JPH0980675A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material which has excellent quick processing aptitude, and is improved in adhesion resistance, free from pressure failure, and relieved from sweating or bleeding, and density unevenness and color shading. SOLUTION: In a silver halide color photographic sensitive material having at least one silver halide emulsion layer containing a silver halide emulsion containing at least 95 mole % of silver chloride, and at least one nonsensitive layer on one side of a base, the total amount of gelatin contained in the silver halide emulsion layer and the nonsensitive layer is 8g or less per m<2> , and the silver halide photographic sensitive material is hardened with at least one hardener represented by the formula. In the formula, R1 , R2 represent hydrogen atom, alkyl group or substituted alkyl group. R3 represents hydrogen atom, alkyl group, substituted alkyl group, or -(CH2 )m CONR4 R5 . R4 , R5 represent hydrogen atom, alkyl group, or substituted alkyl group. (m), (n) each represent an integer of 0-6.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it has good rapid processing suitability and has improved pressure resistance, density unevenness in images, sweating, bleeding and sticking resistance. The present invention relates to a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, color development processing has become simpler and faster, and it is desired that it can be processed rapidly and that the processing is stable.

From the viewpoint of accelerating the development processing time, silver bromide, silver chlorobromide and silver chloride containing substantially no silver iodide are used as silver halide emulsions applied to color photographic paper. Came. It is known that a silver halide emulsion having a higher silver chloride content has a higher developability and is advantageous for rapid processing.

Further, the development can be performed by speeding up silver development, reducing the amount of silver coated on the light-sensitive material by means such as increasing the coloring efficiency, or reducing the amount of binder to reduce the emulsion film thickness. There is a way to improve sex.

As the color development processing time itself is accelerated by these factors, the proportion of the time of the drying step in the entire processing steps is increasing, and there is also a demand for speeding up the drying after the development processing. Gelatin is used as a binder for each photographic constituent layer of a photographic light-sensitive material, but when the amount of gelatin contained in the photographic light-sensitive material is large, the amount of water in the light-sensitive material brought into the drying step increases, There is a problem that it takes a long time to dry and causes poor drying under high humidity conditions such as during the rainy season. Therefore, it is desired to reduce the amount of gelatin.

When the photographic light-sensitive material contains a large amount of gelatin, the photographic light-sensitive material and the photographic image after the development process are curled due to the shrinkage of gelatin due to the temperature and humidity changes in the atmosphere, which is inconvenient in handling. There is a problem when it occurs. If the curl is large, it tends to stick to one of the rollers when it is pinched by the rollers when it is fed by an automatic processor, etc. Even when it is necessary to pass it, it is difficult to pass through it, and jam jams often occur. Therefore, from this point as well, it is required to reduce the amount of gelatin contained in the photographic light-sensitive material.

By the way, as a recent tendency of printers / processors, it is important that the tolerance for pressure failure is high as the speed is getting higher and higher. There is a demand for a photosensitive material for printing which does not significantly affect the image quality such as feeling. However, if the amount of gelatin applied is reduced from the suitability for rapid processing, the protective property of gelatin against silver halide emulsion is reduced, and the frequency of failure occurrences under pressure increases. It was possible.

The constituents of silver halide color photographic light-sensitive materials, which have become mainstream in recent years, include a lipophilic dye-forming coupler, an ultraviolet absorbing compound, and an antioxidant on a support by a so-called oil protected type method. A silver halide emulsion layer in which oil-soluble additives such as agents are dispersed and contained in the form of oil droplet particles in a state of being dissolved in an organic solvent having a high boiling point is provided.

However, when such oil droplet particles are contained, the components constituting the oil droplet particles are not formed on the surface of the photographic constituent layer when the oil droplet particles are stored for a long period of time after development or placed under high temperature or high humidity. So-called sweating phenomenon that occurs when moving (hereinafter referred to as "sweat")
Say. ) Occurs, or the coupler dye in the oil droplet particles moves in the photographic constituent layers, resulting in a blurred image (hereinafter referred to as “bleeding”).

The developed silver halide color photographic light-sensitive material in which "sweat" has occurred has a deteriorated gloss, and the developed silver halide color photographic light-sensitive material in which "bleeding" has occurred is extremely sharp. Cause a decrease in sex.

The deterioration of "sweat" and "bleeding" becomes more remarkable when the amount of gelatin used as a binder in a silver halide color photographic light-sensitive material is reduced.

The improvement of gloss deterioration due to "sweat" is disclosed in Japanese Patent Publication No.
Although it can be improved to some extent by the method described in No. 6-24256, etc., a large amount of gelatin must be used relative to the amount of oil droplets, resulting in a silver halide color photographic light-sensitive material having a large amount of gelatin, resulting in rapid It contradicts the low gelatin loading silver halide color photographic light-sensitive material, which is an effective means of increasing the processing.

Further, the reduction of the amount of applied gelatin tends to cause uneven density and uneven color after development. If density unevenness and color unevenness are conspicuous, the commercial value will be significantly impaired, so it was difficult to reduce the amount of gelatin.

Further, the reduction of the amount of gelatin attached leads to deterioration of sticking resistance. When a light-sensitive material using gelatin is stored at high temperature and high humidity, the surface becomes sticky, and in severe cases, it sticks to the one that comes into contact with the surface, and the surface condition may be impaired when peeled off. Deterioration of sticking is large due to the reduction of.

[0015]

Therefore, the first aspect of the present invention
The object of (1) is to provide a silver halide color photographic light-sensitive material having excellent rapid processing suitability and free from pressure failure.

The second object of the present invention is to provide a silver halide color photographic light-sensitive material in which sweating and bleeding are improved.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material having improved density unevenness and color unevenness.

A fourth object of the present invention is to provide a silver halide color photographic light-sensitive material having improved sticking resistance.

[0019]

The objects of the present invention are: A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing a silver halide emulsion containing at least 95 mol% of silver chloride and at least one non-light-sensitive layer on one side of a support. , The total amount of gelatin contained in the silver halide emulsion layer and the non-photosensitive layer is 8 g or less per 1 m ² , and the silver halide photographic light-sensitive material is represented by the following general formula (HI). A silver halide color photographic light-sensitive material characterized by being hardened with one hardener.

[0020]

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In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group or a substituted alkyl group. R ₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, - it represents a _{(CH 2) m CONR 4 R} 5.
R _4, R ₅ is a hydrogen atom, an alkyl group, a substituted alkyl group. m and n represent the integer of 0-6.

2. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the light-sensitive material contains at least one betaine surfactant.

3. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the light-sensitive material contains at least one fluorine-containing surfactant.

Is achieved by

The details of the present invention will be described below.

The halogen composition of the silver halide grains according to the present invention is based on silver chlorobromide containing 95% or more of the total silver halide constituting the silver halide grains and containing substantially no silver iodide. Need to be The preferred halogen composition of the silver halide grains is 97 mol% or more, more preferably 98 to 99.99, of the total silver halide constituting the silver halide.
Mol% is silver chloride.

The composition of the silver halide photographic emulsion according to the present invention has any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferable. Quick processing,
From the viewpoint of processing stability, a silver halide emulsion containing preferably 97 mol% or more, and more preferably 98 to 99.9 mol% silver chloride is preferable.

To obtain the silver halide emulsion according to the present invention, a silver halide emulsion having a portion containing silver bromide in a high concentration is particularly preferably used. In this case, the portion containing a high concentration of silver bromide may be epitaxy-bonded to silver halide emulsion grains, a so-called core-shell emulsion, or may be formed only partially without forming a complete layer. May simply have regions with different compositions. Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

In order to obtain the silver halide emulsion according to the present invention, it is advantageous to contain a heavy metal ion. Heavy metal ions that can be used for such purposes include iron,
Iridium, platinum, palladium, nickel, rhodium,
Examples include Group 8 to 10 metals such as osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to the silver halide emulsion in the form of salt or complex salt.

When the heavy metal ion forms a complex, the ligand or ion thereof is a cyanide ion,
Thiocyanate ion, cyanate ion, chloride ion,
Examples thereof include bromide ion, iodide ion, nitrate ion, carbonyl, and ammonia. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to add a heavy metal ion to the silver halide emulsion according to the present invention, the heavy metal compound is added to the physical layer before the formation of silver halide grains, during the formation of silver halide grains and after the formation of silver halide grains. It may be added at any place during each step during aging. In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, a heavy metal compound can be dissolved together with a halide salt and continuously added during the whole or part of the grain forming process.

The amount of the above-mentioned heavy metal ions added to the silver halide emulsion is 1 × 10 ^-9 per mol of silver halide.
Mol or more and 1 × 10 ^-2 mol or less, particularly preferably 1 × 10 ⁻² mol or less.
It is preferably at least 10 ^-8 mol and not more than 5 10 ^-5 mol.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,6
66, JP-A-55-26589, JP-B-55-42
737 and The Journal of Photographic Science (J. Photogr. Sci.) 2
1, 39 (1973), etc., particles having an octahedral, tetradecahedral, dodecahedral or the like shape can be prepared and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape are preferably used, but it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The grain size of the silver halide grain according to the present invention is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm.
m, and more preferably 0.2 to 1.0 μm.

This particle size can be measured using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains of the present invention is preferably monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and a coefficient of variation of 0 is particularly preferred. It is to add two or more kinds of monodisperse emulsions of 0.15 or less to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution and R is the average grain size.) The grain size referred to here is the diameter of spherical silver halide grains. Further, in the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The method of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Further, JP-A-57-92523 and 57-57
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt and a water-soluble solution described in German Patent Publication No. 292,164. Apparatus for continuously changing the concentration of an aqueous halide salt solution, JP-B-56-50
The reaction mother liquor was taken out of the reactor described in No. 1776, etc.,
An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by ultrafiltration may be used.

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

The silver halide emulsion according to the present invention can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and the sulfur sensitizer is preferable. Thiosulfates as sulfur sensitizers,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, inorganic sulfur and the like can be mentioned.

The addition amount of the sulfur sensitizer according to the present invention is preferably changed according to the kind of silver halide emulsion to be applied and the magnitude of the expected effect, but 5 × 10 5 per mol of silver halide. ^{-10 to} 5 × 10 ^-5 mol range,
Preferably, it is in the range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

As the gold sensitizer according to the present invention, various gold complexes other than chloroauric acid, gold sulfide and the like can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol of silver halide.
It is preferably molar. More preferably, 1 × 10 ⁻⁵
Mol to 1 × 10 ⁻⁸ mol.

A reduction sensitization method may be used as the chemical sensitization method for the silver halide emulsion according to the present invention.

The silver halide emulsion according to the present invention has the purpose of preventing fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuations during storage, and preventing fog that occurs during development. Antifoggant known in
Stabilizers can be used. As examples of preferred compounds that can be used for such purposes, JP-A-2-14
The compound represented by the general formula (II) described in the lower column of the specification of page 6036 can be mentioned, and more preferable specific compounds include (IIa-1 )-(IIa-8), (IIb-1)-(IIb
-7) or 1- (3-methoxyphenyl) -5
Compounds such as -mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned. These compounds, depending on their purpose,
It is added in the steps of preparing the silver halide emulsion grains, the chemical sensitization step, the completion of the chemical sensitization step, and the coating liquid preparation step. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 × 10 ⁵ mol per mol of silver halide is used.
It is preferably used in an amount of about ^-4 mol. When added at the end of chemical sensitization, 1 × 10 1 per mol of silver halide
^-6 mol to ^{1x10 -2} mol is preferable and ^1x10 is preferable.
^-5 mol to 5 x 10 ^-3 mol is more preferable. When added to the silver halide emulsion layer in the coating liquid preparation step,
The amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol, and more preferably 1 × 10 ^-5 mol to 1 × 10 ^-2 mol, per 1 mol of silver halide. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 × per 1 m ^2.
An amount of about 10 ⁻⁹ mol to 1 × 10 ⁻³ mol is preferable.

The total amount of gelatin contained in the silver halide color photographic light-sensitive material of the present invention is determined by accelerating the processing step,
In order to speed up the drying process, it should be 8 g / m ² or less, preferably 7.5 g / m ² or less. The lower limit is not particularly limited, but generally it is preferably 4.0 g / m ² or more in view of physical properties or photographic performance. The amount of gelatin is the moisture measurement method described in the Pagui method.
It is calculated in terms of the weight of gelatin containing 11.0% water.

The jelly strength (according to the Pagui method) of gelatin used in the present invention is preferably 250 g or more, and particularly preferably 270 g or more.

The calcium content of the gelatin used in the present invention (by the Pagui method) is preferably 1000 pp.
m or less. Treatment with an ion exchange resin column is generally preferably used to reduce the amount of calcium in gelatin.

The molecular weight of gelatin used in the present invention is not particularly limited, but preferably the average molecular weight is from 10,000 to 10,000.
200,000.

The gelatin used in the silver halide color photographic light-sensitive material of the present invention may be lime-processed gelatin or acid-processed gelatin, and may be cow bone, cow hide, pig skin or the like. Gelatin produced as a raw material may be used, but lime-processed gelatin made from cow bone or pig skin is preferable.

The gelatin used in the silver halide color photographic light-sensitive material according to the present invention is hardened with a hardener represented by the following general formula (HI).

[0057]

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In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group or a substituted alkyl group. R ₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, - it represents a _{(CH 2) m CONR 4 R} 5.
R _4, R ₅ is a hydrogen atom, an alkyl group, a substituted alkyl group. m and n represent the integer of 0-6.

The hardener represented by the general formula (HI) useful in the present invention is shown below, but the present invention is not limited thereto.

[0060]

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[0061]

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The method for synthesizing these hardeners is described in US Pat.
411,856.

The silver halide color photographic light-sensitive material according to the present invention contains, in addition to the hardener represented by the general formula (HI),
A hardener known in the photographic industry can be used in combination with the hardener represented by the general formula (HI). Hardeners preferably used in combination with the hardener represented by the general formula (HI) include vinylsulfone hardeners and chlorotriazine hardeners other than those of the present invention (for example, JP-A-1-216340).
Compounds II-1 to II-13 and III described on pages 0 to 21
-1 to III-10), or JP-A-2-82237.
No. 1,129,245 and the like, which are carboxy-active hardeners.

The amount of the hardener used in the present invention is such that the hardener is used in the photographic constituent layers of the silver halide color photographic light-sensitive material.
1.0-1000 mg / m ² , preferably 10-500
mg / m ^2, which is about 0.1 to 100 mg, preferably 1.0 to 50 m when converted per 1.0 g of gelatin.
g.

The hardener used in the present invention may be added to the coating solution in advance, or may be mixed with the coating solution immediately before coating.

The hardener used in the present invention may be added to all of the photographic constituent layers coated on the support, or may be added to any layer (one layer or plural layers). You may add.

Next, the betaine type surfactant and fluorine-containing type surfactant according to the present invention will be explained.

The betaine surfactants used in the present invention include carboxybetaine type, sulfobetaine type,
There are imidazolium type etc. Some specific examples of the betaine-based surfactant used in the present invention are shown below, but the present invention is not limited thereto.

[0069]

[Chemical 6]

[0070]

[Chemical 7]

[0071]

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The amount of the betaine surfactant used in the present invention is 0.0001 to 1.0 g / m ² , preferably 0.0005 to 0.5 g / m ² , and more preferably It is 0.001 to 0.2 g / m ² .

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

Formula [FA] (Cf)-(Y) n In the formula, Cf is an n-valent group containing at least 3 fluorine atoms and at least 2 carbon atoms, and Y is -COO.
_{M, -SO 3 M, -OSO 3} M or -P (= O) (OM)
Represents ₂ , where M represents a hydrogen atom, an alkali metal atom or an ammonium group, and n is 1 or 2.

The fluorine-containing anionic surfactants which are more preferably used include those represented by the following general formula [FA '].

General formula [FA '] Rf- (D) _t -Y In the formula, Rf represents a fluorine-substituted alkyl group or aryl group having 3 to 30 carbon atoms, and D is -O-, -COO-, -C.
ON (R ¹ )-or —SO ₂ N (R ¹ ) — represents a divalent group having 1 to 12 carbon atoms and containing at least one bond,
Here, R ¹ represents an alkyl group having 1 to 5 carbon atoms, and t
Is 1 or 2 and Y is -COOM, -SO
₃ M, -OSO ₃ M or -P (= O) (OM) ₂
Here, 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.

[0077]

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[0078]

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[0079]

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[0080]

[Chemical 12]

[0081]

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[0082]

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

The fluorine-containing cationic surfactant used in the present invention is a compound represented by the following general formula [FK].

[0085] Formula [FK] R'f-G-J ⁺ L ^- However, R'f is a 1-20C hydrocarbon group having a carbon, at least one hydrogen atom is substituted with 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, -C _k F _{2k + 1} (k = 1
20, in particular _{3~12), HC q F 2q -} , - C q F
_2q-1 (q = 2 to 20, especially 3 to 12). Examples of G include

[0087]

[Chemical 15]

The following may be mentioned.

As an example of J ⁺ ,

[0090]

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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 alkylene group or an arylene group, p is 0 to 6 and q'is 2 to 20
Represents

[0093] In addition, L ^- as an example of

[0094]

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Mention may be made of:

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

[0097]

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[0098]

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[0099]

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In the present invention, particularly poorly soluble -SO ₂ N is used.
It is more preferable to use a fluorine-containing cationic surfactant having at least one bond (R ')-. Here, the term "poorly soluble" means that 2.0 g of the surfactant was added to 100 ml of pure water at 23 ° C., stirred for 1 hour, left at 23 ° C. for 24 hours, and then precipitates and suspended matters were visually observed. Sometimes poorly soluble. For example, FK-1, FK-8, FK-15, F
K-16 and the like correspond, but are not limited to these and can be divided by the above test.

Some of these fluorine-containing surfactants according to the present invention are trade names of Megafac F from Dainippon Ink and Chemicals, and Fluorad from Minnesota Mining and Manufacturing Company. Fluorad) FC under the trade name Imperial Chemical Industry, Inc. under the trade name Monflor, EI Dupont Nemerus
They are commercially available from And Company under the trade name Zonyls or from Farbeberke Hoechst under the trade name Licowet VPF.

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

The total amount of the fluorinated cationic surfactant and the fluorinated anionic surfactant used in the present invention is 1.0 to 0.0001 g / m ² , preferably 0.3 to 0.0005 g. / M ² , more preferably 0.1
5 to 0.001 g / m ² is preferable. When used in combination, two or more kinds of fluorine-containing cationic surfactants and two or more kinds of fluorine-containing anionic surfactants may be used in combination. In addition, a fluorine-containing nonionic surfactant, a fluorine-containing betaine surfactant, and a hydrocarbon surfactant may be used in combination. The addition ratio of the fluorinated anionic surfactant to the fluorinated cation surfactant of the present invention is preferably 1:10 to 10: 1 and more preferably 3: 7 to 7: 3 in terms of molar ratio.

In practicing the present invention, any method of adding the above compound to the surface layer coating solution and coating it, or overcoating or permeating the surface layer is used. In the case of an organic solvent-based coating solution, it can be added as it is after dissolution in an organic solvent. The coating solution to which the compound is added is, for example, a dip method described in US Pat. No. 3,335,026, for example, US Pat. No. 2,674,167.
Can be applied or permeated by a method such as a spray method as described in No.

The betaine type surfactant and the fluorine-containing type surfactant used in the present invention may be used alone or in combination.

The betaine surfactant and / or fluorine-containing surfactant used in the present invention is either a silver halide emulsion layer or a non-photosensitive hydrophilic colloid layer constituting the light-sensitive material of the present invention. Although it may be added to the above, when it is applied by multilayer simultaneous coating, it is preferably added to the layer closest to the support and / or the layer farthest from the support in the multilayer.

Further, an aqueous solution of a betaine surfactant and / or a fluorine-containing surfactant may be incorporated into the silver halide photographic light-sensitive material of the present invention by a method of overcoating or permeating the surface layer. I can.

In the silver halide photographic light-sensitive material of the present invention, dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, dyes having absorption in the visible region include AI described in JP-A-3-251840, page 308.
Dyes described in JP-A-6-3770 and dyes described in JP-A-6-3770 are preferably used. Examples of the infrared absorbing dye include general formula (I) described in the lower left column of page 2 of JP-A-1-280750. , (II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and are preferable because there is no contamination by residual color. Specific examples of preferred compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column of the same publication.

The amount of these dyes added is 680 nm for an untreated sample of a light-sensitive material for the purpose of improving sharpness.
Is more preferably 0.7 or more, and even more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention because the whiteness can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm by combining it with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention, and as the blue-sensitive sensitizing dye, JP-A-3-2
BS-1 to 8 described in page 28 of JP 51840 can be preferably used alone or in combination. Examples of the green photosensitive sensitizing dye include G
S-1 to S-5 are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. Issue 1
It is preferable to use the compounds S-1 to S-17 described on pages 5 to 17 in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone or dimethylformamide or water and adding it as a solution, or as a solid dispersion. You may add.

The coupler used in the silver halide photographic light-sensitive material according to the present invention forms a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Any compound that can be used can be used, but as a typical example, a yellow dye-forming coupler having a spectral absorption maximum wavelength in the wavelength range of 350 to 500 nm, a wavelength range of 500
Typical examples are magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of -600 nm and cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
Couplers represented by general formulas (C-I) and (C-II) described in the lower left column of page 5 of JP-A-4-114154 can be exemplified. Specific compounds are described in the same specification on page 5, lower right column to page 6, lower left column, CC-1 to CC.
-9 may be mentioned.

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, there are described general formulas (MI) and (M) described in JP-A-4-114154, page 4, upper right column. -II) can be mentioned. Specific compounds are listed in the lower left column of page 4 to the upper right column of page 5 in the same publication, MC-1 to MC-1.
There can be mentioned those described as MC-11. More preferred of the magenta coupler,
The general formula (M-
Among them, the couplers represented by I), of which the RM of the general formula (M-I) is a tertiary alkyl group, are particularly preferable because of their excellent light resistance. MC-8 to MC-11 described in the upper column of page 5 of the publication are preferable because they are excellent in the reproduction of colors ranging from blue to purple and red, and are also excellent in the depiction of details.

A yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is represented by the general formula (Y-I) described in JP-A-4-114154, page 3, upper right column. A coupler can be mentioned. Specific compounds include those described as YC-1 to YC-9 in the lower left column of page 3 of the same publication. Among them, a coupler in which RY1 in the general formula [Y-1] in the specification of the publication is an alkoxy group or a coupler represented by the general formula [I] in the specification of JP-A-6-67388 can reproduce a preferable yellow color tone. preferable. Of these, particularly preferred examples of compounds include YC-8, YC-9 and JP-A-6-6 described in the lower left column of page 4 of JP-A-4-114154.
No. 7388, page 13-14
Compounds represented by (1) to (47) can be mentioned. The most preferred compounds are disclosed in JP-A-4-81847, page 1 and page 11, page 1 to 1.
It is a compound represented by the general formula [Y-1] on page 7.

When the oil-in-water type emulsion dispersion method is used for adding the coupler and other organic compounds used in the silver halide photographic light-sensitive material of the present invention, it is usually highly water-insoluble with a boiling point of 150 ° C. or higher. In the boiling point organic solvent, if necessary, a low boiling point and / or a water-soluble organic solvent is used in combination to dissolve,
It is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high-boiling organic solvent that can be used to dissolve and disperse the coupler, dioctyl phthalate, diisodecyl phthalate, phthalates such as dibutyl phthalate, tricresyl phosphate, phosphates such as trioctyl phosphate, Is preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

Further, instead of the method using a high-boiling point organic solvent or in combination with a high-boiling point organic solvent, a water-insoluble and organic solvent-soluble polymer compound is optionally added to a low-boiling point and / or water-soluble organic solvent. It is also possible to employ a method in which the surfactant is dissolved in a hydrophilic binder such as an aqueous gelatin solution and the resulting mixture is emulsified by various dispersing means using a surfactant. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

Preferred compounds as the surfactant used for dispersing the photographic additives and adjusting the surface tension during coating include a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. The thing contained is mentioned. Specifically, A-1 described in JP-A-64-26854 is described.
To A-11. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is preferable that the time from dispersion to addition to the coating solution and the time from addition to the coating solution and coating are short, respectively.
It is preferably within the time, more preferably within 3 hours and within 20 minutes.

An anti-fading agent is preferably used in combination with each of the above-mentioned couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by the general formulas I and II described on page 3 of JP-A-2-66541,
Phenolic compounds represented by the general formula IIIB described in JP-A-3-174150, amine compounds represented by the general formula A described in JP-A 64-90445, JP-A 6-
General formulas XII, XIII, XIV described in JP-A No. 2-182741;
The metal complex represented by XV is particularly preferable for the magenta dye. Further, the compound represented by the general formula I ′ described in JP-A-1-196049 and the compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in JP-A-4-114154, page 9, lower left column, the compound described in the same specification, page 10, lower left column. Compounds such as (A'-1) can be used. In addition to this, US Pat.
The fluorescent dye-releasing compounds described in No. 74,187 can also be used.

In the silver halide light-sensitive material according to the present invention, a compound which reacts with an oxidized product of a developing agent is added to a layer between the light-sensitive layers to prevent color turbidity or to form a silver halide emulsion layer. It is preferable to add it to improve fog and the like.
The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. A particularly preferable compound is the compound represented by the general formula II described in JP-A-4-133056, and the specification of the same publication.
Compounds II-1 to II-14 and 17 described on pages 3 to 14
The compound 1 described in the page is mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog and improve the light resistance of the dye image. Preferred examples of the ultraviolet absorber include benzotriazoles. Particularly preferred compounds are those represented by the formula III-3 described in JP-A-1-250944 and JP-A-64-666.
No. 46, a compound represented by the general formula I;
UV-1L to UV-27 described in 3-187240
L, compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

For the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

Further, in order to prevent the growth of mold and bacteria, which adversely affect the photographic performance and the image storability, the colloidal layer is disclosed in Japanese Patent Laid-Open No. 3-1.
It is preferable to add a preservative and an antifungal agent as described in Japanese Patent No. 57646. Further, in order to improve the physical properties of the surface of the light-sensitive material or the sample after processing, a protective layer is provided in JP-A-6-18585.
It is preferable to add a slip agent or a matting agent described in Japanese Patent Laid-Open No. 43-43250 and Japanese Patent Laid-Open No. 73250/1990.

As the support used in the silver halide photographic light-sensitive material of the present invention, any material may be used. Paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, A vinyl chloride sheet, polypropylene which may contain a white pigment, a polyethylene terephthalate support, baryta paper or the like can be used. Of these, a support having a waterproof resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water resistant resin layer on the surface of the support is 13% by weight for improving the sharpness.
The above is preferred, and more preferably 15% by weight.

The degree of dispersion of the white pigment in the water resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the coefficient of variation described in the above publication.

Further, it is more preferable that the value of the center surface average roughness (SRa) of the support is 0.15 μm or less, and further 0.12 μm or less because the effect of good gloss can be obtained.
In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

The silver halide photographic light-sensitive material according to the present invention may be directly or undercoated after the support surface is subjected to corona discharge, ultraviolet irradiation, flame treatment or the like, if necessary. It may be applied through one or more undercoat layers for improving antistatic property, dimensional stability, abrasion resistance, hardness, antihalation property, frictional property and / or other properties). Good.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

To form a photographic image using the silver halide photographic light-sensitive material of the present invention, the image recorded on the negative is optically combined with the silver halide photographic light-sensitive material to be printed. It may be imaged and printed, or after the image is once converted into digital information, the image is formed on a CRT (cathode ray tube) and then formed on the silver halide photographic light-sensitive material to be printed. Printing may be performed, or the scanning may be performed by changing the intensity of the laser light based on digital information and scanning.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and is particularly preferably applied to a light-sensitive material for forming an image for direct viewing. For example, color paper, color reversal paper, a photosensitive material for forming a positive image, a photosensitive material for a display, and a photosensitive material for a color proof can be used. In particular, it is preferably applied to a light-sensitive material having a reflective support.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds may be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-methyl-4- (N-ethyl-N- (β
-Hydroxyethyl) amino) aniline CD-6) 4-Amino-3-methyl-N-ethyl-N
-(Β- (Methanesulfonamido) ethyl) aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9) 4-amino-3-methyl-N-ethyl-N
-Methoxyethylaniline CD-10) 4-Amino-3-methyl-N-ethyl-
N- (β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-
N- (γ-hydroxypropyl) aniline In the present invention, the color developing solution using the above-mentioned color developing agent can be used in any pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0. Is preferred, and it is more preferably used in the range of pH 9.8 to 12.0.

The processing temperature for color development according to the present invention is 35.
The temperature is preferably from 70 ° C to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.

The color development time is conventionally about 3 minutes and 30 seconds, but in the present invention, it is preferably 40 seconds or less, more preferably 25 seconds or less.

To the color developing solution, known developer component compounds can be added in addition to the above color developing agent. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

The silver halide photographic light-sensitive material of the present invention is bleached and fixed after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a water washing process is performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed. The developing apparatus used for the development processing of the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is conveyed across rollers arranged in a processing tank.
The endless belt method may be used in which the photosensitive material is fixed and conveyed on a belt, but the processing tank is formed in a slit shape and the processing solution is supplied to the processing tank and the processing solution is conveyed. A spray method for atomizing, a web method by contact with a carrier impregnated with a treatment liquid, a method with a viscous treatment liquid, and the like can also be used. When processing a large amount, it is usually a running process using an automatic developing machine, but at this time, the smaller the replenishing amount of the replenisher is, the more preferable, and the most preferable processing form from the environmental suitability is,
The method of replenishment is to add the treatment agent in the form of tablets, and the method described in Kokai Kokai 94-16935 is most preferable.

[0143]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After subjecting this reflective support to corona discharge treatment, a gelatin subbing layer was provided, and then each layer having the constitution shown below was coated to prepare a silver halide photographic material sample 101. The coating liquid was prepared as follows.

First Layer Coating Liquid Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34.
g, (ST-5) 3.34 g, a stain inhibitor (HQ-
1) 0.34 g, 5.0 g of image stabilizer A, 3.33 g of high-boiling organic solvent (DBP) and high-boiling organic solvent (DNP)
To 1.67 g, 60 ml of ethyl acetate was added and dissolved.
A yellow coupler dispersion was prepared by emulsifying and dispersing 220 ml of 0% gelatin aqueous solution using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 1 and 2.

HC-1 was added as a hardening agent to the second, fourth and seventh layers so that the total amount was 0.12 g / m ² . Surfactants (SU-2) as coating aids,
(SU-3) was added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount became 0.04 g / m ² .

[0148]

[Table 1]

[0149]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: di (2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinyl pyrrolidone HQ-1: 2,5-di-t-octyl hydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-Di (1,1-dimethyl-4-hexyloxycarbonyl) butyl hydroquinone Image stabilizer A: Pt-octylphenol

[0151]

[Chemical 21]

[0152]

Embedded image

[0153]

Embedded image

[0154]

Embedded image

[0155]

Embedded image

[0156]

[Chemical formula 26]

[0157]

Embedded image

(Preparation of blue-sensitive silver halide emulsion) 40 ° C.
In 1 liter of a 2% gelatin aqueous solution kept at
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag potassium bromide 1.0 g Water added 600 ml (solution D) Silver nitrate 300 g Water added 600 ml After addition is complete, Kao Atlas Desalination was performed using a 5% aqueous solution of DEMOL N and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.71μ.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained. Next, the addition time of (A solution) and (B solution) and (C solution) and (D solution)
A monodisperse cubic emulsion EMP-having an average grain size of 0.64 μm, a variation coefficient of grain size distribution of 0.07, and a silver chloride content of 99.5 mol% in the same manner as EMP-1 except that the addition time was changed.
1B was obtained.

The EMP-1 was optimally chemically sensitized at 60 ° C. using the following compounds. Also EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (green-sensitive silver halide emulsion) Preparation) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%. Next, an average particle size of 0.50
A monodisperse cubic emulsion EMP-2B having a particle size of .mu.m, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The EMP-2 was optimally chemically sensitized at 55 ° C. using the following compounds. Also EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above EMP-3 was optimally chemically sensitized at 60 ° C. using the following compounds. Also EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed in a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole In the red-sensitive emulsion, SS-1 was used per mole of silver halide. 2.0 × 10 ^{-3 was} added.

Next, based on this sample 101, the coating gelatin amount of each layer was changed uniformly so that the total gelatin amount was set to the gelatin amount shown in Table 3, and the hardener used in Sample 101 was set to Table 3. Change to the indicated hardener so that the molar addition amount is the same,
Further, the betaine-based surfactant and the fluorine-containing surfactant according to the present invention were added to the seventh layer of the samples shown in Table 3 to prepare samples 102 to 131.

The following evaluations were performed using the samples thus prepared.

<Evaluation of pressure resistance> An unexposed sample was used with a scratch meter manufactured by Shinto Scientific Co., Ltd., and each of 10 g,
15g, 20g, 25g, 30g, 35g, 40g, 4
After scratching with a φ0.1 mm diamond needle applied with a load of 5 g and 50 g, development was carried out according to the development processing step A described below, and the load at which cyan pressure fog occurred was examined.

The higher the load, the less likely pressure fog will occur, and the better the failure due to pressure.

<Evaluation of Density Unevenness> When a sample subjected to uniform exposure was subjected to the following development processing step A, and the obtained gray sample was subjected to density measurement with a PDA-65 densitometer manufactured by Konica Corporation. The density unevenness was evaluated by the density difference between the highest density and the lowest density. The gray sample was also visually evaluated.

⊚: No unevenness in density observed at all ∘: Some unevenness in density observed, but acceptable as a product Δ: Uneven density observed, not preferable as a product ×: Uneven density observed considerably Not as a product.

<Evaluation of Sweating Performance> Each sample was uniformly exposed to white light, and then the following development processing step A was performed. The obtained sample was stored under conditions of 85 ° C. and 60% RH for 10 days, and the deterioration of gloss due to perspiration of the oil agent on the sample surface was visually evaluated.

◎: "Sweating" is not seen ○: "Sweating" is hardly seen △: "Sweating" is seen, but it is acceptable as a product ×: "Sweating" is seen considerably, and it is not possible as a product × × : "Sweating" is extremely damaging to the image quality.

<Evaluation of bleeding> After a resolution test chart was printed on each sample with green light and the following development processing step A was performed, the obtained sample was subjected to 1 ° C. under conditions of 85 ° C. and 60% RH.
It was stored for 0 days, and the degree of "bleeding" of the dye image was visually evaluated.

◎: "Bleeding" is not seen ○: "Bleeding" is hardly seen △: "Bleeding" is seen, but it is acceptable as a product ×: "Bleeding" is considerably seen, and it is not possible as a product × × : "Bleed" is extremely inferior in sharpness and the image quality is greatly impaired.

<Adhesion Resistance Test> The sample exposed to white light was subjected to the following development processing steps, and the obtained black sample was conditioned at a temperature of 25 ° C. and a humidity of 55% RH for 2 hours, and then 3.
The sample is cut into 5 cm × 12 cm, and the emulsion surfaces are piled up to form a bundle of samples. After fixing it with cellophane tape, leave it for 24 hours under the condition of temperature of 40 ° C. and humidity of 80% RH and then peel it off.
The grade was evaluated.

A: No adhesion has occurred B: Adhesion area is 1 to 10%, no resistance to peeling between samples C: Adhesion area is 10 to 20%, peeling occurs when peeling between samples There is sound and resistance to peeling D ... Adhesion area is 20 to 50%, image surface is damaged when peeling between samples E ... Adhesion area is 50% or more, peeling between samples It destroys the image-forming layer and significantly damages the image surface.

The sample thus prepared was subjected to optical wedge exposure by a conventional method and then developed in the following developing process.

Treatment Step Treatment Temperature Time Replenishment Amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 cc Bleach-fix 35.0 ± 0.5 ° C. 45 seconds 120 cc Stabilization 30-34 ° C. 60 seconds 150 cc Dry 60 to 80 ° C. 30 seconds The composition of the development processing solution is shown below.

Color developer tank solution and replenisher tank solution replenisher pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriamine Sodium pentaacetate 2.0g 2.0g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Water is added to make the total volume 1 liter, and the tank liquid has pH. = 10.10, the replenisher has pH Adjusted to 10.60.

Bleach-fixing solution Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-Amino-5-mercapto-1,3,4-thiadiazole 2 0.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing liquid tank liquid and replenishing liquid o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g Nitrilotriacetic acid trisodium salt 1.5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or ammonia water.

Table 3 shows the results obtained by the above evaluations.

[0184]

[Table 3]

As shown in Table 3, the samples according to the present invention have problems in pressure resistance, image density unevenness, sweating, bleeding, and sticking resistance even if the amount of gelatin applied is lowered in order to improve the rapid processability. It can be seen that the amount of gelatin can be reduced because there is no problem.

Further, in the sample in which the betaine surfactant and / or the fluorine-containing surfactant according to the present invention was added to the seventh layer, the pressure resistance, image density unevenness, sweating, bleeding and sticking resistance were further improved. Therefore, it is understood that the combined use of the hardener of the present invention and the betaine-based surfactant and / or the fluorine-containing surfactant is extremely effective.

Example 2 A process was carried out by changing the process in Example 1 as follows.

Treatment Process Treatment Temperature Time Replenishment Amount Color development 38.0 ± 0.3 ° C. 22 seconds 81 ml Bleach-fixing 35.0 ± 0.5 ° C. 22 seconds 54 ml Stabilization 30-34 ° C. 25 seconds 150 ml Dry 60 to 80 ° C. 30 seconds The composition of the development processing solution is shown below.

Color developing solution tank solution and replenisher solution Tank solution replenisher solution Pure water 800 ml 800 ml Diethylene glycol 10 g 10 g Potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.5 g 10.5 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxyamine 3. 5g 6.0g Triethanolamine 10.0g 10.0g Diethylenetriamine pentaacetic acid sodium salt 2.0g 2.0g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to bring the total volume to 1 liter The solution is adjusted to pH = 10.10 and the replenisher is adjusted to pH = 10.60.

Bleach-fixing solution tank solution and replenishing solution tank solution replenishing solution diethylenetriamine pentaacetate ammonium ferric dihydrate 100 g 50 g diethylenetriamine pentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml 2-amino-5-mercapto-1 , 3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml Add water to make the total volume 1 liter, and use potassium carbonate or glacial acetic acid to make the tank solution pH = 7.0 and the replenisher solution Adjust to pH = 6.5.

Stabilizing liquid tank liquid and replenishing liquid o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g PVP 1.0 g Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g Ethylenediaminetetraacetic acid 1 0.0 g Ammonium sulfite (40% aqueous solution) 10 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

Evaluation was made in the same manner as in Example 1, and it was confirmed that the effects of the present invention were effectively obtained.

Example 3 In Example 2, NPS manufactured by Konica Corporation was used as an automatic processor.
-868J, ECOJET-P was used as a treatment chemical, and running treatment was performed according to process name CPK-2-J1. Evaluation was performed in the same manner as in Example 1, and it was confirmed that the effects of the present invention were obtained.

[0194]

According to the present invention, a silver halide color having good rapid processing suitability, excellent pressure resistance, improved image density unevenness, sweating and bleeding, and further having no sticking resistance and no problem. A photographic light-sensitive material is obtained.

Claims (3)

[Claims] 1. A halogenation having on one side of a support at least one silver halide emulsion layer containing a silver halide emulsion containing at least 95 mol% of silver chloride and at least one non-photosensitive layer. In the silver color photographic light-sensitive material, the total amount of gelatin contained in the silver halide emulsion layer and the non-light-sensitive layer is 8 g or less per 1 m ² , and the silver halide photographic light-sensitive material has the following general formula (HI). A silver halide color photographic light-sensitive material characterized by being hardened with at least one hardener represented by Embedded image [In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group, or a substituted alkyl group. R ₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, - it represents a _{(CH 2) m CONR 4 R} 5. R _4, R ₅ is a hydrogen atom, an alkyl group, a substituted alkyl group. m and n represent the integer of 0-6. ] 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the light-sensitive material contains at least one betaine-based surfactant. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the light-sensitive material contains at least one fluorine-containing surfactant.