JPH04110936A - Spectrally sensitized silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the hue reproducibility to a bluish green color, the stability at the time of production and the preservable property of the produced photosensitive material with lapse of time by using a fine particle silver halide having a specific halogen compsn. in at least one kind of silver halide emulsions. CONSTITUTION:The wavelength lambdaG to afford the max. sensitivity of the spectral sensitivity of the green sensitive silver halide emulsion is 525nm<=lambdaG<=560nm and the sensitivity SG 500 at 500nm is >=1/4 the sensitivity SGmax. at the wavelength lambdaG. The fine particle silver halide having the halogen compsns. expressed by formulas I, II are used for at least one kind of the silver halide emulsions which are spectrally sensitized to a green sensitivity and are incorporated into the above-mentioned layers. The means for constituting the spectral sensitivity distribution of the green sensitive layers include a means for spectrally sensitizing, for example, the arbitrary silver halide with a sensitizing dye having an absorption spectrum in a desired wavelength region, or a means for optimizing the halogen compsn. of the silver halide and the distribution thereof to have the desired spectral sensitivity without using the sensitizing dye. The color reproducibility to the bluish green color, the stability at the time of production and the preservable property of the photosensitive material with lapse of time are improved in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a spectrally sensitized silver halide photographic light-sensitive material, and more specifically, it has excellent color reproducibility, particularly for blue-green color, and The present invention relates to a silver halide color photographic light-sensitive material that has excellent color reproducibility with respect to light sources including fluorescent lamp light sources, as well as stability during production and excellent storage stability over time of the produced light-sensitive material.

[Background of the invention]

In recent years, the high sensitivity of silver halide multilayer color photographic materials,
There is an increasing demand for higher image quality, and even though the three major elements of image quality - graininess, sharpness, and color reproducibility - have all reached a considerable standard, further improvements in sensitivity and image quality are needed. is required.

Of the three factors mentioned above, in terms of color reproducibility in particular, color purity has improved, but the reproducibility of colors, which have traditionally been said to be difficult to reproduce in photographs, has not changed much. . That is, the hue reproducibility still has many deficiencies. For example, violet colors such as violet and blue-violet that reflect light with wavelengths longer than 600 nm, or green colors such as blue-green and yellow-green, will be reproduced as completely different colors from the actual colors, which will disappoint the user. Sometimes.

Spectral sensitivity distribution and glabellar effect (interimage effect, hereinafter referred to as IIE) are major factors related to color reproducibility.
There is.

Regarding IIE, the following is known. That is, it is known to add a compound that compiles with the oxidized product of a color developing agent to form a development inhibitor or its precursor in a silver halide multilayer color photographic light-sensitive material. It is known that by inhibiting the development of other color-forming layers using a development inhibitor, IIE is produced and the effect of improving color reproducibility is produced.

Further, in a color negative film, it is possible to provide an effect similar to that of IIE by using a colored coupler in an amount greater than the amount that offsets unnecessary absorption. However, when colored couplers are used extensively, the minimum density of the film increases, making it extremely difficult to judge color/density correction during printing, resulting in poor color quality in the resulting prints. occurs often.

Incidentally, these techniques particularly contribute to improving color purity among color reproducibility. The so-called diffusive DIR, in which the mobility of inhibitor groups and their precursors, which have been frequently used recently, is high, greatly contributes to the improvement of color purity. However, it is difficult to control the directionality of IIE, and although it can achieve high color purity, it also has the disadvantage of changing the hue. 725,529, etc.) On the other hand, the spectral sensitivity distribution is described in U.S. Patent No. 3,672.
No. 898 discloses an appropriate spectral sensitivity distribution for reducing variations in color reproducibility due to differences in light sources during photographing. However, this is not a means to improve the aforementioned poor color reproducibility.

In Japanese Patent Application Laid-Open No. 61-34541, which also discloses a technology that combines spectral sensitivity distribution and LIE, an attempt has been made to improve the colors that are difficult to reproduce with the aforementioned color film, and some results have been achieved. It seems that it will be possible. A typical example is not only the conventional IIE from the center wavelength of each of the blue, green, and red sensitive layers, but also the IIE from a wavelength other than the center of gravity of each color-sensitive layer. .

This technology seems to be effective to some extent in improving the hue reproducibility of specific colors, but specifically, in order to develop IIE, in addition to the original blue-sensitive, green-sensitive, and red-sensitive bad light layers, , I
It has the disadvantage that it requires an IE expression layer and a different type of photosensitive silver halide, increases the amount of silver, and increases the number of production steps, resulting in high production costs. However, the effect was not sufficient.

For the above reasons, conventional silver halide color photographic materials have been insufficient in terms of hue reproduction. In particular, it was difficult to faithfully reproduce blue-green colors, and the hues were sometimes far removed from the actual colors.

The inventors of the present invention focused on this blue-green hue reproducibility and conducted intensive studies. As a result, the spectral sensitivity distribution of the green-sensitive silver 10-genide emulsion layer was shifted to the shorter wavelength side than before, resulting in the highest sensitivity. It has been discovered that the above problem can be improved by designing the wavelength λG to be 525 to 560 nm.

However, it has been found that even with the combination of the above techniques, very unsatisfactory color reproducibility can be obtained when photographing under fluorescent lighting, which is common these days, or under mixed light of strobe light and fluorescent lighting. That is, even if only a fluorescent light source or a strobe light is used, if there is an influence from the fluorescent light, the color reproduction will be greenish.

On the other hand, as a technique for improving high sensitivity and graininess using silver halide grains,
No. 8538, No. 61-14636, No. 61-2451
No. 51 and the like disclose so-called core/shell type silver halide grains in which silver iodide is localized inside the grains.

However, in these emulsion techniques, the surface of the silver halide grains constituting the emulsion has a low iodine content, and when spectrally sensitized with the sensitizing dye used in the above techniques, which generally tends not to have strong adsorption, Sufficient color sensitization efficiency could not be obtained, and furthermore, the storage stability of the produced photographic material over time could not be said to be satisfactory.

Also, JP-A-48-51627 and JP-A-59-774
No. 43 discloses a method of adding water-soluble iodide to a silver iodobromide emulsion for the purpose of improving color sensitization sensitivity.

Although this method is effective in adjusting the spectral sensitivity distribution and reducing desorption of the sensitizing dye under high temperature conditions by increasing the adsorption of the sensitizing dye on the surface of silver halide grains, If water-soluble iodide is added until the adsorption of the sensitive dye is sufficiently increased, there is a drawback that sensitivity will be lowered. In addition, in this method, the adsorption reaction of iodide ions onto the surface of silver halide grains is very fast, and the adsorption is uneven.
Moreover, since the emulsion is unstable, the sensitivity of the obtained emulsion often changes over time even when stored in a refrigerator, making it difficult to produce a product with stable quality.

[Purpose of the invention]

The purpose of the present invention is to provide excellent hue reproducibility, particularly for blue-green, and excellent color reproducibility for light sources including fluorescent light sources, as well as stability during manufacturing and storage stability over time of the manufactured photosensitive material. An object of the present invention is to provide a silver halide color photographic light-sensitive material which has excellent properties and high sensitivity.

[Structure of the invention]

In order to develop a silver halide photographic light-sensitive material that satisfies these demands, the present inventors have conducted intensive research and found that at least one blue-sensitive silver halide emulsion layer and one green-sensitive halogen emulsion layer are formed on a support. silver oxide emulsion layer, red-sensitive silver halide emulsion layer (hereinafter referred to as ``blue-sensitive layer'', ``green-sensitive layer'', respectively)
In a silver halide color photographic light-sensitive material having a green-sensitive silver halide emulsion layer (sometimes abbreviated as "red-sensitive layer"), the wavelength λG giving the highest sensitivity in the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer is 5.
25 nm≦λG≦560 ns, and the sensitivity S at 500 nm (,500 is the sensitivity SC at the wavelength λG, wax is 4 or more in one layer, and the silver halide emulsion is spectrally sensitized to the green sensitivity contained in the core layer. The above object is achieved by a silver halide color photosensitive material characterized in that at least one of the above is formed using fine grain silver halide having a halogen composition represented by the following general formula (1). I discovered that.

General formula ■ A g Cj! m B r b I cHowever, general formula■
Medium, a, b, and c satisfy the following conditions.

0≦all O≦b<1 0<c≦1 m<c (m: surface immersion composition of silver halide emulsion to be spectrally sensitized) a+b+c=1 The present invention will be explained in more detail below.

In the present invention, the spectral sensitivity distribution refers to the spectral sensitivity distribution of 400
Exposure is applied with spectral light from nm to 700 nm at intervals of several nl11, and the exposure amount that provides a constant density at each wavelength is defined as the sensitivity at each wavelength, and the sensitivity is defined as a function of wavelength.

In the present invention, any appropriate means can be used to set the spectral sensitivity distribution of the green-sensitive layer to the structure of the present invention described above. For example, it is possible to spectral sensitize any silver halide with a sensitizing dye that has an absorption spectrum in the target wavelength range, or to optimize the halogen composition and distribution of silver halide without using a sensitizing dye to achieve the desired wavelength range. There are means for imparting a desired spectral sensitivity, and further means for adjusting the spectral sensitivity distribution to a desired level by using an appropriate optical absorber in the light-sensitive material. Of course, these means may also be used in combination.

In the present invention, sensitivity SG50 at 500r++s
0 is 174 or more of the sensitivity SλG at the wavelength λG, but more preferably 173 or more.

The spectral sensitivity distribution defined in the present invention is the sensitivity at any density point in the minimum density of the green-sensitive layer, but the sensitivity at the density point of the minimum density + 0.7 is the spectral sensitivity distribution defined in the present invention. If it has, the effects of the present invention will be noticeable.

At least one of the silver halide emulsions spectrally sensitized to green sensitivity contained in the green-sensitive layer of the light-sensitive material of the present invention is prepared by using fine-grain silver halide emulsions having a halogen composition represented by the above general formula (1). The fine-grained silver halide that can be used in the present invention includes silver iodide, silver chloroiodobromide, silver iodobromide, etc., but fine-grained silver iodide is preferable. .

Regarding fine grain silver iodide (AgI), cubic r-AgT and hexagonal β-Agl are generally known, and the fine grain AgI used in the present invention may have either crystal structure. , or a mixture thereof.

The grain size of the fine grain silver iodide used in the present invention is preferably 0.2 μm or less, more preferably 0.02 μm or less.
~0.1 μm.

Next, the amount of fine silver halide grains added will be described.

The amount of fine silver halide grains to be added is 1/100 dmol or less per mole of mother grains, where d (μm) is the average grain size of the mother grains, that is, the grains to be grown by adding fine silver halide grains. is preferable, more preferably 1/20,000 d to 1/300 d mol per mol of mother particles, and most preferably 115,000 d to 11,500 d mol per mol of mother particles.

The fine-grained silver halide used in the present invention preferably has good monodispersity and is
It is preferable to prepare while controlling pH and pAg.

In the present invention, the fine grain silver halide is preferably added at any step from the chemical ripening step to immediately before coating, and more preferably during the chemical ripening step.

The chemical ripening process referred to here means that a chemical sensitizer is added after the physical ripening and desalting operations of the mother particles are completed.
This refers to the period from then until the point at which an operation is performed to stop chemical ripening. In addition, as a method to terminate chemical ripening,
Methods such as lowering the temperature, lowering the pH, and using a chemical ripening stopper are known, but in consideration of the stability of the emulsion, etc., the method using a chemical ripening stopper is preferable. Examples of the chemical aging stopper include halides (e.g., potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (e.g., 4-hydroxy-6-methyl-1,3°3a, 7-chitrazaindene, etc.) are known.

These compounds may be used alone or in combination.

Further, the addition of the fine grain silver halide of the present invention may be carried out in several steps at intervals of time, or another chemical ripening agent may be added after the addition of the fine grain silver halide. .

The temperature of the mother grain emulsion liquid when adding fine grain silver halide is preferably in the range of 30 to 80"C, and
A range of ˜65° C. is particularly preferred.

Further, in the present invention, after the addition of fine grain silver halide,
It is preferable that the coating be carried out under conditions such that part or all of the silver halide particles disappear immediately before coating, and a more preferable condition is that 20% or more of the added fine grain silver halide disappears immediately before coating.

To quantify the amount lost, centrifuge the emulsion or coating solution after addition of fine-grain silver halide under appropriate conditions, and then measure the absorption spectrum of the supernatant to determine the absorption of a fine-grain silver halide solution with a known concentration. This can be done by comparing it with the spectrum.

In the present invention, in order to spectrally sensitize at least one of the green-sensitized silver halide emulsions, at least one sensitizing dye represented by the following general formula [I] and the following general formula By using in combination at least one kind of sensitizing dye represented by
) is also referred to as the sensitizing dye of the present invention).

General formula CI) General formula (n) In the formula, R1, R2, R' and R5 each represent an alkyl group or an alkenyl group. R3 represents a hydrogen atom, an aryl group or an alkyl group. x' and x'' represent charge-balancing counterions, and nl and nz represent values necessary to neutralize the charge of the entire molecule of 0 or more.

ZI and Z2 each represent an atomic group necessary to form a benzoxazole nucleus or a naphthoxazole nucleus.

Z3 and Z4 are pyrroline nucleus, lysine nucleus, quinoline nucleus, indolenine nucleus, benzimidazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, respectively. , represents the atomic group necessary to complete the benzoselenazole nucleus or naphthoselenazole nucleus.

The sensitizing dye of the present invention will be explained in more detail.

In the compounds represented by the general formula CI) and the general formula (II) used in the present invention, R', R''R4 and R5 each represent a branched or straight-chain alkyl group having 1 to 10 carbon atoms (for example, methyl , ethyl, propyl, butyl, pentyl, i-pentyl, 2-ethyl-hexyl, octyl, decyl, etc.) or alkenyl groups having 3 to 10 carbon atoms (e.g. 2-propenyl, 3-butenyl, 1-methyl-3-propenyl) , 3-pentenyl, 1-methyl-3-phthynyl, 4-hexenyl, etc.).These groups include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), alkoxy groups (
(e.g., methoxy, ethoxy, etc.), aryloxy groups (e.g., phenoxy, P-)lyloxy, etc.), cyano groups, carbamoyl groups (e.g., carbamoyl, N-methylcarbamoyl, N,N-tetramethylenecarbamoyl, etc.), sulfamoyl groups (e.g., sulfamoyl , N, N-3-
oxapentamethyleneaminosulfonyl, etc.), methanesulfonyl group, alkoxycarbonyl group (e.g., ethoxycarbonyl, butoxycarbonyl, etc.), aryl group (e.g., phenyl, carboxyphenyl, etc.), acyl group (e.g., acetyl, benzoyl, etc.), acylamino It may be substituted with a substituent such as a group (for example, acetylamino, benzoylamino, etc.), a sulfonamide group (for example, methanesulfonamide, butanesulfonamide, etc.), and preferably a water-soluble group (for example, a sulfo group, a carboxyl group, etc.). phosphono group, sulfato group, hydroxyl group, sulfino group, etc.). Examples of the alkyl group substituted with a water-soluble group represented by R' and R2 include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl,
Examples of the alkenyl group substituted with a water-soluble group include sulfopentyl, 3-sulfobutyl, hydroxyethyl, carboxyethyl, 3-sulfinobutyl, 3-phosphonopropyl, p-sulfobenzyl, and 0-carboxybenzyl. Examples include 4-sulfo-3-butenyl and 2-carboxy-2-propenyl.

In general formula (1), it is preferable that either one of R1 and R2 has a water-soluble group.

Ions that cancel out the charges within the molecules represented by Xl and X2 are selected from anions and cations. Anions include inorganic and organic ones, specifically halogen ions (e.g. chlor, bromine, iodine, etc.), organic acid anions (e.g. P-toluenesulfonate, p-chlorohenzenesulfonate, methanesulfonate, etc.). ion), tetrafluoroboron ion, perchlorate ion, methyl sulfate ion, ethyl sulfate ion, etc.

Cations include inorganic and organic ones, specifically hydrogen ions, alkali metal ions (for example, lithium, sodium, potassium, cesium, etc.), and alkaline earth metal ions (for example, magnesium, calcium, strontium, etc.). ion), ammonium ion, organic ammonium ion (e.g. trimethylammonium,
triethylammonium, tripropylammonium,
ions such as triethanolammonium and pyridinium).

The benzoxazole nucleus represented by Z I 22 also includes one having a substituent on the ring. Specifically, substituents on the ring include halogen atoms (e.g., chlorine, bromine, fluorine, etc.), alkyl groups having 6 or less carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, etc.) Aryl groups (e.g., phenyl groups, etc.), alkoxy groups (e.g., methoxy, ethoxy, butoxy groups, etc.) having up to 4 carbon atoms, hydroxy groups (e.g., phenoxy groups, etc.), acyl groups (e.g., acetyl groups, etc.) having up to 6 carbon atoms, propionyl group, benzoyl group, etc.) alkoxycarbonyl group having 8 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.) hydroxy group, cyano group,
Examples include trifluoromethyl group.

Z3 and 24 are respectively pyrroline nucleus, pyridine nucleus, quinoline nucleus, indolenine nucleus, benzimidazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazoline nucleus, thiazole nucleus, benzothiazole nucleus,
It represents a naphthothiazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, or an atomic group necessary to complete a naphthoselenazole nucleus, and the above-mentioned heterocyclic nucleus also includes those having a substituent on the ring. As a substituent on the ring, Zl
, and the same substituents as mentioned in the explanation of the heterocyclic nucleus represented by Zl.

7.3. Among the heterocyclic nuclei represented by Z4, preferred are benzothiazole, naphtho(2,ld)thiazole, naphtho(2,3-d)thiazole, benzoxazole, and naphtho(2゜1-d). ) oxazole series, naphtho(2,3-d) oxazole series, benzoselenazole series, naphtho(2,1-d) selenazole series, naphtho(
2,3d) It is the nucleus of selenazole type and quinoline type.

Specific examples of the sensitizing dyes represented by the general formulas (1) and (I[,) are shown below, but the sensitizing dyes used in the present invention are not limited to these compounds.

N-a) R3 N.

■ COCH.

■2 COCH.

(χl)n□ (CL) 3S02e (CL) 1s (he (CI(2) asOze CzHs CJs e QC) Iff cooctt yu e e QC)13 COOC)I3 C.L. (CL) 3303” (CL) 3303e (cnz) ssOse (cu.) 3SOffe (CHHz) zsO3e CJs (C) lz) ssOse C. )Is Cz)Is CJs (C) 1m), SO. e CzHs CJs C. L floor ■-9 1-1.

-n ■-13 (Cllz)s5th” CzHs C,H.

(Cl　z)　zsO　y　ye (CHz) zsO3” (CHz) ss (he (CHz)JHSOzCHz (CL)zsOse (CHHz)4SO3θ (C’z)zsO3e R’t (CHI)asOze (CHHz) sS(h” 2HS (CHHz) asO3e (CHHz) ssch” (CHHz)ssOse (CH2)asose (CL)zOcH3 (cL) 4sOie (C) lz) zs(he zFIs CzHs ○ CzHs CJs CzHs CH.

Hz C Sesame Hma CJs ■-19 ■ C) 13 CI(3 (CHz) zsOse (Cllz) ss(he (CHHz)ssOs” (CHHz)ssOse CJs CJs (X’). 1 Na' )IN8 (C2)ls)ko HNe(CJs)s )IN’ (Czl(s):1 Na' (X’)ni HNe(CzHs) Iθ )IN” (CzHs)z Na'! ′ niΦ Na@ HN’ (CJs)s LiΦ HNe(CJs) floor ■４ ■ ■ ■ (CHHz)is03θ (CH2)3 O3Li ■ (CHz)4S(he ChzChCHFz (II-a) (χ2)n.

■6 s t Cl (CHHz)4SO3e (CHHz)4SO3”’ to C e (CHI)ss(he CH2COOH OCH x OCH:+ (CL)3SO,,e (CHI)3SOffe OCH 3 OH (Clh)! So,e (CH2)ZSO3e OH3 e (CHHz)zcOOH (CHHz) 3S03e (X”)n.

Na' Na' Na@ ■ ■ ■ ■ ■ ■-15 ■ ■ 5O3H-N(CzHs)3 ■-12 ■ ■ ■-18 Shifigo ShiH3 hindrance ■7 ■ CH3 ■-21 cttz ■-22 ■ ■-23 e ■-24 C1h ■-25 ■-26 ■-27 [■ b] ■8 CH3 (CHHz) 3SO3θ (CHHz)3SO3)1 CH3 (CHHz) 3S03e (CHz)isOJ Cz)Is C, Hl t (CHri3503e cnzcoott e (coz) 3SOffθ C,H.

■-29 ■ (X”)n.

aeB r0 (CHHz)asOJ ■ ■-32 ■ (CHHz)3S03e C2H.

■-37 ■ ■-39 ■ ■ ■-36 ■-40 ■ zHs zus [■ C] (X2). .

Zui ■9 ■10 (X”).

C, H5 e 2H5 BP, θ ole (CH2) 3503e LiΦ ■-46 CR3 t C,H.

C, H5 F3e ■-47 CR3 e Js (CHHz) 35Oz” Nα ■9 ■IO (X”)n.

zH5 r0 ■ CHs CR3 C38? r0 [■ d] (x”)n.

Communicating V eyes (X.

■ ■ (CH2)3SO3e (CHz) 5sO3e ae ■-51 CR3 zos Js e ■-52 CRz zHs (CHl) 3SO3e ■-53 OC, H5 (CHx) 3SO3e (CHz) 3SO3e LiΦ ■-54 t (CH z) asO2e CH Tsu ■-55 ■-56 The sensitizing dyes represented by the general formulas CI] and (II) according to the present invention are described, for example, in the Journal of the American
Chemical Society, (J, A fog.

Chem, Soc, ), 67, 1875-1899 (
1945)), F.M. Palmer, The Chemistry of Heterocyclic Compounders (T.
he Chemistry of Heterocycle
ic Compounds) Volume 18, The Cyanine
Dice and Relay Compounder (The
Cyanine Dyes and Re1ated
Compounds) (A, Weissherger
ed, published by Interscience, New Yo
rk1964), U.S. Patent Nos. 3,483.196, 3,541,089, 3.598.595, and 3
, No. 598.596, No. 3.632.808, No. 3.
Those skilled in the art can easily synthesize the compound by referring to the methods described in JP-A No. 757.663, JP-A-60-78445, and the like.

The optimum concentration of the sensitizing dye of the general formula [I] [■] can be determined by methods known to those skilled in the art. For example, a method may be used in which the same emulsion is divided, each emulsion contains a different concentration of sensitizing dye, and the performance of each emulsion is measured.

The amount of the sensitizing dye added in the present invention is not particularly limited, but is from 2X10-' mol to 1 mol per mol of silver halide.
It is preferable to use
Preferably, 0-6 moles to 5X10-3 moles are used.

Methods well known in the art can be used to add the sensitizing dye to the emulsion. For example, these sensitizing dyes can be directly dispersed in emulsions or dissolved in water-soluble solvents such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, fluorinated alcohols, dimethylformamide, or mixtures thereof. Alternatively, it can be diluted or dissolved in water and added to the emulsion in the form of a solution.

Ultrasonic vibrations can also be used during the dissolution process.

As described in U.S. Pat. No. 3,469,937, the dye is prepared by dissolving the dye in a volatile organic solvent, dispersing this solution in a hydrophilic colloid, and adding this dispersion to an emulsion. A method is also used in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added to an emulsion, as described in Japanese Patent Publication No. 46-24185.

Further, the dye can be added to the emulsion in the form of a dispersion by an acid dissolution/dispersion method. Other additions to emulsions include U.S. Pat.
The methods described in each specification of No. 5 can also be used.

The timing of adding the sensitizing dye represented by the general formula (1), Cl1) used in the present invention to the emulsion is during the manufacturing process from the time of silver halide grain formation to just before coating on the support. It can be added at any time.

Specifically, before the formation of silver halide grains, during the formation of silver halide grains, after the completion of silver halide grain formation until the start of chemical sensitization, at the start of chemical sensitization, during chemical sensitization, and during chemical sensitization. Any time selected from the end of chemical sensitization and the time of application may be used. It may also be added in multiple portions. The order in which the stabilizer and antifoggant are added does not matter, but preferably during particle formation or chemical ripening, i.e.,
It is added in a step before preparing the coating solution. General formula (I) (I
The sensitizing dye represented by I) can be added by dissolving each sensitizing dye in the same or different solvents and mixing these solutions before adding them to the emulsion, or adding them separately to the emulsion. However, it is more preferable to mix the solution before adding it to the emulsion.

The sensitizing dye used in the present invention can also be used in combination with other sensitizing dyes.

The sensitizing dye used in the present invention can also be used in combination with a compound that provides a supersensitizing effect.

In the present invention, when at least one sensitizing dye represented by general formula CI) and at least one sensitizing dye represented by general formula (It) are used, the reflection spectrum of the spectrally sensitized emulsion is The absorption maximum observed during measurement and the reflection in an emulsion in which the sensitizing dye contained in the emulsion is adsorbed solely on silver halide grains having the same halogen composition and crystal habit as those contained in the emulsion. A distance of 5 ni or more from any absorption maximum in the spectrum is preferable because the wavelength range to be constituted in the present invention is spectrally sensitized in a superchromatic sensitized manner. More preferably, the wavelength difference is 7 nn or more, and it is particularly preferable that the wavelength difference is 7 nn or more.

In the present invention, the reflection spectrum of an emulsion is measured, for example, by the following method.

A coating solution is prepared by adding common photographic additives such as surfactants and hardeners to the emulsion of the present invention, and the coating solution is coated onto a subbed triacetyl cellulose support and dried to form a coated sample. create. The reflection spectrum of the prepared sample can be measured using an ordinary spectrophotometer (for example, Hitachi Self-Recording Spectrophotometer Model U-3210 manufactured by Hitachi, Ltd.) equipped with an integrating sphere.

In the present invention, the green light sensitivity is further increased by using at least one sensitizing dye selected from the general formula [■], the general formula [■], and the general formula [■],
It becomes preferable Mr. B.

General formula (III) □ R' (X3). , R? General formula (IV) General formula (V) In the formula, zs and zb represent an atomic group necessary to form a benzimidazole nucleus, and Z? , Zll represent an atomic group necessary to form a naphthoxazole nucleus. Z9 represents the atomic group necessary to form the benzoxazole nucleus,
Y represents a sulfur or selenium atom, and Zlo represents a benzothiazole nucleus or a benzoselenazole nucleus. R6, R
? , RIOR” RI3 R is general formula CI)
is synonymous with R1 and R1, and Rat and RIS are R3
, X3x' and xs are synonymous with X I and X Z, and n 3+ n 4+ n s is n I +
It is synonymous with n2. R8 and RQ represent an alkyl group, an alkenyl group or an aryl group. Z7゜Z″, Z9
．． The heterocyclic nucleus represented by Zlo includes those having substituents on the ring similar to those described for 2, +, and 22.

Examples of the alkyl group and alkenyl group represented by Re and Rq include the same groups as shown in the explanation for R' and R'', and the aryl group includes a phenyl group.

The benzimidazole nucleus represented by z', z'' includes those having substituents on the ring.Specifically, the substituents on the ring include the following.

Examples of acyloxy groups include acetoxy and propionoxy groups, and examples of alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl,
There are groups such as propoxycarbonyl, aryloxycarbonyl groups include phenoxycarbonyl, tolyloxycarbonyl, β-natofukidicarbonyl, etc., and halogen atoms include chlorine, bromine,
Examples of acyl groups include acetyl, propionyl, and benzoyl, and examples of alkylsulfonyl groups include methylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, and ethylsulfonyl. Examples of the arylsulfonyl group include phenylsulfonyl and p-tolylsulfonyl; examples of the carbamoyl group include carbamoyl and N-methylcarbamoyl; and examples of the sulfamoyl group include sulfamoyl and N-methylcarbamoyl. sulfamoyl, morpholinosulfonyl,
Examples include groups such as piperidinosulfonyl. Examples of the perfluorohydrocarbon group include perfluorobutyl group,
Examples include groups such as perfluorophenyl.

General formula [■], general formula (IV) and general formula [V] are shown below.
Specific examples of sensitizing dyes represented by are shown below, but the sensitizing dyes used in the present invention are not limited to these compounds.

Margin below [m a] C,)l.

C1l'lS h (x”)n.

emptiness ■ ■ ■ (X')n.

■ J e e tHs C,H.

■ i t (CHI) 5sOxe zHs (CIlz)4Soyuθ CutCFxCIIh (CIlt) ysO3e (cH2)zsoze ■ l e to C l floor Vlgo Q COOC,H3 COOCiHq N r ■-13 r ■-14 0NHz e ■１１ to C 0OCJs COOCaH* N r r 0NII2 e (GHz) iso, e (CHHz)ysOse (C)Iz)4sOie (CHHz) 5s03e (CHz)sS(h” (CI’1z)4sOie (CH,)zsOxe (CL)+S03θ C, H.

(CHz)xSOiθ CM.

(CH2), 503e (CL) 4SOJ (X 3) n.

Na@ Na@ Na@ Na@ ■ C.F.

■ C.F.

(CHri5sO2e (CH,), S(he (C)It)is(h” (CHI)350. H (cl, so, e (CHHz)asOie Na@ Na@ floor ■+3 ■ V” ■ (x3). .

ll-18 J C1! r (C+ ■-19 ■-20 ll-21 ■-22 SO□CR.

C.F.

0CHa C,H.

(CHHz) 4503e (CHHz)ssOse (CH2)sSOle (CHi) xs(he (CHHz) 5sOsθ (CHz)xSO3e (CHHz)ssOse e Na@ 8NΦ(C!Hs)s CH, C)l=c)l (CHx)*CHSO,θ CH.

■-24 N 1I N CI! (CHI)3S Off’9 (CIll) 5503θ Na@ ■ ■ CH2CH20COCH:1 CH2CH20COCH:1 ■ (1,H2C)lZOcH3 CH2C) 120cH3 ■ CHzCHzOCHzCFzCFzH zH5 (IV) hindrance I.G. 81 weight ■ 2H5 CH3 IV-2 C, H5 CH3 CH3 ■ C2H3 C, H3 C2H.

IV-4 CzHs (CH2) 3SO,e C2H.

IV-5 (CHHz) 5sO3e (C1h) ysO3e 2H3 IV-6 (CH2) 3SO3e (CHHz)3SO3e Margin below (X　’)n4 ■e e r0 HN's (CzHs) y ■ 70, zo\iOCH3 h ■ CFzCHFz (IV) (X),.

disability IV-9 ■-10 ■-11 ■-12 CzHs CzHs (CHHz):1SO3θ (CHHz)xsOse RI + L CH3 CH.

C,H.

I2 C, I5 C,H.

(X), 1 ■-13 (CHI) 3SO3e C, I5 ■-14 (cH,), SO, θ (CH2)3S03θ 2H5 ON’ (CzHs)s IV-15 (CHz)zS(he (CH2)! 5O3e ’, V-a: M ~′ ■Ib ■-7 ・○ ○ ○ Cf! ○ mouth e CH.

R1″ (X')n, R” ■-Drop R13 H(CH2) ts(he CL (CHz)zsO+e(CHt)t
s(h” (CHz) hsO3e CHs CH3 ffi 口(CL)zsOxe (CHri5sOse(CH
z)is(he CJs (CH2)2SOffe (CH2)45Of
fθ(cHd2S03θ (clISO3e C2N.

CJs C,H.

C,H.

C,)l.

(×5). .

HNΦ(CJs) Na@ emptiness ■-14 v-]5 ■1k e e ○ e e CHs t ○ 1.Ill ■I? R1) (CL)ISOje (CH2)4SOffe (CHz)xs(he (CHI)isOie (CHi)zsOze (CHz)2S(he (CHz) ssOle (CHI)ssoxe (CL)zsOse (CHz)ssoxe R+a (CL) C. H.

(CL)ssoxe CH.

cuzcooe (CHz)zS(he C,H.

CH2COOe CH. COOθ CH. COOH C. H.

CJs CtHs C. ll.

C. H.

C.J.

CtHs ○ C. H.

(X5)n5 ・■ IN” (CJz)i H)l@(CtHs)s (V b] (×5). .

Fall ■z.

e z C1! ■zz l3 (C) Iz) zsO3” (CHHz): +5 (he I5 2H5 (χ5)n.

Na@ 2H5 CH3 (CHri3Soffe 2H5 )(fB CH,C00e Js “Li” l CH.

(CHz) 3SO3e (CHz) 4S03θ ZH5 H)1Φ(C2H,OH) y The sensitizing dyes represented by the general formulas (II[), (IV) and [■] according to the present invention are represented by the above-mentioned general formula [ ■〕.

It is similar to the sensitizing dye shown in (n) and can be easily synthesized by those skilled in the art.

As a method for adding the dyes represented by the general formula (II[), (TV) or (V), each sensitizing dye is added in the same or different solvent as the sensitizing dye represented by the general formula CI), (n). These solutions may be mixed prior to addition to the emulsion, or they may be added separately to the emulsion.

A preferred method is to mix a solution of the sensitizing dye represented by the general formula (1) and the general formula (I[) before adding it to the emulsion; A part of the sensitizing dye is divided and used alone, or with the general formula (II[),
It can also be added in combination with a sensitizing dye represented by (IV) or (V).

Alternatively, a method in which a sensitizing dye represented by the general formula (1) or (II) and a sensitizing dye represented by the general formula (I[I], [IV) or (V) are added as a mixed solution to an emulsion. is also preferable.

The silver halide emulsion used in the color photographic material of the present invention can be chemically sensitized by conventional methods.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. As a binder for the emulsion, it is advantageous to use gelatin (however, it is not limited to this)
.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

The present invention can be preferably applied to color negative films, color reversal films, and the like.

In the emulsion layer of the color photographic light-sensitive material of the present invention, a coupler for color development is used for -C.

Competitive couplers and oxidized forms of developing agents can be used as color couplers, which have a correcting effect. , antifoggants, chemical sensitizers,
Spectral sensitizers and chemicals that release photographically useful fragments, such as desensitizers, can optionally be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layers may contain dyes that are leached or bleached from the light-sensitive material during the development process.

A formalin scavenger-1 fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color cast prevention agent, a development accelerator, a development retardant, and a bleach accelerator can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Any material such as polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain a dye image using the color photosensitive material of the present invention,
After exposure, commonly known color photographic processing can be performed.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all the examples below, the amount added in the silver halide photographic light-sensitive material is expressed in grams per column unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver.

Preparation Example 1 of Emulsion Silver iodobromide emulsions I to C shown in Table 1 were prepared according to the method described in JP-A-60-138538.

Table 1 Next, an aqueous solution containing 5% by weight of ossein gelatin was added to the reaction vessel, and while stirring at 40°C, 1 mol each of a 3.5N silver nitrate aqueous solution and a 3.5N hydrium iodide aqueous solution was added for 30 minutes. By adding at a constant rate, fine silver iodide particles (
A) was prepared. At this time, the pAg being added is the usual PAg.
It was maintained at 13.5 using a control means.

The produced silver iodide was a mixture of βAgl and r-A'gl with an average grain size of 0.06 μm.

Silver iodobromide emulsions I to C were optimally subjected to chemical ripening using sodium thiosulfate, chloroauric acid and ammonium thiocyanate.

Furthermore, 4-hydroxy-6methyl-1.3.3a,7-chitrazaindene was used as a chemical ripening stopper.

In this chemical ripening process, fine grain silver iodide or a comparative compound was added to prepare a chemical ripening process agent according to the present invention and a comparative emulsion.

Table 2 shows the manufacturing conditions for the prepared emulsion.

Margin Example 1 (Preparation of Samples Na 101 to NCL 104) Each layer having the composition shown below was sequentially formed on a triacetyl cellulose film support from the support side to prepare a multilayer color photographic material sample Nα101-1111104. Created.

1st layer; antihalation layer (HC) black colloidal silver 0.15 UV absorber (UV-1) 0.20 colored coupler (
CC-1) 0.02 high boiling point solvent (Oil-1)
0.20 high boiling point solvent (Oil-2)
0.20 gelatin 1.6
2nd layer; Intermediate layer (IL-1) Gelatin 1.3 3rd layer; Red-sensitive emulsion layer (R) Silver iodobromide emulsion (Em-1) 0.4 Silver iodobromide emulsion (Em-2) 0 .3 Sensitizing dye
(S-2) 3.4X10-' (mol/silver 1 mol) sensitizing dye (
S-5) 3.2XIO-' (mol/silver 1 mol) Cyan coupler (C-1) 0.50 Cyan coupler (C-
2) 0.13 colored cyan coupler (C
C-1) 0.07 DIR Compound (D-1) 0.006DI
R compound (D-2) 0.01 high boiling point solvent (
Oil-1) 0.55 gelatin
1.0 4th layer; Intermediate layer (IL-2) Gelatin 0.8 5th layer; Green-sensitive emulsion layer (G) Silver iodobromide emulsion described in column A of Table-3 0.6 B of Table-3 Silver iodobromide emulsion described in the column 0.2 magenta coupler (M-1
) 0.6 color magenta coupler (CM-1
) 0.10 DIR compound (DIR-19) 0.02 High boiling point solvent (Oil-2) 0.70 Gelatin 6th layer; Yellow filter layer (YC) Yellow colloidal silver additive (HS-1) Additive (HS -2) Additive (SC-1) High boiling point solvent (Oil-2) Gelatin 7th layer; blue-sensitive emulsion layer (B) Silver iodobromide emulsion (Em-3) Silver iodobromide emulsion (Em-2) Sensitizing dye (S-10) 5.8X10-' (mol/silver yellow coupler (Y-2) DIR compound (D-1) DIR compound (D-2) High boiling point solvent (Oil-2) Gelatin 8th layer ; First protective layer (PRO-1) Silver iodobromide emulsion (Em-4) 1.0 0.05 0.07 0.07 0.12 0.15 1.0 0.25 0.25 1 mol) 0.38 0.003 0.006 0.18 1.3 0.3 Ultraviolet absorber (UV-1) 0.07 Ultraviolet absorber (UV-2) 0.1 Additive (HS-1)
0.2 additive (HS-2)
0.1 High boiling point solvent (Oil-1) 0.
07 High boiling point solvent (Oil-3) 0.07 Gelatin 0.8 9th layer; 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethyl methacrylate (average particle size 3 μm) 0.02 Gelatin 0.5 In addition to the above composition, coating aids, dispersion aids, hardeners, and dyes were appropriately added to each layer.

Em-1: average silver iodide content 7.5 mol%, average grain size 0
．． 55 μm Em-2: average silver iodide content 2.5 mol%, average grain size 0
．． 36 μm Em-3: average silver iodide content 7.5 mol%, average grain size 0
．． 65 μm Em-4: Average silver iodide content 2.0 mol%, average grain size 0
．． 08 μm Each sample was exposed to light as described below and processed in the following processing steps.

(i) Wedge exposure using a white light source (11) Wedge exposure using a three-wavelength fluorescent lamp light source with the same light intensity as the light source in (i) Wedge exposure processing step using a spectrum light source of 480n1M to 600nm every 2nm: Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds water washing 3 minutes 15 seconds fixing 6 minutes 30 seconds water washing 3 minutes 15 seconds stabilization 1 minute 30 seconds drying The processing solution composition used in each processing step is shown below. show.

Color developer 4-amino-3-methyl-N-(β hydroxyethyl)-aniline sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine ηg acid salt 2.0 g Anhydrous potassium carbonate
37.5 g potassium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g Add water and 1
Set to 1.

Bleach solution Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid
Add 10.0 g of water to make In, and use ammonia water to adjust the pH to 6.0.
Adjust to.

Fixer ammonium thiosulfate 175.0 g Anhydrous ammonium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to make 11,
Adjust the pH to 6.0 using acetic acid.

Stabilizing liquid formalin (37% aqueous solution) 1.5 d Conidax (manufactured by Konica Corporation) 7.5 d Add water to 1
Set to 1.

The results are summarized in Table 3.

As is clear from Margin Table 3 below, it can be seen that the samples according to the present invention have improved storage stability over time and suitability for fluorescent lighting without impairing sensitivity. In addition, sample No. 107 to which the dye represented by the general formula (V) is further added has higher sensitivity than the sample to which no dye is added, and is found to be a more preferable embodiment.

Example 2 (Preparation of Samples Nα201 to 205) Multilayer color photographic material samples Nα201 to 205 were prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

1st layer; antihalation layer (HC) black colloidal silver 0.15 UV absorber (UV-1) 0.20 colored coupler (
CC-1) 0.02 high boiling point solvent (Oil-1)
0.20 high boiling point solvent (Oil-2)
0.20 Gelatin 1.6 Second layer; Intermediate layer (IL-1) Gelatin third layer; Low sensitivity red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (
Em-1) Silver iodobromide emulsion (Em-2) Sensitizing dye (S-1) 3.2X10-' (mol/silver 1) Sensitizing dye (S-2) 3.2X10-' (mol/silver 1) Sensitizing dye (S-3) 0.2X10-' (mol/silver 1) Cyan coupler (C-1) Cyan coupler (C-2) Colored cyan coupler (CC DIR compound (D-1) DIR compound (D-2) ) High boiling point solvent (Oil-1) Gelatin 4th layer; High-sensitivity red-sensitive emulsion layer (R-H) 1.3 0.4 0.3 mol) mol) mol) 0.50 0.13 0.07 0 .006 0.01 O055 1,0 Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye
(S-1) 1.7X10-' (mol/silver 1 mol) sensitizing dye (
S-2) 1.6X10-' (mol/silver 1 mol) sensitizing dye (
S-3) 0, lX10-' (mol/silver 1 mol) Cyan coupler (C-2) 0.23 Colored cyan coupler (CC-1) 0.03 DIR compound (D-2) 0.02 High boiling point solvent (Oil-1) 0.25 gelatin
1.0 5th layer; Intermediate layer (IL-2) Gelatin 0.8 6th layer; Low-sensitivity green-sensitive emulsion layer (GL) A4 in Table 4! Silver iodobromide emulsion spectrally sensitized to green sensitivity as described in iii.
0.6 Silver iodobromide emulsion spectrally sensitized to green sensitivity listed in column B of Table 4. 0.2 Magenta coupler (M
-1) 0.17 magenta coupler (M-2)
0.43 colored magenta coupler (CM-1)
0.10 DIR compound (D-3) 0.02 High boiling point solvent (Oil-2) 0.70 Gelatin
1,0 7th layer; high-sensitivity green-sensitive emulsion layer (
G-H) Silver iodobromide emulsion spectrally sensitized to green sensitivity described in column C of Table 4 0.9 magenta coupler (
M-1) 0.03 magenta coupler (M-2)
0.13 Colored Magenta Coupler (CM-1
) 0.04 DIR compound (I)-3) 0.004 High boiling point solvent (Oil-2) 0.35 Gelatin
1.0 8th layer; yellow filter layer (yc) yellow colloidal silver 0.1
Additive (H3-1) 0.07 additive (
HS-2) Additive (SC-1) High boiling point solvent (Oil-2) Gelatin 9th layer; Low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (
Em-1) Silver iodobromide emulsion (Em-2) Sensitizing dye (S-9) 5.8X10-' (mol/silver 1) Yellow coupler (Y-1) Yellow coupler (Y-2) DIR compound (D -1) DIR compound (D-2) High boiling point solvent (Oil-2) Gelatin 10th layer; High sensitivity blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (Em-5) Sensitizing dye (S- 10) 3.0X10-' (mol/silver 1 mol) sensitizing dye (
S-11) 0.25 0.07 0.12 0.15 1.0 0.25 0.5 mol) 0.60 0.32 0.003 0.006 0.18 1.3 1.2X10-' (mol/silver 1 Yellow coupler (Y-1) Yellow coupler (Y-2) High boiling point solvent (Oil-2) Gelatin 11th layer; 1st protective layer (PRC)-1) Silver iodobromide emulsion (
Em-4) Ultraviolet absorber (UV-1) Ultraviolet absorber (tJV-2) Additive (H3-1), Additive (H3-2) High boiling point solvent (Oil-1) High boiling point solvent (Oil-3 ) Gelatin 12th layer; 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2 μm) Polymethyl methacrylate (average particle size 3 μm) Gelatin mol) 0.18 0.10 0.05 1 .0 0.3 0.07 0.1 0.2 0.1 0.07 0.07 0.8 0.13 0.02 0.5 In addition to the above composition, each layer also contains a coating aid. 5O22 dispersion aid 5U-1, hardener H-1. H-2 dye Al-1,A
1-2 was added appropriately.

The emulsion used in the above sample was a monodisperse emulsion of high internal iodine content as shown below.

Em-1: average silver iodide content 3.5 mol%, average grain size 0
．． 55 μm Em-2: average silver iodide content 2.5 mol%, average grain size 0
．． 36 μm Em-3: average silver iodide content 7.5 mol%, average grain size 0
．． 65 μm Em-4: Average silver iodide content 2.0 mol%, average grain size 0
．． 08 μm Em-5: average silver iodide content 8.5 mol%, average grain size 1
．． 02 μm In this example, the hue reproducibility of a blue-green cloth and the stability of the manufactured sample during manufacturing were evaluated.

Each sample was subjected to the same treatment as in Example 1.

table As is clear from 4, The sample of the present invention was manufactured Excellent stability during construction, And blue-green color reproduction is also good. It can be seen that it is.

Example 1 below The structure of the compound used in 2 is shown. vinegar.

■ M M-1 C ■ M and.

D-3 H 0■ V Leaf V C, H9 2H5 (1;H2)35s3゜ (L; tlzJ 3S03″ C ■ [(CH.

CH30zC)Iz) :1CCH2SOZCH2CH
2] zNCHzCHzSOaKU (Alkanol XC) C U-2 i U し11z-L, υυ tliL t'zL;
Nυ C (Mixture 2:3) IJ υi tHs C,H.

Example 2 of Preparation of Emulsion of Al-2 Size 3 and 5 U3 The following emulsion was prepared according to the method described in Japanese Patent Application No. 224002/1983.

Em-2: average particle size 0.27 μm, average shape modification composition 8.0
Core/shell emulsion Em-Ho with a mol% surface modification composition of 0.5 mol%: average grain size 0.38 μm, average modification composition 8.5
A core/shell emulsion with a mol% surface modification composition of 0.1 mol% The above silver iodobromide emulsion was optimally chemically sensitized using sodium thiosulfate, chloroauric acid and ammonium thiocyanate.

In addition, 4-hydroxy-6-
Methyl-1,3,3a,7-chitrazaindene was used.

In this chemical ripening step, the same fine grain silver iodide (A) as used in Example 1 or a comparative compound were added to prepare a chemical ripening emulsion of the present invention and a comparative emulsion. The prepared emulsion and manufacturing conditions are shown in Table 5.

Example 3 Multilayer color photographic material samples Nos. 301 to 305 were prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

1st layer; antihalation layer black colloidal silver 0.20 UV absorber (UV-1) 0.20 high boiling point solvent (Oil
-1) 0.20 gelatin
1.40 2nd layer; intermediate layer gelatin 1.30 3rd layer; low sensitivity red-sensitive emulsion layer internal highly modified silver iodobromide emulsion (average normality composition 8.0 mol%,
Average particle size: 0.27 μm) 0.80 Sensitizing dye (SD
-1) '3.0X10-' sensitizing dye (SD-2
) 4.0X10-' Cyan coupler (C-1
) 0.45 colored cyan coupler (CC
-1) 0.06 DIR compound (D-1) 0.05 High boiling point solvent (Oil-1) 0.50 Gelatin
0.90 4th layer; intermediate layer gelatin 1.00 5th layer; highly sensitive red-sensitive emulsion layer internal highly modified silver iodobromide milk (average normality composition 8.5 mol%,
Average particle size: 0.38 tt m) 1.20 Sensitizing dye (SD-1) 2.5X10-' Sensitizing dye (SD-2) 3.5X10-' Cyan coupler (C-1) 0.15 Colored cyan coupler (CC-1) 0.02 DIR compound (D-1) 0.08 High boiling point solvent (Oil-1) 0.25 Gelatin
0.90 No. 611; Interlayer color stain prevention agent (SC-1) 0. IQ high boiling point solvent (Oil-2) 0.10 gelatin
1.00 7th layer - low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion magenta coupler (M-1) listed in Table 6 Colored magenta coupler (DIR compound (D-2) DIR compound (D-3) High boiling point Solvent (Oil-2) Gelatin 8th layer; High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion magenta coupler (M-1) listed in Table-6 Colored magenta coupler (DIR compound (D-2) DIR compound (D- 3) High boiling point solvent (Oil-2) Gelatin 9th layer; Yellow filter layer Yellow colloidal silver 0.80 0.53 CM-1) 0.09 0.01 0.03 0.70 1.30 0.90 0 .17 CM-1) 0.06 0.04 0.01 0.40 0.80 0.10 Color stain inhibitor (S C-1) 0.10 High boiling point solvent (Oil-2) 0.10 Gelatin
l, 00 10th layer: Highly modified silver iodobromide emulsion inside the low-speed blue-sensitive emulsion layer (average normality composition 8.0 mol%,
Average particle size 0.27 μm) 0.50 sensitizing dye (S
D-6) 8.0X10-' Yellow coupler (Y-1) 0.95DIR compound (D-1
) 0.05 high boiling point solvent (Oi 1-2)
0.10 gelatin 0
．． 50 11th layer; high sensitivity blue-sensitive emulsion layer internal highly modified silver iodobromide emulsion (average normality composition 8.5 mol%,
Average particle size: 0.38 um) 0.50 Sensitizing dye (S
D-6) s, oXlo-' Yellow coupler (Y-1) 0.20DIR compound (D-1
) 0.01 high boiling point solvent (Oil-2)
0.02 Gelatin 0.
40 12th layer; 1st protective layer Fine-grained silver iodobromide (average particle size 0.08 μm) 0.20 Ultraviolet absorber (UV-1) 0.07 Ultraviolet absorber (UV-2) 0.10 High boiling point solvent (Oi
l-1) 0.07 high boiling point solvent (Oil-3)
0.07 Gelatin 0
．． 60 13th layer; 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) o, is Polymethyl methacrylate (average particle size 3 μm) 0.04 Slip agent (WAX-1) 0.04 Gelatin
The structure of the compound used in Example 3 is shown below 0.60.

Below margin C-1 0 mouth M-1 rσ 0i ■ D D D H C V-1 D-4 D-5 D-6 H υH H Weight average molecular weight M w =3,000 (CHt)asO3H-N(CzHs )s In addition to the above composition, coating aid 5u-1, dispersion aid 5u-2, viscosity modifier, hardening agent H-1, H-2, stable side 5T-1, antifoggant AF- ], w: 100,000 and w:
1,100,000 of two types of AF2 were added.

T H CHzCOOCsHI7 F (CHz””CH30□CHz)z.

Regarding the obtained sample, Example 1. In the same manner as in Example 2, sensitivity, storage stability over time, and color reproducibility of blue-green cloth were evaluated. However, the sensitivity is a relative value when the sensitivity of sample Nα301 is set as 100.

As is clear from Table 6, the samples of the present invention have good blue-green color reproducibility and are excellent in both sensitivity and storage stability over time.

〔Effect of the invention〕

The present invention provides excellent color reproducibility, particularly for blue-green, and excellent color reproducibility for light sources including fluorescent lamp light sources, as well as stability during manufacturing and storage stability over time of manufactured photosensitive materials. An excellent and highly sensitive silver halide color photographic material has been provided.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. , the wavelength λG giving the highest sensitivity in the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer is 525 nm≦λG≦560 nm, and the sensitivity SG500 at 500 nm is 1/4 or more of the sensitivity SGmax at the wavelength λG, and At least one of the green-sensitized silver halide emulsions contained in the layer is formed using fine-grain silver halide having a halogen composition represented by the following general formula (1). Characteristic silver halide color photosensitive material. General formula (1) AgCl_aBr_bI_c However, in general formula (1), a, b, and c satisfy the following conditions. 0≦a<1 0≦b<1 0<c≦1 m<c (m: surface iodide composition of silver halide emulsion to be spectrally sensitized) a+b+c=1