JPH03215848A - Silver halide color photographic sensitive material having improved color reproducibility - Google Patents

Abstract

PURPOSE:To provide the color photographic sensitive material having improved purple color reproducibility and flesh color reproducibility by specifying the spectral sensitivity distributions of silver halide emulsion layers varying in color sensitivity and the masking characteristics of color developing couplers. CONSTITUTION:The spectral sensitivity distribution SR(lambda) of the red sensitive silver halide emulsion layer of the color photosensitive material having the blue sensitive silver halide emulsion layer contg. the color coupler which develops a yellow color, the green sensitive silver halide emulsion layer contg. the coupler which develops a magenta color and the red sensitive silver halide emulsion layer contg. the color coupler with develops a cyan color is so determined that (A) the wavelength lambdaR<max> to maximize the SR(lambda) attains 595 nm<=lambdaR<max=635nm (B) the wavelength on the long wave side of the wavelength lambdaR<50> to decrease the SR(lambda) to 50% of SR(lambdaR<max>) attains 630nm<=lambdaR<50=650nm. In addition, the masking characteristics of the green density obtd. by red color separating and exposing are so determined as to attain overmask of at least >=0.04 green density in the exposure to give the min. red density +0.30.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved color reproducibility.

[Prior art]

In recent years, the image quality of silver halide color photographic light-sensitive materials (hereinafter abbreviated as color light-sensitive materials) has improved significantly, but color reproducibility is still not satisfactory. The spectral sensitivity distribution and interimage effect (hereinafter abbreviated as IIB) of color photosensitive materials are factors that have a particularly large effect on color reproducibility.
can be mentioned.

In Japanese Patent Publication No. 49-6207, deterioration of color reproducibility due to changes in color temperature of the light source is prevented by using a filter layer or the like to bring the spectral sensitivity distributions of the blue and red photosensitive layers toward the green photosensitive layer. However, such a change in the spectral sensitivity distribution causes a significant decrease in sensitivity, and although changes in reproduced colors due to changes in color temperature are reduced, the color reproduction gamut becomes narrower due to the large overlap in the spectral sensitivity distribution between each layer. The drawback was that highly saturated colors were not reproduced, resulting in dull colors.

In general, when aiming at faithful hue reproduction in controlling the spectral sensitivity distribution, shortening the wavelength of the red light layer is also important from the point of view of bringing it closer to human visual sensitivity. In particular, for the color reproduction of blue-purple flowers that contain so-called red color, it is essential to shorten the wavelength of the red light layer.

However, as mentioned in Section 2, the shift to shorter wavelengths in the red-sensitive layer resulted in a decrease in saturation, which caused problems in skin tone reproduction, which is particularly important for color reproduction in color photographs. That is, there is a drawback that the healthy reddish characteristic of skin color is lost, resulting in a lifeless color reproduction.

In addition, the technology that defined spectral sensitivity and IIE was published in JP-A-62-1.
No. 60449. This technique applies IIE directionality to each color-sensitive layer.

Furthermore, JP-A-62-160448 discloses a technique in which a cyan photosensitive layer is provided, and IIE is applied to the red sensitive layer, with the purpose of obtaining a negative spectral sensitivity corresponding to the spectral intensity of the human eye. However, the color reproducibility of these materials is still not sufficient, and a photosensitive material with good color reproducibility has been desired.

(Object of the Invention) Therefore, the object of the present invention is to provide a color photographic material that faithfully reproduces hues, and in particular, provides a color photographic material that has good reproduction of purple hues and skin tones. There is a particular thing.

[Structure of the Invention] The present inventors have completed the present invention as a result of extensive research into the spectral sensitivity distribution of silver halide emulsion layers that vary in color sensitivity, and the masking characteristics and color reproducibility of color-forming couplers. Ta.

That is, at least one blue-sensitive silver halide emulsion layer containing a yellow-producing color coupler, a green-sensitive halide recording emulsion layer containing a magenta-producing coupler, and a cyan-producing color coupler each contained on a support. In a color photosensitive material having a red-sensitive silver halide emulsion layer, the spectral sensitivity distribution SR(λ) of the red-sensitive silver halide emulsion layer is such that (a) the wavelength λRmax at which Sl1(λ) reaches a maximum is 595 nm≦λ , +1″a′-≦635nm (mouth) SR
(λ] is 50% of So(λRllll+lX) The wavelength on the long side of λRso is 630nm≦λR5°≦650r+m, and the masking characteristic of the green density obtained by red separation exposure is the minimum red density + 0. 1. A silver halide color photographic light-sensitive material, characterized in that it is an Oher mask with a green density of at least 0.04 or more at an exposure dose of 30.

The present invention will be specifically explained below.

In the present invention, the spectral sensitivity distribution of the red-sensitive layer has a maximum wavelength λmAN of 595 nm≦λ1″ゝ≦635 nm.The light-sensitive material whose wavelength is shortened beyond the above range has a low saturation of reproduced colors. If there is a shortage, it will cause disadvantages.

λRIIaX is preferably in the range of 600 nm≦λR″W≦625 nm, more preferably 605 nm≦λllIll!X≦620 nm.

Also, S. (λ) is S R(λR””) 0) 5
It is essential that the wavelength on the long side of wavelength λ2'', which is 0%, is 625 nm≦λRso≦650 nm.When exhibiting characteristics that extend to long waves beyond the above range, red reproduction is good, but violet reproduction deteriorates. However, it is undesirable because it becomes reddish and becomes highly dependent on the photographing light source.

Preferably 630nm≦λR5°≦645nm More preferably 630nm≦λR50≦640nm It is.

Further, the wavelength on the short wave side of the wavelength λRso at which SR(λ) is 50% of SR(λ♂ax) is 575 nm≦λ,'. ≦600 nm is preferable.

In the tree invention, the spectral sensitivity distribution has a minimum density of −+−0.
The sensitivity that gives a density of 1 can be obtained by plotting the sensitivity on the horizontal axis wavelength.

In the present invention, the spectral sensitivity distribution of the red-sensitive layer can be obtained, for example, by using a suitable combination of spectral sensitizing dyes having the structural formulas shown below.

The spectral sensitivity distribution of the present invention is based on at least one of the multiplying dyes represented by the general formula (1) shown below and the general formula (III).
) can be formed by combining at least one sensitizing dye represented by the formula (I), (IT), or (III). It's good to be able to combine each one.

In addition, supersensitizers can be used in addition to the sensitizing dyes represented by the general formula (1)(n)(In). Penzothiazoles and quinolones, and quinoline derivatives described in Japanese Patent Publication No. 57-24899 can also be used depending on the purpose.

General 2N) (n) (III) will be explained in detail below.

L (lower white general formula (T)) In the above general formula (1), Rl represents a hydrogen atom, an alkyl group, or an aryl group, and R2 and R3 each do not represent an alkyl group. , each represents a sulfur atom or a selenium atom.

Next, z+. zz, Z'3 and Z4 are hydrogen atom, halogen atom, hydroxyl group, alkoxy group, amino group, acyl group, acylamino group, acyloxy group, aryloxy group, alkoxycarbonyl group, aryloxy group, alkoxy group, respectively Represents a luponylamino group, a sulfonyl group, a carbamoyl group, an aryl group, an alkyl group, or a cyano group. Z1 and Z2 and/or Z'' and Z4 may be linked to each other to form a ring. Also, X and e represent an anion. m represents ■ or an integer of 2; When forms an inner salt, m represents 1.

General formula (U) (X2e),, In the above general formula (n), R4 represents a hydrogen atom, an alkyl group, or an aryl group, and R5. RbR7 and R8
each represents an alkyl group.

Y3 and Y4 represent a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom, but when Y3 is a sulfur atom, an oxygen atom, or a selenium atom, it does not have the above R5.

Moreover, Y3 and Y4 do not become nitrogen atoms at the same time.

Next, z', z6, z' and Z8 are hydrogen atoms, respectively.
Halogen atom, hydroxyl group, alkoxy group, amino group, acyl group, acylamino group, acyloxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxyluponylamino group, carbamoyl group, aryl group, alkyl group, cyano group or a sulfonyl group. Z5 and Z6 and/or Z7 and Z
0 may be connected to each other to form a ring. Moreover, X20 represents an anion. n represents an integer of 1 or 2; however, n represents 1 when the sensitizing dye forms an inner salt.

General formula (III) (x30)n In general formula (Ill), R9 represents a hydrogen atom, an alkyl group or an aryl group, and R104, RI2 and R'' each represent an alkyl group.

Next 29. Z10. Zl1 and 212 are a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acyl group, an acylamino group, an acyloxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxyluponylamino group, and a carhamoyl group, respectively. group, aryl group, alkyl group, cyan group or sulfonyl group.

Z9 and Z10 and/or Zl1 and 212 may be connected to each other to form a ring.

Moreover, X30 represents an anion. n represents an integer of 1 or 2, and n represents 1 when the sensitizing dye forms an inner salt.

(I 1) (CH2)4503θ (C}1.)4803+1 (■ 2) C 2I+ , ? C11■)3S03θ (I 3) C. l15 (CHz) 4S03 e (I 4) C. l+, Bre? C11■)4COOI1 (■ 5) (I 6) (1-7) (■ 8) (I 9) +1LI (Cllz) zsO*θ (Clh) as(hl+ (I 10) (I 11) (■ 12) (CII2) 4s03e? C｝ 1 ■) 4s (HL + (I13) (I 14) (I 15) C2H5 C 2i +, BRE (■ 17) e (I 20) ?C11■) 350z" (CI+2) as[]sll (I 21) CIIzCILzCll503" (CI12) 430311 C113 (■ 22) (CI12) 35Oz e (CI+2) 4sOJa ?C11■) 350 3” ?C11■ )350.+1 CI12CI12CII503 e ?C11■),803+1 Clh (Cll 2) 350 3e (C11.) 330311N (C2115) 3 (Cl1
2) 3503” ?C11■冫zsOillN(Czlls)3(I 28) (Cllz) asO3” (CI12) 4sO311a (Cllz) ssOs e (CI12) 3503+1 (I 31) ? C11 ■) 3503L: I ((;112) 3sO3Na (■ 32) (I 33) (1 -35) (I 36) (I 38) (I 39) (I 40) (I 41) (■ 42) ( I 43) (I 44) (■ 45) (I 46) (■ ■) (■ 2) (U-3) C.ll5 C2115 C.ll5 (■ 4) (■ 5) (■ 6) C z It s Czlls ?C11■)20COCl13 C11, 2f7 (■ 7) (■ 8) (■ 9) C 2 It 5 C 2I+ 5 28 (II-10) (■ 11) (■ 12) CJs C113 C21140CI+3 (I[- 13) (■ 14) (II-15) C2+14011 02 II 5 (■ 16) C 2It 5 S03e (■ 17) C2115 (■ 18) C. l+5? C11 ■) 350. θ? C11■)4S0311・N(C2115)3(II
-1.9) C2115 (■ 20) C2115 (■ 21) C2115 (Clh) 3S (h ” (Cllz) 3sOaNa (■ 22) (■ 23) (■ 24) (■ 25) C 2 II S (It- 26) C2115 (■ 27) (:2115 (Cllz) zcOo e ?C11■)2COOI+ (■ 28) (■ 29) (■ 30) (■ 31) (TI-32) (■ 33) (■ 34) ( TI-35) (■ 36) (■ 37) (■ 38) (■ 39) (CI+2) asOs e (Cllz) 4sO3Na (■ 40) C 2+1 5 (CII2) 4503 e (■ ■) (■ 2) ( ■ 3) ([;Ilz冫.50.'d (CI+2) 3SQ311 (■ 4) C z II s C. II 5 (CI+2)3503θ C.l15 (■ 5) C 2II S C.I1, (CI+2) 3S03 e (Ctlz) :+50Ja (■ 6) ?II■CI+20COCI+3 ?IIZCII■OCOCth (Cth) 3sO3 e C21{S 41 (■ 7) (■ 8) C2115 C.I+,, (CI+2) 2CII-S03 e ( CI+2) zclI-50Ja C113 C113 (■ 9) ?II■Cll.OCI!3 CI12CIhOCI+3 42 (■ 10) (■ 11) Czlls C.l+, (■ 12) C.l+. C.I+5 ?Il■CIbClh ( (;lhノ35U3ri female (■ 13) (■ 14) C. I+ 5 C2115 C 2I+ 5 (CI!z)4sOaθ (■ 15) Czlls Cz If s 44 (III-16) C.H5 C z It s (■ 17) C.II5 CtH5 (■ 18) C2HS CHzCIlzCIIzOCOCHs 49 (■ 19) (I[l-20) (■ 21) ・46 (■ 22) C z II s C211, (■ 23) C.I+, C 2 II 5 (■ 24) C. H, C. H, (CLLZ) ZSOS (CLL 2) ZSO3NA (■ 25) C 2i1 5 (■ 26) CZLLS (I [I -27) C2115 C.I + 5 CZLLS CZ CZ }!s C.l15? C11■)<50sθ (■28) (III-29) (■30) C2HS C. l{5 C. H5 C 2 It S C. H, C 2 I+ 5 Br':'n) Next, the masking technique used in the present invention will be described. Masking techniques such as colored couplers and caprimasks are generally used in color non-gauge films to correct for secondary absorption (incorrect absorption) of colored couplers. For example, a cyan coloring coupler has absorption not only in the red density but also in the blue and green regions.A colored cyan coupler is used in the red-sensitive layer to correct this secondary absorption, and the green density is essentially a cyan coloring coupler. The color density is kept constant so that it does not depend on the color density, improving color reproducibility.

In the present invention, in addition to correcting the incorrect absorption of the green portion of the cyan coupler, the present invention requires an Oher mask technique that develops the green density in a counterimage manner as the cyan image develops. This technique is similar to the interimage effect (IIE) from the red-sensitive layer to the green-sensitive layer; It has the advantage of being able to control TIE.

In the present invention, the massing characteristic of the green density obtained by red separation exposure is the minimum red density + 0. It is an Oher mask with a green density of at least 0.04 or more at an exposure amount that gives 3.0. Preferably, it is an Oher mask with a size of 0.07" or more. The upper limit is not particularly limited, but is approximately 0.15. The above-mentioned Oher mask characteristics can be obtained by using a photosensitive material such as Eastman Kodak's Lanten filter No. 2.
It is obtained by performing decomposition exposure using a red filter such as No. 9, performing the development process described in Examples, and then measuring using a Status M filter. The degree of Oher mask is the green density of the unexposed area and the cyan color development D of red separation exposure.
nirt 0. It can be determined from the difference in green density at an exposure amount that gives a red density of 30.

The Oher mask characteristics described in 2 can be obtained by various methods. If Ohermask characteristics can be obtained as a result, it is particularly preferable to use a colored coupler.

The method of use may be appropriately controlled depending on the type of colorless coupler or color 1 coupler to obtain overmask characteristics, but the following method is effective.

■ A method of using a large amount of colored cyan coupler compared to colorless cyan 51 coupler. In this case, when obtaining Ohermask characteristics at a relatively low end of the characteristic curve as in the present invention, it is effective to shift the ratio of the colored tosian coupler in the red-sensitive layer with the highest sensitivity to the highest among the red-sensitive emulsion layers. Yes, it is preferable.

■ A method of obtaining an Ohermask by selecting a combination of cyan couplers in which the color 1-cyan coupler has higher reactivity with the oxide of the developing agent than the colorless cyan coupler, and preferentially reacting the color 1-cyan coupler. In this case as well, it is most effective when the combination of the two is realized in the highest sensitivity layer. Specifically, a preferred combination is a combination in which a 2-equivalent colored cyan coupler is used and a 4-equivalent cyan coupler is used.

The cyan coupler effectively used in the present invention will be described below.

Color 1/cyan coupler that can be preferably used in the present invention can be represented by the following general formula (1).

52 coop * (J+T-N=N R.3 In the formula, coup represents a cyan coupler residue, * represents a coupling site of the cyan coupler, , J represents a divalent linking group, and C represents O or 1 and R3 represents an aryl group.

The cyan coupler residue represented by COUP includes a phenol coupler and a naphthol coupler residue, and a naphthol coupler residue is particularly preferred.

A preferred divalent linking group represented by J can be represented by the following general formula [2].

General formula [2] In the formula, R6 represents an alkylene group having 1 to 4 carbon atoms or an arylene group, R7 represents an alkylene group having 1 to 4 carbon atoms, and the Al53 kylene group of Re and R is an alkyl may be substituted with a group, a carboxy group, a hydroxyl group, or a sulfo group.

R, Z are 1C- -o-, -s-, -so? IG 50■ -, 150■Nll -. -CONI
I-, -COONIICO- -NH50■1.
-OCO-, and R and RIG represent an alkyl group or an aryl group.

R8 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, a cyano group, a nitro group, a sulfonyl group,
It represents an alkoxy group, an aryloxy group, a carboxy group, a sulfo group, a halogen atom, a carbonamide group, a sulfonamide group, a carhamoyl group, an alkoxycarbonyl group, or a sulfamoyl group.

P represents 0 or a positive integer, q represents O or l, and T represents an integer from 1 to 4. When P is 2 or more, R
6 and Z may be the same or different. When T is 2 or more, R8 may be the same or different.

54 As the aryl group represented by R3,! When the number is 10, phenyl and naphthyl groups are preferred.

The phenyl group and naphthyl group can have a substituent, and the substituent includes an octalokene atom, an alkyl group,
Alkoxy group, aryloxy group, hydroxy group, anoloxy group, car, noxyl group, alkoxycarbonyl group, aryloxysulfonyl group, mercabuto group, argylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, Acyl group, acylamino group,
These include sulfonamide F group, carhamoyl group, and sulfamoyl group.

In the case of oligo-1, the aryl group represented by R3 is preferably a naphthol group represented by the following general formula (3).

General formula [3] In the formula, R9 is a linear or branched alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, probyl group, isopropyl group, butyl group, sec-butyl group, L- butyl group, etc.), and M is a photographically inert cation, such as hydrogen, an alkali metal cation such as sodium or potassium atom, ammonium, methylammonium, ethylammonium, or ethyl ammonium. , 1-ethylammonium, ethanolammonium, soethanolammonium, pyridinium, Pibe IJ
Represents sium, ayulinium, 1-lucinium, P-nitroanilinium, anisidium, etc.

Next, specific examples of typical color 1 couplers represented by general formula (l) will be shown, but the invention is not limited thereto.

5G CC ■ CC 3 (111 50JNa Curse CC 7 CC 9 0H COOC2115 COCH: 1 CC 12 0 ■ CC 13 COOC+6lL+3 (sec) 61 CC l4 The above compounds are disclosed in Japanese Patent Application Laid-open No. 1-123341, No. 5
No. 565957, No. 56-94347, Special Publication No. 1977-
No. 11304, No. 44-32461, No. 48-178
No. 99, No. 53-34733, U.S. Patent No. 3,0
34,892, British Patent No. 1,084,480, and the like.

Cyan couplers used with the colored cyan couplers of this invention are generally colorless cyan couplers.

The colorless cyan coupler 6z according to the present invention is a phenol type coupler or a naphthol type coupler, and preferable ones have the following general formula [4], (
5] or [6].

General 2 [4] Oi1 8 general formula [5] 011 8 general formula [6] 0H ? In the formula, A represents a hydrogen atom or a group capable of being separated by reaction with an oxidized product of a color developing agent.

R1, R2 and R3 each represent a group used in a conventional phenol or α-natofur coupler; specifically, R1 is a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon residue, N
Examples include -arylureido group, acylamino group, -■-R' or -S-R' (where R4 is an aliphatic hydrocarbon residue), and when two or more R7s exist in the same molecule, 2 The two or more R1 groups may be different groups, and the aliphatic hydrocarbon residues include those having substituents.

In addition, when these substituents contain an aryl group, the aryl group is an alkyl group, an argenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group. group, carboxy group, alkoxycarbonyl group, ryoloxycarbonyl group, sulfo group, sulfamoyl group, carhamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, aryl Sulponyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxy group, mercapto group etc.

Examples of R2 and R3 include groups selected from aliphatic hydrocarbon residues, aryl groups and heterocyclic residues, or one of these may be a hydrogen atom,
It also includes those in which these groups have substituents. Further, R2 and R3 may jointly form a nitrogen-containing heterocyclic nucleus.

The aliphatic hydrocarbon residues may be either saturated or unsaturated, and may be straight-chain, branched, or
Any ring-shaped one may be used. Preferably, an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, L-butyl, isobutyl, dodecyl, octadecyl, cyclophyl, cyclohexyl, etc.), an alkenyl group (e.g., allyl, octenyl, etc.) be.

Aryl groups include phenyl group, naphthyl group, etc.
In addition, heterocyclic residues include pyridinyl, kyl/IJyl,
Representative groups include chenyl, piperidyl, imidazulyl, and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, ditro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, peterocycle, alkoxy , aryloxy, arylthio, arylazo, acylamino, carhamoyl, ester,
Examples include groups such as acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino.

The leaving group represented by A includes any group known as a leaving group for 2-equivalent phenolic cyan couplers and 2-equivalent naphyl-based cyan couplers, but more preferably << is a halogen atom ( For example, fluorine,
chlorine, etc.), substituted or unsubstituted alkoxy groups (e.g., 1-oxy group, 2-methoxyethoxy group, 3-carpoxyproboxy group, n-hexadecyloxy group), substituted or unsubstituted aryloxy groups (e.g., phenoxy group, 1-naph-1-xy group, 4-methoxyphenoxy group,
4-L-octylphenoxy group, 4-methanesulfonylphenoxy group, 3-pentadecylphenoxy group, etc.),
Substituted or unsubstituted heterocyclic oxy groups (e.g., 2-pyridyloxy group, 4,6 dimethoxy-1.3.5-triazin-2-yloxy group, etc.), substituted or unsubstituted alkylthio groups (e.g., methylthio group) , 2-methanesulfonylethio group, n-todecylthio group), substituted or unsubstituted arylthio group (e.g. phenylthio group, 4-n-todecylphenylthio group, 2methoxy-5-
t-octylphenylthio group) substituted or unsubstituted alkylsulfonyl group (e.g. methylsulfonyl l, n
monodecylsulfonyl group, 4-hy1-loxybutylsulfonyl group), substituted or unsubstituted heterocyclic group (e.g. 3-21-[:IG wabiraduryl group, morbolino method, l-henzyl-5ethoxy hydantoin-3-yl group, etc.).

Among these, particularly preferable examples of X include a hydrogen atom, a chloro atom, a fluorine atom, an aryloxy group, a heterocyclic oxy group,
and an alkoxy group. Aryloxy groups are particularly preferred.

The silver octalokenide emulsion used in the light-sensitive material of the present invention includes:
Although any silver halide emulsion can be used, silver iodobromide emulsions are particularly effective.

The emulsion can be chemically sensitized by a conventional method, and the emulsion used in the blue-sensitive layer and the green-sensitive layer is optically sensitized to a desired wavelength range using a known and publicly available sensitizing dye. can.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as a binder for the emulsion.

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

For each of the emulsion layers of the blue-sensitive layer and the green-sensitive layer, known and commonly used couplers can be used.

Furthermore, by compounding with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, Compounds that release photographically useful fragments such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer.

A formalin scavenger, a fluorescent brightener, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog preventer, a development accelerator, a development retardant, a bleaching accelerator, etc. can be added to the photosensitive material.

As the support, polyethylene terephthalate film, cellulose triacetate film, etc. can be used.

To obtain a dye image using the 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 indicates the number of durams per m2 unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver.

Example 1 On a triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare a multilayer color photographic material sample-No. 1 was produced.

Sample-No. 1 (comparison) 1st layer; antihalation layer (H(,-1) black colloid 0.18 UV absorber (UV
~1) 0. 2 3W O High boiling point solvent (Oif-1) 0.18 Geladin 1.4 2nd layer; 1st intermediate layer (l l..-1) Gelatin
1.0 Third layer; low-speed red-sensitive emulsion layer (RL
) Iodobromide emulsion (average grain size 04 μm) 1.0 Sensitizing dye (+-40) 1.8X10-5 (mol/silver 1 mol) Sensitizing dye (1-6)]. 6xlL' (monoray/1 monoray) Soan coupler (C-]) 0.70 colored cyan coupler (CC-1) 0.13DIR compound (D-1) 0.04DIR compound (D-
3) 0. OI high boiling point solvent (Oip.-)
) 0.64 gelatin
1.2 4th layer, medium-sensitivity red-sensitive emulsion layer (RM) Iodobromide emulsion (average grain size 0.7 μm) 0.8 Sensitizing dye (1-40) 2.1X10-5 (monoret/1 emulsion) 1 mol) Sensitizing dye (1-6) L9Xl O-' (monoole/t 1 monole) Cyan coupler (C-1) 0.28 Colored cyan coupler (C(,-1) 0.0 2 7
DIR compound (D-]. ) 0.0 1
5 High boiling point solvent (Oie-1) 0.26 Gelatin 0.62 5th layer; High sensitivity red-sensitive emulsion layer (RI{) Silver iodobromide emulsion (average grain size 0.8 μm) 1. 'l O sensitizing dye (14
0)I. 9X] O-5 (mol/silver 1 mol) Sensitizing dye (1-6) I. 7
Cyan coupler (CC-1) 0.0 2 5DI
R compound (D-1) 0.025 High boiling point solvent (Oiff-1) 0.17 Gelatin
1.2 6th layer; 2nd intermediate layer (
IL-2) Wa2 Gelatin 0.8 7th layer; low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm) 1.0 Sensitizing dye (SD-4)6. 8XI O-' (mol/mol of silver) Sensitizing dye (SD-5) 6.2x 1 0-' (mol/mol of silver) Magenta coupler (lvl-1) 0.54 magenta coupler (M-2 ) 0.19 Color Tomagenta Cuffiller (Group C-1) 0.06DIR Compound (D-2) 0.017DIR Compound (
D-3) 0.01 high boiling point solvent (Oiff
-2) 0.81 gelatin
1.8 8th layer; medium-sensitivity green-sensitive emulsion layer (GM) silver iodobromide emulsion (average grain size 0.7 μm) 0.7 sensitizing dye (SD-6)]. 9X1 0-' (mol/silver 1 mol) Sensitizing dye (SD-7) 1.2X1 0-' (mol/silver 1 mol)
molar) r7'3 Sensitizing dye (SD-8) I. 5x10-S (mol/mol of silver) Magenta coupler (M-1) 0.08 Magenta coupler (M-2) 0.03 Colored magenta coupler (CM-1) 0.0 4DIR compound (D-2) 0. 018 High boiling point solvent (O
if-2) 0.30 gelatin
0.8 9th layer; high-sensitivity green-sensitive emulsion layer (G
H) Silver iodobromide emulsion (average grain size 1.0 μm) 1.7 Sensitizing dye (SD-6) I. 2X10-' (mol/silver 1 mol) Sensitizing dye (SD-7) I, OXIO-' (mol/silver 1 mol) Sensitizing dye (SD-8) 3.4 X 1 0-6 (mol/silver 1 mol) Magenta coupler (M-1) 0.09 Magenta coupler (M-3) 0.04 Colored magenta coupler (CM-1) 0.10 High boiling point solvent (O
if-2) 0.31q4 Gelatin 1.2 10th layer;
Yellow filter layer (YC) yellow koroit silver
0.10 color stain prevention agent (SC-1)
0.1 high boiling point solvent (Oin-2)
0.13 Gelatin 0.7 Formalin Scahanger (ns-1) 0. 0 9
Formalin Skahanger (US-2) 0. 0
7 11th layer; low-speed blue-sensitizing emulsion layer (BL) sensitizing dye (
Sl)-9) 5.2xl O-' (monole/1 monolayer) Sensitizing dye (SD-10) 1.9X10-5 (mol/silver 1
mole) Yellow coupler (Y-1) 0.65 Yellow coupler (Y-2) 0.24 DIR compound (D-1) 0.03 High boiling point solvent (O
ij2-2) 0.18 gelatin
1.3q9 Volmarinskahanger (+13-1) 0.
0 8 12th layer; High sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain size 1.0 μm) 1.0 Sensitizing dye (
SD-9) 1.8X10-' (mol/1 mole) Sensitizing dye (SD-10) 7.9xl O-' (monoole/
Yellow coupler (Y-1) 0.15 Yellow coupler (Y-2) 0.05 High boiling point solvent (Oiff-2) 0.07 Gelatin
1.30 Formalin Scahanger (11S-]) 0. 0 5 formalin scavenger (+18-2) 0. 1 2 Thirteenth layer; first protective layer (Pro 1) fine grain silver iodobromide emulsion
0. 4 (average particle size 0.08 um A
gl 1 mol%) ultraviolet absorber (UV-1)
0.07 Ultraviolet absorber (UV-2) 0
．． 10 High boiling point solvent (Oin-1) 0.07
High boiling point solvent (Oiff-3) 0.074 q et al. formalin scavenger (us-1) 0. 1
3 Formalin Scahanger (HS-2) 0.37 Gelatin 1, 3 14th layer; 2nd protective layer (Pro 2) Alkali-soluble manoto agent (average particle size 2 μm) 0.13 Polymethyl methacrylate (average particle size 3 μm ) 0.02 Sliding agent (WAX-1) 0.04 Gelatin 0.6C 4I+ , C 2 0H M 1 Cp. M 2 CI2. W Y 1 CC 1 011 D 1 OH D 2 01 { D 3 011 Oil 1 0iff 3 SC ■ 0H 011 UV ■ UV 2 C. H5 WAX ■ CH3 (Jl3 C113 CH3 Si 0{Si 0}-rr S+ Clh CH. CH. CH3 Weight average molecular weight h 3,000 S u 1 NaO:+S CIlCOOCall+ 7 C}12COOCIllI17 SR 2 CzH7(iso) 50Ja HS 1 H S 2 SD 5 (CH.) 4S030 ?C} 1■) 350311N (C2115) 3 Trade SD 8 (CI+2) 450:l○ C2115 SD 9 SD 10 H ■ H 2 ST 1 0H Geshang"2 Composition In addition, coating aid SR-1, separation aid S
R-2, viscosity modifier, hardener H-I, l]2, stabilizer S
T-1, antifoggant AF-kawa, Mw: 10,0
Two types of AF: 00 and M w + L 100,000
2 was added.

The average particle size is expressed as a cubic particle size.

Each emulsion was optimally gold and sulfur sensitized.

Next, sample No. The sensitizing dyes used in the third layer, fourth layer, and fifth layer in No. 1 were changed as shown in Table 1, and the fifth layer
By changing the amount of color coupler contained in the layer as shown in Table 1,
Trial i4 No. 2~No. 7 was produced.

Furthermore, sample No. 2~No. In the third, fourth, and fifth layers of Sample No. 7, the total amount of sensitizing dye added was the same as Sample No. 7. ] so that it is equimolar. In Table 1, the molar ratios of the amounts of sensitizing dyes added are shown in parentheses after the example dyes.

Also, sample No. 1~No. Each emulsion contained in Example No. 7 was optimally chemically sensitized using gold and sulfur sensitizers in a conventional manner.

In addition, in order to determine the spectral sensitivity distribution, color development was performed by the following processing steps, spectral exposure was performed, and each parameter determining the spectral sensitivity distribution was measured at a density of 1.0. In addition, red-sensitivity exposure was performed using a Wratten filter N029 manufactured by Ys 1-Mankodasoku Co., Ltd., and the difference in density (ΔD) between the green density and the unexposed area was determined at an exposure amount that gave a resolved red density of minimum density +0.3. It is shown in Table 1. Note that the higher the density value of ΔD, the more overmasked it is.

The process was continued until three times the capacity of the stabilization tank was filled with replenisher.

(The replenishment amount is the value per 1 m2 of photosensitive material.) However,
The stabilization process was carried out using a 3-tank counter force tank 1, in which the final tank was replenished with the stabilizing liquid, and the O-half tank flowed into the previous tank.

? 9 In addition, part of the overflow of the stabilization tank following the fixing tank (
2 7 5 mj2/m2) was poured into a stabilizing tank.

The composition of the color developing solution used is as follows.

Potassium carbonate 30 g Sodium hydrogen carbonate 2. 7 g potassium sulfite 2.8 g sodium 1.lium bromide
1.3g Hydroxylamine sulfate 3.2g Sodium chloride 0,6g 4-amino-3-methyl-N-ethyl=N (β-hydroxyl ethyl) Aniline sulfate 4.6g Diethylene 1-liaminepentaacetic acid 3,Og hydroxide Potassium 1.3g Add water to make IC,
using potassium hydroxide or 20% sulfuric acid.
Adjust to o1.

The composition of the color developer replenisher used is as follows.

Potassium carbonate 40 g Sodium bicarbonate 3 g 9o Potassium sulfite 7 g Sodium bromide 0.5 g Hydroxylamine sulfate 3.2 g 4-amino-3-methyl-N
Monoethyl-■ (β-hydroxylethyl) Aniline sulfate 6.0g Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide
Add 2g water and 1! and pHIO using potassium hydroxide or 20% sulfuric acid. Adjust to 12.

The composition of the bleaching solution used is as follows.

1,3 diaminopropane 4i! PM Ferric ammonium 0.35 mol Sodium ethylenethiamontetraacetic acid 2 g Ammonium bromide 150 g Glacial acetic acid
40 mIV. ammonium nitrate
Add 40 g of water to bring the temperature to 1°C, and adjust to pi-+4.5 using aqueous ammonia or glacial acetic acid.

q( The composition of the bleach replenishment solution used was: Ru.

It is as follows: 3 diaminopropanetetraacetic acid ferric ammonium 040 mol ethylenediamontetraacetic acid disodium 2 g ammonium bromide 170 g ammonium nitrate
50 g glacial acetic acid
61 me water was added to bring the temperature to 1°C, and pna. s and bleach tank solution pl
Adjust as appropriate to maintain +.

The compositions of the fixer and fixer replenisher used are as follows.

Ammonium thiosulfate 100g Ammonium thiocyanate 150g Anhydrous sodium bisulfite} I
Jum 20 g Sodium Metabisulfite
4.0g Ethylene diamine 1-raacetic acid disodium 1.0 g9″2
- Add water to 700 mI2 and adjust to pl+6.5 using glacial acetic acid and aqueous ammonia.

The compositions of the stabilizing solution and stabilizing replenisher used are as follows.

1,2henzisothiazolin-3-one 0.1 g Hexamylenetetramine 0.2 g Hexahydro L3,5- Tris(2-hydroxyethyl)-
5- Add 0.3 g of 1-riazine water and proceed II! ．．
Binding, pl17 using potassium hydroxide and 50% sulfuric acid
．． Adjusted to 0.

After storing the treated sample in a constant temperature and humidity chamber at a temperature of 65°C and a relative humidity of 60% for 14 days, the maximum density and the blue density (transmission) of the unexposed area were measured using an optical densitometer (PDA65) (manufactured by Konica ■).
was measured as a representative characteristic, and the difference in blue density (transmission) between the sample and the sample that was not treated in a constant temperature and humidity chamber was determined.

The results are shown in Table 1.

93 In the table, EDTA-Pe is ferric ammonium ethylenediaminetetraacetate, and NTA-Fe is ferric ammonium nitrilotriacetate.
Iron ammonium, DTPA・re means ferric ammonium diethylene 1・liaminepentaacetate, (A-1) 4
e, (A-4) Fe, etc. are (A-1), (A-4) respectively.
) and other ferric ammonium salts.

94 In order to examine the color reproducibility of the obtained sample, a close-up of a person's face, a color chart containing gray, red, skin tone, and purple, and a purple cloth were photographed, and the above-mentioned development process was performed, and the obtained non-woven fabric was photographed. Printed on color paper (Konica Color PC Paper Type SR). The color reproducibility of the obtained color chart was measured using a colorimeter CMS-120 manufactured by Murakami Color Research Institute.
The chromaticity was measured using the L*a*b* color system using 0, and the difference from the original is shown in Table 2 as the distance between the a* and b planes. A smaller number indicates a more faithful reproduction. At this time, 18
Color matching was performed so that the % gray reflector became gray in line 96.As can be seen from Table 2, simply changing the spectral sensitivity distribution to short waves does not have a great effect on color reproduction, but sample No. 4～
As seen in No. 7, the improvement in spot color reproduction when combined with the Oher mask is significant. Sample No. uses a large proportion of colored coupler in the red color layer and increases the reactivity ratio of colored coupler and colorless cyan coupler. 7 showed the most favorable color reproducibility.

Claims (1)

[Scope of Claims] A blue-sensitive silver halide emulsion layer each containing at least one yellow color-forming color coupler, a green-sensitive silver halide emulsion layer containing a magenta color-forming coupler, each on a support;
In a color light-sensitive material having a red-sensitive silver halide emulsion layer containing a color coupler that develops cyan color, the spectral sensitivity distribution S_R(λ) of the red-sensitive silver halide emulsion layer is the maximum of (a) S_R(λ). Wavelength λ_R^m^a^
x is 595nm≦λ_R^m^a^x≦635nm (b) S_R(λ) is 50 of S_R(λ_R^m^a^x)
%, the wavelength on the long side of λ_R^5^0 is 630 nm≦λ_R^5^0≦650 nm, and the masking characteristic of the green density obtained by red separation exposure gives the minimum red density +0.30. A silver halide color photographic light-sensitive material characterized by an overmask with a green density of at least 0.04 or more in terms of exposure amount.