JPH01259358A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the max. optical density and the min. optical density of the title material, without deteriorating the graininess of a sensitive material by incorporating a prescribed monodisperse emulsion and a specified yellow dyestuff in the sensitive material, and by specifying a silver iodide content in a photosensitive emulsion. CONSTITUTION:The sensitive material contains the monodisperse emulsion (A) having a mean particle size of <0.3mum and the yellow dyestuff shown by formula I, and the mean silver iodide content in the whole of photosensitive silver halide emulsion is specified to <=6mol.%. In the formula, X and Y are each cyano or carboxyl group, etc., R1 and R2 are each hydrogen or halogen atom, etc., R3 and R4 are each hydrogen or alkyl group, etc., L is a methine group. The dyestuff shown by the formula is composed of a compd. shown by formula II, etc., and the emulsion A is incorporated in one or more layers of the photosensitive emulsion layer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material containing a novel yellow dye.

(Prior Art) Generally, in silver halide photographic materials, for the purpose of light absorption filters, antihalation, or sensitivity adjustment of light-sensitive emulsions, the constituent layers of the light-sensitive material are designed to absorb light of a specific wavelength. The inclusion of dyes is well known, and therefore, it has been conventionally practiced to color hydrophilic colloid layers with the above-mentioned dyes.

Silver halide photographic light-sensitive materials are formed by forming a hydrophilic colloid layer such as a photosensitive silver halide emulsion layer on a support, and imagewise exposure is performed to record an image on the photosensitive silver halide emulsion layer. In this case, it is necessary to control the spectral composition of light incident on the silver halide emulsion layer in order to improve color reproducibility.

In such cases, a dye capable of absorbing light in a wavelength range that is not needed by the silver halide emulsion layer is usually added to the hydrophilic colloid layer that is located on the side farther from the support than the photosensitive silver halide emulsion layer. A method is used in which a filter layer is formed by incorporating the compound into a filter layer so that only light in a target wavelength range is transmitted.

For example, for red-sensitive emulsions and green-sensitive emulsions, a yellow filter layer is provided on the side closer to the subject than the emulsion layer in order to prevent blue light, which is unnecessary and undesirable for color reproduction, from entering the emulsion layer.

The dye used in this yellow filter layer not only has good absorption spectrum characteristics, but also has low diffusion to other layers, especially the blue-sensitive emulsion layer, when coated. By doing so, it is necessary that there is little residual color on the photosensitive material.

For this purpose, yellow colloidal silver has traditionally been used as a yellow filter.

(Problems to be Solved by the Invention) However, especially in the case of color reversal photosensitive materials, since a silver halide solvent is contained in the black and white developer, neighboring photosensitive silver halide emulsions with colloidal silver as a core are Dissolution physical development occurs, resulting in extremely undesirable problems such as deterioration of graininess and decrease in maximum density. According to the research conducted by the present inventors, when the grain size of the emulsion is small, there is a strong tendency for the graininess to deteriorate and the maximum density to decrease.

On the other hand, there are many known yellow dyes that can replace yellow colloidal silver. For example, the pyrazolone oxonol dyes described in British Patent No. 506°385, US Pat. No. 3,2
47,127, azo dyes described in U.S. Pat. No. 2,390,707, styryl dyes described in U.S. Pat. No. 2,255,077, British Patent No. 584, Hemioxonol dyes described in US Pat. No. 609, U.S. Patent No. 2,493.7
Merocyanine dyes described in U.S. Pat. No. 47, U.S. Pat.
Examples include cyanine dyes described in US Pat. No. 843.486 and closed methylene hengelidene dyes described in US Pat. No. 4,420,555.

Although the use of these yellow dyes improves the problems often seen when using colloidal silver, such as deterioration of graininess and decrease in maximum density (Dmax), it is said that the minimum density (Dmin) increases. It turns out that a new problem arises.

The object of the present invention is to achieve high D without deterioration of graininess.
The object of the present invention is to provide a silver halide color photographic light-sensitive material that provides a high Dmin and a low Dmin.

(Structure of the Invention) An object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one red-sensitive emulsion layer, one green-sensitive emulsion layer, and one front window emulsion layer on a support. The photographic material contains a monodispersed silver halide emulsion with an average grain size of less than 0.3 μm and at least one compound represented by the following general formula (I), and the total photosensitivity contained in the photographic material This was achieved using a silver halide color photographic light-sensitive material characterized in that the average silver iodide content in the silver halide emulsion is 6 mol % or less.

General formula (1) R1 In the formula, X and Y may be the same or different, and include a cyano group, a carboxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfonyl group. group, represents a sulfamoyl group. Moreover, X and Y may be connected to each other to form a ring.

R+ and Rz may be the same or different, and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxy group, a substituted amino group, a carbamoyl group,
Represents a sulfamoyl group or an alkoxycarbonyl group.

R,, R, may be the same or different and represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, or a sulfonyl group. R3 and R1 may be linked to each other to form a 5-membered ring or a 6-membered ring.

Furthermore, R1 and R3, and R2 and R4 may be linked to each other to form a 5-membered ring or a 6-membered ring.

L represents a methine group.

The present invention will be explained in more detail.

If the grain size of the -C-sensitive silver halide emulsion is made smaller, the sensitivity will be reduced accordingly, but the graininess will also be improved. However, when colloidal silver is used in the yellow filter layer, especially in the case of a color reversal photosensitive material, even if the particle size is reduced, the improvement in graininess is small compared to the decrease in sensitivity. This is because, as mentioned above, dissolution physical development occurs with colloidal silver as the core, and in particular, when the grain size of the emulsion is small, the dissolution physical development also becomes large, and it is thought that the improvement in graininess is small. This also causes a decrease in Dmax.

On the other hand, when the yellow filter layer uses a diffusion-resistant yellow dye, there is no dissolution physical development using the colloidal silver as a nucleus, and when the grain size of the light-sensitive emulsion is reduced, the granularity, which lowers the sensitivity, improves. do.

Further, a decrease in Dmax is not caused. However, when the silver iodide content of the silver halide emulsion is high (particularly 6.5 mol % or more), the Dmin becomes high, which is a very undesirable result.

However, according to the research of the present inventors, surprisingly,
It has been found that when the average silver iodide content of the total photosensitive silver halide emulsion is set to 6 mol% or less, there is no adverse effect of increasing Dmin, and moreover, graininess is better and Dmax is higher than when colloidal silver is used. Ta.

This is because when the silver iodide content of the photosensitive silver halide emulsion is high, when it is developed, iodide ions are converted to AgBr1 on the surface of the fine grain emulsion of less than 0.3μ, and the development speed in the first development is By being very late,
This seems to result in an increase in Dmin of the color reversal photosensitive material.

The average silver iodide content of the total photosensitive silver halide emulsion of the present invention is preferably 5.7 mol% or less, particularly preferably 5.5 mol% or less.

Further, the monodisperse silver halide emulsion of the present invention having an average grain size of less than 0.3 μm may be a light-sensitive silver halide emulsion or a substantially non-light-sensitive silver halide emulsion. The monodisperse silver halide grains of the present invention having an average grain size of less than 0.3μ preferably have an average grain size of less than 0.05μ. The average particle size of the present invention is 0. Monodisperse silver halide grains of less than 3 μm may be contained in a photosensitive silver halide emulsion layer or in a non-photosensitive hydrophilic colloid layer.

In the present invention, a monodisperse AgX emulsion having an average grain size of less than 0.3 μm is contained in at least one of the photosensitive AgX emulsion layers. The monodisperse emulsion is contained in an amount of preferably 10 wt% or more, more preferably 30 wt% or more of the grains in the layer containing the emulsion.

The yellow filter layer of the present invention and the photosensitive silver halide emulsion layer may be directly adjacent to each other, but a non-photosensitive hydrophilic colloid layer may be provided between them on one or both sides of the yellow filter.

Further, in the present invention, the photographic light-sensitive material has the following general formula (I
) containing at least one compound represented by the general formula (T) R1 1 - 2 where X and Y may be the same or different, a cyano group,
Carboxy groups, alkylcarbonyl groups (alkylcarbonyl groups that may be substituted, such as acetyl, promonyl, heptanoyl, toticayyl, hexatecanoyl, 1-oxo-7-chloroheptyl groups, etc.), arylcarbonyl groups (substituted For example, benzoyl, 4-aminobenzoyl, 4-nitrobenzoyl, 4-methanesulfonylaminobenzoyl, 4-ethanesulfonylaminobenzoyl, 4-propanesulfonylaminobenzoyl, 4-trifluoromethanesulfonylaminobenzoyl. , 4-trifluoroacetylaminobenzoyl, 4-trichloroacetylaminobenzoyl, 3-hydroxy-4-methanesulfonylaminobenzoyl, 3-methanesulfonylaminobenzoyl, 3-propanesulfonylaminobenzoyl, 2-methanesulfonylaminobenzoyl, 4- Methoxybenzoyl, 3-nitrobenzoyl, 4-methylaminocarbonylaminobenzoyl, 4-ethylaminocarbonylaminobenzoyl, 4-ethoxycarbonylaminosulfonylaminobenzoyl, 4-methoxycarbonylaminosulfonylaminobenzoyl, 3-methylaminocarbonylaminobenzoyl, 4-methoxy-3
-methanesulfonylaminobenzoyl, 4-ethoxy-
3-methanesulfonylaminobenzoyl, 4-(2-hydroxyethoxy)-2-hydroxybenzoyl, 3-
chlorobenzoyl group, etc.), alkoxycarbonyl group (
An alkoxycarbonyl group that may be substituted, such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl , hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2- (2
-chloroethoxy)ethoxycarbonyl, 2- (2-
(2-chloroethoxy)ethoxyfethoxycarbonyl group, etc.), aryloxycarbonyl group (an aryloxycarbonyl group that may be substituted, such as phenoxycarbonyl, 3-ethylphenoxycarbonyl, 4
-ethylphenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl, 4-
methoxyphenoxycarbonyl, 2,4-di(t-amyl)phenoxycarbonyl group, etc.), carbamoyl group (carbamoyl group that may be substituted, such as carbamoyl group, ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenyl group) Carbamoyl, 2-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-ethoxycarbonylphenylcarbamoyl, 4-propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,4 -di(t-amyl)phenylcarbamoyl, 2-chloro-3-(dodecyloxycarbonyl)phenylcarbamoyl, 3-(hexyloxycarbonyl)phenylcarbamoyl, etc.), sulfonyl groups (e.g., methylsulfonyl, decylsulfonyl,
phenylsulfonyl group, etc.), sulfamoyl group (sulfamoyl group that may be substituted, such as sulfamoyl, methylsulfamoyl group, etc.).

In addition, X and Y may be connected to each other in a ring (for example, a pyrazolone ring, a pyrazolotriazole ring, a pyrazoloimidazole ring, an oxindole ring, an oxindasipyridine ring,
isoxacilone ring, barbisolic acid ring, dioxytetrahydropyridine ring, indanedione ring, etc.).

R,, R2 may be the same or different (, hydrogen atom, halogen atom (e.g. F, C1, Br, ■), alkyl group (alkyl group which may be substituted, e.g. methyl, ethyl, 2-chloroethyl, propyl, hexyl groups, etc.), alkoxy groups (alkoxy groups that may be substituted, such as methoxy, ethoxy, 2-chloroethoxy, butoxy, hexyloxy, octyloxy groups, etc.), hydroxy groups, carboxy groups , substituted amino group [amino group substituted with an acyl group derived from aliphatic carboxylic acid or sulfonic acid (e.g. acetylamino, hexylcarbonylamino, methanesulfonylamino, ethanesulfonylamino, hexanesulfonylamino group, etc.), alkylamino groups (e.g. methylamino, ethylamino, propylamino, hexylamino groups, etc.), dialkylamino groups (e.g. dimethylamino, diethylamino, dipropylamino groups, etc.)], carbamoyl groups (
A carbamoyl group that may be substituted (for example, carbamoyl, methylcarbamoyl, ethylcarbamoyl group, etc.), a sulfamoyl group (a sulfamoyl group that may be substituted (for example, sulfamoyl, methylsulfamoyl, ethylsulfamoyl group, etc.), Represents an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, pentyloxycarbonyl group, octyloxycarbonyl group, etc.).

R3 and R- may be the same or different, and include a hydrogen atom, an alkyl group (an alkyl group that may be substituted, for example,
Methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, 2-ethylhexyl, octyl, dodecyl, hexadecyl, 2-chloroethyl, 3-chloropropyl, 2-7'lomoethyl, 2-hydroxyethyl,
Cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 2-methoxyethyl, 3-methoxypropyl, 2-ethoxyethyl, 2-octyloxyethyl, 3-ethoxypentyl, 2-isopropoxyethyl, acetylmethyl, 2-acetylethyl , benzoylmethyl, acetyloxymethyl, 2-(ethylcarbonyloxy)ethyl, 2-(heptanoyloxy)ethyl, 2-(isopropylcarbonyloxy)ethyl, benzoyloxymethyl, 4-chlorobenzoyloxymethyl, 4-nitro Benzoyloxyethyl, acetylaminoethyl, 2-(
Ethylcarbonylamino)ethyl, methylcarbamoylmethyl, 2-methylaminoethyl, 2-(ethylamino)ethyl, 2-(dimethylamino)ethyl, 2-(diethylamino)ethyl, 2-methylureidoethyl, carboxymethyl, 2- Carboxyethyl, 3-carboxypropyl, 6-carboxyhexyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, butoxycarbonylmethyl, 2-(butoxycarbonyl)ethyl, 3-
(octyloxycarbonyl)propyl, 2.2.2-
Trifluoroethoxycarbonylmethyl, propyloxycarbonylmethyl, isopropyloxycarbonylmethyl, 2-(propyloxycarbonyl)ethyl, 3-
(t-amyloxycarbonyl)propyl, (2-ethylhexyl)oxycarbonylmethyl, 2-(ethoxycarbonyl)ethyl, phenyloxycarbonylmethyl, ethylsulfonylmethyl, 2-(methylsulfonyl)
Ethyl, 2-(butylsulfonyl)ethyl, methylsulfonylaminemethyl, 2-(methylsulfonylamino)
Ethyl, 2-(ethylsulfonylamino)ethyl, 3-
(ethylsulfonylamino)propyl, methylcarbamoylmethyl, 2-methylureidoethyl, phenylmethyl groups, etc.), alkenyl groups (alkenyl groups that may be substituted, such as 3-hexenyl), aryl groups (substituted Good aryl groups, examples: phenyl, 4-chlorophenyl, 4-cyanophenyl, 4-hydroxyphenyl, 4-carboxyphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-octyloxyphenyl , 4-methylphenyl, 4-nitrophenyl group, etc.), acyl group (an acyl group that may be substituted, such as acetyl, propionyl, benzoyl, 4-methoxybenzoyl group, etc.), sulfonyl group (sulfonyl group that may be substituted) represents a 5- to 6-membered heterocycle (such as a piperidine ring), and R, , R, , morpholine ring, etc.).

Furthermore, R1 and R:I, and R2 and R4 may be linked to each other to form a 5- to 6-membered heterocycle.

L represents a methine group (a methine group that may be substituted; examples of the substituent include methyl, cyano group, etc.).

In the general formula (1), preferably, X is a cyano group;
Y is an arylcarbonyl group; R1 is a hydrogen atom iRz is L
is the ortho position of hydrogen atom, halogen atom, hydroxy group, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, alkylsulfonamide group having 1 to 3 carbon atoms,
Alkylcarbonamide group having 1 to 3 carbon atoms; R3, R4
may be the same or different, and may be an alkyl group or a phenyl group having 1 to 7 carbon atoms, and R3 and R4 may form a 5- to 6-membered ring; this is the case when L is a methine group.

Specific examples of Y, R2, R3, and R can be arbitrarily selected from those mentioned above.

In the general formula (1), the case represented by the following general formula [■] is more preferable.

General formula (II) In the general formula (n), R11 is an alkyl group having 1 to 3 carbon atoms, R1□ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms,
R13 and RI4 may be the same or different and have a carbon number of 1 to
3, and at least one terminal of R13 and RI4 is (R1, represents an alkyl group having 1 to 5 carbon atoms).

Next, specific examples of compounds used in the present invention will be given, but the present invention is not limited thereto.

(Exemplary compound) 1゜0:= :X::c
Engineering = Q Q Engineering z
00 engineering
○ ○ ヱ 工○○
00 U ■oo
oooo.

00 U ○
OOo 0
Q ○NN :c
:e Engineering :I: 0 0
xxQ II
Q of Q
W Q Hit
O○ ■ = = Q ■ Q ○ = = = = oo o.

OOO○ = 工 = ==
= ■ O ■-OQ-○ ○ OOOOO OQ = co IJ ■
−〇 −, = = of
ω 燑 ＝
Work 00 Z
Z: e O:
:c:c :c:co
o Q Q Q
IJQQ
.

II II
II ■ 0
Compensation Q-=-10::l: = Q Q■
O0=== 工 =の■ RO
=-c< O 工■ -prisoner nohe he
The compound represented by H-S2[I] is disclosed in JP-A-61-205,934, JP-A-62-222,248,
Patent Application No. 183,945/1983, U.S. Patent No. 4°420.
It can be easily synthesized by the method described in No. 555 and the like.

Particle size in the present invention is 0. Monodisperse silver halide grains of 3 μm or less have a grain size distribution defined by the following formula. In other words, when the standard deviation S of the particle size distribution is divided by the average particle size 〒-, the value is 0.2
Refers to something less than 0.

In the case of spherical silver halide grains, the average grain size referred to here refers to the average diameter of the grains, and in the case of grains with shapes other than cubic or spherical, the projected image is converted to a circular image of the same area. When the individual grain size is ri and the number of grains is n, r is defined by the following.

-Σn□r Engineering The above particle size can be measured for the above purpose by various methods commonly used in the technical field. A typical method is Loveland's "Particle Size Analysis Method A,"
S, T, M, Symposium on Ride Microscopy, 1955, pp. 94-122, or
[Theory of the Photographic Process] co-authored by Mies and James,
It is described in Chapter 2 of the 3rd edition, published by Macmillan (1966). The particle size can be measured using the projected area of the particle or an approximate diameter value.

The silver halide grains used in the silver halide emulsion layer according to the present invention preferably contain the above-mentioned monodisperse silver halide grains in an amount of 70% or more of the total grains in the same silver halide emulsion layer, particularly It is preferable that all the grains are monodisperse silver halide grains.

The monodisperse halogenated root particles used in the present invention may be used alone, or two or more types with different average particle diameters may be used. n
Two dispersible silver halide grains can be optionally combined and used preferably.

The shape of the silver halide grains according to the present invention may be, for example, hexahedral, octahedral, dodecahedral, plate-like, spherical, etc., or may be a mixture of various shapes. .

To produce silver halide grains with a grain size of 1'r't, grains of a desired size can be obtained by a double jet method while keeping pAg constant. Monodisperse silver halide grains can also be produced by a double jet method in the presence of a silver halide solvent such as ammonia, 1,000-onythyl or thiourea.

The preferred grain size of the monodisperse emulsion is 0.15 to 0.
25 μm, and its composition is silver bromide, silver iodobromide, silver chlorobromide, or silver chloride, especially silver bromide or silver iodobromide.
(AgT 10 mol% or less) is preferable.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), No. 17643.
(December 1978), pp. 22-23, “■, Emulsion preparation and
dtypes)', and same No. 18716 (1
November 979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Beaumontel (P, Glafki
des.

Chemie et Ph1sique Photog
raphique paul montel.

1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F. Duffin, Photo
graphicIEmulsion Chemistry
y (Focal Press+ 1966)),
Zelikman et al., “Production and Coating of Photographic Emulsions J,” published by Focal Press (V, L, Zelikmam et a
l、Makingand Coating Photo
graphic Emulsion+ Focal
Press+1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
No. 4 and British Patent No. 1. 413. Monodispersed emulsions such as those described in No. 748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), No. 14
Vol. 248-257 (1970); U.S. Patent No. 4.
434゜226, 4,414,310, 4,4
33.048, British Patent No. 4,439,520, and British Patent No. 2,112,157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

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

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Nα1
7643 and the same No. 1B716,
The relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Additives II RD17643 RD187161
Chemical sensitizers, page 23, page 648, right column 2 Sensitivity enhancers Same as above 3 Spectral sensitizers, pages 23-24, page 648, right column - Super sensitizers
Page 649 Right column 4 Brightener Page 24 5 Anti-fogging agent Page 24-25 Page 649 Right column and stabilizer 6 Light absorber, F Page 25-26 Page 649 Right column - Ilter dye Page 650 Right column Ultraviolet absorber 7 Anti-stain agent Page 25 right column Page 650 left to right column 8 Dye image stabilizer Page 25 9 Hardener page 26 Page 651 left column 10 Binder Page 26 Same as above 11 Plasticizer,
Lubricant 27 pages, 650 right page 12 Coating aids, Table pages 26-27 Same as above "Surfactant 13 Static/preventive 27 True Same Top stopper" Various color couplers can be used in the present invention, and their specific details are as follows. An example is the research disclosure mentioned above (
RD) No. 17643, ■-C-G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401゜752, Special Publication No. 5
No. 8-10739, British Patent No. 1,425,020,
Same 1st. 476, 760, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4,351°897, European Patent No. 73,636, US Patent No. 3,061,432, No. 3. 725. No. 067, Research Disclosure Nα24220 (June 1984), JP-A-1986-
No. 33552, Research Disclosure Nα242
30 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630, U.S. Pat.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4,228,23
No. 3, No. 4,296.200, No. 2,369,92
No. 9, No. 2,801°171, No. 2,772.1.
No. 62, No. 2゜895.826, No. 3,772,
No. 002, No. 3,758,308, No. 4. 33
4. No. 011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121゜36
No. 5A, U.S. Patent No. 3,446. -622, same No. 4,
No. 333.999, same No. 4. 451. No. 559, No. 4,427,767, European Patent Cylinder 161.626A
Preferably, those described in No.

Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No. 1764.
Section 3 ■-G, U.S. Patent Cylinder 4. 163. No. 670,
Special Publication No. 57-39413, U.S. Patent No. 4.004,9
No. 29, No. 4,138,258, British Patent Cylinder 1,1
46,368 is preferred.

Couplers having appropriate diffusivity for coloring dyes include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820, U.S. Pat.
, No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097.140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , multi-equivalent couplers described in JP-A No. 4,310,618, etc., DIR redox compound releasing couplers described in JP-A-60-185950, etc., and dyes that exhibit color after separation described in European Patent No. 173.302A. Examples include couplers that emit light.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. etc. are listed.

In the light-sensitive material according to the present invention, it is preferable that auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation agent, a back layer, and a white reflective layer are provided in addition to the silver halide emulsion layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are those described in Research Disclosure Magazine No. 976
No. 55. Also, Research Disclosure Magazine No. 17643, Section XV, p.28-2
The coating method described in 9 can be used.

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

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side. Furthermore, each of the above-mentioned emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-light-sensitive layer may be present between two or more emulsion layers having the same color sensitivity. good. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The present invention can be applied to various color photosensitive materials.

For example, typical examples include color reversal film for slides or television, and color reversal paper. It can also be applied to full-color copying machines and color hard copies for storing C, R, and T images. The present invention also applies to "Research Disclosure" magazine Nα17123 (published in July 1978).
It can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers as described in .

The color photographic material according to the present invention includes the above-mentioned RD, N
o, pages 28-29 of 17643, and Nα187 of the same.
16-651 left column to right column can be used for development processing.

(Example) Hereinafter, the present invention will be explained in detail with reference to Examples.

However, the present invention is not limited only to these examples.

Example 1 Preparation of Sample 101 A multilayer color light-sensitive material consisting of each layer having the following composition was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm, and designated as Sample 101.

1st layer: antihalation layer black colloid 0. 25g/rrrUltraviolet absorber U-10.04g/BUltraviolet absorber U-20.1g/BUltraviolet absorber U-30.1g/A Gelatin layer containing high boiling point organic solvent ○-10.1cc/r+ ( 2nd layer: Gelatin layer containing interlayer compound H-10.05g/M high boiling point organic solvent 0-2 0.05cc/m (dry thickness 1μ) 3rd layer: 1st red-sensitive emulsion Layer sensitizing dye S-1 (0,93 mg/n() and S-2 (0
, 04 mg/m2), monodispersed silver iodobromide emulsion silver amount......0.33 g/m2 (iodine content 4 mol%, average grain size 0.35 μ, grain size (hereinafter simply referred to as the coefficient of variation) 19%) A 1 0. 60mg/rd Coupler C-10,13g/rI (Coupler C-20,033g/M High boiling point organic solvent 0-2 0.08cc/n (containing gelatin layer (dry film thickness 0.7μ) 4th layer: 2 red-sensitive emulsion layers sensitizing dyes S-1 (1,1 mg/n() and S-2 (0,
Monodisperse silver iodobromide emulsion spectrally sensitized at 0.04 mg/m'') Silver amount: 0.53 g/m'' (iodine content: 3 mol%)
, average particle size 0. 55μ, coefficient of variation 16%) A-40.02mg/n (Coupler C-10.40g/n (Coupler C-20.07glrd) Gelatin layer containing high-boiling organic solvent 0-2 0.22cc/n (dry film thickness '', 7μ) 5th layer: 3rd red-sensitive emulsion layer
, 04 mg/m") Monodisperse silver iodobromide emulsion spectrally sensitized Silver amount...0.53 g/m" (iodine content 2 mol%, average grain size 0.07 μ, coefficient of variation 17%) A- 71.2 mg/Icaplar C-60, 35g/Bocaplar C-80, 20g/rrf High boiling point organic solvent 0-2 0.24cc/n (contains gelatin layer (dry film thickness 1.8μ) 6th layer: intermediate layer A-1010mg/rrf A-115mg/Compound H-1 0.1g/rd High boiling point organic solvent 0-2 0. Gelatin layer containing Ice/nf (dry film thickness 1μ) 7th layer: First green-sensitive emulsion Layer sensitizing dyes S-3 (2.2 mg/rrf) and S-4 (1
,0mg/m") monodisperse silver iodobromide emulsion spectrally amplified Silver amount...0.5g/i (Iodine content 3 mol%, average grain size 0.35μ, coefficient of variation 19%) A 5 0.12mg/rr?
Coupler C-30, 21 g/ni Gelatin layer containing high boiling point organic solvent 02 0.17 cc/ni (dry film thickness 0.7 μm) 8th layer: 2nd green emulsion layer Sensitizing dye S-3 (0.29 g /a) and S-4 (0,3
Monodisperse silver iodobromide emulsion spectrally sensitized with mg%mt)
Silver amount: 0.5 g/Bo (Iodine content 2.5 mol%, average particle size 0゜5μ, coefficient of variation 18%) A-60.2 mg/Bo Coupler C-30.2 g/M High boiling point organic solvent 0 -2 0. Gelatin N containing 13 cc/A (dry film thickness 1.7μ) 9th layer: 3rd green emulsion layer containing enhancing dyes S-3 (0.9 g/B) and S-4 (0.3 m
Monodisperse silver iodobromide emulsion spectrally sensitized at
Silver amount: 0.5 g/po (iodine content: 2 mol%)
, average particle size 0.6 μ, coefficient of variation 17%) A-21.5 mg/Bocoupler C-40.2 g/rrf High boiling point a solvent 0-2 0. Gelatin layer containing 03cc/nf (dry film thickness 1.7μ) 10th layer: Yellow filter layer Yellow colloid 0.1g/Bo compound H-10.02g/Bo compound H-20.03g/rrf High boiling point organic solvent 0-2 0. Gelatin layer containing 04 cc/bo (dry film thickness 1 μ) 11th layer: 1st blue-sensitive emulsion layer Tabular silver iodobromide emulsion spectrally sensitized with sensitizing dye 5-33 (1,0 g/bo)) Amount of silver: 0.6 g/bo (Iodine content: 3 mol%, grains with a diameter/thickness ratio of 7 or more occupy 50% of the projected area of all grains. Average thickness of grains: 0.10 μ) A- 70.5mg/rrf Coupler C-50.5g/ITf High boiling point organic solvent 0 2 0. Gelatin layer containing lcc/bo (dry film thickness, 5 μ) 12th layer: 2nd blue-sensitive emulsion layer: Tabular iodobromide spectrally sensitized with sensitizing dye S-5 (2,0 g/bo)) 1 liter of silver emulsion 4. 1 g/rr ((Particles with an iodine content of 2.5 mol% and a diameter/thickness ratio of 7 or more occupy 50% of the projected area of all particles. Average thickness of particles 0.15 μ) A-1210 mg/n ( Coupler C-71, 2g/Bocoupler C-80, 2g1rd High boiling point organic solvent 0-2 0.23cc/n (containing gelatin layer (dry film thickness 3μ)) 13th layer: First protective layer A-130, 10mg/ rrf Ultraviolet absorber U-10,02g/B Ultraviolet absorber U-20.03g/B Ultraviolet absorber U-30,03g/A Ultraviolet absorber U-4 0.29g/A High boiling point organic solvent 0-2 0 Gelatin layer containing 28cc/m (dry film J￥2μ) 14th layer: Fine grain silver iodobromide emulsion covered with the surface of the second protective layer Silver amount...0.1g/rrr (Iodine content 1 mol% , average particle size 0.06μ) Yellow colloidal silver amount for yellow filter layer...0.01g/PoA-810mg/rrf Polymethyl methacrylate particles (average particle size 1.5μ) Contains A-91.0mg/rd In addition to the above composition, each layer of gelatin layer (dry film thickness 0°8μ) contains antifoggant A-3, gelatin hardener H.
-3, and a surfactant were added.

The compounds used to prepare the samples are shown below.

t　CsH++ Usll　l　? (t) C-4 CH8 M-C. H.

L　UaFlq -I A-7 C, F, tsO, NcH, coOK C,H.

i -1O Preparation of Sample 102 Sample 102 was prepared in exactly the same manner as Sample 101 except that the average grain size of the emulsions in the third and seventh layers of Sample 101 was set to 0.28 μm.

Preparation of Sample 103 The 9th and 111th emulsions of Sample 101 were prepared in such a way that the ratio of the emulsions in each layer to a monodisperse emulsion with an average grain size of 0.20μ, an iodine content of 3 mol%, and a coefficient of variation of 13% was 8. Sample 103 was prepared in exactly the same manner as Sample 101 except that the value was changed to:2.

Preparation of Sample 104 The iodine content of the total photosensitive emulsion of Sample 103 was set to 5°5 mol%.
Sample 104 was prepared in exactly the same manner as Sample 103 except for the following.

Preparation of Sample 105 The iodine content of the total photosensitive emulsion of Sample 103 was set to 6°5 mol%.
Sample 104 was prepared in exactly the same manner as Sample 103 except for the following.

Preparation of samples 106 to 110 Samples 101, 105, 102, 103, 104
Apply exemplified compound 3 instead of yellow colloid layer fi0
．． Samples 101 and 1, respectively, except when using 3g/rff
Sample 1 in exactly the same manner as 05, 102, 103, 104.
06-110 were produced.

Preparation of Samples 111-115 Samples 111-115 were prepared in exactly the same manner as Sample 109 except that the compounds shown in Table 1 were used in place of Compound 3 in the 10th layer of Sample 109.

Samples 101 to 115 prepared as above were exposed through a continuous wedge, and after the development process described below, the density was measured.
Maximum concentration (Dmax), minimum concentration (Dmin) and sample 1
Relative sensitivity was determined with the sensitivity of cyan, magenta, and yellow of 01 as 100.

The graininess was determined as a value 1000 times the RMS graininess.

Processing process Time Temperature first development 6 minutes 38°C water washing 2 〃 38〃 inversion
2 〃 38〃Color development
6 minutes 38°C adjustment 2
38〃Bleaching 6
〃 38〃 Fixed arrival 4 〃
38〃Water wash 4〃
38. The composition of each treatment liquid was as follows.

m4 nitrilo-N,N,N -2,0g Trimethylenephosphonic acid pentasodium salt Sodium sulfite 30g Hydroquinone monosulfonic acid 20g Potassium potassium carbonate 33g 1-Phenyl-4-methyl-4-2,0g Hydroxymethyl- 3
- Pyranolidone Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide 2.0mg Add water
10100O! pH 9.60 The pH was adjusted with hydrochloric acid or potassium hydroxide.

Inverted Namitrilo-N, N, N -3.0g trimethylenephosphonic acid pentasodium salt stannous chloride dihydrate 1. Ogp-aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid
Add 15mg water 1
000mjl! pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Color developer Nitrilo-N, N, N-2.0g Trimethylenephosphonic acid pentasodium salt Sodium sulfite 7.0g Trisodium phosphate dodecahydrate 36g Potassium bromide
1.0g potassium iodide
90mg sodium hydroxide 36
0g Citrazic acid 1.5g N-Ethyl-N-(β-methane 1g Sulfonamidoethyl)-3 = Methyl-4-aminoaniline sulfate 3.6-Cythiaoctane-1.81.0g-Diol Add water to 1000ml pH 11,
80 pH was adjusted with hydrochloric acid or potassium hydroxide.

Kaede Shigyo Ethylenediamine 4 Acetic Acid 2 Sodium 8.0 g Thorium Salt Dihydrate Sodium Sulfite 12 g 1-1000 Glycerin 0. Add 4mf water
1000 mf pH 6.20 pH was adjusted with hydrochloric acid or sodium hydroxide.

Ethylenediaminetetraacetic acid, 2.0g thorium salt, dihydrate Ethylenediaminetetraacetic acid, Fe 120g (II
I) ・Ammonium・potassium dichloride bromide
100g ammonium nitrate
Add 10g water 1
000ml pH 5.70 The pH was adjusted with hydrochloric acid or aqueous ammonia.

Definition solution Sodium thiosulfate 80g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water
1000ml pH' 6.60 pII was adjusted with hydrochloric acid or thorium hydroxide.

Stabilized formalin (37%) 5. 0mff
Polyoxyethylene-P-0,5mj2 monononylphenyl ether (average degree of polymerization 10) Added water to 1000100OH without adjustment From the results in Table 2, Tables 1 and 2, the following can be said.

(2) Dmax is higher when the yellow dye of the present invention is used than when colloidal silver is used in the yellow filter layer.

(Samples 101 and 106, 102 and 108, 103 and 10
9,104 and 110. Comparison of i05 and 107) ■ Grain improvement when using an emulsion of less than 0.3μ in the photosensitive silver halide emulsion layer is better in the present invention than when colloidal silver is used in the yellow filter layer. big.

(Comparison of samples 101, 102, 106, 108, sample 1
．． Comparison of 01, 103, 106, 109)■ When silver halide grains of less than 0.3μ are used in the photosensitive silver halide emulsion layer and the yellow dye of the present invention is used in the yellow filter layer, Dmin is: When the average silver iodide content of the globally modified silver halide grains of the present invention is 6 mol % or less, it is low.

(Comparison of Samples 107 and 109 and 110) Example 2 Samples 101 to 115 exploded in Example 1 were exposed in the same manner as in Example 1, and the following rapid exposure was performed. The results are shown in Table 3.

First development 6 minutes 38°C First washing 45 seconds 38p inversion
45 〃 38p color development 6
Minutes 38°C Bleach 2
ll 38p bleach fixing 4 / 38〃Second washing (1) 1〃
38〃Second water washing (2) 1〃 38〃The composition of each treatment liquid was as follows.

First developer Nitrilo-N,N,N -2.0g Trimethylenephosphonic acid pentasodium salt Sodium sulfite 30g Hydroquinone monosulfonic acid 20g Potassium potassium carbonate 33g 1-Phenyl-4-methyl-42.0g-Hydroxymethyl-
3-Pyrazolidone Potassium bromide 19m 2.5g Potassium thiocyanate 1.2g Potassium iodide 2. Omgp) (9,60 pH) was adjusted with hydrochloric acid or potassium hydroxide.

First washing solution Mother liquor Ethylenediaminetetramethylene 2.0gDisodium phosphonate phosphate 5.0gpH7,
00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Nitrilo-N,N,N-3.0g Trimethylenephosphonic acid, pentasodium salt, stannous chloride dihydrate 1. Ogp-Aminophenol O, 1g Sodium hydroxide 8g Glacial acetic acid
15mj! pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Color developer Nitrigo N, N, N-2.0g Trimethylenephosphonic acid pentasodium salt Sodium sulfite 7.0g Trisodium phosphate dodecahydrate 36g Potassium bromide
1.0g potassium iodide
90mg sodium hydroxide 3.
0 g Citrazic acid 1.5 g N-ethyl-N-(β-methane 1 g Sulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 3.6-Cithiaoctane-1. 1.0 g 8-diol pH 11.80 pH was adjusted with hydrochloric acid or potassium hydroxide.

10.0g thorium salt, dihydrate ethylenediaminetetraacetic acid, Fe 120g (II
I) Ammonium dihydrate Ammonium bromide 100g Ammonium nitrate 10g Bleach accelerator
Add 0.005 mol water
1000mj2pH6.30 The pH was adjusted with hydrochloric acid or aqueous ammonia.

! Internal fixer: ethylenediaminetetraacetic acid/Fe(III) 50g/
Ammonium dihydrate ethylenediamine tetraacetic acid dinato 5. Og Thulium Dihydrate Ammonium Thiosulfate 80g Sodium Sulfite 12.0g Add water
1000100O6,60 pH was adjusted with hydrochloric acid or aqueous ammonia.

The second washing liquid tap water is passed through a mixed bed column packed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas). The solution was treated with water to reduce the concentration of calcium and magnesium ions to below 3 mg/2, and then 20 mg/l of sodium isocyanurate dichloride and 1.5 g/2 of sodium nitrate were added. The pH of this solution is 6.5
~7°5.

Song Dinglang formalin (37%) 5.0mj2 polyoxyethylene-p-0,5ryl monononyl phenyl ether (average degree of polymerization 10) Add water IOO0m4 Without adjusting pH According to Table 3, it was clear in Example 1 Among the effects that resulted, 0. When silver halide grains of less than 3 μm are used, the effect of not increasing Dmin in the present invention is more remarkable.

(Effects of the Invention) According to the present invention, this silver halide color photographic light-sensitive material has good graininess, a high maximum density, and a low minimum density. In the present invention, since colloidal silver is not used in the yellow filter, there is no disadvantage of deterioration of graininess or decrease in maximum density.Moreover, since the compound shown in the above-mentioned format [■] is used, a yellow dye is used. It also does not have the disadvantage of increased minimum concentration seen in some cases.

(3 others) Procedures? 111 Seisho Special Show Office! f%T;s 116
34 June 2/Day 1, 1st place display 1986 Patent Application No. 87356 2, Title of invention Silver halide color photographic light-sensitive material 3, Person making the amendment Relationship to the case: Name of patent applicant (520) 'Hashi Photo Film Co., Ltd. 4,
Agent address: 29th floor, Kasumigaseki Building, 3-2-5 Dengaseki, Chiyoda-ku, Tokyo, 100, Japan Post Office Private Box No. 49, Kirigawa Building, Sakae) Hi-Toku Tomoe Kogyo Kogyo Office゛) 6. Amendment Number of claims increased by: 07, Counterprint of amendment: Section 8 of [Detailed Description of the Invention] of the specification, Contents of the amendment: 1) Changed "closed" to "open chain" on page 5, line 18 of the specification. to correct.

2) On page 8 of the same Ministry, line 16, ``Dissolution physical development also increases f'' is corrected to ``Because dissolution of silver halide grains due to dissolution physical development increases.''

5) Circular page 10, line 7 “becoming small” is “not small”
and correct it.

4) Line 3016 of the same book, “0.3 μm or less” is changed to “0.6 μm”
"Less than m".

5) Lines 7 to 2 from the bottom of page 51 of the same book: “In accordance with the present invention...
·preferable. ” to be deleted.

6) Same book, page 44, line 20 to page 45, line 1 r0.07μ.”
is corrected to "α7μ".

7) Circular page 46 line 4 r ([1,2q, p/m2)
Correct J to r (0,919/l112)J.

8) Correct the Ministry of Finance, page 46, line 14 r(0,9,9/fi2)J to r(o,9■/”2)J.

9) Ministry of Finance, page 47, line 10 “(1°OF/l!12))J
is corrected to r(1,0mg/m2)J.

10) Circular page 48, line 2 r (2,0g/It2))J
is corrected as r (2-0j1g/WL2).

11) The structural formula of rC-6J on page 52 of the same book is ” and correct it.

12) Same book, page 67, line 14, “sodium thiosulfate” is replaced with “
ammonium thiosulfate”.

16) On page 72 of the circular, line 1, "Rapid amount" is corrected to "Rapid processing."

14) From the bottom of page 76 of the circular, line 9 “Ammonium thiosulfate 80g” is corrected to “Ammonium thiosulfate 150gJ.”

Claims (1)

[Scope of Claims] A silver halide color photographic material having at least one red-sensitive emulsion layer, one green-sensitive emulsion layer, and one blue-sensitive emulsion layer on a support, wherein the photographic material has an average grain size. A monodisperse silver halide emulsion of less than 0.3 μm and at least one compound represented by the following general formula [I], and an average of all light-sensitive silver halide emulsions contained in the photographic light-sensitive material. A silver halide color photographic light-sensitive material having a silver iodide content of 6 mol% or less. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, X and Y may be the same or different from each other, and include a cyano group, a carboxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, Represents an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group, or a sulfamoyl group. Moreover, X and Y may be connected to each other to form a ring. R_1 and R_2 may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxy group, a substituted amino group, a carbamoyl group, a sulfamoyl group, or an alkoxycarbonyl group. R_3 and R_4 may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, or a sulfonyl group. R_3 and R_4 may be connected to each other to form a 5-membered ring or a 6-membered ring. Furthermore, R_1 and R_3, and R_2 and R_4 may be connected to each other to form a 5-membered ring or a 6-membered ring. L represents a methine group.