JPH08314042A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material having high sensitivity and excellent picture quality, especially in sharpness, and improved in pressure desensitization. CONSTITUTION: This silver halide photographic sensitive material has at least each one of blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and red-sensitive silver halide emulsion layer on a supporting body. At least one silver halide emulsion layer contains such planer silver halide particles as described below. Each particle has two or more silver halide layers having different contents of silver iodide in the particle. The inner layer of these layers has a larger silver iodide content than in the outer layer and contains silver iodide with the max. content of silver iodide between >=5mol% and <=10mol%. The particle has >=2 aspect ratio and five or more dislocation lines. Moreover, the photosensitive material contains a fluorine-contg. surfactant.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION 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 having improved sensitivity, pressure resistance and image quality.

[0002]

2. Description of the Related Art In recent years, the demand for silver halide emulsions for photography has become more and more intense. For example, they have extremely high performance such as high sensitivity, excellent graininess, high sharpness, and excellent pressure resistance. It has been demanded. As a silver halide grain technology for achieving high sharpness, in order to reduce light scattering by silver halide grains, which is one factor that deteriorates sharpness, the grain thickness with respect to the light entrance direction is deviated from the light scattering length. It is known to design. In this case, in order to prevent the graininess from deteriorating, it is necessary to design on the thin side with respect to the particle thickness that causes light scattering. Therefore, an octahedron,
It is known that in a silver halide grain having a shape such as a hexahedron, the grain size becomes small, the light receiving efficiency per grain becomes small, and the sensitivity is lowered. As one method for solving this problem, it is known to use tabular silver halide grains (hereinafter, also referred to as "tabular grains"). Regarding tabular silver halide grains, US Pat.
No. 434, 226, No. 4,439, 520, No. 4, 4
No. 14,310, No. 4,433,048, No. 4,41
4,306, 4,459,353, JP-A-58-
111935, 58-11936, 58-1
No. 11937, No. 58-113927, No. 59-99.
No. 433 and the like. Further, as a technique for enhancing the photosensitive quantum efficiency itself of silver halide grains, a technique of using a core having a high silver iodide content inside the grain is known,
A technique for providing a core having a high silver iodide content inside a tabular grain is disclosed in JP-A-63-92942.

In recent years, demands for higher sensitivity and higher image quality have become more and more intense, and the use of such silver halide grains provided with a high iodine core phase is not limited to high-sensitivity light-sensitive materials but also to common color negative light-sensitive materials. Was also mandatory.

On the other hand, a grain having such an internal high iodine core has a drawback that pressure desensitization is remarkable, which is a big problem in handling a light-sensitive material using such a silver halide grain. There is. Pressure desensitization is improved by decreasing the silver iodide content of the internal high-iodity core phase,
It causes a decrease in photographic sensitivity and cannot be put to practical use. Furthermore,
When tabular grains are used, the pressure resistance tends to deteriorate due to the shape factor.

By the way, as a technique for improving the pressure fog of silver halide grains, iodine ions are rapidly added to the mixed solution during the formation of silver halide grains to locally increase the silver iodide content in the grains. The technology is JP-A-62-58237.
Issue. These techniques improve pressure resistance characteristics by localizing dislocation lines, silver iodide or high silver iodide containing phases inside the silver halide grains, but the effect is to improve pressure fog. there were. In addition, JP-A-3-2
Nos. 37450, 4-350850 and the like also show examples of tabular grains in which a silver iodide-containing phase and a dislocation line are introduced, but pressure desensitization is not mentioned.

It is considered that the pressure desensitization is caused by physical stress, and from this viewpoint, it is easily inferred that the amount of gelatin, which is the main binder of the hydrophilic colloid layer, is increased and improved. However, in this case, the sharpness is deteriorated due to the increase of the dry film thickness of the coating film, and the processing stability is adversely affected due to the delay of the developing property. Further, in order to prevent scratch-like pressure generated by rubbing dust adhering to the film surface, it is considered that antistatic property is imparted to indirectly reduce the pressure. For example, as a conductive material, Japanese Patent Publication No. 57-18175. , 57-18176,
57-56059, 58-56856, 59-1
06115, 60-51693, JP-A-54-159.
222, ibid 55-7763, ibid 55-65950, ibid 5
There are cationic polymers shown in 5-67746 and the like. However, the effect is not sufficient, especially when the silver halide light-sensitive materials are stacked or wound in a roll and sealed and stored under high temperature and high humidity, the sticking resistance is remarkably poor and the smoothness of the surface of the light-sensitive material is lost. On the contrary, it was found that the scratched pressure was deteriorated. This is commonly known as having a backing layer on the back surface of the film support 120.
(Brownie), 220, 4 × 5, etc. appear remarkably in the film.

Further, the deterioration of the sticking resistance deteriorates the transportability of the film, which causes a trouble in the processing equipment.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material having high sensitivity, excellent image quality, particularly sharpness, and improved pressure desensitization.

[0009]

The above object of the present invention has been achieved by the following constitution.

(1). A silver halide color photographic light-sensitive material having at least one blue light-sensitive silver halide emulsion layer, green light-sensitive silver halide emulsion layer and red light-sensitive silver halide emulsion layer on a support. At least one of the emulsion layers has at least two silver iodide-containing silver halide phases having different silver iodide contents inside the grain, and the inner phase of the phase is more silver iodide than the outer phase. A tabular halogen having a large content, the phase containing silver iodide having a maximum silver iodide content of 5 mol% or more and less than 10 mol%, an aspect ratio of 2 or more, and 5 or more dislocation lines. A silver halide color photographic light-sensitive material containing silver halide grains, wherein the photographic light-sensitive material contains a fluorine-containing surfactant.

(2). The silver halide color photographic light-sensitive material according to (1), wherein the fluorine-containing surfactant is contained in the uppermost layer of the photographic constituent layers.

(3). As the fluorine-containing surfactant,
The silver halide color photographic light-sensitive material as described in (1) or (2), which contains a fluorinated cation type surfactant and a fluorinated anion type surfactant in combination.

(4). The maximum silver iodide content is 5 mol%
It is above 8 mol% and is characterized by (1)-
The silver halide color photographic light-sensitive material according to any one of (3).

(5). The silver halide color photographic light-sensitive material described in any one of (1) to (4), wherein the dislocation lines are present inside the grain and in the fringe portion.

(6). The silver halide color photographic light-sensitive material as described in any one of (1) to (5), wherein the variation coefficient of the circle-converted diameter of the projected area of tabular silver halide grains is 20% or less.

(7). The silver halide color photographic light-sensitive material according to any one of (1) to (6), wherein the dislocation line introduction position is at the interface between the maximum silver iodide-containing phase and the phase adjacent to the outside thereof.

(8). The silver halide color photographic light-sensitive material according to any one of (1) to (7), wherein the total amount of gelatin on the side of the photosensitive silver halide emulsion layer on the support is 12 g / m ² or less. material.

(9). The silver halide color according to any one of (1) to (8), which has a backing layer on the surface of the support opposite to the photosensitive silver halide emulsion layer side. Photographic material.

The present invention will be described in more detail below.

In the present invention, the tabular silver halide grain means that it has two parallel principal planes and has a diameter corresponding to a circle of the principal plane (a diameter of a circle having the same projected area as the principal plane) and a principal plane. A particle having a ratio of distance (that is, particle thickness), that is, an aspect ratio of 2 or more.

At least 50% of the total projected area of all the tabular silver halide grains of the present invention is preferably tabular grains having an aspect ratio of 3 or more, more preferably 5 or more and less than 8. .

The diameter of the tabular grains of the present invention is 0.3 to 10
μm, preferably 0.5 to 5.0 μm, more preferably 0.5 to 2.0 μm. The particle thickness is 0.05 ~
It is preferably 0.8 μm.

In the present invention, the particle diameter and particle thickness can be measured by the method described in US Pat. No. 4,434,226.

The coefficient of variation of the circle-converted diameter (diameter of a circle having the same projected area as the main plane) of the tabular grain projection surface of the present invention (standard deviation of diameter distribution divided by average diameter) is a tabular shape. It means the size distribution of the particles, preferably 30% or less, and more preferably 20% or less.

The halogen composition of the silver halide grains is preferably silver iodobromide or silver chloroiodobromide,
The silver iodide content is preferably 1 to 15 mol%,
More preferably, it is 3 to 10 mol%.

The intergranular distribution of the silver iodide content of the silver halide grains of the present invention is the variation coefficient of the silver iodide content (the standard deviation of the silver iodide content intergrain distribution is the average silver iodide content. It is preferably 30% or less, more preferably 20% or less.

The tabular grain of the present invention has at least two phases having different halogen compositions inside the grain,
The silver iodide content of the phase having the highest silver iodide content is 5 mol%.
It is not less than 10 mol% and preferably not less than 5 mol% and not more than 8 mol%. The volume fraction of the particles in the phase is preferably 30% or more and 90% or less.
It is more preferably 0% or more and 60% or less. The silver iodide content of the phase adjacent to the outer side of the phases may be lower than the silver iodide content of the maximum silver iodide containing phase, but is preferably 0 to 8 mol%, more preferably 2 to 5 mol%. Mol%. The maximum silver iodide-containing phase needs to be adjacent to the low silver iodide-containing phase on the outer side thereof, but the adjacent phase does not necessarily have to completely cover the maximum silver iodide-containing phase. Absent.

The structure relating to the halogen composition in the grain is X
It can be investigated by a line diffraction method, a composition analysis method by EPMA, or the like.

The silver iodide content on the surface of the tabular grain of the present invention may be higher than the silver iodide content of the maximum silver iodide containing phase inside the grain. The silver iodide content on the grain surface in the present invention means a value measured by the XPS method or a value measured by the ISS method, which may be either. When measured by the XPS method, preferably 0 to 1
It is 2 mol%, and more preferably 5 to 10 mol%.

The surface silver iodide content by the XPS method of the present invention is determined as follows. Cool the sample to -115 ° C or less in an ultrahigh vacuum of 1 x 10 ^-8 torr or less, and use X for a probe.
X-ray source voltage 15 kV, X-ray source current 4 as MgKα
Irradiate with 0 mA, Ag3d5 / 2, Br3d, I3d3
/ 2 Measure for electrons. The integrated intensity of the measured peak is corrected by the sensitivity factor, and the halide composition of the surface is determined from the intensity ratio of these.

The maximum silver iodide-rich phase inside the grain referred to in the present invention does not include the high iodine localized region produced by the above-described operation for forming dislocation lines.

As the method for producing tabular grains, the methods known in the art can be appropriately combined. For example, JP-A 61-6643, 61-146305, and 6
2-157024, 62-18556, 63-
No. 92942, No. 151618, No. 63-16345
No. 1, No. 63-220238, No. 63-31244
It is possible to refer to a known method according to the issue. For example, pA in the liquid phase in which silver halide is produced, which is one of the double jet method, double jet method and double jet method.
A so-called control double jet method for keeping g constant and a triple jet method in which soluble silver halides having different compositions are independently added can also be used. A forward mixing method may be used, or a method of forming grains in the presence of excess silver ions (so-called reverse mixing method) may be used. A silver halide solvent can be used if necessary. Ammonia, thioethers and thioureas can be mentioned as the silver halide solvent often used. U.S. Pat.
No. 271,157, No. 3,790,387, No. 3,
No. 574,628 can be referred to. Also,
The mixing method is not particularly limited, and a neutral method that does not use ammonia, an ammonia method, an acidic method, or the like can be used, but it is preferably pH (hydrogen ion concentration) from the viewpoint of reducing fogging of silver halide grains. Logarithm of the reciprocal of)
It is 5.5 or less, more preferably 4.5 or less.

The silver halide grains of the present invention may contain iodide ions, but in this case, the method of adding iodide ions in grain growth is not particularly limited, and iodide ions such as potassium iodide may be added. Alternatively, it may be added as fine silver iodide grains.

The silver halide emulsion of the present invention is described in JP-A-1-
183417, 1-183644, 1-183
It is also preferable to grow grains by using fine silver halide grains in the same manner as the grains disclosed in Japanese Patent No. 645. In particular, as in the claims of Japanese Patent Application No. 3-218608, the number of silver halide fine grains used for grain growth is two or more, and it is preferable that at least one of them comprises only one halogen element.

Further, as in the claims of JP-A-2-167537, a halogen grown in the presence of silver halide grains having a solubility lower than that of the growing silver halide grains for at least one period of the grain growth process. An emulsion containing silver iodide grains is desirable, and silver iodide is particularly desirable as silver halide grains having a small solubility product.

Dislocations of tabular grains are described, for example, in J. F. Ha
Milton, Photo. Sci. Eng. , 11
(1967), 57 and T.S. Shiozawa, J .; S
ci. Photo. Sci. Japan, 35 (197)
2), 213, that is, the direct method using a transmission electron microscope at low temperature can be used for observation.

That is, the silver halide grains, which were taken out so as not to apply a pressure that would cause dislocation to the grains from the emulsion, were placed on a mesh for an electron microscope to prevent damage (printout etc.) due to an electron beam. Observation is performed by a transmission method while the sample is cooled so as to prevent it. At this time, the thicker the particles, the more difficult it is for an electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 kV for a thickness of 0.25 μm). From the grain photograph obtained by such a method, the position and number of dislocations of each grain when viewed from the direction perpendicular to the principal plane can be determined.

The dislocation position of the tabular grain of the present invention is not limited to a particular position, but
It is preferable that the tabular grains are present on the fringe portion and the main plane side. The fringe portion of the tabular grain refers to the outer periphery of the tabular grain, and more specifically, in the vertical line dropped from the center of gravity of the tabular grain projection surface viewed from the main plane side to each side of the grain, the length of the vertical line is Outside 50% (side), preferably outside 70%, more preferably 80
It means the area outside%.

The number of dislocations in the tabular grains of the present invention is preferably 30% or more (the number) of grains containing 5 or more dislocations, more preferably 50% or more, and 80% or more. Is particularly preferable. Further, the number of dislocations is more preferably 10 or more.

Fringe portion and inside of particle (other than fringe portion)
When there are dislocation lines in, it is preferable that there are 5 or more dislocation lines inside the grain, and it is more preferable that there are 5 or more dislocation lines both inside the fringe portion and inside the grain.

The method of introducing the dislocation lines of the present invention is not particularly limited, but a method of adding an aqueous solution of an iodine ion such as potassium iodide and a water-soluble silver salt solution by a double jet at the position where the dislocation is desired to be introduced, or iodine. A method of adding fine silver halide grains, a method of adding only an iodine ion solution, JP-A-6-
It can be carried out by a method using an iodide ion-releasing agent as described in No. 11781. A method of adding an iodine ion aqueous solution and a water-soluble silver salt solution with a double jet,
A method of adding fine silver iodide grains and a method of using an iodide ion releasing agent are preferable, and a method of using fine silver iodide grains is more preferable. The aqueous solution of iodine ions is preferably an aqueous solution of alkali iodide, and the aqueous solution of water-soluble silver salt is preferably a silver nitrate solution.

The dislocation is introduced preferably after the formation of the maximum silver iodide-containing phase inside the grain, more preferably after the formation of the phase and before the formation of the adjacent phase. Further, in relation to the position of the whole grain, it is preferable to introduce the silver in an amount corresponding to 50 to 95% of the silver amount in the whole grain, and more preferably 60 to less than 80%.

The fluorine-containing surfactant used in the present invention includes anionic type, cationic type, nonionic type and betaine type.

Examples of the fluorine-containing anionic surfactant preferably used in the present invention include those represented by the following general formula [I].

[0045]

Embedded image

(In the formula, Cf represents an n-valent group containing at least 3 fluorine atoms and at least 2 carbon atoms,
Y represents -COOM, -SO ₃ M, -OSO ₃ M or -P (= O) (OM) represents a _2, where M is hydrogen or an alkali metal atom or an ammonium group, l is 1 or 2 Is. ) More preferably used fluorine-containing anionic surfactants include those represented by the following general formula [II].

[0047]

Embedded image

(In the formula, Rf represents a fluorine-substituted alkyl group or aryl group having 3 to 30 carbon atoms, and D represents -O-, -COO.
-, -CON (R ¹ )-or -SO ₂ N (R ¹ )-represents a divalent group having 1 to 12 carbon atoms and containing at least one bond, wherein R ¹ is ^{1 to 1} carbon atoms. 5 represents an alkyl group, t is 1 or 2, and Y is -COOM, -SO ₃ M, -OSO ₃ M or -P (= O) (OM).
₂ , M represents a hydrogen atom, an alkali metal atom or an ammonium group. Next, specific examples of the compound will be given, but the present invention is not limited thereto.

[0049]

Embedded image

[0050]

[Chemical 4]

[0051]

Embedded image

[0052]

[Chemical 6]

[0053]

[Chemical 7]

[0054]

Embedded image

It is particularly preferable to use a fluorine-containing anionic surfactant containing at least one bond of —SO ₂ N (R ₁ ) —.

The fluorinated cationic surfactant used in the present invention is a compound represented by the following general formula [III].

[0057] Formula (III) R'f-G-J ⁺ L ^- However, R'f is a 1-20 hydrocarbon group having a carbon number,
At least one hydrogen atom is replaced by a fluorine atom. G represents a chemical bond or a divalent group. J ⁺ represents a cationic group and L ⁻ represents a counter anion.

As an example of R'f, -CkF ₂ k ₊₁ (k = 1 to 2
0, especially 3 to 12), HCqF ₂ q−, −CqF ₂ q ₋₁ (q = 2 to 20,
In particular, 3 to 12) can be mentioned, and as an example of G,

[0059]

[Chemical 9]

Mention may be made of:

As an example of J ⁺ ,

[0062]

[Chemical 10]

The following may be mentioned.

R ′ and R ″ represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, A ′ represents an alkyl group or an arylene group, p is 0 to 6 and u is 1 to 20. , V
Represents 0 to 6 and j represents 0 to 6.

[0065] In addition, L ^- as an example of

[0066]

[Chemical 11]

There may be mentioned:

Specific examples of the fluorine-containing cationic surfactant preferably used in the present invention are given below.

[0069]

[Chemical 12]

[0070]

[Chemical 13]

[0071]

Embedded image

In the present invention, it is more preferable to use a fluorine-containing cationic surfactant having at least one bond of —SO ₂ N (R ′) — which is hardly soluble. Here, the sparingly soluble means that 2.0 g of the surfactant is added to 100 ml of pure water at 23 ° C.
After stirring for 24 hours and leaving at 23 ° C for 24 hours, it is considered to be sparingly soluble when a precipitate or a floating substance is visually observed. For example FK-
1, FK-8, FK-15, FK-16, etc. correspond, but are not limited to these and can be divided by the above test.

The fluorine-containing anionic surfactant according to the present invention or the fluorine-containing cationic surfactant according to the present invention is, for example, US Pat. Nos. 2,559,751 and 2,567,011.
2,732,398, 2,764,602, 2,806,866, 2,8
09,998, 2,915,376, 2,915,528, 2,934,450
No., No. 2,937,098, No. 2,957,031, No. 3,472,894,
No. 3,555,089, No. 2,918,501, British Patent No. 1,143,927,
1,130,822, Japanese Patent Publication No. 45-37304, JP-A No. 47-9613,
50-121243, 50-117705, 49-134614, 50
-117727, 52-41182, 51-12392
Journal of the British Chemical Society (J. Chem. Soc.) 1950, page 2789, 1957.
Year 2574 and 2640, Journal of the American Chemical Society (J. Amer. Chem.
Soc.) Volume 79, page 2549 (1957), Oil Chemistry (J. Japan. Oil Che
mistsSoc.) Vol. 12, p. 653, Journal of Organic Chemistry (J.Org.Che)
m.) Volume 30, page 3524 (1965) and the like. Among these fluorine-containing surfactants according to the present invention, a certain type is named Megafac F from Dainippon Ink and Chemicals Incorporated, and Fluorad FC from Minnesota Mining and Manufacturing Company. Under the trade name of Imperial Chemical Industry, under the name of Monflor under the trade name of EIDupont, under the name of ZONELS from Nemeras & Co. or under the name of Licowet from Farbeberke Hoechst. They are marketed under the trade name VPF.

In the present invention, it is particularly preferable to use a fluorine-containing cationic surfactant and a fluorine-containing anionic surfactant in combination.

The total amount of the fluorinated cationic surfactant and the fluorinated anionic surfactant used in the present invention is preferably 0.1 to 1000 mg, preferably 0.5 to 3 per 1 m ^2.
The amount is preferably 00 mg, more preferably 1.0 to 150 mg. When used in combination, two or more kinds of fluorine-containing cationic surfactants and fluorine-containing anionic surfactants may be used together. In addition, a fluorine-containing nonionic surfactant, a fluorine-containing betaine surfactant and a hydrocarbon-based surfactant may be used in combination. The addition ratio of the fluorinated anionic surfactant and the fluorinated cation surfactant of the present invention is 1: in a molar ratio.
It is preferably 10 to 10: 1, more preferably 3: 7 to 7: 3.

The fluorine-containing anionic surfactant and the fluorine-containing cationic surfactant according to the present invention are not particularly limited in their places of addition, but they may be added to the surface protective layer or the surface layer on the back layer side. You may add.

In the present invention, it is excellent in terms of achieving both high image quality and surface properties, and in particular, the total amount of gelatin on the side having the photosensitive emulsion layer from the support is preferably 15 g / m ² or less, and further 12 g. Most preferred is / m ² or less.

In the present invention, the silver halide emulsion is represented by Research Disclosure 308119 (hereinafter RD308).
119) can be used. The description is shown below.

[Items] [Page of RD308119] Iodine structure 993 IA Item Production method "" and 994 E Item Crystal habit (normal crystal) "" Crystal habit (twin crystal) "" Epitaxial "" Halogen composition (uniform) 993 IB term Halogen composition (non-uniform) "" Halogen conversion 994 IC term Halogen substitution "" Metal-containing 994 ID term Monodisperse 995 IF term Solvent addition "" Latent image formation position (surface) 995 IG term Latent image formation position (internal) ) "" Applicable sensitizer (negative) Item 995 IH Applicable sensitizer (positive) "" Use by mixing emulsions "IJ Item Desalination" Item II-A The silver halide emulsion of the present invention is physically and chemically ripened. Further, those subjected to spectral sensitization can be used. Additives used in such a process, Research Disclosure No.17643, No.18716 and No.308119 (respectively,
Hereinafter, abbreviated as RD17643, RD18716 and RD308119).

The places described below are shown.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-AA, B, C, D, H, I, J Item 23 -24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known photographic additives usable in the present invention Agents are also described in Research Disclosure above. Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, XIII C Item 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubrication Agent 1006 XII 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matting agent 1007 XVI Developer (included in light-sensitive material) Item 1011 XXB Various couplers can be used in the invention, and specific examples thereof can be used. Are described in Research Disclosure above. Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VII C to G item Magenta coupler 1001 VII-D item VII C to G item Cyan coupler 1001 VII-D item VII C to G item Colored coupler 1002 VII-G item VII G item DIR coupler 1001 VII-F item VII F item BAR coupler 1002 VII-F item Other useful residues Release coupler 1001 VII-F item Alkali-soluble coupler 1001 VII-E item Invention The additive used for can be added by the dispersion method described in RD308119XIV.

In the present invention, the aforementioned RD17643 page 28, R
The supports described in D18716 pages 647-8 and RD308119 XIX can be used.

The light-sensitive material of the present invention includes the above-mentioned RD308119VII.
An auxiliary layer such as a filter layer or an intermediate layer described in the section -K can be provided.

The light-sensitive material of the present invention is the above-mentioned RD308119VII-
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section K can be adopted.

The present invention can be applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. .

The present invention is commonly called 120 (Brownie), 2
It has outstanding performance for a color photographic light-sensitive material having a product packaging form of 20, 4 × 5.

The light-sensitive material of the present invention is the above-mentioned RD17643 28-29.
Development can be carried out by a usual method described in XIX of page RD18716, page 647 and RD308119.

[0090]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1 << Preparation of Seed Crystal Emulsion-1 >> A seed crystal emulsion was prepared as follows.

Japanese Patent Publications 58-58288 and 58-58
An aqueous solution of silver nitrate (1.161 mol) was added to the following solution A1 prepared at 35 ° C. using the mixing stirrer shown in No. 289.
And a mixed aqueous solution of potassium bromide and potassium iodide (2 mol% of potassium iodide) at the same time while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV. Was added over 2 minutes to form nuclei. Subsequently, the liquid temperature was raised to 60 ° C. over 60 minutes, the pH was adjusted to 5.0 with an aqueous sodium carbonate solution, and then an aqueous silver nitrate solution (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% potassium iodide) was added over 42 minutes by the simultaneous mixing method while maintaining the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing with water were immediately performed using a usual flocculation method.

The obtained seed crystal emulsion had an average sphere-converted diameter of 0.24 μm, an average aspect ratio of 4.8, and 90% or more of the total projected area of silver halide grains had a maximum side ratio of 1.0.
The emulsion consisted of hexagonal tabular grains of .about.2.0. This emulsion is called seed crystal emulsion-1.

[Solution A1] Ocein gelatin 24.2 g Potassium bromide 10.8 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml << Silver iodide Preparation of Fine Particle Emulsion SMC-1 >> 5 L of 6.0 wt% gelatin aqueous solution containing 0.06 mol of potassium iodide
While vigorously stirring, 7.06 mol of silver nitrate aqueous solution and 7.06 mol of potassium iodide aqueous solution, 2 L each, were added over 10 minutes. During this time, the pH is 2.0 using nitric acid.
The temperature was controlled at 40 ° C. After the particles were prepared, the pH was adjusted to 5.0 with an aqueous sodium carbonate solution. The average grain size of the obtained silver iodide fine grains was 0.05 μm. This emulsion is called SMC-1.

<< Preparation of Emulsion Em-1 >> 4.5 wt.% Containing 0.178 mol of seed crystal emulsion-1 and 0.5 ml of a 10% ethanol solution of polyisoprene-polyethyleneoxy-disuccinate sodium salt. % Inactive gelatin aqueous solution 700ml kept at 75 ° C, pAg 8.3, p
After adjusting H to 5.0, particle formation was performed by the following procedure by the simultaneous mixing method with vigorous stirring.

1) 2.121 mol of silver nitrate aqueous solution and 0.
174 mol of SMC-1 and potassium bromide aqueous solution,
The pAg was added while keeping the pH at 8.3 and the pH at 5.0.
(Formation of Host Particles) 2) Subsequently, the temperature of the solution was lowered to 60 ° C., and pAg was adjusted to 9.6. Then, 1.028 mol of silver nitrate aqueous solution and 0.
032 mol of SMC-1 and potassium bromide aqueous solution,
pAg was added while keeping the pH at 9.6 and pH at 5.0.
(Shelling of host particles) Each solution was added at an optimum rate so as to prevent the formation of new nuclei and the Ostwald ripening between particles from progressing through the formation of particles. After completion of the above addition, water washing treatment was carried out at 40 ° C. using a usual flocculation method, and then gelatin was added and redispersed to adjust pAg to 8.1 and pH to 5.8.

The obtained emulsion had a grain size (cubic 1 having the same volume).
The emulsion was tabular grains having a halogen composition shown in Table 1 having a side length of 0.65 μm and an average aspect ratio of 4.5. When the emulsion was observed with an electron microscope, no grains having dislocation lines were present.

<< Preparation of Emulsion Em-2 >> 4.5 wt% containing 0.178 mol of seed crystal emulsion-1 and 0.5 ml of a 10% ethanol solution of polyisoprene-polyethyleneoxy-disuccinate sodium salt. % Inactive gelatin aqueous solution 700ml kept at 75 ° C, pAg 8.3, p
After adjusting H to 5.0, particle formation was performed by the following procedure by the simultaneous mixing method with vigorous stirring.

1) 2.066 mol of silver nitrate aqueous solution and 0.
230 mol of SMC-1, and an aqueous potassium bromide solution,
The pAg was added while keeping the pH at 8.3 and the pH at 5.0.
(Formation of Host Particles) 2) Subsequently, the temperature of the solution was lowered to 60 ° C., and pAg was adjusted to 9.6. Then, 0.071 mol of SCM-1 was added and aging was carried out for 2 minutes. (Introduction of dislocation line) 3) Then, 0.959 mol of silver nitrate aqueous solution and 0.03
0 mol of SMC-1 and an aqueous potassium bromide solution were added to pA.
g was added while keeping the pH at 9.6 and pH at 5.0. (Shelling of host particles) Each solution was added at an optimum rate so as to prevent the formation of new nuclei and the Ostwald ripening between particles from progressing through the formation of particles. After completion of the above addition, water washing treatment was carried out at 40 ° C. using a usual flocculation method, and then gelatin was added and redispersed to adjust pAg to 8.1 and pH to 5.8.

The obtained emulsion had a grain size (cubic 1 of the same volume).
The emulsion consisted of tabular grains having a halogen composition shown in Table 1 having a side length of 0.65 μm and an average aspect ratio of 4.0. When this emulsion was observed with an electron microscope, 80% or more (number) of grains had 5 or more dislocation lines both in the fringe portion and inside the grains.

<< Preparation of Emulsion Em-3 >> 4.5% by weight containing 0.178 mol of seed crystal emulsion-1 and 0.5 ml of a 10% ethanol solution of polyisoprene-polyethyleneoxy-disuccinate sodium salt. % Inactive gelatin aqueous solution 700ml kept at 75 ℃, pAg 9.0, p
After adjusting H to 5.0, particle formation was performed by the following procedure by the simultaneous mixing method with vigorous stirring.

1) 0.692 mol of silver nitrate aqueous solution and 0.
297 moles of SMC-1 and potassium bromide aqueous solution,
pAg was added while maintaining pH 9.0 and pH 5.0.

2) Subsequently, 2.295 mol of silver nitrate aqueous solution, 0.071 mol of SMC-1, and potassium bromide solution were added while keeping pAg at 9.0 and pH at 5.0.

During the grain formation, each solution was added at an optimum rate so that the formation of new nuclei and Ostwald ripening between grains did not proceed. After completion of the above addition, water washing treatment was carried out at 40 ° C. using a usual flocculation method, and then gelatin was added and redispersed to adjust pAg to 8.1 and pH to 5.8.

The obtained emulsion had a grain size (cubic 1 of the same volume).
The emulsion consisted of tabular grains having a halogen composition shown in Table 1 having a side length of 0.65 μm and an average aspect ratio of 4.3. When the emulsion was observed with an electron microscope, no grains having dislocation lines were present.

<< Preparation of Emulsion Em-4 >> In the preparation of Emulsion Em-2, the silver nitrate aqueous solution at the time of forming the host grains was changed to silver 2.
Em-4 was prepared in the same manner as Em-2 except that the amount of 121 mol was changed to 0.174 mol of SMC-1.

The obtained emulsion had a grain size (cubic 1 of the same volume).
The emulsion consisted of tabular grains having a halogen composition shown in Table 1 having a side length of 0.65 μm and an average aspect ratio of 4.1. When this emulsion was observed with an electron microscope, 80% or more (number) of grains had 5 or more dislocation lines both in the fringe portion and inside the grains.

<< Preparation of Emulsion Em-5 >> In the preparation of Emulsion Em-4, an aqueous silver nitrate solution at the time of forming host grains was 2.09
3 mol of SMC-1 to 0.202 mol of pAg of 8.6
Em-5 was prepared in the same manner as Em-4 except that the pAg at the time of introducing dislocation lines and shelling the host grains was changed to 9.4.

The emulsion thus obtained had a grain size (cubic 1 having the same volume).
The emulsion consisted of tabular grains having a halogen composition shown in Table 1 having a side length of 0.65 μm and an average aspect ratio of 6.6. When this emulsion was observed with an electron microscope, 80% or more (number) of grains had 5 or more dislocation lines both in the fringe portion and inside the grains.

<< Preparation of Emulsion Em-6 >> In the preparation of Emulsion Em-4, the shell formation was started after the formation of the host grains, and the addition of the silver nitrate aqueous solution, SMC-1 and the potassium bromide aqueous solution was stopped during the shell formation. , Em-4 was carried out in the same manner as Em-4, and Em-6 was prepared in the same manner as Em-4 except that the shell formation was performed again.

The resulting emulsion had a grain size (cubic 1 of the same volume).
The emulsion consisted of tabular grains having a halogen composition shown in Table 1 having a side length of 0.65 μm and an average aspect ratio of 4.4. When this emulsion was observed with an electron microscope, 5% or more dislocation lines were observed in both the fringe portion and the inside of the grains in 80% or more (the number) of grains.

<< Preparation of Emulsion Em-7 >> In the preparation of Emulsion Em-4, an aqueous silver nitrate solution and SMC at the time of forming host grains were prepared.
-1, Em-7 was prepared in exactly the same manner as Em-4 except that the addition rate of the aqueous potassium bromide solution was set to 1/3.

<Preparation of Emulsion Em-8> Em was prepared in the same manner as in Preparation of Emulsion-4 except that the aqueous silver nitrate solution was changed to 2.188 mol and SMC-1 was changed to 0.108 mol during the formation of host grains.
Em-8 was prepared in the same manner as in -4.

The obtained emulsion was a tabular grain having a grain size (cubic one side length of the same volume) of 0.65 μm and an average aspect ratio of 4.1 and having a halogen composition shown in Table 1. When the particles were observed with an electron microscope, 80% or more (number) of particles had 5 or more transition lines in both the fringe portion and inside the particles.

The characteristics of each emulsion thus obtained are shown in Table 1.

[0116]

[Table 1]

1) Silver iodide content of each phase (mol%) and ()
The volume inside is the volume fraction (%) in the silver halide grains of each phase. X indicates a dislocation line introduction position.

2) Aspect ratio at 50% of the sum of all projected areas of silver halide grains in each emulsion.

3) Coefficient of variation of projected surface circle equivalent diameter of tabular grains: In each of the above emulsions Em-1 to Em-7, a sensitizing dye SD-described later was added.
1. Using SD-5 and SD-6, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added, and according to a conventional method,
Chemical sensitization was performed so that the fog-sensitivity relationship was optimal.

Example 2 Sample 101, which is a multilayer color light-sensitive material composed of layers having the compositions shown below, was prepared on an undercoated cellulose triacetate film support. The coating amount for silver halide and colloidal silver, the amount expressed in terms of metallic silver in the unit of g / m ^2, and a coupler, the amount, expressed in units of g / m ² for the additive, also, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer.

Sample 101 First layer: Antihalation layer Black colloidal silver 0.18 Ultraviolet absorber (UV-1) 0.30 High boiling point solvent (Oil-1) 0.37 Gelatin 1.59 Second layer: Intermediate layer Gelatin 1.27 Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion A 0.63 Sensitizing dye (SD-1) 1.7 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.5 × 10 ^-4 Sensitizing dye (SD-3) 1.5x10 ^-4 Sensitizing dye (SD-4) 1.3x10 ^-5 Cyan coupler (C-1) 0.71 Colored cyan coupler (CC-1) 0.09 DIR compound (D-1) 0.005 High-boiling-point solvent (Oil-1) 0.65 Gelatin 2.05 Fourth layer: medium-sensitive red-sensitive layer Silver iodobromide emulsion B 0.71 Sensitizing dye ( SD-2) 2.5 × 10 ^-4 sensitizing dye (SD-3) 1.4 × 10 -5 sensitizing dye (SD-4) .2 × 10 ^-4 Cyan coupler (C-1) 0.27 Colored cyan coupler (CC-1) 0.04 DIR compound (D-1) 0.01 DIR compound (D-2) 0.015 High boiling solvent (Oil-1) 0.32 Gelatin 0.83 Fifth layer: High-sensitivity red-sensitive layer Silver iodobromide emulsion C 1.52 Sensitizing dye (SD-2) 2.1 × 10 ⁻⁴ Sensitizing dye (SD -3) 1.2 × 10 ^-5 sensitizing dye (SD-4) 1.8 × 10 ^-4 cyan coupler (C-2) 0.13 DIR compound (D-1) 0.006 DIR compound (D- 2) 0.016 High boiling point solvent (Oil-1) 0.17 Gelatin 1.04 Sixth layer: Intermediate layer Gelatin 1.00 Seventh layer: Low sensitivity green sensitive layer Silver iodobromide emulsion A 0.76 Sensitization dye (SD-1) 1.8 × 10 -4 sensitizing dye (SD-5) 1.8 × 10 -4 sensitizing dye (SD- ) 1.8 × 10 ^-4 Magenta coupler (M-1) 0.10 Magenta coupler (M-2) 0.25 Colored magenta coupler (CM-1) 0.11 DIR compound (D-1) 0.004 DIR Compound (D-3) 0.013 High boiling point solvent (Oil-2) 0.49 Gelatin 1.10 Eighth layer: Medium-sensitive green sensitive layer Silver iodobromide emulsion B 0.55 Sensitizing dye (SD-1) 1.53 × 10 ⁻⁴ Sensitizing dye (SD-5) 1.53 × 10 ⁻⁴ Sensitizing dye (SD-6) 1.53 × 10 ⁻⁴ Magenta coupler (M-1) 0.07 Magenta coupler ( M-2) 0.17 Colored magenta coupler (CM-1) 0.08 DIR compound (D-1) 0.001 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.33 Gelatin 0.78 9th layer: High sensitivity green sensitive layer Em- 0.82 Sensitizing dye (SD-1) 1.4 × 10 -4 Sensitizing dye (SD-5) 1.5 × 10 -4 Sensitizing dye (SD-6) 1.4 × 10 -4 Magenta coupler (M-2) 0.10 Magenta coupler (M-3) 0.03 Colored magenta coupler (CM-2) 0.03 DIR compound (D-1) 0.001 DIR compound (D-3) 0.004 High Boiling point solvent (Oil-2) 0.31 Gelatin 0.91 10th layer: Intermediate layer Gelatin 0.50 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.08 High boiling point solvent ( Oil-2) 0.10 Gelatin 1.00 12th layer: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion A 0.16 Silver iodobromide emulsion D 0.16 Sensitizing dye (SD-7) 1.7 × 10 ^-4 sensitizing dye (SD-8) 4.0 × 10 -4 sensitizing dye (SD-10) .1 × 10 ^-6 yellow coupler (Y-1) 0.24 Yellow coupler (Y-2) 0.66 High boiling solvent (Oil-2) 0.18 Gelatin 1.19 13th layer: middle sensitivity blue-sensitive layer Silver iodobromide emulsion B 0.46 Sensitizing dye (SD-7) 1.3 × 10 ⁻⁴ Sensitizing dye (SD-8) 3.0 × 10 ⁻⁴ Sensitizing dye (SD-10) 1.6 × 10 ^-6 Yellow coupler (Y-1) 0.07 Yellow coupler (Y-2) 0.20 DIR compound (D-4) 0.01 High boiling point solvent (Oil-2) 0.05 Gelatin 0.84 14 layers: high-sensitivity blue-sensitive layer Silver iodobromide emulsion E 0.41 Sensitizing dye (SD-7) 0.9 × 10 ⁻⁴ Sensitizing dye (SD-9) 2.0 × 10 ⁻⁴ Yellow coupler ( Y-1) 0.06 Yellow coupler (Y-2) 0.18 High boiling point solvent (Oil-2) 0.05 Gelatin 0. 7 Fifteenth Layer: First Protective Layer Silver iodobromide emulsion (average grain size 0.04 μm, silver iodide content 4.0 mol%) 0.30 UV absorber (UV-2) 0.030 UV absorber (UV-3) 0.015 UV absorber (UV-4) 0.015 UV absorber (UV-5) 0.015 UV absorber (UV-6) 0.10 High boiling point solvent (Oil-2) 0 0.07 High boiling point solvent (Oil-3) 0.07 Gelatin 1.44 16th layer: Second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.18 Polymethylmethacrylate (average particle size 3 μm) 0.02 Surfactant K-1 (dodecyl sulfosuccinate / Na) 0.004 Sliding agent (WAX-1) 0.05 Gelatin 0.55 In addition to the above composition, compounds SU-1, SU-2 and viscosity modifiers V-1, hardener H-1, H-2, stable ST-
1, antifoggant AF-1, average molecular weight 10,000 and 1,100,
000 of two AF-2, dyes AI-1, AI-2, AI
-3, compounds FS-1, FS-2, and preservative DI-
1 was appropriately added to each layer.

The structures of the compounds added to the respective layers of the above light-sensitive material are shown below.

[0123]

[Chemical 15]

[0124]

Embedded image

[0125]

[Chemical 17]

[0126]

Embedded image

[0127]

[Chemical 19]

[0128]

Embedded image

[0129]

[Chemical 21]

[0130]

[Chemical formula 22]

[0131]

[Chemical formula 23]

[0132]

[Chemical formula 24]

[0133]

[Chemical 25]

[0134]

[Chemical formula 26]

[0135]

[Chemical 27]

The emulsion used in the above sample is as follows. The average particle size is shown as a particle size converted into a cube. To each emulsion, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added, and chemical sensitization was performed according to a conventional method so that the fog-sensitivity relationship was optimized.

Emulsion name Average AgI average particle size Crystal habit Diameter / content (mol%) (μm) Thickness ratio Emulsion A 8.0 0.40 Normal crystal 1 Emulsion B 8.0 0.55 Normal crystal 1 Emulsion C 8 0.0 0.70 Normal crystal 1 Emulsion D 2.0 0.30 Normal crystal 1 Emulsion E 8.5 0.85 Normal crystal 1 Emulsions A and D contain 1 × 10 ⁻⁷ mol / 1 mol Ag of iridium .

Then, the fifth silver halide emulsion was changed to the sample 101, and the fluorine-containing surfactant was added as shown in Table 2, except that the samples 101 to 102 were prepared in the same manner as the sample 101.
12, 115 were produced. Here, in the sample 113, a fluorine-containing surfactant was added to the 15th layer.

Further, for the sample 111, the first layer to the first layer
A sample 114 was also prepared in which the gelatin used in the layers up to 6 layers was all 70%. The amount of 0.004 mg / m ² was added to all samples to which the fluorine-containing surfactant was added.

Each sample was subjected to wedge exposure with white light according to a conventional method, and a developing treatment step described later was performed to measure the sensitivity.

Note that the sensitivity is characterized by the reciprocal of the exposure amount that gives the minimum density (fog) +0.2 for the magenta density of sensitometry, and shown in Table 3 as a relative value when the sensitivity of Sample 101 is 100.

For the evaluation of sharpness, exposure was performed through a MTF pattern with white light according to a conventional method, the MTF of a magenta color image was measured, and the value of spatial frequency (cycle / mm) giving 50% reproduction was obtained and compared. did.

The following sticking resistance (adhesion resistance) was evaluated for samples 101 to 115.

Samples 101 to 115 were 35 mm wide and 7 mm long.
Cut into four pieces of 0 mm each and store for one day in an atmosphere of 23 ° C. and 80% RH so that they do not touch each other. After that, 4 sheets are piled up with the emulsion layer on top, and a cardboard of the same size is sandwiched with a load of 800 g at 40 ° C.
It was stored under an atmosphere of 80% RH for 3 days. After that, the sample was peeled off, the area of the adhesion portion was measured, and the adhesion resistance was compared.

<< Adhesion Resistance Evaluation Rank >> Rank Area of Adhesion Part A 0 to 10% B 10 to 30% C 30 to 50% D 50 to 80% E 80 to 100% Further, pressure desensitization is evaluated by the following method. did.

The unexposed sample was allowed to stand in an atmosphere of 23 ° C. and 55% RH for 24 hours to make the water content of each sample uniform, and then the sample was fixed in the same atmosphere so that the support became downward and horizontal, and the curvature was increased. A load of 4.5 g was applied to a needle having sapphire with a radius of 0.025 mmφ at its tip, and each sample was pulled at a speed of 1 cm / sec. After that, white exposure is uniformly performed so that the density after development becomes a density of fog +0.4, and a development process is performed. Finally, the magenta density variation value (ΔD) of the processed sample due to scratching of the sapphire needle was measured using a transmission densitometer model 310 manufactured by X-RITE. When the density fluctuation value is large and becomes lower than the background fog + 0.4 (ΔD has a negative value), pressure desensitization occurs.

Furthermore, in the same manner as the sticking resistance evaluation of the sample,
Each sample was stored in an atmosphere of 23 ° C. and 80% RH for 1 day, and then 4 sheets were piled up, and a cardboard of the same size was loaded with a load of 800 g for 3 days in an atmosphere of 40 ° C. and 80% RH. After peeling, the above-mentioned pressure desensitization resistance was evaluated for the sample after peeling.

<< Development processing >> Processing step Processing time Processing temperature (℃) Replenishment amount * (mL) Color development 3 minutes 15 seconds 38 ± 0.3 780 Bleach 6 minutes 30 seconds 38 ± 2.0 150 Water washing 3 minutes 15 seconds 20 ± 10 200 Settling 6 minutes 30 seconds 38 ± 2.0 830 Washing 3 minutes 15 seconds 20 ± 10 200 Stability 1 minute 30 seconds 38 ± 5.0 830 Drying 2 minutes 55 ± 5.0 − In the above, the replenishment rate is 1 m of photographic light-sensitive material. It is a value per ² .

The color developing solution, the bleaching solution, the fixing solution, the stabilizing solution and the replenishing solution thereof were prepared as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g sodium bromide 1.3 g nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g potassium hydroxide 1.0 g Water was added to make 1 liter, and the pH was adjusted to 10.1.

<Bleach> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150 g Glacial acetic acid 10 ml Water was added to make 1 liter, and the pH was adjusted to 6.0 with ammonia water. did.

<Fixer> Ammonium thiosulfate 175 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to make 1 liter, and pH was adjusted to 6.0 with acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water was added to make 1 liter.

<Color development replenisher> Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyl Ethyl) aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water was added to make 1 liter, and the pH was adjusted to 10.18 with potassium hydroxide or 20% sulfuric acid.

<Bleach Replenisher> Water 700 ml 1/3 Diaminopropane tetraacetate Iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g Ammonia water or glacial acetic acid was used to adjust the pH to 4.0 After that, water was added to make 1 liter.

<Fixing Replenisher> Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Ammonium water or glacial acetic acid was used to adjust the pH to 6.5, and then water was added to make 1 liter.

<Stable Replenisher> Same as the stabilizer.

Table 3 shows all the above results.

[0159]

[Table 2]

[0160]

[Table 3]

*: Normal temperature and normal humidity storage **: High temperature and high humidity sticking test history As is apparent from Table 3, the samples using the tabular silver halide grains according to the present invention have improved pressure desensitization resistance. The effect is emphasized by the combined use with the fluorine-containing surfactant, and the effect is remarkable especially in the sample in which the high temperature and high humidity condition is recorded. This was completely unexpected to the inventor. Further, in Sample 114, the amount of gelatin applied was drastically reduced, and there was concern about pressure desensitization resistance.
This was also unexpected, and when used in combination with a fluorine-containing surfactant, the degree of deterioration was small and a sharp effect was obtained.

Example 3 A backing layer was coated on one surface of a support of a cellulose triacetate film having a thickness of 100 μm and coated on both sides with a subbing layer, and Samples 101 to 101 prepared in Example 2 on the other side. 114
In the same manner as above, multiple coating is applied, and each is slitted into a shape with a width of about 60 mm and a length of about 800 mm, and processed into a product packaging form commonly known as 120 (Brownie) (excluding moisture-proof packaging bag), 23 ° C, 55% After leaving the sample in the RH atmosphere for 24 hours to make the water content of each sample uniform, the sample rolled in the same atmosphere is fixed without opening and the radius of curvature is 0.5 mmφ.
Each sample was pulled at a speed of 1 cm / sec by applying a load of 200 g to a needle having sapphire at the tip. Thereafter, white exposure was performed uniformly so that the density after development would be a density of fog + 0.4, and the development treatment described in Example 2 was carried out. The result is the same as in Example 2 for the sample of the present invention. An outstanding pressure desensitization resistance and improved sticking resistance were confirmed.

[0163]

According to the present invention, a silver halide color photographic light-sensitive material having high sensitivity, excellent image quality, particularly sharpness, and improved pressure desensitization can be provided.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03C 7/00 530 G03C 7/00 530

Claims (9)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one layer of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. At least one of the silver halide emulsion layers has at least two silver iodide-containing silver halide phases having different silver iodide contents inside the grain, and the inner phase of the phase is the outer phase. Silver iodide content is higher than
The phase contains silver iodide having a maximum silver iodide content of 5 mol% or more and less than 10 mol%, an aspect ratio of 2 or more, and tabular silver halide grains having 5 or more dislocation lines. And a photographic light-sensitive material containing a fluorine-containing surfactant. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the fluorine-containing surfactant is contained in the uppermost layer of the photographic constituent layers. 3. The fluorine-containing surfactant contains a combination of a fluorine-containing cation-type surfactant and a fluorine-containing anion-type surfactant.
Or the silver halide color photographic light-sensitive material described in 2. 4. The maximum silver iodide content is 5 mol% or more and 8.
4. The silver halide color photographic light-sensitive material according to any one of claims 1 to 3, which is less than mol%. 5. The silver halide color photographic light-sensitive material according to claim 1, wherein the dislocation lines are present inside the grain and in the fringe portion. 6. The silver halide color photographic light-sensitive material according to any one of claims 1 to 5, wherein a variation coefficient of a circle-equivalent diameter of a projected area of tabular silver halide grains is 20% or less. material. 7. The silver halide color photograph according to claim 1, wherein the dislocation line introduction position is at the interface between the maximum silver iodide-containing phase and the phase adjacent to the outside thereof. Photosensitive material. 8. The silver halide according to claim 1, wherein the total amount of gelatin on the side of the photosensitive silver halide emulsion layer on the support is 12 g / m ² or less. Color photographic light-sensitive material. 9. The backing layer according to claim 1, which has a backing layer on the surface of the support opposite to the photosensitive silver halide emulsion layer side. Silver halide color photographic light-sensitive material.