JPS6389839A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide sharpness to green- and red-sensitive layers by forming blue-, green- and red-sensitive layers and incorporating flat silver halide particles into the blue-sensitive layer and nonflat silver halide particles into the green- or red-sensitive layer. CONSTITUTION:Each of blue-, green- and red-sensitive layers is formed in two layers having higher and lower sensitivities. Flat silver halide particles having >=5:1 average aspect ratio are incorporated into at least one of the blue-sensitive layers so as to improve the sharpness. Tetragonal silver halide particles such as cubic, tetradecahedral or octahedral particles or nonflat silver halide particles having <=5:1 aspect ratio are incorporated into at least one of the green- or red-sensitive layers so as to prevent the lowering of the sharpness on the lower frequency side. When the nonflat particles are singly dispersed particles, the graininess can be improved.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, particularly a silver halide color photograph with improved sharpness and graininess and suitable for photographing. It relates to photosensitive materials.

(Prior Art) In recent years, demands on silver halide emulsions for photography have become increasingly strict, and even higher standards have been made for photographic performance such as high sensitivity, high contrast, excellent graininess, and sharpness.

In order to meet these demands, we aim to improve sensitivity including improving color sensitization efficiency using sensitizing dyes, improve the sensitivity/graininess relationship, improve yarniness, and improve covering power.
The technique of using tabular grains is disclosed in U.S. Patent No. ≠Ko 3≠226. Same 4L≠/Hiroshi J/0. Same 4tμ330μt%IWI4
A4A/4AJOA, disclosed in Hirohiro 3!3.

Mako, Tokukai Akira! r-//jri No. 30, samezr-//J?
Same as jμ issue! ? -/L JjtO issue, each publication also has an aspect ratio! A photographic light-sensitive material with high sensitivity and improved graininess, sharpness, and color reproducibility using a tabular silver halide emulsion having the following structure in a high-sensitivity layer is disclosed.

According to these patents, tabular grains have low scattering properties, so using them in the blue light-sensitive layer improves sharpness, and using tabular grains in the green or red light-sensitive layer also improves graininess. .

Furthermore, in JP-A-77-77R4'7, a flat silver halide emulsion with a 7 spectral ratio of 181 or more is used in the high-speed layer, and a monodisperse silver halide emulsion is used in the low-speed layer. A multilayer color photographic material with improved sharpness and color reproducibility is disclosed.

OtherResearch Disclosure
21330KFi, By setting the thickness of the planographic grain to t-fAa, the emulsion in the layer above the layer using the tabular grain reflects more light, increasing the sensitivity of the upper layer and minimizing the reflection. A method is disclosed in which K is applied so that the sharpness of the upper layer is not impaired.

Despite the various advantages of tabular grains that can utilize their properties, our experiments have shown that if all tabular grains are used in the green or red photosensitive layer, the sharpness on the low frequency side deteriorates.

In order to achieve photographic performance such as high sensitivity, high contrast, and excellent comparative clarity, for example, it is necessary to call lj3μ
It is known that monodisperse silver halide emulsions with a narrow particle size distribution, such as those described in Cor. In addition, by using core/7L type emulsion grains that have silver halide phases of different compositions inside the emulsion grains, the functions of the emulsion grains from light reception to image formation are controlled by the core and shell parts of the emulsion grains. Another effective method is to increase the utilization of the incident light by separating it as much as possible.

Furthermore, it is considered preferable to narrow the inter-grain halogen composition distribution in order to obtain a high-contrast emulsion.

However, depending on the size of the monodisperse silver halide emulsion, light scattering is large, and in particular when the blue photosensitive layer 1- is composed of a monodisperse emulsion, the sharpness of the green and red photosensitive layers is not practical due to the light scattering. The h level becomes unsatisfactory.

(Problems to be Solved by the Invention) Therefore, the problems to be solved by the present invention are the deterioration of sharpness on the low frequency side that occurs when tabular grains are used in the green or red photosensitive layer and the blue photosensitive layer. This is a deterioration in the sharpness of the green and red photosensitive layers that occurs when the photosensitive layer is composed of a monodispersed emulsion.

Therefore, the object of the present invention is to improve the sharpness of green and red photosensitive layers caused by the above matters,
Another objective is to improve the graininess of both layers.

(Structure of the Invention) An object of the present invention is to provide a silver halide color photographic light-sensitive material having blue, green and red light-sensitive layers on a support and capable of forming a multicolor image, each light-sensitive layer having at least a high-sensitivity layer. At least one layer of the wide-color photosensitive layer consisting of two low-speed layers contains tabular silver halide grains having an average aspect ratio of 21 or more, and at least one of the green photosensitive layer or the red photosensitive layer contains Virtually monodisperse and average aspect ratio! :/Achieved by a silver halide color photographic light-sensitive material containing the following non-tabular silver halide grains.

Halogen of the present invention 4km alternating 1. It has a multilayer structure in which emulsion layers containing a binder and silver halide grains for separately recording 49 colors and red light are superimposed, and each emulsion layer has at least a high-speed layer and a low-speed layer. Consists of two layers: a sensitive layer. Particularly practical layer structures include the following.

(1) BH/BL/GH/GL/AH/RL/8(
2) BI-1/BL/GH7RH/
GL/R,L/8(3) B)l/BM/
BL/GH/()M/GL/RH/RIM/RL/5 (4) BH10H/RH/BL/GL/RL/5(
5) B )1/B L /G H/几)i/GM/
GL/f (IM/L) Here, B is the blue-sensitive layer, G is the green-sensitive layer, 几 is the red-sensitive layer, H is the highest sensitivity layer, M is the medium aperture layer, and L is the low sensitivity layer. layer, representing the SFi support, a protective layer, a filter layer,
Descriptions of non-photosensitive layers such as an intermediate layer, an antihalation layer, and a subbing layer are omitted. Among these, a particularly preferable layer structure is (
1) or (3).

When the layer structure is (1), in the present invention, the blue-sensitive layer is at least 24. - Layer (B)>BL)iy Contains tabular iSo silver gunkide grains (hereinafter abbreviated as "tabular grains") having a flat spectral ratio of 187 or more, GH, GL
, R) i, RL, all substantially monodisperse non-tabular silver halide grains (hereinafter abbreviated as "monodisperse non-tabular grains") are used for at least -1-, but BH and BLO Both layers contain tabular grains, G)l, OL, RH%R
, L in which monodisperse non-tabular grains are used in all layers is particularly preferred.

In the silver halide photographic light-sensitive material of the present invention, at least one of the evening light-sensitive layers has an average aspect ratio! : Contains one or more silver halide emulsions. Aspect ratio refers to the diameter:thickness ratio of a particle.

Here, the diameter of a silver halide grain refers to the diameter of a circle with an area equal to the projected area of the grain. The Scx silver generator grains (tabular silver halide grains) used in the present invention specified by the above aspect ratio have an aspect ratio of ! Above, preferably 100 or less, more preferably! that's all! θ or less, particularly preferably 5 or more and 20 or less.

In the present invention, the tabular silver halide grains have a diameter of 0. j
~/! ,0/Jl preferably /,0-,I/Q,0μ
It is m. The thickness of the solid particles is 1Q.

It is less than 17421 meters, preferably less than 0.3 micrometers.

In the layer containing the tabular silver halide grains of the present invention, it is preferable that the tabular grains are present in a weight ratio of 0.000% or more, particularly 6Q or more, based on the total silver halide grains in the core layer.

When the tabular grains used in the present invention are not sensitized by growing different types of silver salts on their surfaces, the halogen composition of the tabular halogenated ice grains is silver bromide and iodine. Silver iodide is preferable, and the amount of silver iodide M is Q~/! Silver iodobromide, which is a molten metal, is more preferable.

A particularly preferred silver iodide content is μ to 70 mol.

(9) The tabular silver iodobromide grain has first and λ-th opposing parallel major faces and a central region extending between the one major face, and further has at least one region extending between the two major faces. Preferably, the particles have an outer region that is displaced in the lateral direction (in a direction parallel to the main surface) and have an internal structure in which the iodide content in the central region is different from the iodide content in the extra-nuclear region. Among these, it is more preferable to have an internal grain structure in which the iodide content in the outer region is lower than the iodide content in the central region. Also, preferably the central area so that the outer area forms a ring in the horizontal direction? It has a compositional distribution surrounding it.

In addition, the change in the natural content rate in the boundary layer between the central region and the outer region may be a sharp boundary surface,
The boundaries may not necessarily be obvious and may change continuously.

As a method for producing tabular grains having such an isogen composition distribution within the grains, JP-A-Sho! 2-/! μλr issue, jlA-//1123 issue, rr-i/3ri issue 27, same! It can be used as a reference for the manufacturing method described in Tartata ≠ No. 33.

The tabular ()Rogge/silveride grains according to the present invention may be polydispersed or monodispersed, but it is more preferable that they be monodispersed. The preferred monodispersity is that the coefficient of variation of the particle size distribution (this particle size is the diameter of the circumscribed circle of the particle) is 2! less than or equal to JP-A-Sho as a method for making emulsions consisting of monodisperse tabular grains! /-3ri0 core issue, same! ≠-2///
≠The original method described in No. 3 can be used.

The particle size referred to herein means the diameter in the case of spherical silver halide grains, and the equivalent spherical diameter in the case of grains having shapes other than spherical.

'19 The coefficient of variation of the particle size distribution is the standard deviation Sf defined by the following equation, which is the ratio value divided by the average particle size 7 multiplied by 100.

In addition, as a convenient method for obtaining an emulsion consisting of monodisperse tabular grains, a seed population consisting of monodisperse spherical grains is prepared by ripening a core grain consisting of multiple twins in the presence of a silver halide solvent. This method is used to make the entire vine and then grow the entire vine. A more preferable method is to make the tabular grains exist in the presence of a tetrazide/de/chemical compound during the growth of the tabular grains, thereby reducing the ratio tS of the tabular grains and improving the monodispersity of the tabular silver halide grains used in the present invention. When sensitization is achieved by epitaxially growing a different type of silver halide on its surface, the aforementioned tabular crystal can be used as it is as the host crystal, or tabular grains made of pure silver iodide can be used as the host crystal. It can also be used. As the silver halide used for epitaxial growth, silver bromide, silver chloride, or silver chlorobromide can be used, and silver bromide is particularly preferred. In the silver halide of Mayu Epitaxial Growth Department! There is no problem even if silver iodide is contained in an amount less than molty.

In the tabular epitaxial type silver halide used in the present invention, the ratio of epitaxial crystals to the total number of moles of silver halide! -30 mole is preferred, and 70-20 mole is most preferred.

The epitaxial growth of the tabular silver halide used in the present invention is preferably performed selectively on limited areas on the silver halide surface, such as edges, corners, annular areas, and the like. Such a silver halide emulsion is disclosed in Japanese Patent Application Laid-open No.
Z Kootsu No. 3!0 No. 3, same! Tar/JJ!
It can be obtained by using No. 4AO Publication No. 161.

The substantially monodisperse halogenated particles used in at least the IN of the green- or red-sensitive layer of the present invention are cubic, /II-hedral, ? It can be a normal crystal with a large facet, and the average aspect ratio! :/Although it may consist of the following twin crystals or a mixture thereof, it is preferable that it is a normal crystal.

In the present invention, monodisperse silver halide grains are those in which the weight of silver halide contained within a grain size range of ±20% around the average grain size "Fy2" is 10% or more of the weight of all silver halide grains. It is preferably 70% or more, particularly preferably 10% or more.

Here, the average particle size r is the frequency n of particles having the particle size rf2.
The combination of i and 11! Define the grain size ri when X rx becomes the maximum.

(Three significant figures, the lowest digit is discarded!) The grain size here means the diameter in the case of spherical silver halide grains, and the equivalent of a sphere in the case of grains with shapes other than spherical. It is the diameter.

The silver halide grains used in the green light-sensitive layer or red light-sensitive layer of the present invention are preferably core/shell type emulsions. As a method for preparing an emulsion consisting of core/shell type normal crystals, a water-soluble silver salt solution and a water-soluble halide solution (t, pAg and p) are added to a gelatin solution containing normal crystal seed particles.
can be obtained by adding i by controlled double jet method. For determining the addition rate, please refer to Tokukai Akihiro! Ko/No., same! ? -113r publication can be referred to.

A method for producing a core/shell type emulsion consisting of twins having an average aspect ratio of j:l or less is described, for example, in Japanese Patent Application Laid-Open No.
/1123 can be referred to. These methods initially form silver iodide nuclei, then add a water-soluble silver salt and a water-soluble halide solution to cause a conversion reaction.
The main feature is that it forms a core consisting of silver iodobromide.

A core/shell type twinned emulsion is produced by ripening a multiple twinned nucleus emulsion in the presence of a silver halide solvent to form a monodisperse spherical seed emulsion, and then growing this by a double jet method. You can also get

The green halide grains preferably used in the present invention (7) and red-sensitive silver halide grains have a grain structure composed of two or more layers having different silver iodide contents; The outermost layer (shell part) of two or more layers
The silver iodide content in the inner layer (core part)
It is preferable that the silver iodide content is lower than the silver iodide content. What is the silver iodide content in the core? ~≠O molti may be used, but preferably l! ~4AO molar ratio, more preferably 2t~≠
This is Omorchi. The silver iodide content of the shell portion is less than Tamorti, preferably 0. J~g, O morch.

In the present invention, the content difference between the core portion with a high silver iodide content and the shell portion with a low silver iodide content of the silver halide grains may have a 7-yave boundary, or may have a continuous boundary that is not necessarily clear. It may also change depending on the situation. As a method of continuously changing the halogen composition at the boundary between the core and the shell, a method of gradually changing the composition of the added halide liquid in the double jet method can be used. Further, the silver iodide composition in the core part and the shell part may be unevenly distributed.

Further, the ratio of the shell portion of the core/shell type silver halide grains is lO to toes, preferably /! ~70%
, more preferably from KO to tO.

In the present invention, silver bromide, silver iodide, and silver iodobromide can be used as the silver halide, but silver iodobromide is particularly preferred, and as long as it does not impair the photographic performance of the emulsion, fj! There is no problem even if L amount of silver chloride is present.

Next, by allowing a hydroxytetrazaindene compound to be present during grain growth of the monodisperse emulsion used in the present invention, a highly monodisperse emulsion can be obtained.

The average grain size of the monodisperse emulsion in the green light-sensitive layer or the red light-sensitive layer in the present invention is 0.001 μm or more, preferably O.S to 2.0 μm from the viewpoint of graininess and sharpness, more preferably #:l:o, z~Q, μμm or 0.4~2.0μ
It is m.

In the present invention, the monodisperse silver halide emulsion used in the green photosensitive layer or the red photosensitive layer has an average grain size of 0.2 μm.
Although two or more types of emulsions having different average grain sizes can be mixed and used as long as the emulsion is larger than that, it is particularly preferable that the emulsion consists of seven emulsions.

In the present invention, the blue light-sensitive layer containing tabular grains is one in which the tabular grains are contained in at least -ifM in the evening light-sensitive layer, but a blue light-sensitive layer containing tabular grains in the entire layer improves 7-yaveness. It is more preferable to do so.

The monodisperse non-tabular silver halide grains according to the present invention are
Although it is used in at least one of the green photosensitive layer and the red photosensitive layer, it is preferably used in at least one of each of the green and red photosensitive layers, and the entire layer in both the green and red photosensitive layers. It is more preferable to use it.

Therefore, the most preferred embodiment is a combination in which tabular grains are used in all layers of the back color g source layer, and monodispersed non-tabular grains are contained in all layers in both the green light-sensitive layer and the red light-sensitive layer. Moth is also preferred because it improves sharpness and graininess without sacrificing high sensitivity.

A dye represented by the following general formula (1) can be used in the blue photosensitive layer. In particular, it is preferable to use these dyes in the tabular grains used in the blue-sensitive layer.

General formula (1) (wherein Zo and Z2 are respectively a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a selenazole ring, a benzoselenazole ring, a naphthoselenazole ring, an imidazole ring, a benzimidazole ring, a naphthimidazole ring, and an oxazole ring) Represents the atomic group necessary to complete a ring, benzoxazole ring, naphthoxazole ring, pyridine ring, or quinoline ring.

At least l') of 几 and R2 are an alkyl group bearing either a carboxyl group or a sulfo group, and one of 几 and 几2 is a carboxyl group or f
c represents an alkyl group having all sulfo groups, and the other represents an alkyl group.

Xe represents an anion, and n represents 1 or λ. ′
! When the sensitizing dye represented by the following general formula 1) forms an inner salt, n is /2-. ) Particularly preferred examples of adducts include the following dyes.

(CH2)3 SO3-(CH2)a 8 C1s N
The amount of a dye used is per mole of silver halide! ×1o-
5 to 2×10 mol is preferable, and 1.2×10−′ to
Particularly preferred is 7×10 6 mol.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mole or less silver iodide. Particularly preferred is about λ molar to about 0. It is silver iodobromide containing silver iodide up to molti.

Silver halide grains in photographic emulsions include those with regular crystal shapes such as cubes, octahedrons, and dodecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. They may contain crystal defects, such as, or their compound forms.

The grain size of the silver halide may be fine grains of about 0.1 micron or less, or large grains with a projected area diameter of up to about 70 microns.

Silver halide photographic emulsions that can be used in the present invention include, for example,
Research Disclosure (R,i)), A/71
13 (/1971/, February), pp. 22-23, Emulsion preparation
nd types)” and the same, i/ryit<,
iP7 years l/month), 4At pages, "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, Chimie et Phy
siquePhotographique Paul
Montel, / 5F≦7), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F, Du
ffin, Photo-graphic Emuls
lon Chemistry (Focal Pres.
s, /yet), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (v.

L., Zelikman et al., Maki
ng andCoating Photography
ic Emulsion.

It can be prepared using the method described in Focal Press, /rita).

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may be a no-like structure. Next, halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide, such as silver rhodan or lead oxide, may be bonded.

Mixtures of particles in various crystalline forms may also be used.

Silver halide emulsions are usually subjected to physical ripening, chemical ripening and fractional sensitization. The addition trains used in such processes are research disclosure/
76143 and 4ir7i Otsu, and the relevant parts 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 locations are listed below.

l Chemical sensitizer - page 23 t! /Lr page right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-241, right page, super sensitizer
Budata page right column 4 Brightening agent
21 5 Anti-fogging agent Pages 244 to λj ≦≠ Page right column and stabilizer 6 Original absorbent, Fucoj-, -Corosada Page 64 right column ~ Ilter dye Page 410 left column Ultraviolet absorber 7 Preventing staining Agent 2! Page right column Page 120 left ~
Right column 8 Rootstock image stabilizer 2! Page 9 Hardener Colo page 41/page left column 10 Binder Colo page Same as above 11
Lubricants for plasticizers Page 27 Page 120 Right column 12
Coating aid, page 6-2~λ7 Same as above Surface activator 13 Static core page Same as above Various color couplers can be used in the present invention, and specific examples thereof can be found in the above-mentioned Glue Search Disclosure (几D )A
/74≠3, ■-C, described in the patent described in O.

As a yellow coupler, for example, U.S. Patent No. J, WJ
J,! 0/No., same No. ≠, 0-λ, tko No. 0, same No. 1I,
No. 324,0244, No. 41-. 440/.

7cj issue, special public Akira! tr-107JF, British Patent No. 7,
Those described in μcoj, No. 020, No. 1, 4t7A, No. 760, etc. are preferred.

As a macenta cobbler! - Compounds of the pyrazolone and pyranloazole series are preferred;
10. t/ri No. 1I, 31/.

No. 197, European Patent No. 77, Ajj, US Patent No. ! ,
04/, 4tJ2 No. J, 72! , 0/; No. 7, Research φ Disclosure A24t! =77(/ri l
≠June), JP-A No. 4O-33112, Research-Disclosure & λ4tCo30 (/?r#,
Unexamined Japanese Patent Application Shoto-a36. gy No., U.S. Patent No. μ,! 00.
AJO issue, same issue! Particularly preferred are those described in No. 0, No. tj+L, etc.

Fan couplers include phenolic and naphthol couplers, as described in US Patent G4T.

0yo2.272 No.μ, 7μ6, 3rd No., same No.≠
, 221. Ko 33, Ko No. 4,200, No. λ, 36, Octopus No. 2, No. 2. tQ! , No. 171, No. 77λ, No. 762, No. 2. Irri! , No. 12, No. J, No. 772.00λ, No. 3. yzr, Jat
No., Same No. μ, 33g, No. 01/, Same Temperature≠, 327. /7
! No. 3, West German Patent Publication No. 3, No. 3, No. 7, European Patent No. 12/, No. 361, US Patent No. 3. Hiro≠Otsu, 622
No. ≠, 333. FW No. 2, same No. μ, ≠! /,! !
No. 1, Hiroshi No. 27,767, European Patent No. 1A/,
Those described in No. 12AA etc. are preferred.

A refined colored coupler that corrects unnecessary absorption of coloring dyes is disclosed in Research Disclosure A/7i<4cj, Section 1-G, U.S. Patent No. 44. /6J, No. 47Q, Tokuko Sho ni'7-J f) Hiroshi/J, U.S. Patent No. μ.

00<1. No. 25P, No. 4', /Jr, No. 23-1, British Patent No. 1. The one described in No. 446,3411 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. @, JAA, 2J7, British Patent No. 2. lλ!
, No. 170, European Patent No. 170, West German Patent (Publication) No. 3. = J4A, those described in J'JJ are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. J, lj/,! No. 20, same No. y-, oro, xii
No. 44. J47,212, British Patent No. 2,10
It is described in No. 2,173, etc.

Couplers that release all photographically useful residues upon coupling can also be preferably used in the present invention. The DIR coupler that releases the development inhibitor is the aforementioned Di7bμ3,
~The patent described in Section F, JP-A-Sho! 7-/! / Rihirogu,
same! 7-/J'4t23μ, same to-7r4L, 2pr
, U.S. Patent No. ≠, λ≠r, No. 42 is preferred.

Among these, for use in combination with the silver halide color photosensitive material of the present invention, those that release a diffusible development inhibitor or its precursor through a coupling reaction with an oxidized form of a developing agent are preferred.

Seven representative examples are shown below.

D-/D-co-j D-da C12/N (J2 As a coupler that releases a nucleating agent or a development accelerator in an image form during development, British Patent No. 1.Of7.IuO, British Patent No. 8g2./ J/, IIt No., Japanese Patent Application Publication No. 1989-/j74
31. same! Those described in P-/70111-0 are preferred.

In addition, examples of couplers that can be used in the photosensitive material of the present invention include competitive couplers described in US Pat.

No. 213.4472, No. 4A, No. 331,391, No. μ, 310. The multi-force coupler described in JP-A No. 40-/11P10, etc., the DI rexized sweet release coupler described in JP-A-40-11P10, etc., European Patent No. 773, No. JO2?
Couplers that release a dye that restores color after separation from the Id are included.

The couplers used in the present invention can be introduced into photosensitive materials by various axiomatic dispersion methods.

Examples of Takana point organic solvents used in the oil-in-water dispersion method are described in U.S.A. Tokken No. 3, 3, λ, Q Core, etc.

Specific examples of latex dispersion process steps, effects, and latex for impregnation are described in U.S. Patent No. μ,/PP.

No. 363, West German Patent Application (OLS) No. 1, J. Hiroshi/.

No. 27 μ and No. λ,! It is described in Hiroshi/, No. 230, etc.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
It is described on page 21 of D, Mu/76 Ko3, and from the right column of page 74A7 of yair'yit to the left column of page t4Lr.

The color 4 true light-sensitive material according to the present invention includes the above-mentioned RD, A
/764JtD21r-2Pjt and the same, return/17
/l tri is written in the left column to the right column and can then be developed by a conventional method.

The color photographic light-sensitive material of the present invention is generally subjected to water washing treatment 1 or stabilization treatment after development, bleach-fixing or fixing treatment.

In the washing process, it is common to use countercurrent washing in tanks larger than one to conserve water. A typical example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-17-114AJ instead of the water washing step.

(Examples) The present invention will be explained below using Examples, but the present invention is not limited thereto.

Example-1 On a triacetic acid cellulase film support with an undercoat,
A multi-colorless photosensitive material sample &/~/l was prepared by coating each layer in multiple layers with the composition shown below.

(Photosensitive layer composition) What is the number corresponding to each component? Application t expressed in /m2
For halides, the coating amount is shown in terms of silver. However, for sensitizing dyes and couplers, the coating amount is expressed in mol units per mol of silver halide in the same layer.

1st/i# (antihalation layer) Black colloidal silver 0.2 gelatin /・Q ultraviolet absorber UV
−/0, 2-dispersion OIL−/
0.02 2nd layer (intermediate layer) Fine grain bromide @ (average grain size 0.07μ) o, /r gelatin /, 0 3rd layer (first red-sensitive emulsion layer) Silver iodobromide emulsion □, 7 gelatin
. , sensitizing dye A
1.0X10-' sensitizing dye B
2, QXlo''-'Cabra-C-i
o, 3 coupler C-20,3 Casoler C-j Q, 2 force f-Ra-C-4t O, 02 coupler C-r 117. o/Dispersion oil 01L-i o,/Dispersion oil (JI
L-, 2Q, / If! (Second red milk cutting layer) Big silver bromide milk 4]/.

Gelatin / 0 sensitizing dye A j×10-' sensitizing dye B
λ×10”” coupler c-I
O,0/Coupler C-20,0! Coupler C-jO, OJ Coupler C-J0.0/ Coupler C-yo, o2 Coupler C-lo, 0λ Coupler C-ta O, OX dispersion oil (JIL-20,/!th layer (middle layer) Gelatin 7 .0 value
Cpd-A O,0t dispersion oil (J
IL-, 20,0t 4th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion 0.6 gelatin
1.0 sensitizing dye C3 x 10
-' Sensitizing dye D Co x 10 -' Coupler C-100,4L Coupler C-// o,t Coupler C-/λ 0.0λ Coupler C-ibu 0,0t Dispersion oil 0IL-10
,0t 7th layer (second green-sensitive layer) Silver iodobromide emulsion O, tazelatin
0.2 sensitizing dye CcoX10
” ' Sensitizing dye D 1.j-×10-'Coupler C-/λ o, or Cutler C-1440,0t Dispersion oil kcJLL-/0.Or Dispersion oil (JIL-j O, O with #M<intermediate layer) Gelatin 1.
J Cp d -A O, A dispersion oil O engineering L-/0. Jth layer (yellow filter layer) Yellow colloidal silver o, -2 gelatin O0! Compound Cpd-
A o, 2 dispersion oil 0IL-/
Q, / 10th layer (first blue-sensitive emulsion 1Ii
li) Silver iodobromide emulsion o, r gelatin
/, 0 sensitized color cumulative E
jX/Q-'sensitizing dye F
3 x lo-' coupler c-ij
o, Takapura C-/j
O, 0t dispersion oily IL-J
O,0t 1st/layer (2nd # emulsion layer) Silver iodobromide emulsion O-j gelatin O-j sensitizing dye E
/×10-'So-called color combination F
t×10-'Coupler C-/jo, 2 Coupler-C-/Otsu 0,0t separation oil (JIL-J O,0/1st λ)i
(First protective layer) Gelatin 0. j coupler C-7to, / ultraviolet absorber U
V-2Q, 1 Ultraviolet absorber UV-3o, 2 Dispersion oil 0IL-da 0.0° No. 73
Layer (λth protective layer) Fine grain silver bromide emulsion (average grain size 0.07μ) 0. -2. ? Gelatin 0.2 Polymethylmethacrylate particles (diameter/, jμ) 0.2 Formaldehyde scavenger S-/0-! others
Surfactant W-/ and hardener H-t2 were added.

Sensitizing dye A (0M2)3S03Na Sensitizing dye B Same as above C Same as above D (C)12), 503-(OH2), 5(J3Na Sensitizing dye E Same as above F Coupler C-/Coupler C-λ Coupler C-J NaU31 ;3U3r'4a Kagura C
-μ coupler e-t 11H25 coupler C-+ coupler C-7 QC)i CUNHC) 12C) 12 (JCH3 coupler C-r coupler C-ta coupler C-/.

Coupler C-/2 α Coupler C-73 Coupler C-/HiroU Coupler c-it (the above-mentioned chemical compound D-resurfactant W-
t Formalin scavenger-8-/ Dispersion oil 0IL-/ Same as above (JIL-2 Same as above 0IL-J Ultraviolet absorber uv-i CH8 Ultraviolet absorber UV-λ Ultraviolet absorber UV-3 Chemical compound cpa A Sample A/- Each sample of // is shown in Table / and is multiplication table A, H'
It was prepared by multilayer coating using i and as shown in Ebisu λ.

Samples A7~//f thus obtained, Hiroo
After uniform exposure for 100 seconds with white light of okcyLux and the development process shown below, the graininess was reduced to 10μm.
The micro concentration was measured using a 7 parter and the aMS value (
Standard deviation of transmittance).

In addition, as an evaluation of color image sharpness, MTF (Modu-1a
Transfer Function)
Find i, compare the MTF value at 20 lines/mm as a relative value, and then:

(Table 3) [Processing process] (3r'c) Processing time Color development
3 minutes! Bleach for 30 seconds Wash with water λ minutes 10 seconds R4I-
Rinse with water for 20 seconds and stabilize for 3 minutes.
1 minute Q! The composition of the treatment liquid used in the second treatment step was as follows.

Color developer diethylenetriaminepentaacetic acid /, 0fl-Hydroxyquethylidene- /, /-diphosphonic acid λ, 02 Sodium sulfite ≠, ot Potassium carbonate
! 0,0 potassium bromide
/, 4C5'potassium iodide
/, 3~hydroxylua sulfate 2.
4c1≠-(N-ethyl-N-β-hydroxyethylamino) -λ-methylaniline sulfate 4! , J.P.
Add water to 1.01 pH 10
,0 bleaching solution ethylenediaminetetraacetic acid ferric ammonium salt ioo, of ethylenediaminetetraacetic acid disodium salt 10. Of ammonium bromide /jTO, Of ammonium nitrate 10. Add water
1. olpHb,.

Fixer Ethylenediaminetetraacetic acid disodium salt i, ori Sodium sulfite ≠, 01 Ammonium thiosulfate aqueous solution (7096) /7ta, 0ytt1
Sodium bisulfite ≠, add 4g water /, 04 pH 4, J Stabilizing liquid formalin (≠0%) λ, Oml polyoxyethylene-p-monononylphenyl ether (average degree of polymerization /θ) 0. Add JP water and as you can see from i, oβ63, the second son uses tabular grains for the blue photosensitive layer, and the sharpness is good (sample AI and 3), and tabular grains are used for part of the blue photosensitive layer. It can be seen that it is more advantageous in terms of sharpness to use a flat plate for all layers of the blue light-sensitive layer, which consists of at least two layers.

(Sample Mugu, jl ta) In addition, it is better to use monodisperse non-tabular grains in the green or red photosensitive layer for better graininess. It has been found that it is more favorable for graininess to use it in all of the green and red photosensitive layers than to use it in either the green or red photosensitive layer or a portion of both side photosensitive layers. . (Sample shop, 7
, t, ri) Therefore, the combination (sample A) in which flat plates are used in all layers of the blue light-sensitive layer and monodisperse non-tabular grains are used in all layers of the green and red side light-sensitive layers is the most effective in the present invention. This can be said to be a preferable embodiment.

Example 2 On a base coated cellulose triacetate film support,
Each layer having the composition shown below was coated in layers to prepare multilayer color photosensitive material samples of /2 to λ.

(Photosensitive layer composition) The meanings and units of numbers are the same as in Examples.

1st layer; antihalation layer black colloidal silver ・・・・・・・・・・・・ Silver o
, it gelatin ・・・・・・・・・・・・
i, IA.

λth layer; middle layer λ,! -G-t-pentadecylhydroquinone ・・・・・・・・・ 0. /
IC-2/・・・・・・・・・・・・
0.07C-23・・・・・・・・・・・・
0,0.2U-/・・・・・・・・・River o,orU-λ・・・・・・・・・
... o, orHBS-/ ...
・・・・・・・・・-o, i.

HBS-ko ・・・・・・・・・・・・
0. OJ gelatin ・・・・・・・・・・・・
/, 0 3rd layer; 1st red-sensitive emulsion layer silver iodobromide hole 4j ・・・・・・・・・・・・
Silver 0.10 sensitizing dye■ ・・・・・・・・・・・・
6.2Xio-s sensitizing dye ■・・・・・・・・・
... / , zXio-5 sensitized color accumulation ■ ...
...Old... J,! X10-'sensitizing dye■ ・
・・・・・・・・・・・・ u, oXio-'C-22・
・・・・・・・・・・・・ 0. /≠HBS-/
Yuyu...0.00jC-3!
・・・・・・・・・・・・ o, o
or gelatin ・・・・・・・・・・・・
/, 2Q μth layer; 2nd red-sensitive emulsion layer silver iodobromide emulsion ......... Qian /
,/! Sensitized color tree ■ ・・・・・・・・・・・・ j
, /X10-5 sensitizing dye■ ・・・・・・・・・
... 1. ≠×10−' sensitized color accumulation■ ・・・・
...... Ko, jX/ 0"-'sensitizing dye■
・Old・・・・・・・・・ J, O×1O-5C-Here ・・・・・・・・・・・・ o, ot.

C-λ3...1 old... o, oor
C-3!・・・・・・・・・・・・ o
,oo4tHB8-t River・・・・・・・・・
o, ooz gelatin ・・・・・・・・・
... i, z.

IT layer; Third red-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・ @/
#0 sensitizing dye■ ・・・・・・・・・・・・ Yo,
oXio-5 sensitized color accumulation■ ・・・・・・・・・・・・
・1. ≠×IO” sensitizing dye■ ・・・・・・・・・
... λ, 14x10" sensitizing dye■ ...
・・・・・・・・・ j , /X/ 0-5C-2!
...・---#-0,0/koC-23・
・・・・・・・・・・・・ 0,003C-
2 μ o, oo
4AHBs-/ ・・・・・・・・・・・・
0.3λ gelatin ・・・・・・・・・
... 1.63rd layer is middle layer gelatin /, 0th layer is gelatin;
First green-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・ Record 0
．． 3j sensitizing dye ■ ・・・・・・・・・・・・ J
, OxI O-” sensitizing dye ■ ・・・・・・・・
... 1.0x10'''sensitizing dye■ ...
...Pa°... J, rX/ 0"'"4C++4C
++Kot・-・-+++Shoukuwa+ 0. lko0C-2
/ ・・・・・・・・・・・・ 0.0
2IC-, z7 0.0J0C
-2r ・・・・・・・・・・・・
0.02JH8B-/・・・・・・・・・
・・・・・・ 0. λ0 gelatin...
・・・・・・・・・ 0.70th layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・ Silver 0
,7! r-sensitized color probe■ ・・・・・・・・・・・・
-, /XIO” sensitizing dye■ ・・・・・・・・・・・
・・7.0X10-”sensitizing dye VU ・・・・
...... Ko, ΔX10-'C-λt
・・・・・・・・・River O9oλ1C-2! r
...... Old... 0.00μC-,
2/ ・・・・・・・・・・・・ 0.
002C-27・・・・・・・・・・・・ 0.
003H8B-i ・・・・・・・・・・・・
O0/! Gelatin ・・・・・・・・・・・・
・・ 0.10th layer: 3rd green-sensitive emulsion layer silver iodobromide ・・・・・・・・・・・・ Silver i
, t.

Jll! Sensitive pigment■ ・・・・・・・・・・・・-s, z
Xio-'sensitizing dye■ ・・・・・・・・・・・・
r, oxio-' sensitizing dye ■ °...°・澹-...' J, OxI0-'C-, xbu-・
...... σ, O//C-27...old...
... o, ooi) IB8-2 ...
・・・・・・・・・ 0.62 gelatin
・・・・・・・・・・・・ /, 74 as 10th layer; yellow filter layer yellow colloidal silver ・・・・・・・・・・・・ Silver o
, orλ, j-t-pentadecylhydroquinone ・・・・・・・・・ 0.0
3ze2chin ・・・・・・・・・・・・
o, yr 1st I layer; 1st fr sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・ Silver 0
．． 2≠sensitizing dye■ ・・・・・・・・・・・・ j
, ! ×10-'C-λta...
... Q, λ7C-21 ...
...... o, oozHB8-i ・
...Old... o, xr gelatin
・・・・・・・・・・・・ 1. 12th No; λ Night-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・ Silver O
1≠! Sensitizing dye ■ ・・・・・・・・・・・・ λ
,/×10""'C--ta ・・・・・・・・・
・・・ 'o, ori rHBS-/ ・・
・・・・・・・・・ θ6θ3 gelatin
O, Hiro 6 13th layer; 3rd f-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・ Silver 0
．． 77 Sensitized color cord ■ ・・・・・・・・・・・・ λ
, λX10-'C-27 ・・・・・・・・・
-0, 0J 6HB S -/ ・・・・・・・・・
・・・・・・ 0.07 gelaten
o, t 7th μ layer; 1st protective layer silver iodobromide (1 mol of silver iodide, average grain size 0.07 μ) ・・・・・・・・・・・・ Silver O0! U-/
・・・・・・・・・・・・ 0. //U-
・Old...Old... a, /7) iB
,9-/・・・・・・・・・・・・
Q, riO 7th layer; 2nd protective layer polymethyl methacrylate particles (diameter approx. /, ! μm) ・Hyakuban...φ・・φ・ O, j HiroS -/ -0a...6.0 .0. 50, /J'S+-………… 0.10 Gelatin ・・・・・・・・・・・・ 0
．． 72 Each layer contains gelatin hardener H-1 in addition to the above composition.
and surfactants were added.

Structure of the good compound used in the examples U-/ -J C-λl α C-λ- h SυN a S (J C12n z s (n) -j 0 0C)i2 C-3/ C-3+2 C-33 (t) C, H□1 C-Jμ S-λ) IBs-/ tricresyl phosphate) 1B
s-λ Dibutyl phthalate HB8-J Tri-n-hexyl phosphate sensitizing dye ■ C2H5 菟C2i-i5 ■ (SHI M2), 3U31Na Sensitizing dye Emulsion a-n
It was made by applying multiple layers like a coat.

The sample &72-22'1:f thus obtained was exposed and developed in the same manner as in Example/, and its sharpness and graininess were evaluated in the same manner. However, the exposure of the RMS measurement sample was changed to JLuxK.

The measurement results are shown in Table 6.

As can be seen from the figure, the same effects of the present invention as in Example 1 were obtained even when the skin material, emulsion, and layer structure shown in Example A were used.

Example-3 Using the same material, emulsion and layer structure as Example 1, Example/
Among them, sample No. 2, which is the most preferred embodiment, is disclosed in JP-A-61-
The actual legend/
It was clarified by using the same evaluation method.

Using emulsions A to G in Table 7 of Example 1,
After applying i# and exposing and developing Examples/Travelling, the sharpness and graininess were all evaluated using the same method (Table r
) Table 7 Emulsion names A to G are based on 2.

Example-4 In the sample shop of Example 1, couplers (C
-14) The following sample size λ6 was prepared by replacing the coupler (C-/j) with the coupler (C-/j) in an equal mole amount.

Sample A and zA t-1 were exposed and developed in the same manner as in Example 1, and then the sharpness and graininess were compared using the same method. (Ebisu?) As is clear from Table 2, the sample &amp;
No. 2 is excellent in terms of sharpness compared to the hazy color of the sample using C-/J. Therefore, the sharpness improvement effect of the present invention is achieved by DIR
It can be seen that this is more noticeable in the sample using the coupler IC-/J.

In the above examples, the same effects can be obtained by comparing the sharpness and graininess by the same method as each example after the same exposure and the waterless washing process shown below. It has been found that the combination of using tabular grains in the photosensitive layer and monodisperse non-tabular grains in the green and red photosensitive layers results in significant improvements in sharpness and granularity without sacrificing high sensitivity. .

Development processing step> Perform development processing at 3r"c according to the processing steps below.

Color development J minute l! seconds Bleach constant M　　　I minutes to /j seconds Rinse 2 minutes Stable 4co seconds The composition of the next treatment solution used in each step is as follows.

Color developer diethylenetriaminepentaacetic acid IR/, 0fl-hydroxyethylidene-7゜l-disulfonic acid λ, or sodium sulfite μ, Q2 Potassium carbonate
Jo, Of Potassium Bromide
1. ≠2 potassium iodide
/, Jη hydroxylamine sulfate 2.
llf Hiro-(N-ethyl-N-β-hydroxyethylamine)-λ monomethylaniline sulfate ≠,! ? Add water /, 0 pH 10,0 Bleach-fix solution Ethylenediaminetetraacetic acid/ferric ammonium salt 100,01 Ethylenediaminetetraacetic acid disodium/λ water salt! , O? Sodium sulfite 10. Of ammonium thiosulfate aqueous solution (70 t) Add 220.0 rtl water /, 019 H,
Talins liquid water /, 0
1 Ethylenediaminetetraacetic acid disodium salt 0,29 Sulfanilamide O1 λ 2 Stabilizing liquid formalin (37 w/v) λ, 0 Gopolyoxyethylene-p-monononylphenyl ether (average gravity 10) 0.3 ft water /1 (Effects of the Invention) According to the present invention, a silver halide color photographic material having high sensitivity and improved sharpness and graininess can be obtained.

Specifically, tabular grains are used in the evening light-sensitive layer to improve sharpness, and non-tabular emulsions are used in the green or red light-sensitive layer to improve sharpness on the low frequency side. prevent deterioration,
Furthermore, it has been found that the grain shape is significantly improved by using substantially monodisperse non-tabular silver halide grains.

Patent applicant: Fujisha
．． J No. 2, Title of the invention, Silver halide color photographic light-sensitive material 3, Relationship to the amended case Patent applicant's address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture.

! f604, Subject of amendment The description in the "Detailed Description of the Invention" column 5 of the description and the "Detailed Description of the Invention J" section of the description of the contents of the amendment is amended as follows.

l) Replace page j3 with Attachment-7.

K) No.! Page 6, line 1 "flat plate" "tabular grain" and correct it.

3) Page 6, line 3 "tabular grain" "tabular grain" and correct it.

≠) No. 00th line "flat plate" "tabular grain" and correct it.

j) Page j6/line j [flat plate] "tabular grain" and correct it.

t) Replace page 73 with attached sheet-C.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material which has blue, green and red light-sensitive layers on a support and is capable of forming a multicolor image, each light-sensitive layer is composed of at least two layers, a high-speed layer and a low-speed layer; At least one of the layers has an average aspect ratio of 5
: non-tabular grains containing tabular silver halide grains of 1 or more, and having an average aspect ratio of 5:1 or less, which is substantially monodisperse in at least one of the green light-sensitive layer or the red light-sensitive layer. 1. A silver halide color photographic material comprising an emulsion consisting of silver halide grains.