JPH034220A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance the sensitivity and gradation of a sensitive material without deteriorating the graininess by spectrally sensitizing a prescribed silver halide emulsion with a specified dyestuff. CONSTITUTION:The silver halide emulsion of this sensitive material has >=20% relative standard deviation of the silver iodide contents of the silver halide particles and has been spectrally sensitized with a dyestuff represented by formu la I (where each of Z1 and Z2 is a group of atoms required to form a desired nucleus, each of R1 and R2 is (substd.) lower alkyl, X(-) is an anion and n is 1 or 2). A compd. represented by formula II may be used as the dyestuff represented by the formula I. The silver halide emulsion may be produced by mixing emulsions having different silver iodide contents and a fluorine-contg. surfactant may be incorporated into a desired layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic emulsion, and more particularly to a silver halide photographic light-sensitive material having high sensitivity and excellent gradation.

[Background of the invention]

One of the most important factors for image reproduction of silver halide photographic materials is gradation.

Conventionally, for the gradation design of monodisperse silver halide emulsions, a method has been used in which two or more types of emulsions having different grain sizes are appropriately blended.

For example, it is known that when three types of particles with large, medium, and small particle sizes are mixed, a photosensitive material with high sensitivity and rich gradations can be obtained by increasing the ratio of small particles to large particles. It is being

However, although high sensitivity can be obtained by increasing the proportion of large particles, there is a problem in that, as a matter of course, granularity is significantly deteriorated.

Therefore, the development of silver halide emulsions with high sensitivity and excellent graininess is the most important issue in this industry, and although many proposals have been made, the current situation is still not satisfactory.

[Purpose of the invention]

Therefore, the first object of the present invention is to provide a silver halide photographic material which is highly sensitive and has excellent gradation. A second object of the present invention is to provide a silver halide photographic material with improved graininess and sharpness.

Other objectives will become apparent from the description below.

[Structure of the invention]

As a result of extensive research, the present inventors have discovered that the above objects of the present invention can be achieved by the following silver halide emulsion, and have completed the present invention.

That is, in a silver halide photographic light-sensitive material having at least one /% silver halide emulsion layer on a support, each grain of the silver halide emulsion has a relative standard deviation of silver iodide content of 20%. % or more, and is achieved by using a silver halide photographic material which is spectrally sensitized with at least one dye represented by the following general formula [I].

General formula CI) In the formula, ZI and z2 are nonmetallic atomic groups necessary to complete the benzthiazole nucleus, benzselenazole nucleus, naphthothiazole nucleus, or naphthoselenazole nucleus, each of which may have a substituent, R1 and R2 is a lower alkyl group or a substituted lower alkyl group, Xe is an anion, n is a positive integer of 1 or 2, and when forming an inner salt, n is l.

The present invention will be explained in detail below.

In the present invention, the "relative standard deviation of the silver iodide content of individual grains" refers to the silver iodide content when the silver iodide content of at least 100 emulsion grains is measured using, for example, an X-ray microanalyzer. This value is obtained by multiplying the standard deviation of the content by the average silver iodide content by 100. A specific method for measuring the silver iodide content of individual emulsion grains is described in, for example, European Patent No.
No. 47,868A.

The grains of the present invention have a relative standard deviation of silver iodide content of each grain of 20% or more, more preferably a relative standard deviation of 20% or more.
It is preferably 0% or more and 50% or less.

The silver iodide content of individual emulsion grains can be measured, for example, by
It can be measured by analyzing the composition of each individual particle using an analyzer.

In the grains of the present invention, it is most preferable that there is no difference in the individual silver iodide content among the grains, and the individual normality distribution of the final grains is basically 20% or more, but preferably 20% or less. The object of the present invention cannot be achieved because the gradation, graininess, and sharpness are not excellent.

In order to obtain a silver halide emulsion having a relative standard deviation of silver iodide content of 20% or more according to the present invention, it is preferable to mix emulsions having different silver iodide contents.

In that case, the upper limit is 3 types MIX.

When trying to give a MIX emulsion an iodine distribution expressed by a certain relative standard deviation, the central mol% of the emulsion is
In this case, emulsion A having a lower silver iodide content and emulsion C having a lower silver iodide content are required.

The iodine mole % of A and C is preferably z to 2 times that of B, but may be more or less than this if necessary.

The relative standard deviation (iodine distribution) of the old X particle is 20-50%
is preferable, and in the case of the above three types of old X, the B emulsion is 50 to 90
In a preferred embodiment of the present invention, emulsions A and C are mixed with old X in a proportion of 10 to 50%.

Next, the dye represented by the general formula CI) of the present invention will be described.

In the formula, zl and Z each represent a group of nonmetallic atoms necessary to complete a benzthiazole nucleus, a pentselenazole nucleus, a naphthothiazole nucleus, or a naphthoselenazole nucleus with or without a substituent, and the benzthiazole nucleus Examples include benzthiazole, S-chloropenthiazole, 5-methylbenzthiazole, 5-methoxybenzthiazole, 5-hydroxybenzthiazole, 5-hydroxy-6-methylbenzthiazole, 5.
6-dimethylbenzthiazole, 5-ethoxy-6-
Examples of the benzselenazole core include benzselenazole, such as methylbenzthiazole, 5-phenylbenzthiazole, 5-carboxybenzthiazole, 5-ethoxycarbonylbenzthiazole, 5-dimethylaminobenzthiazole, and 5-acetylaminobenzthiazole. , 5-chlorobenzselenazole, methylbenzselenazole, 5-methoxybenzselenazole,
5-Hydroxybenzselenazole, 5.6-dimethylbenzselenazole, 5.6-dimethoxybenzselenazole, 5-ethoxy-6-methylbenzselenazole, 5-hydroxy-6-methylbenzselenazole 5 Examples of the naphthothiazole nucleus include -7enylbenzselenazole, such as β-naphthothiazole, β, β-naphthothiazole, and the like; examples of the nathoselenazole nucleus include β-naphthoselenazole nucleus. R, and R2
lower represents a lower alkyl group or a substituted lower alkyl group, such as methyl group, ethyl group, n-propyl group, β-hydroxylethyl, β-carboxyethyl group, γ-carboxypropyl group, γ-sulfopropyl group, γ -Represents a sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, sulfoethoxyethyl group, etc.

xe represents an anion, such as a halogen ion, perchlorate ion, thiocyanate ion, benzenesulfonate ion, P-1-luenesulfonate ion, methylsulfate ion, etc. Further, n represents a positive integer of 1 or 2, and when the dye forms an inner salt, n is l. ] The sensitizing dye of the present invention is a thia or selena carbocyanine substituted with an ethyl group at the meso position on the trimethine chain, and has a sensitizing property advantageous for spectral sensitization in a specific wavelength range.

As an illustration, typical examples of the sensitizing dye of the present invention are shown, but the present invention is not limited thereto.

These sensitizing dyes according to the present invention are disclosed in British Patent No. 660.4.
No. 08, US Pat. No. 3,149,105, and the like.

The above dyes according to the invention can be directly dispersed into emulsions. Alternatively, they can be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a composite solvent thereof, and then added to the emulsion in the form of a solution.

The amount of the sensitizing dye according to the present invention added to the silver halide emulsion varies depending on the type of silver halide and the amount of silver, but the preferable amount is o per mole of silver halide.
,oos~1. og, more preferably 0.01 to 0
．． It is 6g.

These sensitizing dyes, singly or in combination, are added to the silver halide emulsion by the method of the present invention to obtain the desired spectral sensitivity.

The above-mentioned sensitizing dye according to the present invention may be added at any time from before the end of the desalting process to just before the end of the chemical ripening process, but preferably during the chemical ripening process. Particularly preferably, it is at the start of chemical ripening.

The desalting method may be any method used in the industry, such as Research Disclosure +
-(Research Disclosure) 176
43 ・Page 23 left column ``・The agglomeration method or the noodle washing method described in 1978 may be used.

Next, as a preferred embodiment of the present invention, the desired effects of the present invention can be satisfactorily achieved by using a fluorine-containing surfactant in at least one layer of the silver halide photographic material of the present invention.

Fluorine surfactants include nonionic, anionic,
Examples include those having a cationic or betaine structure, preferably a fluoroalkyl group having 4 or more carbon atoms.

Examples of ionic groups include anionic surfactants such as sulfonic acid or its salts, carboxylic acids or its salts, and phosphoric acid or its salts, or amine salts, ammonium salts, sulfonium salts, phosphonium salts, and aromatic amine salts. Examples include cationic or betaine type surfactants, and nonionic surfactants having polyalkylene oxide groups, polyglyceryl groups, and the like.

These fluorine-containing surfactants are disclosed in U.S. Pat. No. 4,335
．． No. 201, No. 4,347.308, British Patent No. 1,4
No. 17.915, No. 1,439.402, Special Publication No. 1972
-26687, 57-26719, 59-38
No. 573, JP-A-55-149938, JP-A No. 54-48
No. 520, No. 54-14224, No. 58-20023
No. 5, No. 57-■46248, No. 58-196544
Examples include compounds described in the specification of No. 1, etc.

Preferred specific examples of these are shown below, but the present invention is not limited thereto.

-I -2 -3 -4 CJ　　7SOsK CtFrsα)ONa CHF H7CH1CJO5O3Na C,H.

CsF+ySO2N CH2C00KH -10 H(CF2hCHzOOCCH! H(CFthCH!OOCCH5OsNa-11 C,H,0OC-C)f-5o,Na F-12 CM.

CH.

-13 CH3 eI C,F, 7502NCH,CH,C)+20CH2C
H2N-CH2COO”CH.

-14 1”14° Shirll -15 CM.

CH 7- -26 C7F, 5COO (CH2CH.O juice aH-27 C1.F□COO cost 1 ( 2 CH 2 0 h1H-
29 CH.

C. Fl 7SO2N(CH.CH20)IH -18 -20 -21 δH3 -22 L -30 c, oL I c. p, 7SO2N(CH2CH20)=mouth HC. H
.

C a F + r So 2 N CH, CH,]
H3 C,H.

CH.

4 C, Fl, CH2CH20-(CH2CH20-)rY
H5 C,H.

C.I.F. , So2N-co. cooi CHzCH20)
'jH7 C,F. IO(-CH,CH20,)-iCH3F-3
8 C,F, ,Coo-(C)I,CH-0 juice (CH2C
H20') Tel HCH3 The above-mentioned fluorine-containing surfactant may be added to any of the layers constituting the silver halide photographic light-sensitive material, for example, the surface protective layer, intermediate layer, undercoat layer, or back layer. It is added to non-light sensitive layers such as sublayers or silver halide emulsion layers.

More preferred are the emulsion layer and its surface protective layer, and the backing layer and its surface protective layer. These may be used not only in one-sided layers but also in both-sided layers at the same time.

Two types of these fluorosurfactants may be used in combination,
Alternatively, it may be used in combination with other synthetic surfactants.

Although the amount added varies depending on the type of compound, silver halide emulsion layer 1 of the silver halide photographic light-sensitive material according to the present invention
．． 0.0001 to 2 g per x, preferably 0.001
~0.5g.

In the case of hydrophilic colloid layers other than the silver halide emulsion layer, the amount is 0.0001 to 2 g, preferably 0.001 to 0.00 g.
At 5g, the object of the present invention works well.

Next, the silver halide emulsion used in the present invention will be described.

In the hydrophilic colloid layer of the silver halide photographic light-sensitive material according to the present invention, a vinyl sulfone compound can be preferably used as a gelatin hardening agent.

The vinyl sulfone curing agent preferably used in the present invention may be any compound as long as it has at least two vinyl sulfone groups in one molecule, but in particular, compounds with the general formula Examples include compounds represented by (H).

General Formula (H) Here, R represents a hydrogen atom or a lower alkyl group, preferably a hydrogen atom or a methyl group.

Z is an n-valent group containing at least one each of oxygen, nitrogen, and sulfur atoms, and the atom contained in Z is preferably an oxygen atom or a nitrogen atom.

m is 1 or 2, and n is 2 or 3.

Next, specific examples of the compound of general formula [H] will be given.

H(CHz””CH302CH20CIhSO2CH=
CHzH-2CHz-CH3OzCHzCHzCFIz
CHzOCHzC1 (zcHzcH2sOzcH=cH
zH-3CHz””CHSO2CH2CH20CH2C
HzOCHiCH2SO2CH=CHzH-4CH2=
CH502CH2C11,0CI(2CH2NHCON
HCH2CH20CH2CH2SO2CH=C)12-
8) 1-9 -10 -11 CH2-CB502CH20C)L2C)! 2SOzC
1 (ICH20CH2SO2CH=CH2CH2-CH
SO2CH! So CH= C) I2CH2=CH5
O2CH, CH25O, CH=CH25O, CH=CI
(.

B H-13CHz -CB5(:hCH2CONHCH2
CHxNHCOCH2SO2CH-CH3I-14'
(CH,=C)150IC)1,0H20-CB,C)
+2kejso.

H-15CCCHx-CB5(:hCHx”fsCCH
xSChCHyCH2]zN CH=CH25OsK
H-17(CH2"'CH302CHz')zc'fc
H2so, CH=CH20SO,Na)2) 1-18 CH,SO,CH=CH2 (CH,CH,SO,C)IccH5O,+CI(,C
I(,CH,N).

CH25OICH=CHz CH2 CF2 SO, to H-19 CH.

-27 SO, CHTSCH.

H-20(CH, -CH5OzCH*'+NCH-21
Co(CHtC)I2SO2CH=C)lx)zH-2
2NH(CH2ClhSOzCH=CFI2)zH-2
8 -29 -30 -31 -32 -33 -34 -35 So, C) I-CO.

CHxC(CH20CHtSO2CH-C)It)zN
(CHzCHzOCFlzS(hC)I-CHz)tH
+ yCa C(CH2SO2CH-CH2)+CH
! -CH5O2CHzCHCH*5OzCH-CH25
O2CH-CH2Br)! zc C(CHzSOzCH-CI(z)x
(C)I, -CH30□CHx'1xCHCHCC
HzSOICII-CHz'h(CHI-C)IsO,
CH,)3C-CH20CH, C(C)I, 5o2CH
-CH2).

(CHz-C)lsOzcH2)xc CHzSCh
CH2CHzCQH-38CH20CH(SO*(CH
JtSOzCH=CH2 Preferred vinyl sulfone hardeners used in the present invention include, for example, German Patent No. 1,100,
Aromatic compounds such as those described in Japanese Patent Publication No. 44-29622 and Japanese Patent Publication No. 47-25373, alkyl compounds bonded with hetero atoms such as those described in Japanese Patent Publication No. 47-8736. Sulfonamides and ester compounds, JP-A-49-2443
1,3,5-tris[β-vinylsulfonyl]-propionyl]-hexahydro-5 as described in No. 5
-triazine or alkyl compounds such as those described in JP-A-51-44164.

In addition to the above-mentioned exemplified compounds, the vinyl sulfone hardener that can be used in the present invention includes a compound having at least three vinyl sulfone groups in its molecular structure, a group that reacts with vinyl sulfone groups, and a water-soluble compound. compound having a sexual group,
For example, it includes a reaction product obtained by reacting jetanolamine, thioglycolic acid, sarcosine sodium salt, and taurine sodium salt.

In the silver halide photographic light-sensitive material of the present invention, various photographic dyes can be used as filters for halation and irradiation prevention, sensitivity adjustment, color toning agents, and the like.

Among these, particularly preferably used dyes include oxonol dyes of the following general formula (II).

General formula (n) (wherein R1 represents an alkyl group. R2 represents an alkyl group, a heterocyclic group, or an aryl group having at least one group carried from a sulfo group and a carboxyl group or a salt thereof. I, 1 .R2, L3L4 and R5 each represent a methine group. al and I22 are each 0 or I; is 1
represents an integer. ) These dyes of general formula (I[) are disclosed in Japanese Patent Application Laid-Open No. 63-2314.
Specific examples of water-soluble dyes easily synthesized from the pyrazolone derivatives described in No. 45 are shown below.

(3) (4) (9) (10) (11) bu35 ≧υ38 (5) (6) (7) (8) (13) (14) The silver halide photographic material of the present invention includes the above-mentioned General formula (II) In addition to the dyes represented by oxonol dye, Alternatively, azo dyes can also be used advantageously. I can be there.

(2) (14) (15) (16) (17) (4) (5) (6) (7) -CH.

C00H -C00C2H.

(8) (9) (10) (11) (12) R.

SO, Na -3o, Na -3O,Na 2 So, Na 13o, Na 5o, Na -3O,Na 3 So, Na -3O,Na R.

SO, Na 5o, Na SO3Na 5o3Na The silver halide grains contained in the silver halide photographic light-sensitive material of the present invention are silver halide containing silver iodide, and include silver iodochloride, silver iodobromide, and chloroiodobromide. It can be any silver. In particular, silver iodobromide is preferred from the standpoint of obtaining high sensitivity.

The average silver iodide content in such silver halide grains is 0.05 to 10 mol%, preferably 0.5 to 8 mol%, and a high concentration of at least 20 mol% or more is contained inside the grains. There is a localized area where silver iodide is localized.

In this case, it is preferable that the inside of the particle be as far inward as possible from the outer surface of the particle, and in particular 0.00 mm from the outer surface.
It is preferable that the localized portion exists at a distance of 1 pm or more.

Further, the localized portion may exist in a layered manner inside the particle, or may have a so-called core-shell structure, with the entire core serving as the localized portion. In this case, it is preferable that part or all of the core part of the particle excluding the shell part having a thickness of 0.01 μm or more from the outer surface is a localized part with a silver iodide concentration of 20 mol % or more.

In addition, the concentration of silver iodide in the localized portion is 30 to 40
The preferred range is mole %.

The outside of such localized areas is usually coated with silver halide without silver iodide.

That is, in a preferred embodiment, the distance from the outer surface is 0.0
1 pm or more, especially 0.01-1.5. A shell portion um thick is formed of silver halide (usually silver bromide) without silver iodide.

In the present invention, Q
, inside the particles separated by O1pm or more) at least 2
A method for forming a localized portion of silver iodide at a high concentration of 0 mol % or more may be one that does not use seed crystals.

If seed crystals are not used, the reaction liquid phase containing the protected gelatin (
Since there is no silver halide that can serve as growth nuclei in the mother liquor (hereinafter referred to as mother liquor) before the start of ripening, first, silver ions and halide ions containing high concentration iodine ions of at least 20 mol % are supplied to form growth nuclei. let Then, addition and supply are continued to grow particles from the growth nuclei. Finally, a shell layer having a thickness of 0.01 μm or more is formed from silver halide containing no silver iodide.

If seed crystals are used, at least 20 mol% of the seed crystals alone
The above silver iodide may be formed and then covered with a shell layer. Alternatively, the amount of silver iodide in the seed crystal is O or within the range of 10 mol% or less, and at least 20 mol% of silver iodide is formed inside the grain in the step of growing the seed crystal,
This may be followed by coating with a shell layer.

In the silver halide photographic light-sensitive material according to the present invention, at least 5 of the silver halide grains present in the emulsion layer are
Preferably, 0% of the particles are grains having localized silver iodide portions as described above.

Another preferred embodiment of the present invention is to use a monodisperse emulsion having a localized silver iodide portion as described above.

The monodisperse emulsion referred to herein means, for example, The
Photographic Journal, 79
．． Trivelli in 330-338 (1939),
From a silver halide emulsion in which at least 95% of the grains, by number or weight, are within ±40%, preferably within ±30%, of the mean grain diameter when the mean grain diameter is measured by the method reported by Sm1th. It means something.

Such monodisperse emulsion grains are made using simultaneous mixing techniques, similar to ordered silver halide grains. The conditions for simultaneous mixing are the same as those for producing regular silver halide grains.

Methods for producing such monodispersed emulsions are known, for example, J. Ph.
ot, Sic,, 12.242=251 (1963
) JP-A-48-36890, JP-A No. 52-16364,
JP-A-55-142329, JP-A-58-49938
It is stated in each publication of the issue.

In order to obtain the above-mentioned monodispersed emulsion, it is particularly preferable to use seed crystals and to supply silver ions and halide ions using the seed crystals as growth nuclei to grow grains.

The broader the particle size distribution of this seed crystal, the wider the particle size distribution of the particle growth nuclei. Therefore, in order to obtain a monodisperse emulsion, it is preferable to use seed crystals with a narrow particle size distribution at the seed crystal stage.

The silver halide grains described above used in the silver halide photographic material of the present invention include, for example, T, )I.

“The Theory o(the
Photographic Proc-ess” No. 4
Edition, published by Macmi11an (1977) 38-10
Neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, Funtrol bead double jet method, conversion method, core/
It can also be manufactured by applying a method such as a shell method.

Silver halide emulsions with surface latent images can be prepared by the so-called controlled double jet method, in which the pH and EAg in the reaction vessel are controlled by gradually increasing the amount of silver ion solution or halide solution added. You can also do it.

Furthermore, cadmium, palladium salts, zinc, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be allowed to coexist in the stage of silver halide grain formation or physical ripening. good. moreover,
The surface latent image type silver halide emulsion may be a monodisperse emulsion.

Here, the monodisperse emulsion is one in which T≦0,20, where r is the average grain size of silver halide grains and σ is the standard deviation thereof.

In the present specification, the average grain size refers to the diameter in the case of spherical silver halide, and in the case of grains with shapes other than spherical, it is the average based on the diameter when the projected image is converted to a circular image of the same area. .

Known photographic additives can be used in the silver halide photographic emulsion of the present invention.

Examples of known photographic additives include Research Disclosure's RD-17643 (1978) shown in the table below.
(December 1979) and RD-18716 (November 1979)
Compound additives listed in Chemical sensitizer Sensitizer Dye development accelerator Antifoggant Stabilizer Ultraviolet absorber Filter Dye hardener Coating aid Surfactant Plasticizer Slip agent Static inhibitor RD -17643 page Classification 3 m 23 1V 29 XXI 24 VT 25~26 ■ 26 X 26~27XI 26~27XI 27 649 right to 650 left 651 right 650 right 650 right Matting agent binder 8 x ■ 6 ■ 650 right 651 right The support used in the silver halide photographic emulsion of the present invention is:
Including all known ones, such as polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, styrene films,
They also include baryta paper, paper coated with synthetic polymers, and the like. The emulsion of the present invention can be coated on one or both sides of the support, and when coated on both sides, the emulsion can be applied symmetrically or asymmetrically with respect to the support.

The silver halide photographic material used in the present invention can be developed by a commonly used known method. The developer is a commonly used developer, such as hydroquinone,
Those containing l-phenyl-3-pyrazolidone, N-methyl-p-aminophenol, or p-phenyl diamine alone or in combination of two or more thereof are used, and other developer additives are used. Commonly used agents can be used.

Further, a developer containing an aldehyde hardener can also be used in the silver halide photosensitive material according to the present invention, such as dialdehydes such as maleic dialdehyde or glutaraldehyde and their sodium bisulfite salts. It is also possible to use a developer known in the photographic field.

The total processing time according to the present invention refers to the time from when the photosensitive material of the present invention is inserted into the 10th roller, which is the photosensitive material insertion opening of an automatic processor, after imagewise exposure, through the developing tank, fixing tank, and washing tank. This refers to the time it takes to reach the final roller at the opening of the drying section.

The total process time is 60 seconds or less, more preferably 20 to 60 seconds. If the processing time is less than 20 seconds, the sensitivity may not be high, and color residues and image unevenness may occur when dyes are added.

In addition, the treatment temperature is 60°C or less, preferably 20 to 45°C.
It is.

Below is an example of the breakdown of the total processing time: Processing process Processing temperature ('O) Processing time (seconds)
Enter 1.2 Developer crossing 35 14.6 Fixing operator crossing 33 8.2 Washing + crossing 2
5 7.2 Squeeze 40 5
．． 7 Drying 45
8.1 total 4
5.0 [Examples] Examples of the present invention will be described below. However, it goes without saying that the present invention is not limited to the examples described below.

Example 1 Monodisperse grains of silver iodobromide containing 2.0 mol% of silver iodide with an average grain size of 0.2 μm were used as nuclei, and silver iodobromide containing 30 mol% of silver iodide was heated to pH 9.1. grown at pA g7.7;
After that, equal moles of potassium bromide and silver nitrate were added at pH 8.0 and pAg 9.1, and the average silver iodide content was 0.5.1.0.
．． Seven types of monochromatic emulsion grains having an average grain size of 0.405 .mu.m to 0.70 .mu.m were prepared, giving silver iodobromide grains of 2.0.3 DEG 0 and 4.0 mol %. (Table 1) Excess salts were desalted from the emulsion using a conventional coagulation method.

That is, maintain the temperature at 40°C, add a formalin condensate of sodium naphthalene sulfonate and an aqueous solution of magnesium sulfate,
Agglomerated. After removing the supernatant, add pure water up to 40°C, add magnesium sulfate aqueous solution again, and coagulate.
The supernatant was removed. These particles were each treated with ammonium thiocyanate salt at 1.9X 10-' per mole of silver.
Chemical ripening was carried out by adding appropriate amounts of chloroauric acid, hypo and the spectral sensitizing dye of the general formula (1) according to the present invention as shown in Table 2, and 15 minutes before the completion of the chemical ripening. 200 mg of potassium chloride per mole of silver were added, followed by stabilization with 3×101 mole of 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene.

Separately, as a backing layer, a backing layer solution was prepared consisting of 400 g of gelatin, 2 g of polymethyl methacrylate, 6 g of sodium dodecylbenzenesulfonate, 20 g of the following antihalation dye, and glyoxal, and 5 Qvt% of glycidyl methacrylate and 100% of methyl acrylate.
Polyethylene terephthalate coated as a subbing liquid with an aqueous copolymer dispersion obtained by diluting a copolymer consisting of three types of heptadons: vt% and butyl methacrylate 4Qwt% to a concentration of 10vt%. A lined support obtained by coating one side of the base with a protective layer solution consisting of gelatin, a matting agent, glyoxal, and sodium dodecylbenzenesulfonate was prepared.

The coating amount was 2.5 g/m'' for each of the backing layer and the protective layer, including the amount of gelatin applied.

[Antihalation dye]

Coating sample preparation Emulsion layer additives: diethylene glycol 10 g 1 nitrophinyl triphenyl 7 years old sphonium chlorite 50 mg, 1.3 per mole of silver halide
-Dihydroxybenzene-4-ammonium sulfonate 1g, 2-mercaptobenzimidazole-5-sodium sulfonate 10mg, polyacrylamide (average molecular weight 40,000) 10gll-dimethylol-1-brome-1
- Nitromethane 0 mg Exemplary Dye 16 80 mg/m'' etc. were added.

Also, as a protective layer additive, the following compound was added per 1 g of gelatin: CH2C00(CHz)scIhC)ICOO(CH2)zcFl(CHs)2
20ng So, Na A matting agent made of silica with an average particle size of 7μm 7ωg1 70mg of colloidal silica with an average particle size of 0.013μm etc. were added, and further the fluorine-containing surfactant according to the present invention and the comparative active agent shown in Table 1 were added. In addition, as a hardening agent, CH, -CHSO□-CH20CHz 5OzCH-
An appropriate amount of CHz (example H-.l) was added.

The silver halide emulsion layer and the protective layer were coated on the backing base in order from the support using the slide hopper method at a coating speed of 6.
A sample was obtained by coating two layers simultaneously at 0IIl/win.

The amount of silver is 2.9 g/m", the amount of gelatin is 3 g/m" in the emulsion layer.
', and the protective layer was 1.3 g/m'.

After storing these samples at 23°C and 55% RH for 3 days, one pixel (100
After exposure by changing the light intensity at 1/100,000 second per μm2), automatic developing machine 5RX-501 (manufactured by Konica Co., Ltd.)
The film was processed using a developer and a fixer (the compositions of which are shown below) for a total processing time of 45 seconds.

Composition of developer and fixer Developer solution-1 Potassium sulfite 55.0g Hydroquinone 25.0g 1-7 enyl-3-pyrazolidone 1.2g Boric acid
10.0g Sodium hydroxide 21.0g Triethylene glycol 17.5g 5-Nitropenzimidazole 0.10g Glutaraldehyde bisulfite 15.0g Glacial acetic acid
16.0g potassium bromide
4.0g triethylenetetraminehexaacetic acid 2.
Add 5g water to make 1Q.

Fixer-1 Ammonium thiosulfate 130.9g Anhydrous sodium sulfite boric acid acetic acid (90vt%) Ethylenediaminetetraacetic acid dinatoacetate sodium trihydrate Aluminum sulfate 18hydrate Sulfuric acid (50wt%) Add water to finish with N2.

*Comparative activator Rium 7.3g 7.0g 5.5g 3.0g 25.8g 14.6g 6.77g *Comparative sensitizing dye The following evaluations were made for each sample after development.

γ (gradation) It is expressed by the straight line gamma of the characteristic curve connecting fog+density 0.25 to density 2.0.

Sample No. 3 was expressed as 100 at the sensitivity determined from the exposure amount required to give a density of sensitivity fog +1.0.

し1tll-t 41'Itert The screen after development was visually evaluated according to the following criteria.

■ very bad bad Somewhat good Good very good As is clear from the results in Table 2, According to the present invention hand streetcar Supplementary Positive book The sample is Rich in gradation, and has excellent graininess. Heisei December - 18th, 1 year I understand that.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, each grain of the silver halide emulsion has a relative standard deviation of silver iodide content. is 2
1. A silver halide photographic material, characterized in that it is spectrally sensitized with at least one dye represented by the following general formula [I] in an amount of 0% or more. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Nonmetallic atom group necessary for completion, R_1 and R_2 are lower alkyl groups or substituted lower alkyl groups, X^■ is an anion, n is 1
or a positive integer of 2, and when forming an inner salt, n is 1
It is. ]