JPH01205152A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To stabilize a latent image without causing deterioration of photographic sensitivity nor increase of fog by incorporating a specified compd. into a silver halide photographic sensitive material compsn. CONSTITUTION:An amt. of N-aryl-substituted tellurazolium salt compd. expressed by formula I necessary for stabilizing a latent image is incorporated into a silver halide photographic sensitive material compsn. In formula I, each R1-R7 is an H atom., or a photography suitable substituent, individually; X<-> is an anion. Said photography suitable substitution is known in the prior art, and selected basing on several conventional standards. By this constitution, a silver halide photographic sensitive material having superior stability of latent image is obtd. without impairing the developing characteristic of the silver halide emulsion significantly, particularly, generation of fog against the lapse of time or pressure marks is prevented and satisfactory stabilizing effect for latent images is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material that is stabilized so that latent image regression does not occur.

BACKGROUND OF THE INVENTION Photographic imaging by exposure and development of photographic elements is known to suffer from dark shadows due to regression of the latent image. JP-A-55-12581 describes that certain benzothiazolium salt compounds are effective as latent image stabilizers. Also, US Pat. No. 4,423,140 describes that compounds obtained by alkaline hydrolysis of said compounds are active as latent image stabilizers.

(Problems to be Solved by the Invention) However, when the compounds in the above-mentioned prior art are used as latent image stabilizers, they have a major drawback in that they are accompanied by a decrease in sensitivity, which is inconvenient for silver halide photographic materials. Ta.

Therefore, an object of the present invention is to stabilize a latent image without causing a decrease in photographic sensitivity or an increase in fog.

(Means for Solving the Problems) As a result of intensive research, the present inventors have found that N-allyl-substituted telllazo salt compounds exhibit effects as latent image stabilizers in silver halide photographic emulsions. I found it.

The present invention is a silver halide photographic material containing an N-allyl-substituted tellrazolium salt compound in a latent image stabilizing amount. Such compounds can be described by the following general formula (+).

T.

In the formula, R+, Rz, Rs, Ra, Rs, Rh
and R1 individually represent a hydrogen atom or a photocompatible substituent, and X- represents an anion.

The photocompatible substitutions described above are well known and selected based on a variety of conventional criteria.

For example, they control properties of compounds (e.g. solubility in neutral, acidic or alkaline aqueous solutions) and control the solubility of the product and the stability of its complex with silver, such as fog, sensitivity and gradation. The emulsion should have effective and reasonable properties such as to obtain the desired stabilizing effect without significantly deleterious effects on the photographic properties of the emulsion.

The N-allyl substituted tellurium salt compounds of the present invention are compounds which enable very good latent image stability without significant loss in the developability of the silver halide emulsion. In particular, it is superior to conventional latent image stabilizers in that it prevents fogging over time and pressure blur and exhibits a latent image stabilizing effect.

Those skilled in the art will be able to use substitution compounds selected based on known criteria used to adapt compounds to specific needs.

In the compound represented by the above formula (1), X
- is preferably a harsh ion (e.g., chloride, bromide, iodine, thiocyanate, methylsulfate, ethylsulfate, perchlorate, p-toluenesulfonate and other well-known photographically inert or a harmless anion), R,, R,, R
, R4 and R2 are each preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (e.g. methyl group, ethyl group, t-butyl group, n-octyl group, hydroxyethyl group, cyanoethyl group). , benzyl group, etc.),
Substituted or unsubstituted 7-aryl group having 6 to 20 carbon atoms (e.g., phenyl group, p-methoxyphenyl group, p-chlorophenyl group, m-methoxyphenyl group, p-carboxyphenyl group, p-hydroxyphenyl group) ), and R8 and R1 each represent a hydrogen atom, a substituted and unsubstituted alkyl group having 1 to 10 carbon atoms (e.g., methyl group, js
o-propyl group, n-decyl group, sulfoethyl group, hydroxyethyl group, cyanoethyl group, carboxyethyl group, benzyl group, etc.), substituted or unsubstituted aryl groups having 6 to 20 carbon atoms (e.g. phenyl group, naphthyl group, p-carboxyphenyl group, m-acetamidophenyl group, 0
-Hydroxyphenyl group, etc.) Substituted or unsubstituted carbon number 1
~10 alkoxy groups (e.g., methoxy, ethoxy, n-octyloxy, methoxyethoxy, benzyloxy, etc.), halogen atoms (e.g., chlorine, bromine, iodine, fluorine), cyano, COR*, S Oz
R*, N -CORa, -N-3o□R8; n-butyl group,
ethyl group, methyl group, benzyl group, etc.”) -0M (
However, M is a hydrogen atom, an alkali metal (e.g. sodium,
potassium, etc.), ammonium group) substituted or unsubstituted aryl group having 6 to 20 carbon atoms (e.g. phenyl group, 0-methoxyphenyl group, m-bromophenyl group,
p-sulfamoylphenyl group, m-carboxyphenyl group, etc.), alkyl groups having 1 to 10 carbon atoms (e.g. methyl group, 2-cyanoethyl group, 2-ethylhexyl group, benzyl group, 2-hydroxyethyl group) groups), substituted or unsubstituted aryl groups having 6 to 20 carbon atoms (e.g. phenyl groups,
R16 and R1
1 individually represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (e.g., methyl group, n-propyl group, benzyl group, 2-ethylhexyl group, 2-carboxyethyl group, etc.), substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; Substituted aryl group having 6 to 20 carbon atoms (e.g. 0-chlorophenyl, naphthyl group, p-
methoxyphenyl group, m-sulfophenyl group, 0-hydroxyphenyl group, etc.).

Furthermore, R4 and R1 are bonded to each other to form a 5- to 7-membered substituted or unsubstituted carbocyclic ring (e.g., benzene ring, naphthalene ring, cyclohexene ring, cyclopentene ring, etc.) or a heterocyclic ring (e.g., pyridine ring, pyrimidine ring, pyrazine ring). , etc.) can also be formed. As the substituent on the above condensed ring,
Preferably, the substituents shown in R6 and R7 described above are desirable.

Representative examples of the N-allyl-substituted tellrazolium salt compounds of the present invention are listed below.

■ CH2CH=CH2□ ■ CH2CH=CH2 CL-CH=CH2 Ru C1l　□-C1l=CL C11z CH=CH2 CHz CH=CH2 ■ CHz CH=CH2z GHz C=CHz CL CH=CHz CHz CH=CHz C11z CH=Cllz GHz CH=CHz CH3CI CH=CH! ■ CIl□-C=CI.

■ CH.

■ CHt CH=CH-CH3 ■ CL CH=CHz CHz　Cl1=CHz chant C1(zCll=Cal□ 0H! -CH=CI+□ Next, a method for synthesizing representative compounds of the present invention will be described.

The N-allyl-substituted tellrazolium salts used in the present invention are disclosed in European Patent Application No. 0.136,847 and European Patent Application No. 0.138.
, 362. These teachings require first preparing the corresponding protonated tellrazolium salt, converting it to the corresponding tellrazole by treatment with base, and then quaternizing it.

(Synthesis Example) The following synthesis illustrates the synthesis method of Representative Examples 2 and 3 above of N-allyl substituted tellrazolium salts.

Synthesis 1-2 1,1.1-trichloro-2,■ shown below.

The method for synthesizing 4-henzoxatelradinium internal salt will be exemplified.

((1ri.

[Synthesis 1] 6, 1. 1-1-dichloro-6-methoxy-3-methyl-2,1,4-penzoxatellazinium, internal salt (R,□-OCH3R+, l=H)CqH+o C
13NO2Te Molecular weight 398.133-Methoxyacetanilide (20g = 0.12mol) was added to 1.
1. 2. In 2-tetrachloroethane (80d),
Mixed with tellurium tetrachloride (33 g = 0.13 mol),
The reaction was carried out at 120° C. for 4 hours while stirring in an oil bath. At this time, a precipitate formed in the reactor. The reaction mixture was cooled and the precipitate was collected by filtration, yielding 45 g (94% of theory) of pale white crystals. When recrystallized from ethanol, white crystals with a melting point of 245-256°C (began to darken and decomposed at about 210°C) were obtained. The elemental analysis, infrared absorption spectrum, and nuclear magnetic resonance spectrum of this compound were consistent with the expected structural formula.

[Synthesis 2] 1.1.1-)lichloro-3,6,7-)dimethyl-2
,1,4-penzoxatellazinium, internal salt (RIZ= R+ff=CH3) CIOHI! C1z N0Te Molecular weight 396.
073.4-dimethylacetanilide (41g=0.2
5 mol) to 1.1,2.2-tetrachloroethane (8
0-), tellurium tetrachloride (65g = 0.25mol
) and reacted in an oil bath at 120° C. for 3 hours with stirring. At this time, a precipitate was formed in the reactor. The reaction mixture was cooled and the precipitate was collected by filtration, yielding 61 g (62% of theory) of pale white crystals. When recrystallized from hot acetonitrile, the melting point is 300.
White crystals with a temperature above ℃ were obtained. The elemental analysis, infrared absorption spectrum, and nuclear magnetic resonance spectrum of this compound were consistent with the expected structural formula.

Synthesis 3 to 4 The synthesis method of protonated penzotellazolium salt shown below is illustrated.

T+5 ■ [Synthesis 3] 5-methoxy-2-methyl-3H-benzotellazolium chloride (R,□-〇CH3RI3=H) CqH+o cxNOTe Molecular weight 311.24
6, l, 1-trichloro-6-medoxy 3-
Methyl-2,l,4-henzoxatelradinium, internal salt (synthesis 1) (40 g = 0.10 mole) was suspended in methanol (400 Wd) and water (95 m
l) of sodium hydroxide (9,0 g -0,23 mo
l) solution was added. This formed a clear solution, which was placed in a vessel equipped with a stirrer, nitrogen inlet, and condenser. Under a nitrogen atmosphere, add sodium borohydride (20 g ”
'0.53 mol) was gradually added. The reaction solution turned red immediately upon addition of the sodium borohydride, then an orange precipitate formed, and finally a clear solution. The reaction solution was then cooled to about 10°C and concentrated hydrochloric acid (100+d) was added to -10°C. The resulting precipitate was filtered off (48 g of solid was obtained) and the filtrate was cooled to obtain a second crop of 2 g of solid. Dissolve the first harvest and the second harvest in methanol (500 d) containing a small amount of hydrochloric acid, filter out insoluble components,
The target product was crystallized from the filtrate. This results in crystal 15
g (49% of theory). The infrared absorption spectrum and nuclear magnetic resonance spectrum of this compound were consistent with the expected structural formula.

[Synthesis 4] 2.5.6-drimethyl-3H-penzotellazolium chloride CR1tR+3=CHs) C+oH+t C1l NT e Molecular weight 30
9.251.1.1-) Rechloro 3.6.7-) Dimethyl-2,1,4-henzooxatelradinium, internal salt (synthesis 2) (71 g "0.18 no+)" in a stirrer, nitrogen inlet, 2, comprising a cooler and a powder addition port;
It was placed in 600 methanol in the third flask of 1. Sodium hydroxide (14g -0,36no+) was dissolved in water and added. At this time, the solution in which the penzoxatelradinium salt was dispersed became transparent. Sodium borohydride (15g "0.40no+") was then added until the reaction mixture turned pale brown.Heating was used to accelerate the reaction.The reaction mixture was then heated to about 10°C.
and 17 (ld) of concentrated hydrochloric acid was added at once.

A black precipitate formed immediately and was removed by filtration.

The filtrate was concentrated to about 3001R1 to precipitate crystals. This was collected by filtration, and 60 g of crude crystals (100% of the theoretical amount) were collected by filtration.
above) was obtained. The crude crystals contained inorganic salts. The nuclear magnetic resonance spectrum of this compound did not meet expectations regarding its structure.

Synthesis 5-6 The method for synthesizing penzotellurazole is illustrated below.

O [Synthesis 5] 5-methoxy-2-methylbenzotellurazole (R+z
"0CHs R++=H) C*HqNOTe Molecular weight 274.775-
Methoxy-2-methylbenzotellazolium chloride (synthesis 3) (15 g = 0.050 mole) was suspended in water and sodium bicarbonate was added in excess of the stoichiometric requirement to form the free base product. was extracted with diethyl ether. After washing with saturated sodium sulfate solution, the organic phase was dried and evaporated under reduced pressure, yielding 10 g (74% of theory) of a residual oil, which crystallized after standing.
Its melting point was 52°C to 53°C. This compound is
It was identified by its nuclear magnetic resonance spectrum.

[Synthesis 6] 2.5.6-)limethylbenzotellurazole (Rlz=
R++=Cl1s) C+ e H+ + N Te Molecular weight 272.812.5.6-1 Limethylbenzotellazolium chloride (Synthesis 4) (60g = O, 19
mol) was suspended in water and sodium bicarbonate was added in excess of the stoichiometric requirement to obtain the Ti free base product.

This was isolated by extraction with diethyl ether,
Evaporation to dryness yielded 42 g of cream-colored crystals (theoretical amount of 81
%) (melting point 101°C-102°C). This compound was identified by its nuclear magnetic resonance spectrum.

Synthesis 7 to 8 The method for synthesizing the N-allyl-substituted henzotellrazolium salt (Representative Example 2.3 above) shown below is illustrated.

CHI CH=Cllt [Synthesis 7] 5-methoxy-2-methyl-3-(2-propene-1-
yl)-benzotellazolium trifluoromethanesulfonate (R+ z = OCH3R+ 3= H)C+ z
H+ a F z N Oa S T e Molecular weight 4
64.925-Methoxy-2-methylbenzotellazole (synthesis 5) (2.4 g = 8.8 mmol) was dissolved in dichloromethane (60-) and at room temperature.
Under an atmosphere of nitrogen, a solution of 2-propen-1-yl trifluoromethanesulfonate (0,013 mol) in carbon tetrachloride (50 mffi) was added through the addition funnel. The mixture was stirred for an additional 8 hours at 30° C. after the addition was complete, during which time a nitrogen atmosphere was maintained. The generated solid was taken out by filtration, washed with diethyl ether, and recrystallized with a mixed solvent of acetone and diethyl ether. This yielded 2.6 g (36% of theory) of needle-shaped crystals (melting point 144
-145°C) was obtained.

Elemental analysis, infrared absorption spectrum, and nuclear magnetic resonance spectrum of this compound were consistent with what would be expected for its structural formula.

[Synthesis 8] 2, 5. 6-)limethyl-3-(2-propene-1
-yl)-benzotellazolium trifluoromethanesulfonate (R+z=RI3=CH3) C+aH+bFsNOsSTe Molecular weight 462.94
2,5,6-drimethylbenzotellurazole (synthesis 6) in dichloromethane (60 scraps) (2,4 g = 8,8 m
A carbon tetrachloride solution (39+d) of 2-propen-1-yl trifluoromethanesulfonate (1,1 m+wol) was gradually added to the solution of 2-propen-1-yl trifluoromethanesulfonate (1,1 m+wol) (39+d) at room temperature under a nitrogen atmosphere. After the dropwise addition, stirring was continued for 3 hours at 30°C, during which time a precipitate was formed. 2.0 g of solid collected by filtration (
(49% of the theoretical amount) was recrystallized from a mixed solvent of acetone and diethyl ether.

This resulted in 0.7 g of needle-shaped crystals (melting point 216°C-219
°C) was obtained. Elemental analysis, infrared absorption spectrum, and nuclear magnetic resonance spectrum of this compound were consistent with the expected structural formula.

The compound represented by the general formula (1) of the present invention can be used during the formation of silver halide grains, during physical ripening, during chemical ripening, and during the preparation of a coating solution, but is preferably used during the preparation of the coating solution. Furthermore, instead of being added to a silver halide emulsion, it can also be added to a non-light-sensitive layer in a photographic light-sensitive material.

The amount of the compound of the present invention contained in the photographic light-sensitive material is not particularly limited, but the amount of the compound of the present invention is 10-7 to 10-1 per mole of silver halide.
It is preferable to use it in a range of 1 mol.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. Preferred silver halides contain up to 30 mole percent silver iodide. Silver iodobromide or silver iodochlorobromide. Particularly preferred is silver iodobromide containing from 2 mol % to 25 mol % silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof.

The grain size of silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, Chemie et Physi
que Photography Paul Mo
(1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin
.

Photographic Emulsion Che
mistry (Focal Press+1966)
, "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelikmanet al.
, Making and Coating Photo
graphic EIIIulsion.

Focal Press+ 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or 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 PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald 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.

Two or more types of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling PAg and pH during grain formation. For more information, see Photographic Science and Engineering (Photographic Science and Engineering).
5science and Engineering) Volume 6, pp. 159-165 (1962): Journal of Photographic Science (Journalo
f Photographic 5science), 1
2, pp. 242-251 (1964), U.S. Patent No. 3,
655,394 and British Patent No. 1,413,748
It is stated in the number.

A typical monodispersed emulsion is an emulsion in which silver halide grains have an average grain diameter larger than about 0.1 micron, and at least about 95% by weight of the grains are within ±40% of the average grain diameter. be. The average grain diameter is about 0.25 to 2 microns, and at least about 95% by weight or quantity of the silver halide grains are about 2 to 2 microns in average grain diameter.
Emulsions such as those within the range of 0% can be used in the present invention.

A method for making such an emulsion is described in U.S. Pat. No. 3,574,6.
No. 28, No. 3,655,394 and British Patent No. 1
．． No. 413.748. Also, JP-A-48
-8600, 51-39027, 51-830
No. 97, No. 53-137133, No. 54-48521
Monodisperse emulsions such as those described in Japanese Patent Application No. 54-99419, Japanese Patent No. 58-37635, and Japanese Patent No. 58-49'938 can also be preferably used in the present invention.

By using tabular grains in the silver halide photographic emulsion used in the present invention, it is possible to improve sensitivity, including improvement in color sensitization efficiency by enhancing dyes, improve the relationship between sensitivity and graininess, improve sharpness, and improve development progress. , improved covering power, improved crossover, etc.

Here, the tabular silver halide grains are those having a diameter/thickness ratio of 5 or more, such as those exceeding 8 or those having a diameter of 5 or more and 8 or less.

Further, the diameter of a silver halide grain refers to the diameter of a circle having an area equal to the projected area of the grain. In this technology, the diameter of the tabular silver halide grains is 0.3 to 5.0μ, preferably 0.
．． It is 5 to 3.0μ.

Further, the thickness is 0.4μ or less, preferably 0.3μ or less, more preferably 0.2μ or less.

Generally, tabular silver halide grains are tabular with two parallel planes, and therefore the above-mentioned "thickness" is expressed as the distance between the two parallel planes constituting the tabular silver halide grain. .

These tabular silver halide grains are manufactured by Japanese Patent Publication No. 47-11386.
As described in et al., it is also possible to use monodispersed silver halide grains in terms of grain size and/or thickness.

Here, monodispersed tabular silver halide grains mean a dispersion system in which 95% of the grains fall within ±60%, preferably within ±40% of the number average grain size. Here, the number average grain size is the number average diameter of the projected area diameter of silver halide grains.

The proportion of tabular silver halide grains in the emulsion containing tabular silver halide grains used in this technology is preferably 50% or more, and preferably 70% or more of the total projected area. is more preferable, particularly preferably 90% or more.

The halogen composition of the tabular material is preferably silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride, or silver iodochloride. Silver iodochloride is particularly preferred for use in high-sensitivity photosensitive materials. In the case of silver iodochloride, the silver iodide content is usually 40 mol% or less, preferably 20 mol% or less, and more preferably 15 mol% or less. Furthermore, silver chlorobromide and silver bromide are particularly preferred for photosensitive materials for printing.

The tabular grains may have a uniform halogen composition or may consist of two or more phases having different halogen compositions.

For example, when silver iodobromide is used, the silver iodobromide tabular grains may have a layered structure consisting of a plurality of phases each having a different iodide content. Japanese Unexamined Patent Publication 1983
Preferred examples of the halogen composition of tabular silver halide grains and the distribution of halogen within the grains are described in No. 113928 and Japanese Patent Application Laid-open No. 59-99433. - For boat fishing, the desirable relationship between the relative iodide contents of each phase of tabular silver halide grains is determined by the details of the development process (e.g. development (Amount of silver halide solvent contained in the liquid)
It is desirable to select the most suitable one.

Tabular silver halide grains include, for example, junction-type silver halide crystals in which an oxide crystal such as Pbo and a silver halide crystal such as silver chloride are combined, or epitaxially grown silver halide crystals (for example, on silver bromide). crystals grown epitaxially with silver chloride, silver iodobromide, silver iodide, etc., or hexagonal or octahedral silver iodide with silver chloride, silver bromide, silver iodide, etc.
A crystal obtained by epitaxially growing silver chloroiodobromide may also be used. Examples of these are illustrated in U.S. Pat. Nos. 4,435,501 and 4,463,087.

Regarding the formation site of the latent image, the particles may be such that the latent image is mainly formed on the surface of the particle, or the particle may be such that the latent image is mainly formed inside the particle. This can be selected depending on the purpose of the photosensitive material using the tabular silver halide grains and the depth within the grain of a latent image that can be developed by a developer for processing the photosensitive material.

A preferred method of using the tabular silver halide grains of the present technology is Research Disclosure No. 225.
34 (January 1983), same No. 25330 (
(May 1985), which discloses, for example, a method of use based on the relationship between the thickness of tabular grains and optical properties.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,1
No. 46, U.S. Patent No. 3.505.068, U.S. Patent No. 4,44
No. 4,877 and Japanese Unexamined Patent Publication No. 143331/1984. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. These emulsion grains are
U.S. Patent Nos. 4,094,684 and 4,142,90
No. 0, No. 4,459,353, British Patent No. 2,038
, 792, U.S. Patent No. 4,349,622, 4,
No. 395,478, No. 4,433,501, No. 4,4
No. 63,087, No. 3,656,962, No. 3,85
This method is disclosed in Japanese Patent Application Laid-Open No. 59-162540, etc.

Also, mixtures of particles of various crystal forms may be used.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the silver and halide salts are added, and one or more ripening agents can be used. can also be introduced into the reactor along with the addition of halide salts, silver salts or peptizers. As a further variant, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in U.S. Pat. Nos. 2,222,264 and 2,44.
8,534 and 3,320,069. Also, US Pat. No. 3,271.157, 3.
Commonly used thioether ripening agents such as those described in No. 574,628 and No. 3,737,313 can also be used. Alternatively, thione compounds such as those disclosed in JP-A-53-82408 and JP-A-53-144319 can also be used.

The properties of silver halide grains can be controlled by allowing various compounds to be present during the silver halide precipitation formation process. Such compounds may be initially present in the reactor or may be added along with one or more salts in accordance with conventional methods. Between US patents 2.
448. No. 060, No. 2,628.167, No. 3
Copper, iridium,
The properties of silver halide can be modified by the presence of compounds such as lead, bismuth, cadmium, zinc, (chalcogenic compounds such as sulfur, selenium and tellurium), gold and compounds of group II precious metals during the silver halide precipitation process. I can control it.

As described in Japanese Patent Publication No. 58-1410, by Moisar et al., Journal of Photographic Science, Vol. 25, 1977, pp. 19-27, silver halide emulsions contain particles inside the grains during the precipitation formation process. Can be reduced sensitized.

At the time of chemical ripening, the following chemical sensitizers can be used in addition to the compound of the present invention. Chemical sensitization is described by James (
HoJames), The Photographic Inc. Process, 4th edition, Macmillan Publishing, 1977, (T.
H,Ja+mes+ The Theory of t
hePhotographic Process,
4th ed, Macmillan+ 19? ? )
It can be carried out using activated gelatin as described in page 6, page 76, or in Research Disclosure, Vol. 120, April 1974, 12008: Research Disclosure.
Disclosure, Volume 34, June 1975, 134
52, U.S. Patent No. 2,642,361, U.S. Patent No. 3,297
．． No. 446, No. 3,772,031, No. 3,857,
No. 711, No. 3,901,714, No. 4.266,
pAg as described in No. 018 and No. 3,904.415, and British Patent No. 1,315,755.
5-10, pH 5-8, and temperature 30-80°C using sulfur, selenium, tellurium, gold, platinum, palladium, iridium, or a combination of these sensitizers. Chemical sensitization is optimally carried out in the presence of a gold compound and a thiocyanate compound and as described in US Pat. 857
．． No. 711, No. 4,266.018 and No. 4,0
It is carried out in the presence of a sulfur-containing compound described in No. 54.457 or a sulfur-containing compound such as hypo, a thiourea compound, or a rhodanine compound. Chemical sensitization can also be carried out in the presence of chemical sensitization aids. The chemical sensitization aid used is a compound known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical enhancement aid modifiers include U.S. Patent No. 2,131,038;
No. 3,411,914, No. 3,554,757, JP-A-58-126526, and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143. In addition to or in place of chemical sensitization, U.S. Pat.
For example, reduction sensitization can be performed using hydrogen, as described in U.S. Pat. No. 2,518.698 and U.S. Pat. 743
．． No. 182 and No. 2,743,183 using reducing agents such as stannous chloride, thiourea dioxide, polyamines and 8) can be reduced sensitized by treatment. Also, U.S. Patent No. 3
．． Color sensitization can also be improved by the chemical sensitization method described in No. 917,485 and No. 3,966.476.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine Nuclei, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbic acid nucleus can be applied.

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 enhancing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, a nitrogen-containing heteroartic ring. Nuclear group substituted aminostyrylbene compounds (e.g., U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635,72
No. 1), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743.510), cadmium salts, azaindene compounds, etc., U.S. Pat. No. 3,615. No. 613, 3,6
No. 15.641, No. 3.617,295, No. 3.63
The combinations described in No. 5,721 are particularly useful.

Spectral sensitization of the emulsion of the invention can be carried out at any stage of emulsion preparation.

Spectral sensitizing dyes are generally added to chemically sensitized emulsions before coating. U.S. Patent No. 4. No. 425, No. 426, etc., discloses a method of adding it to an emulsion before or during chemical sensitization. In addition, there is a method in which a spectral sensitizing dye is added to the emulsion before the formation of silver halide grains is completed.
U.S. Pat. No. 2,735.766, U.S. Pat. No. 3,628.
No. 960, US Pat. No. 4,183,756, and US Pat. No. 4,225,666.

In particular, U.S. Pat.
．． No. 666 discloses that by adding a spectral sensitizing dye to the emulsion after the formation of stable nuclei for silver halide grain formation, advantages such as increased photographic sensitivity and enhanced adsorption of the spectral sensitizing dye by the silver halide grains are achieved. It is disclosed that

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

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, and quaternary ammonium for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

For example, U.S. Patent No. 2,400.532, U.S. Pat.
．． No. 549, No. 2,716.062, No. 3.617,
No. 280, No. 3.772.021, No. 3,808.0
No. 03, British Patent No. 1,488°991 can be used.

The silver halide photographic emulsion used in this technology is used to prevent fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance.
Various compounds can be included. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazole, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthion;
Azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1°3.3a
,? ), pentaazaindenes, etc.; many compounds known as anti-capri agents or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. .

In addition to the above means, JP-A No. 60-136,736, JP-A No. 60-222,843, JP-A No. 61-3゜134, JP-A No. 6
No. 1-3,135, No. 61-3゜136, No. 61-3
, No. 137, the performance can be further improved.

The present invention can be applied to all photographic materials that use silver halide, such as black and white photographic materials, color photographic materials,
Further, the method includes negative or positive photosensitive materials, diffusion transfer method, heat development method, etc., and it is applicable to all of these methods.

When applied to color sensitive materials, various couplers can be used.

The term "color coupler" as used herein refers to a compound capable of producing a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer.

Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. These cyans that can be used in the present invention,
Specific examples of magenta and yellow couplers are available from Research.
Disclosure 17643 (December 1978)
It is described in Section 1-D and the patent cited in 18717 (November 1979).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized, and whose coupling active position is substituted with a coupling-off group rather than a square coupler with a hydrogen atom. A two-equivalent coupler is preferable because the amount of coated silver can be reduced. Further, a coupler in which the coloring dye has appropriate diffusivity, a colorless coupler, a DIR coupler that releases a development inhibitor or a coupler that releases a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,40
No. 7,210, No. 2,875.057 and No. 3
, No. 265, 506, etc. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat.
No. 3,933,501 and No. 4,022゜62
0, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,
No. 401,752, No. 4,326', No. 024, Research Disclosure 18053 (April 1979)
), British Patent No. 1,425.020, German Published Application No. 2,219,917, German Patent Application No. 2,261.361,
2.329.587 and 2,433,81
A representative example of this is the nitrogen atom separation type yellow coupler described in No. 2. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group in terms of the hue and color density of the coloring dye. Same No. 2゜34
3.703, 2,600,788, 2,9
No. 08.573, No. 3,062,653, No. 3,
No. 152,896 and No. 3936.015, etc. As the leaving group for the two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the nitrogen atom leaving group described in U.S. Pat.
Particularly preferred are the arylthio groups described in No. 1,897.

Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
061,432, preferably pyrazotllll (5,1-c)(1,2,4)) as described in U.S. Pat. No. 3,725.067
Liazoles, Research Disclosure, 242
20 (June 1984) and JP-A-60-3355
Pyrazolotetrazoles and research described in No. 2
Disclosure, 24230 (June 1984)
and pyrazolopyrazoles described in JP-A-60-43659. U.S. Patent No. 4,500.63 in terms of low yellow side absorption of coloring dye and light fastness.
The imidazo(1,2-b)pyrazoles described in US Pat. .

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. No. 2,474°293 and preferably U.S. Pat.
, No. 212, No. 4゜146.396, No. 4.22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8,233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Pat. No. 2,369.929 and U.S. Pat.
No. 01,171, No. 2. 772. No. 162, No. 2,895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat.
72,002, a phenolic cyan coupler having an alkyl group other than an ethyl group at the meta-position of the phenolic nucleus; US Pat. No. 2.772.162;
No. 758,308, No. 4.126,396, No. 4
, 334,011, 4,327°173, West German Patent Publication No. 3,329.729 and European Patent No. 12
1.365, and U.S. Pat. No. 3,446.
, No. 622, No. 4.333,999, No. 4,45
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in Japanese Patent No. 1,559 and No. 4,427.767. Japanese Patent Publication No. 60-237448, No. 59-26427
Cyan couplers in which the 5-position of naphthol is substituted with a sulfonamide group, amide group, etc., described in No. 7 and No. 59-268135, also have excellent fastness of colored images.
It can be preferably used in the present invention.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color negative photosensitive materials for shadows, as disclosed in U.S. Pat. No. 4,163.670 and Tokuko Showa 5
7-39413, or the yellow-colored magenta couplers described in U.S. Pat. No. 4,004,929, U.S. Pat.
138. No. 258 and British Patent No. 1,146,3
Typical examples include the magenta-colored cyan coupler described in No. 68.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such blur couplers include magenta couplers in U.S. Pat. No. 4,366.237 and British Patent No. 2,125,570.
Also, European Patent No. 96゜570 and West German Application No. 3
, 234,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451.82.
No. 0 and No. 4,080°211. Specific examples of polymerized magenta couplers include British Patent No. 2,102,173 and U.S. Patent No. 4,367.282.
No. 61-232455 and 62-5426
03596.

The various couplers used in the present invention can be used in combination in two or more layers in the same photosensitive layer, or in two or more different layers using the same compound, in order to satisfy the characteristics required for the photosensitive material. It can also be introduced into

Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.1 mole for yellow couplers.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

The present invention may also include a coupler that releases a development inhibitor upon development, a so-called DIR coupler.

As a DIR coupler, for example, U.S. Patent Tube 3°227
．． Those that release heterocyclic mercapto-based development inhibitors as described in Japanese Patent Publication No. 554, etc.; Those that release benzotriazole derivatives as development inhibitors described in Japanese Patent Publication No. 58-9942, etc.; those described in Japanese Patent Publication No. 51-16141, etc. The so-called colorless DIR coupler described in JP-A No. 52-90932 releases a nitrogen-containing heterocyclic development inhibitor with decomposition of methylol after separation; US Patent No. 4. 248. 9
62 and JP-A No. 57-56837, which releases a development inhibitor with an intramolecular nucleophilic reaction after separation. No. 188035, No. 58-98728,
Those that release a development inhibitor by electron transfer via a conjugated system after separation, as described in No. 58-209736, No. 58-209737, No. 58-209738, No. 58-209739, and No. 58-209740; JP-A-57-151944 and JP-A-58-217932 which release a diffusible development inhibitor whose development-inhibiting ability is deactivated in the developer; JP-A-60-182438 and JP-A-60-184248 Examples include those which release the reactive compounds described in No. 3, etc., and generate a development inhibitor or deactivate the development inhibitor by reaction in the film during development.

Among the above-mentioned DIR couplers, those that are more preferable in combination with the present invention are the developer-deactivated type represented by JP-A-57-151944; U.S. Patent No. 4,248,96
No. 2 and JP-A No. 57-154234 and a timing type exemplified by JP-A No. 60-184248, and particularly preferred among them are JP-A Nos. 57-151944 and JP-A No. 5B. -217932, JP-A No. 60-218644, JP-A-60-2225156, and JP-A-60-233650, etc., and developer-deactivated DIR couplers described in JP-A-60-184248, etc. It is a DIR coupler.

In the light-sensitive material of the present invention, a compound that releases a nucleating agent, a development accelerator, or a precursor thereof (hereinafter referred to as "development accelerator, etc.") in an image form during development can be used. A typical example of such a compound is the British Patent Co., Ltd.
97,140 and 2.131,188, and is a coupler that releases a development accelerator etc. by a coupling reaction with an oxidized product of an aromatic primary amine developer, that is, a DAR coupler. .

It is preferable that the development accelerator released from the DAR coupler has an adsorption group for silver halide.
No. 638 and No. 59-170840. Particularly preferred are DAR couplers that produce N-acyl-substituted hydrazines having a monocyclic or fused heterocycle as an adsorption group, which is detached from the coupling active site of the photographic coupler with a sulfur atom or a nitrogen atom. Specific examples of couplers are described in JP-A-60-128446.

Compounds described in JP-A-60-37556 which have a development accelerator moiety in the coupler residue, or JP-A-60-107029 which releases a development accelerator etc. through an oxidation-reduction reaction with a developing agent. The compounds described in can also be used in the photosensitive material of the present invention.

DAR couplers are preferably incorporated into the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention, and
It is preferable to use substantially non-photosensitive silver halide grains in at least one of the photographic constituent layers as described in Japanese Patent Application Laid-open No. 9-172640 or JP-A-60-128429.

The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamide phenols as color-fogging inhibitors or color-mixing inhibitors. It may also contain derivatives and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Known anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Representative examples include hindered phenols, mainly bisphenols, gallic i2 derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. It is mentioned as. Metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer. For example, U.S. Patent No. 3
, 553.794, 4,236.013, Japanese Patent Publication No. 51-6540, European Patent No. 57,160, etc., benzotriazoles substituted with aryl groups, U.S. Patent No. 4,450 , No. 229 and No. 4
．． 195.999, U.S. Pat. No. 3,705,805 and U.S. Pat. No. 3,707.37
Cinnamic acid esters described in No. 5, U.S. Patent No. 3,2
15.530 and the benzophenones described in British Patent No. 1°321.355, U.S. Patent No. 3,761
Polymer compounds having ultraviolet absorbing residues such as those described in , No. 272 and No. 4,431.726 can be used.

U.S. Patent Nos. 3,499,762 and 3.700
．． The ultraviolet absorbing optical brighteners described in No. 455 may also be used. Typical examples of ultraviolet absorbers are described in Research Disclosure, 24239 (June 1984).

The photosensitive material of the present invention can be used as a coating aid, to prevent static electricity, to improve slippage,
One or more surfactants may be included for various purposes such as emulsification dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, contrast enhancement, and sensitization).

The photographic material prepared using the present invention may contain water-soluble dyes in the hydrophilic colloid layer as filter dyes or for various purposes such as anti-irradiation or anti-halation.

As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

In the photosensitive material of the present invention, the method for introducing a lipophilic compound such as a photographic coupler into the hydrophilic organic colloid layer is as follows:
Various methods can be used such as oil-in-water dispersion method, latex dispersion method, solid dispersion method, and alkali dispersion method, and the preferred method can be selected as appropriate depending on the chemical structure and physicochemical properties of the compound to be introduced. can.

The photographic coupler of the present invention can be added to one or more silver halide emulsion layers, preferably according to the latex dispersion method, more preferably according to the oil-in-water dispersion method. When following the oil-in-water dispersion method, the boiling point is 175 at normal pressure.
In a high boiling point organic solvent (hereinafter referred to as "oil") above ℃,
Alternatively, if necessary, it is dissolved in combination with a low boiling point auxiliary solvent, and finely dispersed in water or an aqueous binder solution such as gelatin, preferably in the presence of a surfactant.

A typical example of a high boiling point organic solvent is U.S. Patent No. 2.272.1
No. 91, No. 2,322,027, JP-A-54-317
No. 28, and No. 54-IL8246, etc. (all referred to as phthalates), JP-A No. 1520-1983, No. 55-36869
, U.S. Patent No. 3,676.137, U.S. Patent No. 4,217,
No. 410, No. 4,278,757, No. 4,326
, 022, and 4,353,979 (hereinafter referred to as phosphate or phosphonate), U.S. Patent No. 4,
No. 080,209 (benzoate), U.S. Patent No. 2,5
33.514, same No. 4. No. 106゜940, No. 4,127,413, etc. (all referred to as amide), JP-A-51-27922, JP-A No. 53-13414, JP-A No. 53-13
0028, and US Pat.
6037, 51-27921 51-149028,
51-149028, 52-34715, 53-
1526, 53-15127, 54-58027,
No. 56-64333, No. 56-114940, U.S. Patent No. 3,748,141, No. 3.779.765,
Same No. 4. 004. No. 928, same No. 4,430,42
No. 1, No. 4,430,422, etc. (all of which are aliphatic canebonic acid esters), ``JP-A-58-105147
No. (Aniline), JP-A-50-62632, JP-A-54-9
9432, and U.S. Patent No. 3,912.515 (hereinafter referred to as "hydrocarbon"), and other JP-A-53-146
622, U.S. Patent No. 3,689,271, U.S. Patent No. 3,7
No. 00.454, No. 3,764.336, No. 3.
No. 765,897, No. 4.075,022, No. 4
．． 239□ No. 851, West German Application Publication Tube 2.410.9
Examples include those described in No. 14. Two or more types of high boiling point organic solvents may be used in combination. For example, an example of a combination of phthalate and phosphate is shown in US Patent No. 4.327.1.
It is described in No. 75.

Also, Japanese Patent Publication No. 51-59943, Japanese Patent Publication No. 51-3985
No. 3, No. 56-126830, U.S. Patent No. 2.772,
Dispersion methods can also be used with the polymers described in, for example, No. 163 and No. 4.201.589.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sodium alginate, starch derivatives, etc. iy, conductor; various synthetic hydrophilic materials such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Polymeric substances can be used.

As for gelatin, in addition to general-purpose lime-processed gelatin, acid-processed gelatin and the journal of the Japanese Society of Scientific Photography (Bull).

Soc, Sci, Phot, Japan), N1
16, p. 30 (1966) may be used, or a gelatin hydrolyzate may be used.

In the photographic material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glitaraldehyde, etc.), and N-methylol compounds (dimethylol urea, etc.). Active halogen compound (2,4-dichloro-6-hydroxy-1,3
゜5-triazine, etc.) and active vinyl compounds (1,
3-bisvinylsulfonyl-2-propatol, 1.2
-Bisvinylsulfonylacetamidoethane or a vinyl polymer having a vinylsulfonyl group in the side chain) are preferred because they quickly harden hydrophilic colloids such as gelatin and give stable photographic properties. N-carbamoylpyridinium salts and haloamidinium salts also harden. It's fast and excellent.

The invention is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as necessary. A preferred layer arrangement is in the order of red sensitivity, green sensitivity and blue sensitivity from the support side. Further, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity, or a three-layer structure may be used to further improve graininess. Furthermore, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. It is also possible to have a structure in which emulsion layers of different color sensitivity are inserted between emulsion layers of the same color sensitivity.

Further, in a multilayer multicolor photographic material, a filter layer that absorbs light of a specific wavelength or a layer for preventing halation may be provided. Although the above-mentioned organic dyes can be used as these light-absorbing debris, colloidal silver particles can also be used. A red-sensitive emulsion layer in which a non-light-sensitive fine-grain silver halide emulsion may be used in one or more non-light-sensitive layers of a multilayer multicolor photographic material for the purpose of improving sensitivity by reflecting light or trapping development-inhibiting substances. Generally, a cyan-forming coupler is contained in the emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer, but different combinations may be used depending on the case. For example, it may be used in combination with an infrared-sensitive layer for pseudo-color photography or semiconductor laser exposure.

Furthermore, as disclosed in Japanese Patent Publication No. 33-3481, unnatural color appearance can be removed by incorporating a coupler that develops a color other than a coupler that develops a complementary color to the color sensitivity wavelength of each layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal, which is commonly used in photographic light-sensitive materials. Ru. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments.

It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsion layers, etc. Before or after the undercoat treatment, the surface of the support is treated with:
Glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. may also be applied.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used. U.S. Patent No. 2,681,294 as appropriate
Multiple layers may be applied simultaneously by coating methods such as those described in US Pat.

Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-burning flash pulp are common.

Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, linear or planar microshutter arrays using phosphor screens (CRT, etc.), liquid crystals (LCD), and lanthanum-doped lead titanium zirconate (PLZT) emitted from phosphors excited by electron beams, etc. It is also possible to use an exposure means that combines a light source. If necessary, the spectral distribution used for exposure can be adjusted by eight rounds using a color filter.

Example 1 Silver iodobromide emulsion with a monodisperse double structure sensitized with gold and sulfur with sodium thiosulfate, chloroauric acid, and potassium thiocyanate (6 mol %, average grain size 0.6 μ, core-shell) After 12 pieces (1:1 ratio) were added to each compound shown in Table 1, a stabilizer (4-hydroxy-6-methyl-1°3.3a, 7-titrazaindene) was applied. Auxiliary agent (sodium dodecylbenzenesulfonate), hardener (2,4-dichloro-6-hydroxy-3-
Triazine Na salt> was added and coated on a triacetyl cellulose film support together with a surface protective layer by a coextrusion method, and dried to obtain Samples 1 to 12.

These samples were exposed to light (1/100 seconds) through an optical wedge using a sensitometer, developed with a Kodasoku D-76 developer at 20 DEG C. for 7 minutes, and subjected to conventional fixing and water washing treatments.

When developed immediately after exposure and after exposure at 40°C relative humidity (R
, H, ) 75% atmosphere for 4 days and then developed, the results are shown in Table 1.

The photographic sensitivity is expressed as a relative ratio of the reciprocal of the exposure amount required to obtain an optical density of fog+0.2, and the value of sample 1 developed immediately after exposure was taken as 100.

As is clear from Table 1, the comparative compounds have a strong effect of preventing regression of latent images and also have a sensitizing effect, but they have the major drawback of significantly increasing fog when stored at high temperature and high humidity. However, on the other hand, the compound of the present invention is a very useful compound that has the great advantage of suppressing fogging under high temperature and high humidity, although it has a slightly lower sensitivity and is slightly less effective in preventing latent image regression. It can be said.

Table 1 Comparative Compounds fat CH, -CH=CH, Bre 〃(b) CHz ・CH=CHz Br" (Compound examples (1) and (8) of Japanese Patent Publication No. 12581/1981)
) Example 2 After preparing eight emulsions identical to those used in Example 1, the compounds shown in Table 2 were added to each, and yellow coupler (late *1 and *2 were used in a 1:1 ratio). ) A coupler dispersant (tricresyl phosphate) and the same additives as in Example 1 were added, and the mixture was coated on a triacetylcellulose film support together with a gelatin protective layer and dried to obtain Samples 13 to 20.

These samples were exposed to light using an optical sensitometer and subjected to the color development process described below.

When developed immediately after exposure and after exposure at 40°C, 75% R,
Table 2 shows the results when the samples were stored in a H. atmosphere for 4 days and then developed. As in Example 1, the relative sensitivity was set to 100 for sample 13 developed immediately after exposure.

Further, after uniform exposure for 104 seconds, the emulsion surface of each sample was scratched at a speed of 5 cc+ per second while applying a load of 4 g using a sapphire needle with a radius of about 30 μm at the tip. Subsequently, the following color development treatment was performed at 38°C. The density of scratches caused by scratching with a needle was measured using a microdensitometer, and the difference in density from the area that was not scratched was determined. The results are also listed in Table 2.

As is clear from Table 2, in color development processing, the comparative compounds have a better latent image regression prevention effect than the compounds of the present invention, but are accompanied by a significant increase in pressure capri due to needle scratching. on the other hand,
The compound of the present invention has the advantage that it has an effect of preventing latent image regression and does not increase pressure fog.

Table 2 (*2) Yellow coupler cH, Cl1ff (color development process) Color development 2 minutes 45 seconds Bleached white 6 minutes 30 seconds Water washing 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water Wash 3 minutes 15 seconds Safe, constant, 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Left: Go ■1 Sputum diethylenetriaminepentaacetic acid 1.0g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0g potassium bromide
1.4g potassium iodide 1.3
■Hydroxylamine sulfate 2.4g4~(N
-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5g Add water to pH 1.01 10.0 Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g ethylenediaminetetraacetic acid diester Lium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate
Add 10.0g water
1.0j! pH 6.0 Constantly removed ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0mf Sodium bisulfite 4.6g Add water
1.01 pH 6.6, add 0.3 g of water and 2.0 d polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) to pH 6.6 1.01 Example 3 Sulfur with triethylthiourea Sensitized monodisperse silver chlorobromide emulsion (silver bromide 70 mol%, average grain size 0.5 μm)
) for 4 minutes, then add the compounds shown in Table 2,
Spectral sensitizer (*1) described later, magenta coupler (described later)
*2>, coupler dispersant (tri(n-octyl phosphate)), anti-fading agent (*3 and *4 used in l:1 ratio), anti-capri agent (1-(3-(,3-methylureido)) ) Phenyl-5-mercaptotetrazole), stabilizer (4-hydroxy-6-methyl-1,3,3a.

7-chitrazaindene), a coating aid (sodium dodecylbenzenesulfonate), and a hardening agent (2°4-dichloro-6-hydroxy-5-1-riazine Na salt),
It was coated together with a gelatin protective layer on a paper support laminated on both sides with polyethylene and dried to obtain samples 21 to 24.

Exposure through the master model with a yellow filter (1/10
seconds), and the following color development process was performed. Table 2 shows the results when the samples were treated immediately after exposure and after the samples were stored at 25° C. for 3 days. The relative sensitivity was determined in the same manner as in Example 1, and the value immediately after exposure of Sample 21 was set to 100.

(*1) Spectral sensitizer (*2) Magenta coupler l (*3) Antifading agent 0■ (*4) Antifading agent treatment process Temperature Time Developer solution 33°C 3.5 minutes Bleach-fix solution 33°C 1. Wash with water for 5 minutes 28-35℃ 3.0 minutes Nitrilotriacetic acid 3
Na 2.0g benzyl alcohol
15rnl diethylene glycol
10-NazSO,l 2. O
gKBr O, 5g hydroxylamine sulfate 3.0g 4-amino-3-
Methyl-N-ethyl-N-(β-di(methanesulfonamido)ethyl)-1-phenylenediamine sulfate 5. OgN az
COs (monohydrate) Add 30g water to make 1 liter <pH 10,1) 1. Ammonium thiosulfate (54wt%) 1501111
! NatSOx 15g
NHa (Fe (EDTA)) 5
5 gEDTA・2Na 4g
Add water to make 1 liter (pH 6,9) As is clear from Table 3, the addition of the compound of the present invention suppresses latent image fading, although the sensitivity slightly decreases.

Table 3 Patent applicant Fuji Photo Film Co., Ltd. Showa ≦ 3 years
month to day

Claims (2)

[Claims] (1) A silver halide photographic material containing a compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the formula, R_1, R_2, R_3, R_4, R_5, R_
6 and R_7 individually represent a hydrogen atom or a photocompatible substituent, and X^- represents an anion. (2) In the compound represented by general formula (I), R_
1, R_2, R_3, R_4 and R_5 individually represent a hydrogen atom, an alkyl group, an aryl group, and R_6 and R_7 individually represent a hydrogen atom, an alkyl group, an aryl group,
Alkoxy group, halogen atom, cyano group, -COR_6
, -SO_2R_8, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, R_8 represents an alkyl group, -OM, an aryl group, ▲ there are numerical formulas, chemical formulas, tables, etc. ▼, R_9 represents a hydrogen atom, an alkyl group, an aryl group, R_1_0, R_1_
1 individually represents a hydrogen atom, an alkyl group, or an aryl group, and M represents a hydrogen atom, an alkali metal, or an ammonium group. Moreover, R_6 and R_7 can also be combined with each other to form a 5- to 7-membered carbon ring or heterocycle. The silver halide photographic material according to claim 1, wherein X^- represents an anion.