JPS62133448A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To promote the progress of development by forming a photographic emulsion layer made of a photosensitive silver halide emulsion composed of silver halide grains containing silver iodide, and incorporating a nonphotosensitive emulsion containing fine nonfogged silver halide grains having adsorbed a specified heterocyclic mercapto compound in the photographic emulsion layer or another nonphotosensitive photographic constituent layer. CONSTITUTION:The photographic emulsion layer is made of the photosensitive silver halide emulsion composed of silver halide grains containing silver iodide, and the photographic emulsion layer or the other photographic constituent layer contains the nonphotosensitive emulsion made of the fine nonblurred silver halide grains having adsorbed a specified heterocyclic mercapto compound represented by formula I in which X is -O-, -NH-, or -S-; each of R1-R4 is H or a substituent, and at least one of them is an optionally substituted <=13 C alkyl or aryl group combined directly or through a divalent bonding group. Said compound to be used in typified by formula I-1.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide photographic material (hereinafter referred to as a "photosensitive material"), and particularly relates to graininess, gradation, and development progress. This invention relates to a high-sensitivity photographic material with improved f'.

[Conventional technology]

Generally, in silver halide photographic light-sensitive materials, iodine-containing f? Increasing t is desirable for higher sensitivity. This is thought to be mainly due to the fact that the sensitive wavelength range becomes longer and the absorption rate of blue light increases. - Increasing the blade height with iodine also has the disadvantage of slowing down the progress of development. At this time, with a normal developer, the graininess is improved, but with a developer containing a dialdehyde hardener, the graininess and processing temperature dependence deteriorate due to contagious development. British patent 16113 Hiroshi and German patent for delays in development due to high iodine content! One polyoxyethylene chain' (l-
It is known that the addition of a nonionic surfactant to reduce graininess is effective, but it can be used to reduce graininess and to prevent problems with developing solutions containing dialdehyde hardeners, as disclosed in JP-A-6O-7T7-3. Pressure effects in the processing solution, called roller marks, are likely to occur. In addition, various techniques described below have been disclosed in order to suppress the contagious development that occurs with this developer.

Example t % Kosho j 2-J I t 9 /, RD -
/ If uJ/, ≠ Nitron salt described on page 34c (/,
4cmdiphenyl-J, j-endoani
lin-41.

j-dihydro-/, 2, 4cm triazo
Je or ijJ, j, t-1riphenyl
-koI 3*' 16-tetrazabicyc
Yellow fog prevention effect by adding lo(-2+ / + / ] hex-1en), Men ions other than nitro/ as described in JP-A-6O-1r73λ, tO-//7ko≠01 patent application Sho-5r-23torr Effect of improving processing temperature dependence by addition of triazolium compound, U.S. Pat.
Antifogging effect of mercapto compounds and benzotriazole compounds described in 6o, U.S. Patent λ/31031,
Unexamined Japanese Patent Application Shoyo Hiro-4/j/ri, U.S. Patent No. 323ot t
o, JP-A-10-17-/Tata-17 describes the anti-fogging effect of blue light spectral sensitizing dyes in color developers, and is limited to tabular grains; ≠26, same j
It is known that some blue light spectral sensitizing dyes have an effect of improving the processing temperature dependence as described in the literature. However, these methods have problems such as desensitization and pressure sensitivity.

For example, menion triazolium compounds have a strong process-dependent improvement effect, but they also have a large desensitizing effect (the desensitizing effect is also very large in a developer without dialdehyde), and mercapto adducts have a large desensitizing effect. Blue light spectral sensitizing dyes have problems such as increasing pressure blackening because the desensitization effect is much greater than the treatment-dependent improvement effect.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a high-sensitivity silver halide photographic material containing silver iodide and having improved development progress.

Another object of the present invention is to provide a silver halide photographic light-sensitive material containing silver iodide that exhibits less contagious developability and good graininess when processed with a developer containing a dialdehyde hardener. It is.

(Means for Solving the Problems) The above aspects of the present invention provide a silver halide photographic material having at least one silver halide photographic emulsion layer on at least one side of a support. The layer consists of a sensitive, photosensitive silver halide emulsion (hereinafter referred to as "first emulsion") containing silver iodide and consisting of subsilver halide grains, and the photographic emulsion layer or other constituent layers contain the following general Heterocyclic mercapto adduct represented by formula (I) is adsorbed.
This could be achieved by a silver halide photographic material characterized by containing a substantially non-light-sensitive silver halide fine grain emulsion (hereinafter referred to as the "λth emulsion").

General formula (I) In the formula, X represents 10-1-N)I- or -8-. R
1, R2, ['L3 and R4 represent a hydrogen atom or a group capable of substituting this, and at least one of R2, R3 and R4 is directly substituted or not substituted via a divalent linking group It is a substituted alkyl group or aryl group having 13 or less carbon atoms.

Next, general formula +1) will be explained in detail.

X represents 10-1-NH- or -S-.

Particularly preferably, X is -N)t-.

R1, % R2, R3 and R4 may each be Kltl- or different, and each represents a hydrogen atom or a group capable of being substituted with n. Preferred R1, R2, Ra and R4 are hydrogen atoms and halogen atoms (F, α, Br, etc.)
Substituted friends are unsubstituted alkyl groups (methyl, trifluoromethyl, ethyl, n-octyl, benzyl, etc.), and substituted are unsubstituted aryl groups (phenyl, phenyl, etc.).
p-chlorophenyl group, etc.), substituted or unsubstituted alkoxy groups, aryloxy groups (methoxy group, n-hexyloxy group, phenoxy group, n-octyloxy group,
2-ethylhexyloxy group, etc.), sulfonyl group (methanesulfonyl group, p-toluenesulfonyl group, etc.),
Sulfonamide group (n-octane sulfonamide group, p
-toluenesulfonamide group, etc.), sulfamoyl group (diethylsulfamoyl group, -chlorophenylsulfamoyl group, etc.), carbamoyl group (n-butylcarbamoyl group, ≠-cyanophenylcarbamoyl group, no-ethylhexylcarbamoyl group, etc.). ), amide group (n-
hexaneamide group, n-decaneamide group, benzamide group, no-ethylhexylamino group, etc.), ureido group (3-butylureido group, morpholinocarbonylamino group, etc.), aryl or rykoxycarponylamino group (ethoxycarbonylamino group, 180 -butylcarbonylamino group, phenoxycarbonylamino group)
, aryl or alkoxycarbonyl group (ethoxycarbonyl group, phenoxycarbonyl group, etc.), aryl or alkylaminocarbonyloxy (phenylaminocarbonyloxy group, 1so-y" thylaminocarbonyloxy group, etc.), cyano group, alkyl or fc These are arylthio groups (n-octylthio group, λ-methoxycarbonylphenylthio group, etc.).The carbon number of these substitutable groups is preferably 73 or less, particularly preferably // or less.

Here, at least one of R1, R2, R3, and R4 is a substituted or unsubstituted alkyl group or aryl group having 13 or less carbon atoms directly or via a divalent linking group. Preferably carbon number is 1. /l is a substituted or unsubstituted alkyl group. Particularly preferred divalent linking groups are amide bonds, sulfonamide bonds, ureido bonds, ether bonds, thioether bonds, sulfonyl bonds,
They are carbonyl bond, urethane bond, carbamoyl bond, and sulfamoyl bond.

Xl represents a hydrogen atom or a cation 7 (Na+, K+, Nt (4+, etc.)) for making the molecule neutral.

Next, typical examples of compounds used in the present invention will be listed, but the present invention is not limited to the following compounds.

(n)L; B H17[NI(SU 230
H(n)C3H70CT(s) The adduct of the general formula (I) used in the present invention is
J, Van A11an, B, D, Deacon,
Org, 5ynth,.

■, j6ri (luri63), J, Bunner Be
r.

ヱ, ≠ 6yo (/174), L, B, 5ebrel
,C.

E, Boord, Am, Chem, Soc,
, 4'j, λ3ri0(I5', , 23) or the typical synthesis examples shown below.

Synthesis Example 1 Synthesis method of compound 10 j-amino-λ-mercaptobe/shiimidazole 1.3
9 was dissolved in pyridine, and 6.7 t of hexanoyl chloride was added dropwise under water cooling. After stirring for 1 hour in the stand, it was added to ice water toorttt to precipitate, and the next crystal was collected from F and recrystallized from a mixed solvent of ethanol and water. Yield 7. If Melting point 26λ~λ6 0C (dec) Synthesis example 2 Compound 14 @-prepared method-amino-λ-merkabutobe/shiimidazole z,'
Jy was dissolved in pyridine lλomtyc, and lauroyl chloride lf was added dropwise under water cooling. After stirring at room temperature for 3 hours, the precipitated crystals were added to an ice water zoont and collected, and recrystallized from a mixed solvent of methanol and water.

Yield 1k10.2f Melting point -66~λotsu 7°C1dec
) Synthesis Example 3 Synthesis method of compound 18 j-mercaptobenzimidazole z
, tt to 0rnl of DMF A, 6.3ml of triethylamine under water cooling, and then ethyl chloroformate≠, 3I
d was added dropwise.

After stirring for 30 minutes under water cooling, heptylamine! .

Ko? Add it dropwise and stir for a while. The reaction solution was added to a solution of 3 t of sodium bicarbonate and 200 ml of water, and the resulting precipitate was recrystallized from ethyl acetate. Yield 3. l Melting point 230-23λ0C Synthesis Example 4 Compound 22 - p-octyloxy〇-phenylenediamine Hiroshi, 7?
was added to an ethanol solution of 7.2 tons of potassium hydroxide, and 6 tons of carbon disulfide was added dropwise at 0c.

After further heating and refluxing for φ hour, 3 parts of concentrated hydrochloric acid were added to ice water/jtO- while stirring. The generated precipitate was collected in a furnace and recrystallized from acetonitrile.

Yield 3.7f Melting point CoJOA-Co3λ0C Synthesis Example 5 Synthesis method of compound 23 6-Amino-λ-mercaptove/zothiazolta, If
was added to pyridine 70- and hexanoyl chloride 6 was added under water cooling.
．． 7f was dropped. After stirring at room temperature for 3 hours, rinse with ice water.
The precipitated crystals were collected and recrystallized from a mixed solvent of ethanol and water. Yield t, yt Melting point 17ri~1r
o0c The compound represented by the general formula (I) of the present invention can be used in an amount of 1xlO to 10 mol per 1 mol of silver halide grains of a substantially non-light-sensitive silver halide emulsion, and preferably /xlO , 1 mole is preferable. Most preferably, the amount added is close to the saturated adsorption amount since it is applied to the surface of substantially non-photosensitive silver halide grains. As for the addition method, it may be directly dispersed in a hydrophilic colloid, or it may be added after being dissolved in an organic solvent such as methanol or ethylene glycol.

In the photographic material of the present invention, the seventh emulsion and the second emulsion may be in the same emulsion layer, or may be in separate emulsion layers.

The second emulsion used in the present invention is preferably substantially non-photosensitive to the first emulsion, and is preferably an emulsion that does not contribute to an increase in image density because it is not developed. .

In the present invention, "photosensitive" means that the sensitivity of the photosensitive silver halide emulsion (first emulsion) is higher than the sensitivity of the second emulsion. More specifically, it means a compound having a sensitivity of 100 times or more, more preferably 7000 times or more, the sensitivity of a substantially non-photosensitive silver halide emulsion.

The sensitivity here is defined in the same way as the sensitivity shown below.

Next, two types of emulsions used in the present invention will be explained.

As the photosensitive silver halide emulsion, a conventional silver halide emulsion such as a surface latent image type emulsion is used.

Here, the surface latent image type silver halide emulsion is 1 to 171
After 00 seconds of exposure, development was performed using the surface development (A) method and internal development (B) method shown below.

Furthermore, the emulsion is one in which the sensitivity obtained by surface development (A) is greater than the sensitivity obtained by internal development (B), preferably an emulsion in which the sensitivity of the former is one or more times that of the latter. Here, sensitivity is defined as follows.

OO8 is sensitivity, Eh is maximum density (Dmax) and minimum density (D
density t/2 (Dmax+Dm
Indicates the amount of exposure required to obtain inl.

(Surface development @ (A)) Io
Develop for minutes.

N-Methyl-p-aminophenol (hemisulfate) Co, tg Ascorbic acid 10g Sodium metaborate tetrametal salt 3jg Potassium bromide
Add 7g water
/1 [Internal development (B)] Red blood salt Jg/l and phenosafranin o, oi-24g/
After processing for 70 minutes at about 200C in a bleaching solution containing 100% of
Develop for io minutes at Vc.

N-Methyl-p-aminophenol (hemisulfate) Ascorbic alcohol 10g Sodium metabolate tetrahydrate 3jg Potassium bromide
/g thiosulfate
Add 3g water
/1 Photosensitive halog/Specific V as silver oxide? : Silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used.

Silver iodobromide is preferably used. Here, the content of silver iodide is preferably in the range of 2 to 30 mol to 10 mol.

In addition, as for the halogen composition of the seventh emulsion, its silver iodide content is equal to or similar to the silver iodide content of the first emulsion.
It is preferable that it is above.

The average grain size is preferably larger than the substantially non-light sensitive silver halide emulsion, especially Q.

It is preferable that it is 4 μm or more. The particle size distribution can be narrow or wide. The silver halide grains in the emulsion are regular, such as cubes and octahedrons.
), may have an irregular crystal shape such as a spherical shape or a plate shape, or may have a composite shape of these crystal shapes. It may also consist of a mixture of particles of various crystalline forms. Further, tabular grains having a particle diameter of three times or more the particle thickness are preferably used in the present invention.

Regarding Kafu tabular grains, U.S. Pat.

ll34A, No. 226, 11,4c3'A, 227
This method is described in detail in the specifications of Japanese Patent Application Laid-open No. Shoj I-/27-21 and the like.

The photosensitive silver halide emulsion used in the present invention is
Chimie, Engineering, Fumetographique, by Glafkidea, P.
at PbysiquePhotography
que) J (Paul Mpn
Published by Te1 Publishing, 1947), G.F.D.F.Y.
G., F. Duffin) [Photographic Emulsion Chemistry]
Emulsion Chemistry (published by The Focal Press □, 1966), Gui El Celikman et al.
, L., Zelikman et al.
7g & Coating Photographic x
-r A John (Making and Coati
ngPhotographic Emulsion Moon
(The Focal Pre
It can be prepared using the method described in S.S.

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be the one-sided mixing method, the simultaneous mixing method, or a combination thereof. It's okay.

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 type of 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, the 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.

Twenty-nine or more silver halide emulsions formed separately may be mixed and used.

During the physical ripening process, silver halide grain formation is facilitated by
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

The photosensitive silver halide emulsion is usually chemically sensitized, although so-called primitive emulsions that are not chemically sensitized can be used.

For chemical sensitization, for example, H.)13-G(
H, Fr1eser) ed.
Zilbelhalogenyden(])ieGrundlage
n der PhotographyschenP
rozessc mit silver-halo
Geniden month
schaft.

The method described in 1ytz, p. 673-73 can be used.

That is, a sulfur sensitization method using a sulfur-containing compound that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc., either alone or in combination. It can be used as As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used. For noble metal sensitization, in addition to total complex salts, complex salts of metals in group I of the periodic table, such as lily, iridium, and palladium, can be used.

Various compounds can be added to the above-mentioned photosensitive silver halide emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the photosensitive material. These compounds are hydroxy-6-methyl-/,! ,! a,
A large number of compounds have been known for a long time, including 7-titrazaindene, 3-methyl-benzothiazole, l-7enyl-j-mercaptotetrazole, many heterocyclic compounds, mercury-containing figurines, mercapto compounds, and metal salts. .

An example of a compound that can be used is the book by K. Mess, The Theory of the Photographic Process.
graphic Process) (ij version,
In addition to listing the original documents in 1966), Japanese Patent Application Publication No. 2003-1110002≠, PljO-Otsu 307. No., I5
] j O-/? Reference No. λ, U.S. Patent No. J, 11
0.

Any of the antifoggants described in No. 63 can be used.

Specific examples of silver halide emulsions that are substantially non-photosensitive and have no fog include silver chloroiodide, silver iodobromide, silver chloroiodobromide, silver chloride, silver chlorobromide, and silver bromide. Can be used. Preferably, silver chloride, silver chlorobromide, silver bromide, silver iodobromide or silver chloroiodobromide containing less than λ molti of iodine is used. The average particle size is preferably o, oj-o, or hiroμ, more preferably 0°3μ or less, and particularly preferably 00−2μ or less. A narrow particle size distribution is preferred. The silver halide grains in the emulsion may have a regular crystal shape such as a cube or an octahedron, or may have an irregular crystal shape such as a round shape, a spherical shape, or a plate shape.
It may have a crystalline form (ular). This first emulsion may consist of a mixture of grains of various crystal forms.
It can be prepared using the method described in Dufyn, V.L., Zerichman et al.

Also, US patent @λ, j-ta 2. The so-called conversion type emulsion described in the specification of No. ljO may also be used.

Furthermore, a core-shell type emulsion in which the halogen compositions of the core and shell portions are different may also be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

In any case, the second silver halide emulsion is usually not chemically sensitized on the surface or inside of its grains.

The size of the silver halide grains contained in the second emulsion is preferably O0Uμm0 layer, more preferably 1
ltO, Hiro~o, orμm, particularly preferably 0.
J~o, or μm.

The particle size distribution may be narrow or wide. In the present invention, a so-called monodisperse silver halide emulsion having a narrow grain size distribution in which one layer of grain size, especially a layer of grain size or more, is contained within ±30 cm of the average grain size in terms of grain number or weight, is used in the present invention. I can do it.

The content ratio of the light-sensitive silver halide emulsion (first emulsion) and the substantially non-light-sensitive unfogged silver halide emulsion (first emulsion) in the silver halide photographic light-sensitive material of the present invention is as follows: The type of emulsion used (for example, halogen composition J1) Although it can be changed depending on the type or purpose of the photosensitive material used, the amount of silver in the (second emulsion) to the seventh emulsion, etc. is preferably tata:l to zoo”, soo, especially tata:l
to 70", JO is preferable. The total amount of coated silver per side is preferably Q,j~7 g/m2, especially 0.~!~!
g/m2 is preferred.

Regarding the layer structure of the photographic material according to the invention, several embodiments are conceivable.

■ Two layers, an emulsion layer and a protective layer (auxiliary layer) consisting of a mixture of the first emulsion and an 8gλ emulsion, are provided in order on a support. ■ In ■, the emulsion layer and the protective layer (auxiliary layer) A layer in which an emulsion layer made of the first emulsion is further provided between the support and a layer made of the second emulsion, an emulsion layer made of the first emulsion, and a protective layer (auxiliary layer) are provided in this order on the support. I can list things like that.

(2) Providing a protective layer (auxiliary layer) including a first emulsion layer and a second emulsion layer on a support in order. Examples include the following.

Moreover, these structures may be provided not only on one side but also on both sides of the support.

Note that the auxiliary layer according to the present invention may be provided separately from the protective layer.

The protective layer of the silver halide photographic light-sensitive material of the present invention is a layer consisting of a hydrophilic colloid, and the hydrophilic colloid used includes those mentioned above.

The protective layer may be a single layer or a multilayer.

TFLs such as a matting agent and/or a smoothing agent may preferably be added to the emulsion layer or protective layer of the silver halide photosensitive material of the present invention. Examples of matting agents include those with a suitable particle size (particles with a particle size of 0.3 to 1μ are preferably at least twice the thickness of the protective layer, particularly at least 10 times the thickness of the protective layer).
Preferably used are organic compounds such as water-dispersible vinyl polymers such as polymethyl methacrylate, and inorganic compounds such as silver halide and barium strontium sulfate. Smoothing agents help prevent adhesion failure similar to matting agents, and are particularly effective in improving the frictional properties of motion picture film related to camera compatibility during shooting or projection; , waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or their derivatives, polyalkylpolysiloxanes, polyarylpolysiloxanes, polyalkylarylpolysiloxanes, or alkylene/oxide addition derivatives thereof. Silicones and the like are preferably used.

The silver halide photographic material of the present invention may also be provided with an antihalation layer, an intermediate layer, a filter layer, etc., if necessary.

Various hydrophilic colloids can be used as a binder in the VC in the photographic light-sensitive material of the present invention.

Colloids used for this purpose include, for example, hydrophilic colloids commonly used in the photographic field, such as gelatin, colloidal lupus, polysaccharides, cellulose derivatives, synthetic resins, polyvinyl compounds including polyvinyl alcohol derivatives, acrylamide polymers, etc. can be mentioned. Along with the hydrophilic colloids, hydrophobic colloids can be included, such as dispersed polymeric vinyl compounds, especially those which increase the dimensional stability of the photographic material. Suitable compounds of this type K include water-insoluble polymers made by polymerizing vinyl yarns such as alkyl acrylates or alkyl methacrylates, acrylic acid, sulfoalkyl acrylates or sulfoalkyl methacrylates.

In the photographic material of the present invention, the photographic silver halide emulsion layer and other hydrophilic colloid layers can be hardened with any suitable hardener. These hardening agents include
71.02jr, j3-76026 and 73-7
Vinylsulfonyl compounds as described in No. 74/2:
Hardeners having active halogens include nidioxane derivatives, oxypolysaccharides such as nioxy starch, and the like.

The photographic silver halide emulsion layer may contain other additives, especially those for the photographic emulsion VC, such as lubricants, sensitizers, light-absorbing dyes,
Plasticizers and the like can be added.

The photosensitive material of 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 and halation.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes: hemiokylenol dyes and merocyanine dyes are useful.

In the photographic material of the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

The photosensitive material of the present invention may also contain a surfactant for other purposes. Depending on the purpose, any of nonionic, ionic, and amphoteric surfactants can be used, such as polyoxyalkylene derivatives, amphoteric amino acids (including sulfobetaines), and the like. Such surfactants are described in U.S. Pat.
, too, r3/, U.S. Patent Co., λ7/, 62
No. 2, US Patent λ, Core/, Ako No. 3, US Patent λ, 2
73'.

No. 7.27, U.S. Patent No. 2,717,604c, U.S. Patent λ, 116. Octopus O, U.S. Patent λ, 73ri.

rri No. 1 and Belgian patent ≦! Ko, described in rbu No. 2 n
ing. The aforementioned polyalkylenes/derivatives are also particularly effective as anti-static agents.

In the present invention, fluorine-containing compounds can be used for purposes such as antistatic, antiadhesive, spray injection improvement, and coating aid. As a concrete addition, JP-A-Sho ≠ Tar 1072
No. 2, No. 45o-itsJj, No. 45o-itsJj, No. 77λ,
Same--Hiroshi 1120, same j44-/4cJλ≠, same jA-1jAjA, same j7-21, 7/Y, same! 7
-l reference tkohiro issue, same ja-iiur 4ct issue, same! I
-/ri 674 (reference, same evening t-200, 2J yo issue, % Ganshoj Turco 363 ri 0/no., British Patent No. 1, 21 ri, 3
Ta wo number, same/, Hiro/7. Low molecular weight compounds described in U.S. Pat.

ri6ri issue, same≠, 017. Jri reference, intermediary, 0/4.1
No. 21, 3.474, /, ZJ No. 3.67,
Hiro1 No. 1, same μ, JO'A, 1rj No. 2, JP-A No. 12-
No. 722520, Mukoj44-/Yoj Cococo No. 11-
No. 471112, No. 77-//3uλ, No. j7-/73j, No. r7-/79137, Patent application 1977-20
-Uu J No. 1 “Chemistry Overview 4.27 New Fluorine Chemistry J”
(Nippon Kagaku, 10 years), the polymer compounds described in ``Functional Fluorinated Polymers'' by Kuroyo (Nikkan Kogyo Shimbun, 1212), and the polymer compounds described in JP-A No. 161410/1973 Examples include inorganic compounds.

In the light-sensitive material of the present invention, the emulsion, especially the @l emulsion, may be spectrally sensitized to relatively long wavelength blue light, green light, red light, or infrared light using a sensitizing dye. As the sensitive dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used in ordinary negative-working silver halide emulsions. especially,
It is advantageous to use dye concentrations that do not substantially reduce the inherent sensitivity of the silver halide emulsion. Approximately 1 sensitizing dye per mole of silver halide.

0x10s ~ approx. X10' moles, t<GC ha
= 1 g/mole of sensitizing dye x 10'~
Preferably, axio molar concentrations are used.

Further, the sensitizing dye can be used in any step of the manufacturing process of the photographic emulsion, or can be present in any stage after manufacturing until just before printing. Examples of the former include silver halide grain formation process, physical ripening process,
These include chemical ripening processes.

In the photographic material of the present invention, the emulsion layer and other layers are coated on one or both sides of a flexible support commonly used in photographic materials. Useful flexible supports include films of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, baryta layers or α-olefin polyw-1 such as polyethylene, polypropylene, ethylene/butene copolymer. 7'C is laminated paper etc.

In the photographic material of the present invention, the emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various known coating methods. For application, dip application method,
A roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

The present invention can be used for any photographic material that requires high sensitivity or high contrast. For example, it is used in X-ray photographic materials, lithographic photographic materials, black and white negative photographic materials, color negative photographic materials, and the like.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure I Re5earch Diaclos
ure)/No. 74, No. 2, pages 30 (RD-176
Any of the known methods and known treatment liquids as described in Hiroshi 3) can be applied. Depending on the purpose, this photographic processing may be photographic processing for forming a recorded image (black and white photographic processing) or photographic processing for forming a dye layer (color photographic processing). The processing temperature is usually chosen between 1rOc and 0c, but temperatures lower than /r'C may be above jO'c.

As the developer used in the present invention, in addition to a high-activity developer, a low-activity developer with a lower concentration of active ingredient or a lower pH can be used.

For example, the developer used in black-and-white photographic processing can contain known herbal medicines.

Current main drugs include dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. /-
phenyl-3-pyrazolidone), amine phenols (
Compounds such as N-methyl-p-aminophenol) can be used alone or in combination. Further, a developer containing a dialdehyde hardening agent such as gel tar aldehyde may also be used. For photographic processing of the light-sensitive material of the present invention, JP-A No. 77-7113! It is also possible to process with a developer containing imidazoles as a silver halide solvent as described in No. Also, JP-A-Sho Jr-37tliJ
It can be processed with a developer containing a silver halide solvent and an additive such as indazole or triazole as described in the above. The developer generally contains other well-known preservatives, alkaline agents, pH buffers, antifoggants, etc., and further contains a solubilizing agent, a color thickening agent, a development accelerator, a surfactant, and an antifoaming agent as necessary. , a water softener, a viscosity imparting agent, and the like.

As a special form of development processing, a developing agent is added to the light-sensitive material.
For example, a method may be used in which the photosensitive material is included in the emulsion layer and the photosensitive material is processed in an alkaline aqueous solution to perform development. Research Disclosure 1 for hydrophobic developing agents
No. 6 (FLD-/4'?21), U.S. Patent No. 2. ?
JP, No. 1000, British Patent No. ♂/J, No. 213 or West German Patent No. 1゜! It can be included in the emulsion layer by various methods such as those described in No. 7.71.3. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfurized adducts known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

(Example j Next, the present invention will be specifically explained based on examples.

Example 1 (Preparation of I1 surface-sensitive silver halide emulsion (first emulsion): A silver nitrate aqueous solution was added to a container containing an aqueous solution consisting of potassium bromide, potassium iodide, gelatin, and potassium thiocyanate by the usual ammonia method. and an aqueous solution consisting of potassium bromide and potassium iodide to prepare a silver iodobromide emulsion (AgI = j mol %) having a plate-like shape with an average grain size of /, /μ, It was desalted by the usual flocculation method, sensitized with gold/sulfur using chlorauric acid and thiosulfuric acid, and then sensitized with gold/sulfur using chlorinated auric acid and thiosulfuric acid.
-Methyl-/,j,j,-7-chitrazaindene was added to obtain a photosensitive silver iodobromide emulsion (2).

(2) Preparation of non-photosensitive fine grain emulsion (@ emulsion): Aqueous gelatin solution fj containing a minute amount of potassium bromide
After adding a small amount of ammonia water while stirring at 10c,
Pure silver bromide particles are formed by simultaneously adding a silver nitrate aqueous solution and a potassium bromide aqueous solution while controlling the potential at a constant potential, desalted by a normal agglomeration method, redispersed in a gelatin aqueous solution, and then mixed with a 0.0% aqueous solution of potassium bromide. /r
A monodisperse pure silver bromide emulsion ■-7 (not chemically sensitized) of μ was prepared, and then a compound &6 of the following structural formula was selected from the compounds of the general formula ■-7
Adsorbed into emulsion.

Compound A6 (31) of general formula CI) Preparation of emulsion coating solution: Emulsion ■ is j, !gAg/m2 and emulsion ■-/ are mixed in various amounts ratios shown in Table 1, and then the two emulsions are mixed. Stabilizer≠
-Hydroxy-4-methyl/, 3゜3a, 7-chitrazaindene, coating aid dodecylbenzenesulfonate,
Thickener polypotassium p-vinylbenzenesulfonate compound* was added. As a comparative sample for the present invention, a coating solution containing only emulsion (1) was prepared by adding the following menion triazolium compound A.

Compound A (4) Preparation of coating solution for surface protective layer: Gelatin, thickener polyethylene sodium sulfonate, matting agent polymethyl methacrylate fine particles (average particle size 7.0 μm), hardener N, N'-ethylene bis -(Vinylsulfonylacetamide) Coating aid A coating liquid t-m was prepared comprising sodium t-octylphenoxyethoxyethanesulfonate, a polyoxyethylene surfactant, and a fluorine-containing compound having the following structure.

C8F□7So2N(CaH7)CH2CH2K and CsF 175O2N (C3H71(CH2CH20
+TTH (5) Preparation of coating sample: Coat the above-mentioned emulsion coating solution on both sides of the polyethylene terephthalate support so that the amount of silver per one side is the value shown in Table 1, and the amount of gelatin from the emulsion coating solution is applied to one side. j)/, r
The gelatin from the surface protective layer coating solution was coated in an amount of 1M17m2 per side. Therefore, the total gelatin coating amount for any sample is 3. It is applied so that it becomes /riy7@2.

(6) Sensitometry - Each sample was measured at ≠14 on the 7th day after application while maintaining the temperature and humidity of these samples t-21'C, At RH.
After exposure through a continuous wedge with blue light of 31.0 to 0 μm having a t μm K100 peak, the following developer A and fixer were used at standard development temperature using a Fuji Film automatic processor FPM-3000. Make sure to use 3j0c for 0 seconds of processing including fixing, washing, and drying.

Eluent A Potassium hydroxide λ, lμ2 glacial acetic acid
10. Potassium sulfite
Sodium bicarbonate
7. jOtboric acid
/, 009 diethylene glycol 21. 4t ethylenediaminetetraacetic acid /, 479j-
Methylbenzotriazole o,ottj-nitroimidazole 0.219 Hydroquinone
, io, ootl-phenyl-3-pyrazolidone /, jTO? glutaraldehyde
V, ri3? Sodium metabisulfite 12.
60? Potassium bromide 7,009
Add water to finish.

(Adjust to pHt-100.2j.) Fixer ammonium thiosulfate 200? Sodium sulfite (anhydrous) 20? boric acid
ry Disodium ethylenediaminetetraacetate 0. /? Aluminum sulfate /It sulfuric acid
Add 2 parts of glacial acetic acid and 2 parts of water to bring the total volume to 1/1.

(The pH was adjusted to 4.2) Sensitometry was performed on the processed photographic material and the results are shown in Table 1. In the same table, the sensitivity value is fog +0.
It was calculated as the common logarithm of the reciprocal of the exposure amount required to obtain the transmitted light blackening density of 3, and expressed as a relative value as sensitivity t-/, 00 of sample A/ in Table 1.

In addition, graininess is evaluated and expressed as follows.

A sample was developed under standard development conditions (Jj'C, 21 seconds) and uniformly exposed with the same light source used for normal sensitometry so that the transmitted light blackening rate at time t was /,0. Created. The concentration of this sample was measured using a microdensitometer with a measurement anomie diameter of J4Cμ, and the square root of the root mean value (RMSI) was calculated, and the value was used as a measure of graininess. In other words, this value is large. Seed grain looks coarse.RMS
Value is 01Oj or more 1F! :/, 0.0j6 or more θ, o
s not t# λ, o, ottx or more o, opt less than all 3.
0.031 or more and less than 0.0 da 2 was evaluated as Hiroshi, and less than 0.037 was evaluated as 3.

Furthermore, using developer B having the following composition, the same sample was developed for 2 minutes and 10 minutes using a plate developer instead of an automatic processor.

In this case, fixing and washing were performed in the same manner.

Developer B /-phenyl-3-pyrazolidone o, it hydroquinone 20.0? Sodium ethylenediaminetetraacetate 2.02 Potassium sulfite
to, ot shelf acid ≠, oy potassium carbonate 20.0? Sodium bromide J', or diethylene glycol 30.09 Add water to make /L.

Adjust pH to 10.0 with NaOH.

The results are expressed as relative values in the same manner as in the case of developer A, with the sample point /, the sensitivity of partial development as /, and OO.

As is clear from Table 1, the sample (A3-
The difference is that the amount of developer N
It shows good graininess when processed with On the other hand, it also shows that when processed with developer B, the sensitivity is high, especially when the development time is short. In addition, it has been shown that the sample of the present invention has almost the same graininess and is highly sensitive compared to the sample prepared as a comparison sample to which the menion triazolium compound A was added (A). There is.

This high sensitivity is particularly noticeable when developing for a short time with developer B.

Example λ Silver chloride particles were formed as a non-photosensitive fine grain emulsion in the same manner as in Example (by simultaneously adding a silver nitrate aqueous solution and a sodium chloride aqueous solution while controlling the potential to be constant), and desalted by a normal agglomeration method. and redispersed in gelatin aqueous solution to θ, 20 μm.
Monodisperse silver chloride emulsion ■-co (no chemical sensitization)
Then, from among the compounds of general formula (I), compound 23 having the following structural formula was selected, and the same amount as in Example 7 was prepared.
- adsorbed on λ emulsion.

Compound of general formula (Il &23) Using this emulsion, a coated sample was prepared under exactly the same conditions as in Example 1, and sensitometry was performed. The sample containing the silver fine grain emulsion exhibited clearly better graininess when treated with developer A compared to the same comparative sample as in Example 1. Also, the same comparison as in Example 1 was obtained when treated with developer B for a short time. The following examples demonstrate high sensitivity photography.

Example 3 Substantially non-photosensitive fine grain emulsion ■-l used in Example
Instead of a compound of the general formula tx)-Aj as a surface adsorbent for /-phenyl-! - The same experiment was carried out using the same amount of mercaptotetrazole as in Example 1, but the sensitivity was severely reduced and the effect of the present invention could not be obtained.

(Effect of the invention) A photosensitive silver halide emulsion (first emulsion) containing silver iodide and a substantially non-photosensitive unfogged silver halide emulsion to which the compound of general formula (I) is adsorbed are prepared. When used in combination, it is possible to significantly improve graininess in high-temperature development that contains dialdehyde.By the way, short-term developability can be significantly improved in low-temperature development that does not contain dialdehyde.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Showabu/Yeargetsu Z1 Co. Commissioner of the Patent Office
1. Display of the incident 1985 patent application No.-27411
No. 60 No. 2, Name of M Silver halide photographic light-sensitive material 3, Relationship to the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture 11. I 4. Subject of amendment The description in the "Detailed Description of the Invention" column 5 of the description and the "Detailed Description of the Invention" section of the description are amended as follows.

l) Page j, line 16 After "other constituent layers" [(For example, surface protective layer)” Insert.

2) After "May be added" in the rth line of this page, [Non-light-sensitive fine grain emulsion to which the compound of the general formula (I) of the present invention is not added or a compound other than the general formula (I)] A non-light-sensitive fine-grain emulsion to which . In addition, internal fog type non-photosensitive fine grain emulsions to which the compound of general formula (I) is added are also undesirable because they cause unnecessary fog. ” is inserted.

3) After "may be present" on page 23/line [However, it is non-photosensitive if it is in the same emulsion layer] After the compound of general formula (I) is applied to the silver halide grains , is preferably added to a photosensitive emulsion. ” ? insert.

Example 2! After "preferable" on page 16, "For color sensitive materials, μ~/j moltimol is preferable. The iodine distribution within the grains may be uniform or unevenly distributed in some parts. In particular, if the grains have a high iodine content, Particles with a double structure having a core or particles having a coating layer with a high iodine content on the particle surface are suitable for the present invention.''

j) On page 1, line 17, after "Used.""For materials such as color couplers, high boiling point organic solvents, etc. used in color negative photosensitive materials, please refer to Research Disclosure.
e) The entire description in Volume 174, pages 22-27 (December 1971) may be referred to. ” is inserted.

t) After "may include" in the ≠≠ page line [Next, the present invention will be explained in detail before being explained in Examples.

When photosensitive silver halide grains with high iodine content are developed, iodine ions are released which are immediately deposited on neighboring grains. In this way, when a phenomenon starts with a certain particle, not only does the development layer of the particle itself decrease, but also the onset of the phenomenon of neighboring oil particles is suppressed, causing contagious development and making the grain rough. There are malignant uses such as

Previous attempts have been made to use non-photosensitive silver salts to capture iodine ions released during development and reduce this effect, but this has resulted in various undesirable side effects. For example, could the active ingredients in the emulsion be rendered ineffective by surface adsorption, or could the development inhibitor released from the DIR compound be captured and produce an interimage effect? hinder, etc.

The inventor conducted extensive research into a surface treatment method for non-photosensitive particles in order to reduce the effect of rendering photographically useful components ineffective without causing any damage to the capture of iodine ions.
) was found to have a specifically favorable effect.

Among the many compounds that strongly adsorb to silver halide, it is not clear why this group of compounds has an outstanding effect, but the irreversibly strong adsorption and interaction between silver halide and iodide ions This is presumed to be due to the structure of the adsorption layer. ” is inserted.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on at least one side of a support, wherein the photographic emulsion layer contains silver iodide. A substantially non-photosensitive silver halide emulsion comprising a photosensitive silver halide emulsion consisting of a photographic emulsion layer or other constituent layers in which a heterocyclic mercapto compound represented by the following general formula (I) is adsorbed. A silver halide photographic material characterized by containing a fine grain emulsion. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents -O-, -NH-, or -S-. R_1, R_2, R_3 and R_4 are hydrogen atoms or can be replaced with hydrogen atoms. represents a group, R_1, R_2, R_3
, R_4 is a substituted or unsubstituted alkyl group or aryl group having 13 or less carbon atoms directly or via a divalent linking group. X_1 represents a hydrogen atom or a cation for making the molecule neutral. )