JP3165918B2 - Silver halide color photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, to a silver halide color photographic light-sensitive material having excellent image quality, particularly sharpness, and having less abrasion fog. It is about.

[Prior Art] In recent years, the demand for image quality of color photographic light-sensitive materials has never been stopped. In particular, the enlargement magnification when printing on photographic paper from a photographing screen tends to be large, and a color photographic light-sensitive material having more excellent sharpness is desired.

As one means for improving sharpness, it has been known to reduce the overall thickness of a hydrophilic colloid layer provided on a support. Normally, a photographic material has a photosensitive layer containing silver halide and a non-photosensitive layer such as a protective layer not containing silver halide. If you try to achieve thinner as it is,
Abrasion fog or desensitization is likely to occur.

This abrasion fog means that the surface of the light-sensitive material comes into contact with another substance due to the sensitivity of the silver halide to pressure, and abrasion-like fog or desensitization occurs due to the pressure generated when the surface is rubbed. That means.

Recently, silver halide photographic light-sensitive materials have become significantly faster in manufacturing process such as coating, drying and processing, diversified product forms, complicated packaging machines in processing, and camera. There is a tendency to be used under severe conditions in general, such as downsizing, automatic winding / rewinding, etc., and operating conditions according to various usage purposes.
As a result, scratch fog (desensitization) of the silver halide emulsion
Prevention is becoming increasingly important.

As a method for preventing such abrasion fog, Japanese Patent Application Laid-Open No. 1-267638 discloses a method for improving the thickness by increasing the thickness of the protective layer. Is not a means that can be adopted indiscriminately.

On the other hand, as a method for preventing abrasion fog, there is also a method of imparting smoothness to the surface of a photosensitive material.
No. 7734 and JP-A No. 1-24445.

[Problems to be Solved by the Invention] The present invention has been made to solve the above problems, and an object of the present invention is to provide a silver halide color photographic light-sensitive material which has excellent sharpness and does not easily cause abrasion fog. Is to do.

The present inventors examined the occurrence of abrasion fog in consideration of sharpness with respect to the thickness of all layers, the thickness of the protective layer and the slipperiness, and found that the sharpness was not impaired in a specific range. Was found to significantly improve abrasion fog.

[Means for Solving the Problems] The object of the present invention is to provide a red-sensitive silver halide emulsion layer containing a cyan coloring coupler, a green-sensitive silver halide emulsion layer containing a magenta coloring coupler, and yellow coloring on a support. In a silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer containing a coupler, the total dry film thickness of all hydrophilic colloid layers on the side having the emulsion layer with respect to the support is 17 μm or less, The total dry film thickness of the protective layer is 8.5 to 13.5 of the total dry film thickness of all the hydrophilic colloid layers.
%, And the coefficient of kinetic friction of the surface of the emulsion layer side with respect to the support is 0.25 or less.

 Hereinafter, the present invention will be described in detail.

The total photosensitive film thickness of all the hydrophilic colloid layers on the side having the emulsion layer of the light-sensitive material of the present invention is 17 μm or less.

The total dry film thickness of all the hydrophilic colloid layers can be measured using a film thickness meter (for example, Anritsu E
lectric Co. Ltd., K-402B type). The thickness of each of the protective layer and the other layers was determined by taking a cross section of the photosensitive material with a scanning electron microscope, calculating the ratio of the thickness of the layer to the total thickness of the layer, and determining the total thickness by using the ratio and the thickness gauge. It can be calculated from the total thickness of the hydrophilic colloid layer.

The protective layer is a layer located farthest from the support and located outside the light-sensitive silver halide emulsion layer, and is a layer having substantially no photosensitivity. Although the protective layer may be a single layer,
More preferably, it is composed of two or more layers. When it is composed of two or more layers, the sum of the film thicknesses of those layers is the “sum of the dry film thickness of the protective layer” in the present invention.

In the present invention, the total dry film thickness of the protective layer is 8.5 to 13.5% of the total dry film thickness of all the hydrophilic colloid layers.

In the present invention, the coefficient of kinetic friction of the emulsion layer side surface is 0.25
It must be: As a method for reducing the dynamic friction coefficient of the emulsion layer side surface to 0.25 or less, silica,
Inorganic substances such as titanium dioxide and magnesium oxide, and polymethyl methacrylate, cellulose acetate propionate, by incorporating fine particles of an organic substance such as polystyrene, the surface is roughened to reduce the contact area,
Methods of controlling the coefficient of friction and methods of controlling the coefficient of friction by adding or attaching a so-called sliding agent such as a fatty acid ester compound or an alkyl polysiloxane compound to the protective layer or the surface of the photosensitive material are known. ing.

In the method of controlling the coefficient of friction by roughening the surface, not only abrasion fog but also the ability to prevent the photosensitive material from sticking to each other under high-temperature conditions and to prevent the photosensitive material from adhering to other substances. Further, in the method of controlling the friction coefficient using a sliding agent, the friction coefficient can be controlled without roughening the surface. In the present invention, a combination of both is preferred.

The particle size of the fine particles used in the method of controlling the friction coefficient by roughening the surface is preferably 0.5 to 5 μm, and the fine particles of the inorganic compound are silica, and the fine particles of the organic compound are polymethyl methacrylate, polystyrene, methyl methacrylate. -Methacrylic acid copolymers are preferred. Any amount may be used so that the dynamic friction coefficient is 0.25 or less.

The sliding agent used in the present invention is not particularly limited, and any compound may be used as long as it can reduce the coefficient of friction of the surface of the object when present in the object, as compared with the case where it is not present.

Representative examples of the sliding agent used in the present invention include, for example, U.S. Pat.No. 3,042,522 and British Patent No. 955,061.
Nos., U.S. Pat.Nos. 3,080,317, 4,044,927, 4,047,
No. 958, No. 3,489,567, a silicone-based sliding agent described in British Patent No. 4,143,118, U.S. Pat.No. 2,454,043,
Nos. 2,732,305, 2,976,148, 3,206,311, German Patent Nos. 1,284,295, 1,284,294, etc., higher fatty acid-based, alcohol-based, acid amide-based sliding agents, British Patent No. 1,263,722, U.S. Pat. And ester-based and ether-based sliding agents described in U.S. Pat. Nos. 2,588,765 and 3,121,060 and British Patent 1,198,387.

In the present invention, the following general formulas (I), (II) and (II)
An ester-based slipping agent represented by the formula (I);
V), and the alkylpolysiloxanes represented by the general formulas (V) and (VI) are preferably used.

Among these, a particularly preferred sliding agent is an ester-based sliding agent represented by the general formula (I).

Formula (I) R ₁ —COO—R _{2 In the} formula, R ₁ and R ₂ each represent an alkyl group having 10 to 20 carbon atoms.

In the formula, R ₃ , R ₄ and R ₅ each represent an alkyl group having 10 to 20 carbon atoms.

In the formula, R ₆ represents an alkyl group having 10 to 24 carbon atoms,
m represents an integer of 2 to 4. However, R ₆ may be the same or different.

In the formula, R ₇ is an aliphatic group (eg, an alkyl group (preferably having 1 to 18 carbon atoms), a substituted alkyl group (eg, an aralkyl group, an alkoxyalkyl group, an aryloxyalkyl group, etc.)) or an aryl group (eg, A phenyl group). R ₈ represents a hydrogen atom, an alkyl group (such as a methyl group), or an alkoxyalkyl group (such as a methoxymethyl group). A represents a divalent residue of an aliphatic hydrocarbon. n is 0 or an integer of 1 to 12;
The number 50, q is a number from 2 to 50 (preferably 20 to 30), x is 0
A number of 100100, y represents a number of 1１〜50, z represents a number of 0100100,
x + y + z is a number of 5 to 250 (preferably 10 to 50).

In the general formula (V), a cyclic siloxane having a siloxane unit represented by the following general formula (V-1) or (V-
It also includes a linear siloxane having a terminal group represented by 2).

In the formula, R ₉ represents an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group, an alkoxyalkyl group, an arylalkyl group, an aryloxyalkyl group, a glycidyloxyalkyl group, or the like.

R ₁₀ is an alkyl group having 1 to 20 carbon atoms, 5 carbon atoms
To 20 cycloalkyl, alkoxyalkyl, arylalkyl, aryloxyalkyl, glycidyloxyalkyl and the like.

l is a number of 0 or 1 or more, m is a number of 1 or more, l + m
Represents a number from 1 to 1000, and when l and m are plural, each group may be the same or different. Preferably l +
m is a number from 2 to 500.

In the formula, R ₁₁ independently represents an alkyl group having 1 to 3 carbon atoms, and R ₁₂ independently represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms.
m represents an integer of 0 to 2000.

Hereinafter, among the compounds represented by the general formula (I), typical representative compounds are shown.

Representative examples of the compounds represented by formula (II) are shown below.

Representative exemplary compounds among the compounds represented by the general formula (III) are shown below.

Typical representative compounds among the compounds represented by the general formula (IV) are shown below.

Representative compounds among the compounds represented by formula (V) are shown below.

Representative compounds among the compounds represented by the general formula (VI) are shown below.

The slipping agent used in the present invention is dispersed in a hydrophilic colloid solution using a dissolver-type emulsifying and dispersing machine in the presence of an appropriate dispersing agent, and preferably dispersed and added to a particle size of 0.05 to 5 μm. Alternatively, it may be added directly to the coating solution in the presence of a suitable dispersant or by dissolving and diluting with a suitable organic solvent, or may be sprayed on the surface by spraying or the like.
The above-mentioned slip agents may be used in any combination.

Any amount may be used so that the dynamic friction coefficient becomes 0.25 or less.

The silver halide grains contained in the silver halide emulsion according to the present invention may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide. May be mixed.

The composition of the silver halide grains used in the present invention may be uniform from the inside to the outside of the grains,
The composition inside and outside the particles may be different. When the inside and outside compositions of the particles are different, the composition may change continuously or may be discontinuous.

The grain size of the silver halide grains used in the present invention is not particularly limited, but is preferably in the range of 0.2 to 1.5 μm, and more preferably in the range of 0.25 to 1.2 μm in consideration of sensitivity and other photographic performance.

The particle diameter can be measured by various methods generally used in the art. A typical method is described in Lapland's "Analytical Method for Particle Size," AS, TM Symposium on Right Microcopy, 1955, pp. 94-122, or "Theory of Photographic Processing," Mies and James, 3rd ed. , Published in Chapter 2 of Macmillan, Inc. (1966).

This particle size can be measured using the projected area of the particle or a direct approximation.

If the particles are substantially uniform in shape, the particle distribution can represent this fairly accurately as a diameter or projected area.

The particle size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse, but monodisperse emulsions are preferred. More preferred are monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, particularly preferably 0.10 or less, in the particle size distribution of the silver halide grains.

Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation.

Here, ri is the particle size of each particle, ni represents its number, and the particle size here is the diameter in the case of a spherical silver halide particle, or in the case of a particle having a shape other than cubic or spherical, It represents the diameter when the projected image is converted into a circular image having the same area.

The silver halide grains used in the present invention may be obtained by any of an acidic method, a neutral method, and an ammoniacal method.
The particles may be grown temporarily, or may be grown after seed particles have been made.

The method for producing the seed particles and the method for growing the seed particles may be the same or different.

The form in which the soluble silver salt and the soluble halogen salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferable. As one form of the simultaneous mixing method,
The pAq-controlled double jet method described in -48521 and the like can also be used.

If necessary, a silver halide solvent such as thioether may be used.

Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound or a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide grains according to the present invention may have any shape.

One preferable example is a cube having a {100} plane as a crystal surface. U.S. Pat.Nos. 4,183,756 and
No. 4,225,666, JP-A-55-26589, JP-B-55-42737 and the like and references such as The Journal of Photographic Science (J.photogr.Sci), 21, 39 (1973). According to the described method, particles having a shape such as an octahedron, a tetrahedron, or a dodecahedron can be produced and used.

 Further, particles having twin planes may be used.

As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

The silver halide grains used in the present invention may be a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof during the step of forming and / or growing the grains.
A metal ion can be added using a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, and can be contained inside the particle and / or on the surface of the particle. And / or a reduction sensitization nucleus can be provided on the surface of the grains.

In the emulsion used in the present invention, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or may be kept contained.

The removal of the salts can be carried out according to Research Disclosure No. 17643.

Silver halide grains used in the emulsion according to the present invention,
The particles may be such that the latent image is mainly formed on the surface, or may be the particles that are mainly formed inside the particle. Preferably, the latent image is a particle mainly formed on the surface.

The emulsion used in the present invention can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

Further, an antifoggant, a stabilizer and the like can be added to the silver halide emulsion.

When the present invention is applied to a color light-sensitive material, various dye-forming substances are used, and a typical example is a color-forming coupler.

As the yellow coloring coupler, known acylacetanilide-based couplers can be preferably used. Of these, benzoylacetanilide and pivaloylacetoanilide compounds are advantageous. Specific examples of yellow color couplers are described in British Patent No. 1,077,374,
5-40757, JP-A-47-1031, JP-A-47-25133, JP-A-48-133
-94432, 50-87650, 51-3631, 52-11152
No. 19, No. 54-99433, No. 54-133329, No. 56-30127
Nos., U.S. Pat.Nos. 2,875,057, 3,253,924, 3,265,
Nos. 506, 3,408,194, 3,551,155, 3,551,156
No. 3,664,841, No. 3,725,072, No. 3,730,722,
3,891,445, 3,900,483, 3,929,484, 3,9
33,500, 3,973,968, 3,990,896, 4,012,25
No. 9, No. 4,022.620, No. 4,029,508, No. 4,057,432,
4,105,942, 4,133,958, 4,269,936, 4,2
86,053, 4,304,845, 4,314,023, 4,336,32
No. 7, 4,356,258, 4,386,155 and 4,401,752.

In the present invention, couplers represented by the following general formulas [a] and [aI] can be preferably used as the magenta coloring coupler.

[In the formula, Ar represents an aryl group, Ra1 represents a hydrogen atom or a substituent, and Ra2 represents a substituent. Y represents a hydrogen atom or a substituent capable of leaving by reaction with an oxidized form of a color developing agent, and W represents -NH-, -NHCO- (N atom is bonded to a carbon atom of a pyrazolone nucleus) or -NHCONH-. , M is an integer of 1 or 2. ] In the magenta coloring coupler represented by, Za represents a group of nonmetal atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Za may have a substituent. X represents a hydrogen atom or a substituent capable of leaving by reaction with an oxidized form of a color developing agent.

 Ra represents a hydrogen atom or a substituent.

Examples of the substituent represented by Ra include a halogen atom,
Alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heterocyclic, acyl, sulfonyl, sulfinyl, phosphonyl, carbamoyl, carbamoyl, sulfamoyl, cyano, spiro compound residues, Bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group,
Ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
Examples include an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and a heterocyclic thio group.

These are, for example, U.S. Pat.Nos. 2,600,788 and 3,05
No. 1,432, No. 3,062,653, No. 3,127,269, No. 3,3
No. 11,476, No. 3,152,896, No. 3,419,391, No. 3,
No. 519,429, No. 3,555,318, No. 3,684,514, No.
No. 3,888,580, No. 3,907,571, No. 3,928,044, No. 3,930,361, No. 3,930,866, No. 3,933,500,
Etc., JP-A-49-29639, JP-A-49-111631, and JP-A-49-11631.
9-129538, 50-13041, 52-58922, 53-6
No. 2454, No. 51-118034, No. 56-38043, No. 57-35858
No. 60-23855, British Patent No. 1,247,439,
Belgium Patent Nos. 769,116, 792,525, West German Patent 2,
No. 156,111, JP-B-46-60479, JP-A-56-111
125732, 59-228252, 59-162543, 59-17
Nos. 1956, 60-33552, and 60-45553, West German Patent 1,070,030 and U.S. Pat. No. 3,725,067.

Typical cyan coloring couplers include phenol-based and naphthol-based 4-equivalent or 2-equivalent cyan-forming couplers, and are described in U.S. Pat. Nos. 2,305,410 and 2,356,475.
No. 2,362,598, No. 2,367,531, No. 2,369,929, No. 2,4
23,730, 2,474,293, 2,476,008, 2,498,46
No. 6, No. 2,545,587, No. 2,728,560, No. 2,772,162,
2,895,826, 2,975,146, 3,002,835, 3,4
19,390, 3,446,822, 3,475,563, 3,737,31
No. 6, No. 3,758,308, No. 3,839,044, UK Patent No. 478,9
No. 91, No. 945,542, No. 1,084,480, No. 1,377,233,
Nos. 1,388,024 and 1,543,040, and JP-A Nos. 47-37425, 50-10135, 50-25228, and 5
0-112038, 50-117422, 50-130441, 51
-6551, 51-37647, 51-52828, 51-1088
No. 41, 53-109630, 54-48237, 54-66129
Nos. 54-131931, 55-32071, 59-146050
Nos. 59-31953 and 60-117249.

Gelatin is preferred as the hydrophilic colloid used in the present invention, but other hydrophilic colloids can also be used.

As a preferred example of the hydrophilic colloid, gelatin such as alkali-treated gelatin or acid-treated gelatin is most common, and a part of this gelatin is phthalated gelatin,
Derivative gelatin such as phenylcarbamoyl gelatin,
Examples include albumin, agar, gum arabic, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and copolymers of these vinyl compounds.

The silver halide photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye, or for various purposes such as prevention of irradiation and halation. Such dyes include oxonol dyes, hexoxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxanol dyes, hemioxanol dyes and merocyanine dyes are useful.

In the silver halide photographic light-sensitive material of the present invention, when the hydrophilic colloid layer contains a dye or an ultraviolet absorber, they may be mordanted with a cationic polymer or the like.

Various compounds can be added to the above photographic emulsion in order to prevent a reduction in sensitivity and generation of fog during the production process, storage or processing of the silver halide photographic light-sensitive material.

The silver halide photographic light-sensitive material of the present invention contains, in the photographic constituting layer, U.S. Pat.Nos. 3,411,911 and 3,411,912,
-5331 and the like.

In the silver halide photographic light-sensitive material of the present invention, various additives can be further used according to the purpose. These additives are more particularly described in Research Disclosure
Volume 176 Item17643 (December 1978) and Volume 187 Item18716
(November 1979), and the relevant locations are summarized in the table below.

Examples of the support used in the present invention include cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate,
Examples thereof include a film made of a semi-synthetic or synthetic polymer such as polycarbonate, a baryta layer, and paper coated or laminated with an α-olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer).

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoating treatment.

In the silver halide photographic light-sensitive material of the present invention, a photographic emulsion layer and other hydrophilic colloid layers can be coated on a support or other layers by various coating methods. For the coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, or the like can be used.

In order to obtain an image using the light-sensitive material of the present invention, generally known photographic processing can be performed after exposure.

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited by these.

Example-1 Preparation of Sample 1 On a triacetylcellulose film support, layers having the following compositions were sequentially formed from the support side to prepare a sample 1 of a multilayer color photographic light-sensitive material.

Hereinafter, the addition amount of the silver halide photographic light-sensitive material shows a g per 1 m ² unless otherwise stated. In addition, silver halide and colloidal silver are shown in terms of silver.

First layer; Anti-halation layer (HC-1) Black colloidal silver 0.20 Ultraviolet absorber (UV-1) 0.20 High boiling solvent (Oil-1) 0.20 Gelatin 1.3 Second layer; Intermediate layer (IL-1) Ultraviolet absorber (UV-1) 0.01 High boiling point solvent (Oil-1) 0.01 Gelatin 1.3 Third layer; Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.9 Silver iodobromide emulsion (Em- 2) 0.6 Sensitizing dye (S-1) 2.5 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-2) 2.5 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-3) 0.5 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (Co-1) 1.0 Colored cyan coupler (CC-1) 0.05 DIR compound (D-1) 0.002 High boiling solvent (Oil-1) 0.5 Gelatin 1.4 4 layers: high-sensitivity red-sensitive emulsion layer (RH) silver iodobromide emulsion (Em-3) 2.0 sensitizing dye (S-1) 2.0 × 10 ^-4 (mol / silver 1 mol) sensitizing dye (S- 2) 2.0 × 10 ^-4 Mole / mole of silver) Sensitizing dye (S-3) 0.1 × 10 -4 ( mol / mole of silver) Cyan Coupler (Co-1) 0.25 Colored cyan coupler (CC-1) 0.015 DIR compound (D-2) 0.05 High boiling point solvent (Oil-1) 0.3 Gelatin 1.4 Fifth layer; Intermediate layer (IL-2) Gelatin 0.5 Sixth layer; Low sensitivity green photosensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 1.0 Sensitizing dye (S-4) 5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-5) 1 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (Mo-1) 0.5 Colored magenta Coupler (CM-1) 0.01 DIR compound (D-3) 0.02 DIR compound (D-4) 0.02 High boiling point solvent (Oil-2) 0.4 Gelatin 1.0 7th layer; Intermediate layer (IL-3) Gelatin 0.7 8th layer : High-sensitivity green photosensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 1.3 Sensitizing dye (S-6) 1.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-7) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-8) 0.5 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (Mo-2) 0.05 Magenta coupler (Mo-3) 0.15 Colored magenta Coupler (CM-2) 0.05 DIR compound (D-3) 0.01 High boiling solvent (Oil-3) 0.5 Gelatin 1.0 Ninth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 Color stain inhibitor (SC-1) 0.1 High boiling solvent (Oil-3) 0.1 Gelatin 0.8 10th layer; Low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (S-10) 7 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Yo-1) 0.5 Yellow coupler (Yo-2) 0.1 DIR compound (D-2) 0.01 High boiling solvent (Oil-3) 0.3 Gelatin 0.9 11th layer; High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4) 0.4 Silver iodobromide emulsion (Em-1) 0.3 Sensitized color (S-9) 1 × 10 -4 ( mol / mole of silver) Sensitizing dye (S-10) 3 × 10 -4 ( mol / mole of silver) Yellow coupler (Yo-1) 0.30 Yellow coupler (Yo- 2) 0.05 High boiling point solvent (Oil-3) 0.1 Gelatin 1.0 12th layer; 1st protective layer (PRO-1) Fine grain silver iodobromide emulsion (average particle size 0.08 μAg I2 mol%)
0.4 Ultraviolet absorber (UV-1) 0.10 Ultraviolet absorber (UV-2) 0.05 High boiling solvent (Oil-1) 0.1 High boiling solvent (Oil-4) 0.1 Formalin scavenger (HS-1) 0.3 Formalin scavenger (HS-1) 2) 0.2 gelatin 1.0 13th layer; 2nd protective layer (PRO-2) Surfactant (Su-1) 0.005 Polymethyl methacrylate matting agent (average particle size 3μ)
m) 0.13 gelatin 0.6 In addition to the above composition, each layer contains a coating aid Su-1, a dispersion aid Su-2, a hardener H-1, H-2, H-3, and a stabilizer.
Stab-1 and antifoggant AF-1 were added.

Em-1 Average grain size 0.43 μm Silver iodobromide content 9.0 mol% (uniform) Monodisperse silver iodobromide emulsion Em-2 Average grain size 0.32 μm Silver iodobromide content 2.0 mol% (uniform) mono Dispersible silver iodobromide emulsion Em-3 Average grain size 0.78 μm Silver iodobromide content 6.0 mol% (uniform) Monodisperse silver iodobromide emulsion Em-4 Average grain size 1.1 μm Silver iodobromide content 9.0 mol% (uniform) monodisperse silver iodobromide emulsion Evaluation of Sample The obtained sample was measured by the following method. Table 2 shows the results.

(1) Total film thickness: The total dry film thickness of the hydrophilic colloid layer was measured by using an electronic micrometer (manufactured by Tokyo Seimitsu Co., Ltd.) at a temperature of 23 ° C. and a humidity of 55%. The thickness was calculated by subtracting the thickness of the support from the measured value.

(2) Thickness ratio of protective layer: A section of the photosensitive material sample is photographed with a scanning electron microscope to determine the thickness of the protective layer, and the ratio of the hydrophilic colloid layer obtained in (1) to the total thickness is determined. Was.

(3) Slipperiness: A 100 g load was applied to a needle having a steel ball with a diameter of 5 mm attached to the tip of the needle, and the dynamic friction coefficient when the surface of the emulsion layer side of the sample was slid at a speed of 10 m / min was determined. However, the test was conducted at a temperature of 23 ° C and humidity
Performed under 55% conditions.

(4) Sharpness: Measured by a conventional MTF (Modulation Transfer Function) method. The development was performed by the following developing method.

(5) Scratch fog concentration: The emulsion surface of the sample was scratched at a speed of 10 mm / sec with a load of 3 g under a condition of a temperature of 23 ° C. and a humidity of 55% with a diamond needle having a diameter of 25 μm while applying a load of 3 g.

The sample was developed by the following developing method, and the yellow density of the generated linear fog and the density of the unscratched portion were measured with a microdensitometer to determine the density difference.

Processing step (38 ° C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Used in each processing step The composition of the processing solution is as follows.

[Color developing solution 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -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 Add water to make 1 [bleach solution] Iron ammonium diaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to make 1 and adjust the pH to 6.0 using aqueous ammonia.
Adjust to

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to adjust the pH to 1, and the pH was adjusted to 6.0 using acetic acid.

[Stabilizing solution] Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica) 7.5 ml Water is added to make 1.

Example 2 Preparation of Samples 2 to 10 and Comparative Samples 11 to 17 In Example 1, the type and amount of the
Samples 2 to 10 and Comparative Samples 11 to 17 having the total film thickness and the protective layer film thickness ratio as shown in Table 1 were prepared by changing the gelatin amount of each layer added to each layer as shown in the table.
Was prepared. However, in the samples having different total film thicknesses and the same protective layer film thickness ratio as the total film thickness as the sample 1, the gelatin of each layer was increased or decreased in proportion to the change in the total film thickness. Different samples were prepared by making the thickness ratio of the first to eleventh layers the same as that of sample 1, and increasing and decreasing the amount of gelatin in the twelfth and thirteenth layers.

The sharpness and abrasion fog density were measured in the same manner as in Example-1. Table 1 shows the results.

As is clear from Table 1, those having a total film thickness of 17 μm or less have improved sharpness. Nos. 2, 7, 8, 11, and 12 were samples in which the slipperiness was changed while the protective layer thickness ratio was constant (10.5%), and Nos. 14, 16, and 17 were the protective layer thickness ratios. Is smaller than the former and is constant (6.0%), and the slip property is changed, but the former group in which the thickness ratio of the protective layer is 8% or more improves the slip property. As a result, the rate of improvement of the abrasion fog density is high. In particular, samples having a protective layer film thickness ratio of 8 to 15% with a friction coefficient of 0.25 as a boundary show a remarkable decrease in abrasion fog density as compared with samples outside the range.

On the other hand, when the total thickness is 17 μm or less and the dynamic friction coefficient is 0.25 or less, excellent sharpness can be obtained when the protective layer thickness ratio is 15% or less.

[Effects of the Invention] As described in detail above, according to the present invention, a silver halide photographic light-sensitive material having excellent sharpness and excellent image quality with less abrasion fog can be provided.

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Claims (1)

(57) [Claims] 1. A red-sensitive silver halide emulsion layer containing a cyan color coupler, a green light-sensitive silver halide emulsion layer containing a magenta color coupler and a blue-sensitive silver halide emulsion layer containing a yellow color coupler on a support. In the silver halide color photographic light-sensitive material having the formula (1), the total dry film thickness of all the hydrophilic colloid layers on the side having the emulsion layer with respect to the support is
17 μm or less, the total dry film thickness of the protective layer is 8.5 to 13.5% of the total dry film thickness of all the hydrophilic colloid layers,
And the coefficient of kinetic friction on the emulsion layer side of the support is 0.25
A silver halide color photographic material characterized by the following.