as aluminum chloride, aluminum sulfate, and potassium alum.

As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. These compounds are used in fixer 11
Those containing 0.005 mol or more are effective, especially 0.005 mol or more.
．． 0.01 mol/1 to 0.03 mol/l is particularly effective.

Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate,
Ammonium potassium tartrate, etc.

Examples of citric acid or its derivatives that are effective in the present invention include citric acid, sodium citrate, and potassium citrate.

The fixer further contains a preservative (e.g., sulfite, bisulfite), pHIt buffer (e.g., acetic acid, boric acid), if desired.
, a pH adjuster (eg, ammonia, sulfuric acid), an image preservation improver (eg, potassium iodide), and a chelating agent. Here, the pH 1lI buffer is 10 to 40 g/j because the pH of the developer is high! - more preferably 18-25g
/42 is used.

The fixer further contains preservatives (e.g. sulfites, bisulfites), pH buffers (e.g. acetic acid, boric acid),
pHtl! It can contain a conditioning agent (eg, ammonia, sulfuric acid), an image preservation improving agent (eg, potassium iodide), and a chelating agent. Here, the pHl1 buffer is 10 to 40 g/l because the pH of the developer is high.

More preferably, about 18 to 25 g/l is used.

The light-sensitive material of the present invention exhibits excellent performance in rapid processing using an automatic processor in which the total processing time is 20 seconds to 60 seconds.

In the rapid development process of the present invention, the temperature and time of development and fixing are each about 25 DEG C. to 50 DEG C. and 25 seconds or less, preferably 30 DEG C. to 40 DEG C. and 6 seconds to 15 seconds.

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed. Here, the water washing process is carried out from 2 to
Water can be saved by using a three-stage countercurrent flushing system. Also, when washing with a small amount of washing water, it is preferable to provide a squeeze roller washing tank.
Part or all of the overflow from the washing bath or stabilizing bath can also be used as a fixing solution as described in JP-A-60-235133. By doing so, the amount of waste liquid is also reduced, which is more preferable.

In addition, the washing water contains anti-mold agents (for example, the compounds described in Horiguchi's "Chemistry of Bacteria and Prevention", Japanese Patent Application Laid-open No. 115154/1983), washing accelerators (such as sulfites), chelating agents, etc. You may do so.

The temperature and time of water washing or stabilization bath by the above method is 0.
The heating time is 5 seconds to 30 seconds at 1 to 50°C, preferably 5 seconds to 20 seconds at 15°C to 40°C.

In the present invention, the developed, fixed, and water-washed photosensitive material is dried using a squeeze roller. Drying at 40°C to 80°C
It takes between 30 seconds and 30 seconds.

In the present invention, the total processing time refers to the time from inserting the leading edge of the film into the insertion slot of the automatic processor, to the developing tank, transition area, fixing tank, transition area, washing tank, and transition area.

This is the total time from passing through the drying section until the leading edge of the film emerges from the drying outlet.

〔Example〕

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

Example 1 Preparation of Emulsion A” Water 1
．． 0! Gelatin 20g Sodium chloride 20g 1,3-dimethylimidazolidine-2-1,000 ions 20 ■ Compound example (1) of the present invention (amounts shown in Table 1) Water 40
0I! .

Nitric acid! 100g water 40
0i Sodium chloride 30.5g Potassium bromide 14.0g Potassium hexachloroiridate (I[I) acid (0,001χ aqueous solution) 154
Ammonium hexabromolodium(1) acid (0,001χ aqueous solution) 1.5d
Solutions 2 and 3 were added simultaneously over 10 minutes while stirring to solution 1, which was maintained at 38°C and pH 4.5.
m core particles were formed. Subsequently, the following liquids 4 and 5 were added over 10 minutes. Additionally, 0.15g of potassium iodide
was added to complete particle formation.

”Wed 40
01 Silver nitrate 100g Water 40
02 Sodium chloride 30.5g Potassium bromide 14.0g The compounds shown in Table 1 were then washed with water by the flocculation method according to a conventional method, and 30g of gelatin was added. pH5.1, pAg
7.5, add 8 parts of sodium thiosulfate and 1 part of chloroauric acid.
Chemical sensitization was carried out at 65 DEG C. by adding 2 .mu.m of 1.3.3a, 7-thitraazaindene as a stabilizer to obtain the optimum sensitivity. Finally, a silver iodochlorobromide cubic grain emulsion containing 80 mol % of silver chloride and having an average grain size of 0.20 μm was obtained. (Coefficient of variation 9%) Furthermore, 100pp of phenoxyethanol is added as a preservative.
- Added.

[Adjustment of Emulsion B] 20% each of sodium chloride and potassium bromide
．． Emulsion A and all of the emulsions except that they were changed to 2g and 35.1g (in the same way, the final average grain size was 0.19 containing 50 mol% silver chloride).
A silver iodochlorobromide cubic grain emulsion of μm size was obtained.

(Preparation of Comparative Emulsion C) Sodium chloride and potassium bromide were added to 9.9% each.
Emulsion A was prepared in exactly the same manner as emulsion A except that the amounts were changed to 9g and 56g, and the final average grain size was 0.1B containing 80 mol% of silver chloride, cr
A silver iodochlorobromide cubic grain emulsion of m was obtained.

1. Add 30 mg of D-5 infrared sensitizing dye to the above emulsion and 1 mol of A
In addition, infrared sensitization was performed. Furthermore, for supersensitization and stabilization, 4,4'-bis(4,6-dinaphthoxypyrimidin-2-ylamino)-stilbenzylsulfonic acid disodium salt and 25-dimethyl-3-allyl-benzothiazole 300 each of iodized salts per mole of silver
■ and 4501g were added.

Further, hydroquinone 100 μ/l, polyethyl acrylate latex at a gelatin binder ratio of 25%, and 2-bis(vinylsulfonylacetamido)ethane as a hardening agent at 86 μ/l were added to the polyester support.
It was coated at a rate of 0 g/rrf and 1.0 g/rrf of gelatin.

On top of this, gelatin 0.6g/m, particle size 2 as a matting agent.
．． 5μm polymethyl methacrylate 60■/n? , an upper layer of a protective layer containing colloidal silica with a particle size of 10 μm, 70 μm/a, added with dodecylbenzenesulfonic acid sodium salt as a coating aid, and a fluorine-containing surfactant having the following structural formula (2), and gelatin 0.4 μm/a. Bo, polyethyl acrylate latex 225■/bo, and the dye of the following structural formula ■■ were applied at 10■/po and 20■/rrl, respectively, and a lower protective layer to which dodecylbenzenesulfonic acid sodium salt was added as a coating aid was simultaneously applied. A sample was prepared.

■ C@F,? SO□N CHtCOOKJt (CBriaSOs- (CHz) asOsK Note that it has a back layer and a back protective layer having the following compositions used in this example.

[Back layer]

Gelatin 2゜Og/sodium dodecylbenzenesulfonate dye ■ Dye ■ Dye ■ 1.3-divinylsulfone-2-propatool (back protective layer) Gelatin polymethyl methacrylate (particle size 4.7 μm) Contains sodium dodecylbenzenesulfonate Futsuso surfactant (■ above) Silicone oil 80■/n (70■/Boro 8511g/I90■/Boro 0■/Bo0, 5g/n (30■/ryf 20■/rr1 211g/rrr 100■/ n( (Evaluation of photographic performance) The obtained sample was exposed to xenon flash light with a luminescence time of 10"sec through an interference filter having a peak at 780n- and a continuous wedge. Sensitometry was performed using FC-71ONH at the temperature and time shown below.

However, the developer and fixer are manufactured by Fuji Photo Film.
We used LD835 and LF30B manufactured by Manufacturer.

Development 38°C 14 seconds fixing 37°C 9.7 seconds Washing 26°C -9 seconds squeeze 2.4 seconds drying 55°C 8.3 seconds Total 43.4 seconds The reciprocal of the exposure that gives a density of 3.0 is the sensitivity, and the relative The sensitivity is shown in Table 1. Also, in the characteristic curve, concentrations of 0.1 and 3.
The slope of the straight line connecting the 0 points is also shown in Table 1 as the gradation.

From Table 1, sample Nt15.6.8.1 which is an embodiment of the present invention
It is understood that 0.12.14 has high contrast and little capri.

Example 2 The same procedure as in Example 1 was carried out except that in emulsion A, the compound (1) in 1 part was changed to the type and amount shown in Table 2, and the compound in Table 1 in 5 parts was changed to the compound in Table 2. The results are shown in Table 2.

Example-3 The improvement in the rapid processing suitability of the present invention is shown below.

The sample of Example 1 was evaluated by reducing the line speed of FC-71ONH and increasing the time from development to drying by 1.7 times for a total of 73.8 seconds. Differences from the results of Example-1 are shown in Table-3.

Table 3 From Table 3, it is understood that the present invention has a greater effect in the case of rapid processing.

Example-4 Compounds in liquid 1 and compounds in liquid 5 in emulsion A are shown in Table-4.
It was added as follows.

Furthermore, the sensitizing dye used when preparing the coating sample was changed to the two shown in Table 4. Furthermore, in the evaluation of photographic properties, the peak of the 1,4 filter was changed as shown in Table 4.
One fruit obtained in exactly the same manner as above is shown in Table 4. Good performance is shown when a sensitizing dye of 1 is used for either scanner light source.

Procedural amendment Z name of invention Silver halide photographic materials and their Development processing method 3゜ person who makes corrections Relationship with the incident

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one photosensitive emulsion layer containing silver halide grains on a support, the silver halide grains contain 30 mol% of silver chloride.
It is a silver halide with a ratio of 10^-^ to silver.
Contains 6 mol% or less of an iridium compound, and contains 10^-^3 mol or less of at least one of iron, rhenium, ruthenium, and osmium compounds relative to silver, and further,
A silver halide photographic material containing at least one compound represented by the following general formulas (1-a), (1-b), and (1-c). (1-a) Z-SO_2・S-M (1-b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1-c) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, Z; alkyl group (number of carbon atoms) 1 to 18), aryl group (6 to 18 carbon atoms) or heterocyclic group Y; aromatic ring (6 to 18 carbon atoms), or atomic group M necessary to form a heterocyclic ring; metal atom, organic cation, n ; integer from 2 to 10 (2) A method for developing a silver halide photographic material according to claim 1, characterized in that processing is carried out in an automatic processor for a total processing time of 20 seconds to 60 seconds.