JPH0659366A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic sensitive material having improved sensitivity, graininess and sharpness. CONSTITUTION:This silver halide color photographic sensitive material has at least one blue-sensitive silver halide emulsion layer, at least one green- sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer on the base. The average particle size of the silver halide particles of each of silver halide emulsions contained in the silver halide emulsion layers is <=0.4mum and at least one of the emulsion layers contains a tellurium sensitized silver halide emulsion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide emulsion having a relatively small grain size,
The present invention relates to a silver halide color photographic light-sensitive material having improved graininess and sharpness.

[0002]

2. Description of the Related Art Conventionally, there has been a demand for a technique for enhancing the sensitivity of silver halide color photographic light-sensitive materials and enhancing the image quality (particularly graininess and sharpness) of reproduced color images. Is being researched and developed. In particular, in the light-sensitive material for color duplication, since the required level of graininess and sharpness is high, it is necessary to design the light-sensitive material using an extremely fine grain silver halide emulsion. Fine graining of the silver halide emulsion used not only improves the graininess, but also reduces the grain size by 0.5 μm.
In the following particle size range, the sharpness can be improved by reducing the light scattering, which is very preferable from the viewpoint of image quality improvement. However, especially particle size 0.4μ
In the following areas, the sensitivity decrease due to the atomization of the emulsion is remarkable as compared with the area larger than 0.4 μm, so a technique for sensitizing a silver halide emulsion in this area of grain size has been desired.

The silver halide emulsion used in the silver halide photographic light-sensitive material is usually subjected to various chemical sensitizations. Typical methods include chalcogen sensitization (sulfur sensitization, selenium sensitization, tellurium sensitization), precious metal sensitization (eg gold, platinum),
Methods of reduction sensitization and combinations thereof are known.

Among the above-mentioned sensitizing methods, the tellurium sensitizing method and the tellurium sensitizing agent are described in, for example, US Pat. No. 1,623,
499, 3,320,069, 3,772,0
No. 31, No. 3,531,289, No. 3,655,39
4, British Patent No. 235,211 and 1,121,4.
No. 96, No. 1,295,462, No. 1,396,69
No. 6, Canadian Patent No. 800,958, but a detailed and specific description of tellurium sensitizers is given in British Patent Nos. 1,295,462 and 1,3.
Only 96,696 and Canadian Patent 800,958 were known.

However, with respect to the conventionally known tellurium sensitizer, it is used alone as compared with the sulfur sensitization usually performed in the art, as exemplified in Canadian Patent No. 800,958. In the case of high sensitivity and low fog, noble metal aiming for higher sensitivity, particularly gold-tellurium sensitization in combination with a gold sensitizer has higher sensitivity than gold-sulfur sensitization, but fog is generated. There were drawbacks such as being large.

Therefore, in the ordinary silver halide photographic light-sensitive material, the chalcogen sensitization is generally sulfur sensitization, selenium sensitization or a combination thereof, and tellurium sensitization is not actually used. However, there are very few descriptions in the literature and the like, and in many of the above-mentioned patents, most of the actual experiments describe only sulfur sensitization or selenium sensitization.

During the research on tellurium sensitization, the present inventor found that when tellurium sensitization was applied to fine particles of 0.40 μ or less, the sensitizing effect and a remarkable effect in fog generation were found.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color having improved sensitivity, graininess and sharpness so that an image having sufficient image quality can be obtained even when used for color duplication. It is to provide a photographic light-sensitive material.

[0009]

The objects of the present invention can be achieved by the following constitutions. (1) Each silver halide in a silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer on a support. A silver halide emulsion in which all the silver halide emulsions contained in the emulsion layer have an average grain size of 0.4 μm or less and at least one of the emulsion layers is tellurium-sensitized. A silver halide color photographic light-sensitive material characterized by containing. (2) The silver halide color photographic light-sensitive material as described in (1) above, wherein the silver halide emulsion is subjected to sulfur sensitization and tellurium sensitization. (3) The silver halide color photographic light-sensitive material as described in (1) above, wherein the silver halide emulsion is subjected to sulfur sensitization, selenium sensitization and tellurium sensitization.

The present invention will be described in detail below.

Examples of tellurium sensitizers used in the present invention include, for example, US Pat.
320,069, 3,772,031, British Patents 235,211, 1,121,496, 1,
295,462, 1,396,696, Canadian Patent No. 800,958, Japanese Patent Application Nos. 2-333819, 3-53693, 3-131598, and Journal of Chemical Society Chemicals.・ Communication (J. Chem. Soc. Chem. Com
mun. ) 635 (1980), ibid 1102
(1979), ibid 645 (1979), Journal of Chemical Society Perkin Transactions (J. Chem. Soc. Perkin).
Trans. ) 1,191 (1980), S.I. S. Patai, The Chemistry of Organic Selenium and Tellurium Companies (The Chemistry of Orga)
nic Selenium and Telluriu
m Compounds), Vol 1 (1986),
It is preferable to use the compounds described in Vol 2 (1987).

Specific tellurium sensitizers include, for example:
Colloidal tellurium, telluroureas (eg allyl tellurourea, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N ', N'-dimethyl tellurourea, N, N'-dimethylethylene tellurourea,
N, N'-diphenylethylene tellurourea), isotellocyanates (for example, allyl isotelocyanate), telluroketones (for example, telluroacetophenone), telluroamides (for example, telluroacetamide,
N, N-dimethyl tellurobenzamide), tellurohydrazide (eg N, N ′, N′-trimethyltelulobenzhydrazide), telluroester (eg t-butyl-t)
-Hexyl telluroester), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), diacyl (di) tellurides ( For example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, diethylcarbamoyltelluride, bis (ethoxycarbonyl) telluride), (di)
Tellurides, other tellurium compounds (eg British Patent No. 1,
Negatively charged telluride ion-containing gelatin described in No. 295,462, potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt, allyl tellurocyanate).

Of these tellurium compounds, those represented by the general formula (I) shown in the following chemical formula 1, the general formula (II) shown in the following chemical formula 2 and the general formula (III) shown below are preferable.

[0014]

[Chemical 1] In the formula, R ₁ , R ₂ and R ₃ are aliphatic groups, aromatic groups, heterocyclic groups, OR ₄ , NR ₅ (R ₆ ), SR ₇ and OSiR ₈
(R ₉ ) (R ₁₀ ), X or a hydrogen atom. R ₄ and R ₇ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, R ₅ and R ₆ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and R ₈ , R ₉ and R ₁₀ represent an aliphatic group, and X represents a halogen atom.

Next, the general formula (I) will be described in detail.

In the general formula (I), R ₁ , R ₂ ,
R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀
The aliphatic group represented by is preferably an aliphatic group having 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group having 1 to 20 carbon atoms. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group include methyl, ethyl, n
-Propyl, isopropyl, t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl,
Examples thereof include cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl and phenethyl.

In the general formula (I), R ₁ , R ₂ ,
The aromatic group represented by R ₃ , R ₄ , R ₅ , R ₆ and R ₇ is preferably an aromatic group having 6 to 30 carbon atoms, particularly a monocyclic or condensed ring aryl group having 6 to 20 carbon atoms. And examples thereof include phenyl and naphthyl.

In the general formula (I), R ₁ , R ₂ ,
The heterocyclic group represented by R ₃ , R ₄ , R ₅ , R ₆ and R ₇ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of nitrogen atom, oxygen atom and sulfur atom. Is. These may be a single ring or may form a condensed ring with another aromatic ring or a heterocycle. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group such as pyridyl, furyl, thienyl, thiazolyl,
Examples include imidazolyl and benzimidazolyl.

In the general formula (I), the cation represented by R ₄ and R ₇ represents an alkali metal or ammonium.

The halogen atom represented by X in the general formula (I) is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The aliphatic group, aromatic group and heterocyclic group may be substituted.

The substituents include the following.

Representative substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, amino groups,
Acylamino group, ureido group, urethane group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, phosphoric acid amide group, diacylamino group, Imido group, alkylthio group, arylthio group, halogen atom,
Examples thereof include a cyano group, a sulfo group, a carboxy group, a hydroxy group, a phosphono group, a nitro group, and a heterocyclic group.
These groups may be further substituted.

When there are two or more substituents, they may be the same or different.

R ₁ , R ₂ and R ₃ may be bonded to each other to form a ring together with a phosphorus atom, and R ₅ and R ₆ may be bonded to form a nitrogen-containing heterocycle. .

In the general formula (I), R ₁ , R ₂ and R ₃ preferably represent an aliphatic group or an aromatic group, more preferably an alkyl group or an aromatic group.

[0027]

[Chemical 2] In the formula, R ₁₁ is an aliphatic group, an aromatic group, a heterocyclic group or —N
Represents R ₁₃ (R ₁₄ ), R ₁₂ is —NR ₁₅ (R ₁₆ ), —N
It represents the _{(R 17) N (R 18} ) R 19 or -OR _20. R ₁₃ ,
R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group. Where R ₁₁ and R ₁₅ , R ₁₁ and R ₁₇ , R ₁₁ and R ₁₈ , R
₁₁ and R ₂₀ , R ₁₃ and R ₁₅ , R ₁₃ and R ₁₇ , R ₁₃ and R _18, and R ₁₃ and R ₂₀ may combine to form a ring.

Next, the general formula (II) will be described in detail.

In the general formula (II), R ₁₁ , R ₁₃ ,
The aliphatic group, aromatic group and heterocyclic group represented by R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ have the general formula (I).
Expresses the same meaning as.

In the general formula (II), R₁₃, R₁₄,
R₁₅, R₁₆, R₁₇, R₁₈, R₁₉And R ₂₀Represented by
The sil group is preferably one having 1 to 30 carbon atoms,
Is a linear or branched acyl group having 1 to 20 carbon atoms,
For example, acetyl, benzoyl, formyl, pivaloyl,
Decanoyl can be mentioned.

Here, R ₁₁ and R ₁₅ , R ₁₁ and R ₁₇ , R ₁₁ and R
₁₈ , R ₁₁ and R ₂₀ , R ₁₃ and R ₁₅ , R ₁₃ and R ₁₇ , R ₁₃ and R ₁₈
When R ₁₃ and R ₂₀ combine to form a ring, examples thereof include an alkylene group, an arylene group, an aralkylene group, and an alkenylene group.

Further, the aliphatic group, aromatic group and heterocyclic group may be substituted with the substituents mentioned in formula (I).

In the general formula (II), preferably R ₁₁ represents an aliphatic group, an aromatic group or -NR ₁₃ (R ₁₄ ), and R ₁₂ represents-.
It represents NR ₁₅ (R ₁₆ ). R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ represent an aliphatic group or an aromatic group.

In the general formula (II), more preferably R ₁₁ represents an aromatic group or --NR ₁₃ (R ₁₄ ), and R ₁₂ is --NR ₁₅
Represents (R ₁₆ ). R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ represent an alkyl group or an aromatic group. Here, it is more preferable that R ₁₁ and R ₁₅ and R ₁₃ and R ₁₅ form a ring via an alkylene group, an arylene group, an aralkylene group or an alkenylene group.

The general formula _{(III) R 21 - (Te} ) in _n -R ₂₂ Formula, R ₂₁ and R ₂₂ may be different even in the same, an aliphatic group, an aromatic group, a heterocyclic group, -(C = Y)-
Represents R ₂₃ . R ₂₃ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, NR ₂₄ (R ₂₅ ), OR ₂₆ or SR ₂₇ ,
Y represents an oxygen atom, a sulfur atom, or NR ₂₈ . R ₂₄ ,
R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and n represents 1 or 2.

Next, the general formula (III) will be described in detail.

In the general formula (III), R ₂₁ , R ₂₂ , R ₂₃ ,
The aliphatic group, aromatic group or heterocyclic group represented by R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ has the same meaning as in formula (I).

Further, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R
_The aliphatic group, aromatic group and heterocyclic group represented by ₂₆ , R ₂₇ and R ₂₈ may be substituted with the substituents described in formula (I).

Here, R ₂₁ and R ₂₂ , and R ₂₄ and R ₂₅ may combine with each other to form a ring.

In the general formula (III), preferably R ₂₁ and R
₂₂ heterocyclic group, or - represents a (C = Y) -R _23. R ₂₃ represents NR ₂₄ (R ₂₅ ) or OR ₂₆ , and Y represents an oxygen atom. R ₂₄ , R ₂₅ and R ₂₆ represent an aliphatic group, an aromatic group or a heterocyclic group.

In the general formula (III), more preferably R ₂₁ and R ₂₂ represent-(C = Y) -R ₂₃ . R ₂₃ is NR ₂₄ (R
₂₅ ) and Y represents an oxygen atom. R ₂₄ and R ₂₅ represent an aliphatic group, an aromatic group or a heterocyclic group.

Specific examples of the compounds represented by formulas (I), (II) and (III) of the present invention are shown in the following chemical formulas 1 to 17, but the present invention is not limited thereto.

[0043]

[Chemical 3]

[0044]

[Chemical 4]

[0045]

[Chemical 5]

[0046]

[Chemical 6]

[0047]

[Chemical 7]

[0048]

[Chemical 8]

[0049]

[Chemical 9]

[0050]

[Chemical 10]

[0051]

[Chemical 11]

[0052]

[Chemical 12]

[0053]

[Chemical 13]

[0054]

[Chemical 14]

[0055]

[Chemical 15]

[0056]

[Chemical 16]

[0057]

[Chemical 17] The compounds represented by the general formulas (I), (II) and (III) of the present invention can be synthesized according to already known methods.

For example, Journal of Chemical Society (J. Chem. Soc. (A)) 1969 , 2
927; Journal of Organometallic Chemistry (J. Organomet. Chem.) 4 ,
320 (1965), ibid 1 , 200 (196
3); ibid 113 , C35 (1976); Phosphorus Sul
Fur) 15 , 155 (1983); Chemist Ber. 109 , 2996 (197).
6); Journal of Chemical Society Chemical Communication (J. Chem. Soc.
Chem. Commun. ) 635 (1980); ib
id, 1102 (1979); ibid, 645 (19)
79); ibid, 820 (1987), journal
Of the Chemical Society Perkin Transaction (J. Chem. Soc. Perkin. Tran
s. ) 1 , 2191 (1980); Patay (SP
Atai), The Chemistry of Organo Selenium and Tellurium Campounds (The)
Chemistry of Organo Sele
nium and Tellurium Compou
nds) 216-267 (1987), Tetrahedron Letters.
ers) 31 , 3587 (1990), Journal of Chemical Research, Synopses (J. Che).
m. Res. , Synopses) 2 , 56 (199)
0), Bulletin of the Chemical Society
Of Japan (Bull. Chem. Soc. Jap
an) 62 , 2117 (1989), ibid, 60 ,
771 (1987), Journal of Organic Chemistry (J. Organometall).
ic Chem. ) 338 , 9 (1988), ibi
d, 306 , C36 (1986), Vol. 7 of the Chemical Society of Japan,
1475 (1987), Zeitschrift Chemie 2
6 , 179 (1986), Chemistry Letters (C
chemistry Letters) 3 , 475 (198)
7), Indian Journal of Chemistry
try, Section A) 25A , 57 (198)
6), Angewandte Chemie
Chemie) 97 , 1051 (1985), Spectrochimica A.
Cta, Part A) 38A, 185 (1982), Organic Preparation and Procedia International (Organic Prepar)
ations and Procedures Int
international) 10 , 289 (1978), Organometallics (Organometallic)
s) 1 , 470 (1982).

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride which is presumed to serve as a sensitizing nucleus on the surface or inside of the silver halide emulsion grain.

The following tests can be conducted for the rate of silver telluride formation in silver halide emulsions.

When a large amount is added (for example, 1 × 10 ⁻³ mol / mol Ag), the formed silver telluride has absorption in the visible region. Therefore, regarding sulfur sensitizers, E. Moisar
Is Journal of Photographic
Science, Volume 14, Pages 181 (1966),
The method described in the same, Vol. 16, p. 102 (1968) can be applied. The amount of silver sulfide formed in the silver halide emulsion was determined by the infinite reflectance (in in the visible region (520 nm)).
finite reflectivity) to Kub
The relative silver telluride formation rate can be easily obtained by the same method as that obtained using the elka-Munk equation. Further, since this reaction is apparently close to the first-order reaction, the quasi-first-order reaction rate constant can also be obtained. For example, a silver bromide octahedral emulsion having an average grain size of 0.5 μm (1 kg
The emulsion contains 0.75 mol of AgBr and 80 g of gelatin) at 50 ° C while maintaining pH = 6.3 and pAg = 8.3.
The temperature is kept warm and the tellurium compound dissolved in an organic solvent (for example, methanol) is added at 1 × 10 ⁻³ mol / mol Ag. An emulsion is put into a cell having a thickness of 1 cm with a spectrophotometer having an integrating sphere, and a reflectance (R) at 520 nm is measured with time with reference to a blank emulsion. Kube the reflectance
The pseudo first-order reaction rate constant k (min ⁻¹ ) is obtained from the change in the value by substituting it into the lka-Munk equation (1-R) ² / 2R. If silver telluride is not produced, R = 1 always, so Ku
The value of belka-Munk is the same as that without the tellurium compound and remains 0. The apparent first-order reaction rate constant k under the exact same conditions as in this test method was 1 × 10 ⁻⁸ to 1 × 10 ^0.
Min ^-1 compounds are preferred.

Further, in a smaller addition amount range where absorption in the visible region is difficult to detect, the produced silver telluride can be separated from the unreacted tellurium sensitizer and quantified. For example, a minute amount of Te is quantitatively analyzed by, for example, an atomic absorption method after separation by immersion in an aqueous solution of a halogen salt or an aqueous solution of a water-soluble mercapto compound. The reaction rate greatly varies within a range of several digits depending on the type of compound, the silver halide composition of the emulsion to be tested, the temperature to be tested, pAg, pH and the like. The tellurium sensitizer preferably used in the present invention is a compound capable of forming silver telluride with respect to a specific silver halide emulsion having a halogen composition and a crystal wall to be used. Generally speaking, for a silver bromide emulsion, the temperature is 40 to 95 ° C. and the pH is 3
A compound capable of forming silver telluride in the range of 10 to 10 or pAg of 6 to 11 is preferably used in the present invention, and in this range, the pseudo first-order reaction rate constant k according to the above test method is 1 ×. A compound falling within the range of 10 ⁻⁷ to 1 × 10 ⁻¹ min ⁻¹ is more preferable as the tellurium sensitizer.

The amount of these tellurium sensitizers used in the present invention varies depending on, for example, the silver halide grains used and the chemical ripening conditions, but is generally 10 per mol of silver halide.
^-8 to 10 ^-2 mol, preferably about 10 ^{-7 to} 5 x 10 ^-3 mol is used.

The conditions for the chemical sensitization in the present invention are:
Although not particularly limited, pAg is 6 to 11, preferably 7 to 10, and temperature is 40 to 95 ° C, preferably 50 to 85 ° C.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium together. In particular, it is preferable to use a gold sensitizer together,
Specific examples thereof include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide, and 10 ^-7 to 1 -1 to 1 mol of silver halide
About 0 ^-2 mol can be used.

In the present invention, it is also preferable to use a sulfur sensitizer together. Specific examples include known unstable sulfur compounds such as thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, allylthiourea), and rhodanines, and silver halides. About 10 ⁻⁷ to 10 ⁻² mol can be used per mol.

In the present invention, it is preferable to additionally use selenium sensitization.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. As the unstable selenium compound, for example, JP-B-44-15748 and JP-B-43-
13489, Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-
It is preferable to use the compounds described in No. 229300. Specific examples of the unstable selenium sensitizer include, for example, isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, selenocarboxylic acids (for example, 2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium Can be given.

Preferred types of labile selenium compounds have been described above, but are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and have no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used.

As the non-labile selenium compound used in the present invention, Japanese Patent Publication Nos. 46-4553 and 52-34.
The compounds described in JP-B No. 492 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof.

Of these selenium compounds, those represented by the general formula (IV) shown in the following chemical formula 18 and the general formula (V) shown in the following chemical formula are preferable.

[0072]

[Chemical 18] In the formula, Z ₁ and Z ₂ may be the same or different, and are each an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl, propenyl), an aralkyl group. (Eg, benzyl, phenethyl), aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), heterocyclic group (eg, pyridyl, thienyl). , Furyl, imidazolyl), -NR ₁ (R
₂₎ - represents an OR ₃ or -SR _4.

R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ .

However, R ₁ and R ₂ are a hydrogen atom or an acyl group (for example, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl,
4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl) may be used.

In formula (IV), Z ₁ preferably represents an alkyl group, an aryl group or —NR ₁ (R ₂ ), and Z 1
₂ represents -NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R _{6, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group.

Among the selenium compounds represented by the general formula (IV), more preferable ones are N, N-dialkylselenoureas, N, N, N'-trialkyl-N'-acylselenoureas and tetraalkylselenoureas. , N, N-dialkyl-arylselenoamides, N-alkyl-N-aryl-arylselenoamides.

[0077]

[Chemical 19] In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different, and each may be an aliphatic group, an aromatic group, a heterocyclic group or -OR.
_{7, -NR 8 (R 9)} , - SR 10, -SeR 11, X, represents a hydrogen atom.

R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or hydrogen. Represents an atom, and X represents a halogen atom.

In the general formula (V), Z ₃ , Z ₄ ,
The aliphatic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an aralkyl group (for example, methyl,
Ethyl, n-propyl, isopropyl, t-butyl, n
-Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl).

In the general formula (V), Z ₃ , Z ₄ ,
The aromatic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed ring aryl group (for example, phenyl, pentafluorophenyl, 4-chlorophenyl,
3-sulfophenyl, α-naphthyl, 4-methylphenyl).

In the general formula (V), Z ₃ , Z ₄ ,
The heterocyclic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a 3- to 10-membered saturated or unsaturated group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Represents a heterocyclic group (eg, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, benzimidazolyl).

In the general formula (V), the cation represented by R ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom or a bromine atom. Or represents an iodine atom.

In the general formula (V), preferably Z ₃ , Z ₄ or Z ₅ represents an aliphatic group, an aromatic group or -OR ₇ ,
R ₇ represents an aliphatic group or an aromatic group.

Among the selenium compounds represented by the general formula (V), more preferred are trialkylphosphine selenides, triarylphosphine selenides, trialkylselenophosphates or triarylselenophosphates.

Specific examples of the compounds represented by formulas (IV) and (V) are shown in the following chemical formulas 20 to 27, but the present invention is not limited thereto.

[0086]

[Chemical 20]

[0087]

[Chemical 21]

[0088]

[Chemical formula 22]

[0089]

[Chemical formula 23]

[0090]

[Chemical formula 24]

[0091]

[Chemical 25]

[0092]

[Chemical formula 26]

[0093]

[Chemical 27] The addition amount of the selenium sensitizer varies depending on the activity of the selenium sensitizer used, the kind and size of silver halide, the temperature and time of ripening, etc., but preferably 1 × 10 ⁻ per mol of silver halide. ^{It is 8} mol or more. More preferably 1 ×
It is 10 ⁻⁷ mol or more and 5 × 10 ⁻⁵ mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary. For example, with respect to pH, the effect of the present invention can be obtained in a wide range of 4 to 9.

In chemical sensitization, it is not necessary to set the timing and order of addition of the silver halide solvent, tellurium sensitizer, selenium sensitizer, sulfur sensitizer, and gold sensitizer. The above compounds can be added at the same time as the initial aging (preferably) or during the chemical aging, or at different addition points. In addition, upon addition, the above compounds may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, and acetone and added.

In the present invention, it is also possible to use a reduction sensitizer in combination. Specific examples of the reduction sensitizer include stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives and borane compounds. (For example, dimethylamine borane), a silane compound, and a polyamine compound.

In the present invention, tellurium sensitization is preferably carried out in the presence of a silver halide solvent.

Specific examples of the silver halide solvent include thiocyanates (eg potassium thiocyanate) and thioether compounds (eg US Pat. No. 3,0,3).
No. 21,215, No. 3,271,157, Japanese Patent Publication 58
-30571, compounds described in JP-A-60-136736, particularly 3,6-dithia-1,8-octanediol), tetra-substituted thiourea compounds (for example, Japanese Patent Publication No. 59-
11892, compounds described in U.S. Pat. No. 4,221,863, especially tetramethylthiourea), and thione compounds described in JP-B-60-11341, JP-B-6
The mercapto compounds described in JP-A-3-29727, JP-A-6-63
The mesoionic compound described in 0-163042, the selenoether compound described in U.S. Pat. No. 4,782,013, the telluroether compound described in JP-A-2-118566, and the sulfite salt can be mentioned. Especially among these,
Thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used.
The amount used is 10 ⁻⁵ to 10 per mol of silver halide.
^{About -2} mol can be used.

In the present invention, the silver halide emulsions in the blue, green and red sensitive layers all have an average grain size of 0.4 μm or less. The average here is a number average. Preferably 0.4 to 0.05 μ, more preferably 0.4 to 0.08
Average particle size of μ. If it is less than this, the sensitivity is remarkably lowered, and if it is more than this, the required graininess cannot be obtained.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of blue-sensitive layer, green-sensitive layer and red-sensitive layer provided on the support. It is preferable that each color-sensitive layer is a color-sensitive layer having a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Each color-sensitive layer is a unit photosensitive layer having color sensitivity to blue light, green light, and red light, respectively, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038, for example, a coupler and a DIR compound may be contained, and a color mixing inhibitor may be contained as is commonly used.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each silver halide emulsion layer. Further, for example, JP-A-57-112751, JP-A-62-2.
No. 00350, No. 62-206541, No. 62-20
As described in No. 6543, a low-sensitivity emulsion layer may be provided on the side remote from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, in order from the farthest side from the support, for example, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity Green photosensitive layer (GL) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / G
H / RH / RL order or BH / BL / GH / GL /
It can be installed in the order of RL / RH.

Further, as described in JP-B-55-34932, layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and JP-A-62-6.
3936, from the side furthest from the support, the blue-sensitive layer / GL / RL / GH / RH
It can also be arranged in the order of.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a lower layer. Is a sequence in which a silver halide emulsion layer having a lower photosensitivity than that of the middle layer is arranged, and the photosensitivity is gradually decreased toward the support, and three layers having different sensitivities are included. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, medium sensitivity from the side remote from the support in the same color-sensitive layer is obtained. The layers may be arranged in the order of emulsion layer / high-speed emulsion layer / low-speed emulsion layer.

In addition, for example, high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order.
Also, in the case of four or more layers, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
No. 63-89850, for example,
It is preferable to arrange the donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layers of BL, GL, and RL, adjacent to or close to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

Below, the average particle size of the present invention of 0.
The silver halide grains of 4 μm or less will be described.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material of the present invention is silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 30 mol% or less of silver iodide. is there. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have a regular crystal form such as a cube, octahedron or tetradecahedron, or have an irregular crystal form such as a sphere or a plate. For example, it may have a crystal defect such as a twin plane or a composite form thereof.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), p.648, ibid. Thirty
7105 (November 1989), pages 863-865, and "Graphide's Physics and Chemistry" by Graphide, published by Paul Montel (P. Glafkides, Chemieet).
Phisique Photographique, P
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff).
in, Photographic Emulsion
Chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
otographic Emulsion, Focal
It can be prepared using the method described in Press, 1964).

US Pat. No. 3,574,628,
No. 3,655,394 and British Patent No. 1,413,
The monodisperse agents described in 748 are preferred.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described, for example, by Gatov, Photographic Science and Engineering (Gutoff, Photog.
radical Science and Engine
ering), Volume 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent No. 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which forms a latent image inside the grain, or a type which has a latent image both on the surface and inside. It must be a negative emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 can be used. This core /
A method for preparing a shell type internal latent image type emulsion is described in JP-A-59-1.
No. 33542. The thickness of the shell of this emulsion varies depending on, for example, the development process, but is 3 to 40 nm.
Is preferable, and 5-20 nm is especially preferable.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additive used in such a process is Research Disclosure No. 17643, the same No. 18716 and the same No. No. 307105, and the corresponding portions are summarized in Table A below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having different characteristics of at least one of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. Any of the silver halide grains and colloidal silver thus obtained can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
26,498 and JP-A-59-214852.

The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.4.
μm, and particularly preferably 0.05 to 0.4 μm. The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are within ± of the average grain size). Those having a particle size of 40% or less) are preferable.

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferably silver iodide,
The content is 0.5 to 10 mol%.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized and spectral sensitization is not required. However, prior to adding this to the coating liquid, for example, triazole-based,
It is preferable to add a known stabilizer such as an azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The coated silver amount of the light-sensitive material of the present invention is 4.5 g.
/ M ² or less is preferable, and 3.0 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in Table A below.

Table A Types of Additives RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 page right column 866 page 2 Sensitivity enhancer page 648 page right column 3 Spectral sensitizer, page 23-24 page 648 right column ~ 866 ~ Page 868 Supersensitizer 649 Page right column 4 Whitening agent page 24 647 Page right column 868 page 5 Antifoggant, page 24-25 Page 649 Right column 868-870 page Stabilizer 6 Light absorber, 25- Page 26 Page 649 Right column to page 873 Filter dye, Page 650 Left column UV absorber 7 Anti-staining agent Page 25 Right column Page 650 Left column to Page 872 Right column 8 Dye image stabilizer Page 25 650 Page left column 872 Page 9 Hardener page 26 page 651 left column 874 to 875 page 10 binder 26 page 651 page left column 873 to 874 page 11 plasticizer and lubricant page 27 650 page right column 876 page 12 coating aid, page 26 to 27 page 650 Right column 875 to 876 Surfactant 13 Antistatic agent Page 27 650 Page 850 Right column 876 to 877 Page 14 Matting agent 878 to 879 Also, to prevent deterioration of photographic performance due to formaldehyde gas. To react with formaldehyde as described in U.S. Patent No. 4,411,987 No. and the 4,435,503, it is preferable to add a compound capable of immobilizing the photosensitive material.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be prepared by the method described in JP-A-1-1060.
It is preferable to include a compound described in No. 52, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

In the light-sensitive material of the present invention, the international publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912, or EP317,308A
No. 4,420,555, Japanese Patent Laid-Open No. 1-25
It is preferable to incorporate the dye described in No. 9358.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and No. 17643. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in EP 249,473A are preferred.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and examples thereof include US Pat. Nos. 4,310,619 and 4,35.
No. 1,897, European Patent No. 73,636, US Patent Nos. 3,061,432, 3,725,067, Research Disclosure No. 24220 (198
June, 4), JP-A-60-33552, Research Disclosure No. 24230 (June 1984)
Mon), JP-A-60-43659, JP-A 61-72238.
No. 60-35730, No. 55-118034,
No. 60-185951, U.S. Pat. No. 4,500,63.
No. 0, No. 4,540, 654, No. 4,556, 6
No. 30, those described in International Publication WO88 / 04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers. For example, US Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4 are cited. , 296,200,
No. 2,369,929, No. 2,801,171
No. 2, No. 2,772,162, No. 2,895,82
No. 6, No. 3,772,002, No. 3,758,3
08, 4,334,011, 4,327,
No. 173, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A,
US Pat. Nos. 3,446,622 and 4,333,9
No. 99, No. 4,775, 616, No. 4,451,
No. 559, No. 4,427, 767, No. 4,69
No. 0,889, No. 4,254,212, No. 4,2
Those described in JP-A No. 96-199 and JP-A No. 61-42658 are preferable. Further, pyrazoloazole couplers described in JP-A-64-553, 64-554, 64-555 and 64-556, and imidazole described in U.S. Pat. No. 4,818,672. System couplers can also be used.

Typical examples of polymerized dye-forming couplers are, for example, US Pat. Nos. 3,451,820, 4,080,211, 4,367,282 and 4,409. No. 320, No. 4,576,910,
British Patent 2,102,137, European Patent 341,1
88A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color-forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. Of 307105
Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler which releases the development inhibitor is the above-mentioned R
D17643, Item VII-F and No. 307105,
Patents described in paragraph VII-F, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184248.
Nos. 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

For example, R. D. No. 11449 and 2
The bleaching accelerator-releasing couplers described in JP-A No. 4241 and JP-A No. 61-201247 are effective for shortening the processing time having a bleaching ability, and particularly, the light-sensitive material using the tabular silver halide grains described above. The effect is great when added to. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds which release, for example, a fogging agent, a development accelerator and a silver halide solvent by a redox reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat. No. 4,13.
Competitive couplers described in 0,427, for example, U.S. Pat. Nos. 4,283,472, 4,338,393,
Multiequivalent couplers described in JP-A No. 4,310,618; for example, JP-A-60-185950 and JP-A-62-24.
No. 252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound; European Patent Nos. 173,302A and 31;
No. 3,308A, a coupler that releases a dye that recolors after being released; for example, a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, JP-A-63-75747.
Examples thereof include a leuco dye-releasing coupler; and a fluorescent dye-releasing coupler described in U.S. Pat. No. 4,774,181.

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

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described, for example, in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); of phosphoric acid or phosphonic acid Esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di- - ethylhexyl phenyl phosphonate); benzoic acid esters (e.g., 2
-Ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate); amides (eg, N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone); alcohols or phenols (For example, isostearyl alcohol, 2,4-di-t
ert-amylphenol); aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg, N, N) -Dibutyl-2
-Butoxy-5-tert-octylaniline); hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene) can be exemplified. As the auxiliary solvent, for example, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, Cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide are mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in, for example, US Pat. No. 4,19.
No. 9,363, West German Patent Application (OLS) No. 2,541,
No. 274 and No. 2,541,230.

The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-125747.
No. 272248 and JP-A No. 1-80941, for example, 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2 −
It is preferable to add various antiseptics or antifungal agents such as phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. The present invention can be particularly preferably used for a film for color duplication.

Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness here means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days). Further, the film swelling rate T _1/2 can be measured according to a method known in the art, for example, A. Green et al., Photographic Science and Engineering (Photog.
r. Sci. Eng. ), Vol. 19, No. 2, 124-12
It can be measured by using a swellometer (swelling meter) of the type described on page 9. In addition, T _1/2 is 3 for color developing solution.
The saturated film thickness is defined as 90% of the maximum swollen film thickness reached at 0 ° C. for 3 minutes and 15 seconds, and is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer includes, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener,
It is preferable to contain a binder, a plasticizer, a lubricant, a coating aid, and a surface active agent. The swelling ratio of this back layer is 1
50 to 500% is preferable.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
18716, page 651, left column to right column, and the same No. Thirty
The development can be carried out by a usual method described in 7105, pages 880 to 881.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used. As a typical example thereof, for example, 3-methyl-4
-Amino-N, N-diethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfonamidoethylaniline, 3-methyl-4
-Amino-N-ethyl-β-methoxyethylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more of these compounds can be used in combination depending on the purpose.

The color developing solution contains, for example, a pH buffering agent such as an alkali metal carbonate, borate or phosphate.
It is common to include development inhibitors or antifoggants such as chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine and catecholsulfonic acids; ethylene glycol, Organic solvents such as diethylene glycol; benzyl alcohol, ponoethylene glycol, quaternary ammonium salts,
Development accelerators such as amines; dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; tackifiers; aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos. Various chelating agents represented by carboxylic acids can be used. Examples of the chelating agent include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-.
Representative examples are diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. be able to.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. This black-and-white developer contains, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-p-, for example.
Known black-and-white developing agents such as aminophenols such as aminophenol can be used alone or in combination. The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishing amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenisher. You can also When the replenishment amount is reduced, it is preferable to prevent the evaporation and air oxidation of the liquid by reducing the contact area of the processing liquid with air.

The contact area between the photographic processing liquid and the air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, more preferably 0.1. It is 001-0.05. As a method of reducing the aperture ratio in this way, in addition to a method of providing a barrier such as a floating lid on the photographic processing liquid surface of the processing tank, the movable lid described in JP-A-1-82033 is used. And the slit development processing method described in JP-A-60-216050. Reducing the aperture ratio is preferably applied not only in both the color development step and the black and white development step, but also in the subsequent steps, for example, all the steps of bleaching, bleach-fixing, fixing, washing and stabilizing. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent. .

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Furthermore, processing in two continuous bleach-fixing baths, fixing before bleach-fixing,
Alternatively, the bleaching treatment after the bleach-fixing treatment can be arbitrarily carried out according to the purpose. As the bleaching agent, for example, polyvalent metal compounds such as iron (III), peracids (in particular, sodium persulfate is suitable for color negative films for motion pictures), quinones, and nitro compounds are used. Iron (II) is a typical bleaching agent.
I) organic complex salts, for example complex salts with aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or For example, complex salts with citric acid, tartaric acid and malic acid can be used.
Of these, ethylenediaminetetraacetic acid iron (III) complex salts,
Also, aminopolycarboxylic acid iron (III) complex salts including 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications: for example, U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95631, No. 53-.
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-18426, Research Disclosure No. No. 17129 (July 1978)
A compound having a mercapto group or a disulfide group described in JP-A No. 50-140129; a thiazolidine derivative described in JP-A No. 50-140129;
832, 53-32735, and U.S. Pat. No. 3,70.
Thiourea derivatives described in 6,561; West German Patent No. 1,
127,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,74.
Polyoxyethylene compounds described in JP-B No. 8,430; polyamine compounds described in JP-B No. 45-8836; other JP-A Nos. 49-40943, 49-59644, 53-94927, 54-35727. , 55-
26506 and 58-163940;
Bromide ions can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat. No. 3,893,858.
, West German Patent No. 1,290,812, JP-A-53-9
The compounds described in 5630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

The bleaching agent or bleach-fixing solution preferably contains an organic acid for the purpose of preventing bleach stain, in addition to the above compounds. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically, for example, acetic acid, propionic acid and hydroxyacetic acid are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Of these, the use of thiosulfates is common, with ammonium thiosulfate being the most widely used. It is also preferable to use a thiosulfate solution in combination with, for example, a thiocyanate salt, a thioether compound, or thiourea. Preservatives for fixers and bleach-fixers include sulfite,
Bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferred. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methyl for adjusting the pH. It is preferable to add 0.1 to 10 mol / liter of an imidazole such as imidazole.

The total time for the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. There are ways to increase the effect. Furthermore, a method of further improving the stirring effect by moving the light-sensitive material while making the emulsion surface in contact with the wiper blade provided in the solution to make the emulsion surface turbulent, and increasing the circulating flow rate of the entire processing solution There is a method of making it. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is believed that improved agitation accelerates the supply of bleaching agent and fixing agent into the emulsion film, and consequently increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for developing the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in Nos. 1258 and 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such treatment is particularly effective for shortening the treatment time in each step and reducing the amount of treatment liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as coupler), the use, and further, for example, the rinsing water temperature, the number of rinsing tanks (number of stages), countercurrent, forward replenishment method, etc. It can be set in a wide range according to various conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the
Society of Motion Picture
e and Television Vision Engineer
s Vol. 64, p. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above literature, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the generated suspended matter adheres to the photosensitive material. Occurs. In the processing of the color light-sensitive material of the present invention, a solution to such a problem is disclosed in JP-A-62-2
The method of reducing calcium ion and magnesium ion described in No. 88838 can be used very effectively. Further, as described in JP-A-57-8542, for example, isothiazolone compounds, siabendazoles, chlorine-based germicides such as chlorinated sodium isocyanurate, and others, such as benzotriazole, by Horiguchi "The Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing,
Hygiene Technology Association, “Microbial Sterilization, Sterilization, and Antifungal Technology” (19
1982) It is also possible to use the bactericides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be variously set depending on, for example, the characteristics of the light-sensitive material and the application, but generally 15 to 45 ° C. and 20 seconds to 1
A range of 0 minutes, preferably 25 to 40 ° C. and 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543
All known methods described in Nos. 58-14834 and 60-220345 can be used.

In some cases, the washing treatment may be followed by a further stabilizing treatment. As an example of the stabilizing treatment, a stabilizer containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can be added to this stabilizing bath.

The overflow solution that accompanies the washing with water and / or the supplement of the stabilizing solution can be reused in another step such as a desilvering step.

For example, in processing using an automatic processor,
When each of the above treatment liquids is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color photographic light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, such as Research Disclosure No. 3,342,599. 14, 850 and the same No.
Schiff base type compounds described in 15, 159,
Aldol compounds according to US Pat. No. 24, US Pat. No. 3,71
Metal salt complexes described in 9,492, JP-A-53-135.
The urethane compound described in No. 628 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are, for example, JP-A-56-64339 and JP-A-5-64339.
Nos. 7-144547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 5 ° C.
Used at 0 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

The silver halide light-sensitive material of the present invention comprises
For example, U.S. Pat. No. 4,500,626, JP-A-60-
No. 133449, No. 59-218443, No. 61-2
It can also be applied to the photothermographic materials described in, for example, 38056 and European Patent No. 210,660A2.

[0173]

EXAMPLES Examples will be shown below for further description. Example 1 A cubic silver iodobromide emulsion having an average iodine content of 3.0 mol% was prepared in a gelatin aqueous solution by a control double jet method. By adjusting the preparation temperature and time, the average particle size was 0.58μ, 0.40μ, 0.2
Five emulsions of 9μ, 0.19μ and 0.13μ were prepared.

After the completion of grain formation, desalting was carried out by a usual flocculation method. Subsequently, using chloroauric acid, potassium thiocyanate, and a sulfur sensitizer shown in Table 1 below, chemical sensitization was performed at 60 ° C. so that 1/40 ″ sensitivity was optimum, and Em-1 to 5 were obtained. It was

With respect to the sulfur sensitizers of Em-1 to 5, the sulfur sensitizers, selenium sensitizers and tellurium sensitizers shown in Table 1 were used to optimize the 1/40 "sensitivity. Chemical sensitization was performed at 60 ° C. to obtain Em-6 to 25.

[0176]

[Table 1] Sample 10 prepared by coating the emulsion thus prepared as follows.
1-125 were prepared.

An emulsion layer and a protective layer were coated on a triacetyl cellulose film support having an undercoat layer in the following coating amounts. Coupler 1.0 g / m ² as shown in <emulsion layer> · Emulsion ... Emulsion Em-1 to 25 silver coverage 0.5 g / m ² · following formula 28 shown in Table 1

[0178]

[Chemical 28] ・ Tricresyl phosphate 0.8 g / m ²・ Gelatin 2.5 g / m ² <Protective layer> ・ Gelatin 3.0 g / m ²・ Hardener 0.30 g / m ² shown in the following chemical formula 29.

[0179]

[Chemical 29] These samples were exposed for sensitometry and subjected to the following color development processing.

The density of the treated sample was measured with a green filter.

The development processing used here is 38 under the following conditions.
Performed at ° C.

1. Color development: 2 minutes 45 seconds 2. Bleach ... 6 minutes 30 seconds 3. Rinse with water ... 3 minutes 15 seconds 4. Fixed arrival ... 6 minutes 30 seconds 5. Rinse with water 3 minutes 15 seconds 6. Stability: 3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows. <Color developer> Sodium nitrilotriacetate 1.4 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethyl) 4. 5 g Amino) -2-methyl-aniline sulphate Water was added to 1 liter <bleaching solution> Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediaminetetraacetic acid sodium salt 130 g Glacial acetic acid 14 ml Water was added. 1 liter <Fixer> Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Sodium bisulfite 4.6 g Water was added 1 liter <Stabilizer> Formalin 8.0 ml Water In addition, 1 liter, exposure is 1/40 second Using a wedge exposure of the ordinary.

Further, as a light source, a filter is used for 320
The one adjusted to a color temperature of 0 ° K was used.

The sensitivity is 0.2 from the fog to an optical density.
Compared in terms of. The sensitivity display shows the sensitivity of the sample 101 as 10
It was expressed as relative sensitivity as 0.

Of the obtained results, Samples 101 to 10
3, 106-108, 111-113, 116-11
The results for Nos. 8, 121 to 123 are shown in Table 2 below.

[0186]

[Table 2] From the results of Table 2, samples 116 to 11 in which sulfur sensitization and selenium sensitization were used in combination with sulfur sensitized samples 101 to 103
Sample No. 8 showed a slight increase in sensitivity almost independent of the grain size of the emulsion, while Sample 1 using tellurium sensitization
In 06-108, 111-113, 121-123,
It can be seen that the emulsion having a size of 0.40 μm or less has a larger increase in sensitivity than the emulsion having a size of 0.58 μm and is advantageous in terms of fog.

Further, as the chalcogen sensitization, it is understood that the combined use of sulfur sensitization and tellurium sensitization, and the combined use of sulfur sensitization, selenium sensitization and tellurium sensitization are preferable to tellurium sensitization alone.

In addition to the results of Table 2, Samples 104, 105, 109, 110, 1 coated with smaller emulsions
Similar results were obtained for 14, 115, 119, 120, 124, and 125.

As selenium sensitizers, S-21 and S-3
Using S-3 and S-40, almost the same results as in Table 2 were obtained.

Even when T-39 and T-62 were used as tellurium sensitizers, almost the same results as in Table 2 were obtained.

Based on the above results, a multi-layer color light-sensitive material consisting of each layer having the composition shown below was prepared on a triacetyl cellulose support by using the emulsions of Em-1 to 25, and the sensitivity and graininess were obtained. The sharpness was evaluated.

[0192] The coating amount of each component, the amount of silver for the silver halide and colloidal silver, expressed in units of g / m ^2, also couplers, additives, the amount, expressed in units of g / m ² for gelatin The sensitizing dyes are shown by the number of moles per mole of silver halide in the same layer. First layer: Antihalation layer Black colloidal silver 0.20 Gelatin 2.30 Second layer: Intermediate layer Cpd-1 0.10 Gelatin 0.80 Third layer: First red sensitive emulsion layer Emulsion A Silver 0.19 ExS-4 1.2 × 10 ⁻³ ExC-1 0.29 ExC-2 0.19 ExC-3 0.05 Solv-1 0.10 Solv-2 0.10 Gelatin 2.40 Fourth layer: second Red-sensitive emulsion layer Emulsion B Silver 0.10 ExS-4 5.1 × 10 ^-4 ExC-1 0.12 ExC-2 0.04 Solv-1 0.05 Solv-2 0.05 Gelatin 0.85 Fifth Layer: Third red-sensitive emulsion layer Emulsion C Silver 0.33 ExS-4 2.1 × 10 ^-4 ExC-1 0.085 ExC-2 0.055 Solv-1 0.03 Solv-2 0.03 Gelatin 1 .10 Sixth Layer: Intermediate Layer Cpd-10. 3 Gelatin 0.65 Seventh layer: first green-sensitive emulsion layer Emulsion D silver ^{0.42 ExS-2 1.26 × 10 -3} ExS-3 1.40 × 10 -4 ExM-1 0.25 ExM-2 0.10 ExM-3 0.05 Solv-1 0.42 Gelatin 2.60 Eighth layer: Second green emulsion layer Emulsion E Silver 0.12 ExS-2 8.0 × 10 ^-4 ExS-3 9. 0 × 10 ⁻⁵ ExM-1 0.07 ExM-2 0.03 ExM-3 0.015 ExM-4 0.008 Solv-1 0.15 Gelatin 0.60 9th layer: third green-sensitive emulsion layer emulsion F Silver 0.42 ExS-2 7.8 × 10 ^-4 ExS-3 8.8 × 10 ^-5 ExM-1 0.08 ExM-2 0.03 ExM-3 0.02 ExM-4 0.01 Solv -1 0.14 Gelatin 0.90 10th layer: Yellow filter layer Yellow roller Id silver Silver 0.15 Cpd-1 0.10 Cpd-2 0.05 Gelatin 1.0 Eleventh layer: First blue-sensitive emulsion layer Emulsion G Silver 0.20 ExS-1 2.5 × 10 ⁻³ ExC− 1 0.03 ExY-1 0.70 Solv-1 0.25 Gelatin 1.10 12th layer: 2nd blue sensitive emulsion layer Emulsion H Silver 0.22 ExS-1 2.0 × 10 ⁻³ ExC-10 .01 ExY-1 0.26 Solv-1 0.09 Gelatin 0.45 13th layer: third blue-sensitive emulsion layer Emulsion I Silver 0.37 ExC-1 0.003 ExY-1 0.07 Solv-10 .02 gelatin 0.60 14th layer: 1st protective layer UV-1 0.05 UV-2 0.24 Solv-2 0.12 gelatin 0.50 15th layer: 2nd protective layer B-1 (diameter 1 .70μ) 0.01 B-2 (diameter 1.70μ) 0.01 B 3 0.09 H-1 0.30 In addition to the above the sample 1,2-benzisothiazolin-3-one (average 200ppm to gelatin), n-
Butyl-p-hydroxybenzoate (approx. 1000 p
pm) and 2-phenoxyethanol (approx. 10000)
ppm) was added.

Further, B-4, B-5, W-1, W-2, F
-1 to F-8 and F-9 to F-12 are also added.

The structural formulas of the compounds used to prepare the samples are shown in Chemical formulas 30 to 40 below.

[0195]

[Chemical 30]

[0196]

[Chemical 31]

[0197]

[Chemical 32]

[0198]

[Chemical 33]

[0199]

[Chemical 34]

[0200]

[Chemical 35]

[0201]

[Chemical 36]

[0202]

[Chemical 37]

[0203]

[Chemical 38]

[0204]

[Chemical Formula 39]

[0205]

[Chemical 40] Emulsions A to I among the above Em1 to 25 are shown in Table 3 below.
Samples 201 to 213 were prepared by using as shown in FIG.

These samples were exposed for sensitometry and were subjected to the above color development processing. The density of the treated sample was measured with a red filter, a green filter and a blue filter. For the results of photographic performance, red sensitive layer,
The sensitivities of the green-sensitive layer and the blue-sensitive layer are represented by relative sensitivities when the sensitivity of Sample 201 is 100.

Secondly, in order to evaluate the graininess of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer, the RMS granularity was measured with a red filter, a green filter and a blue filter using an aperture of 48 μmφ. The RMS value of density D _min + 1.0 × 1000 is defined as the RMS granularity (D
_min means the minimum image density). The smaller this value is, the better the graininess is.

Thirdly, in order to evaluate the sharpness, white and white sharp contrast images and white exposure were performed through a filter (frequency 40 cycles / mm) having a linear striped repeating pattern having the same density difference as that of the above. The same process was performed. The concentration was measured with a micro densitometer through a G filter and an R filter, and a square wave response function [Squarewave R defined by the following equation was used.
esponse Function (SRF)].

SRF = (D _max −D _min ) ÷ ΔD D _max : maximum value of micro density of striped pattern image D _min : minimum value of micro density of striped pattern image ΔD: maximum density of sharp contrast image Difference in minimum density The larger the SRF value, the better the sharpness.

The above results are shown in Table 3.

From the results shown in Table 3, it is clear that the light-sensitive material of the present invention provides excellent RMS granularity, excellent red-sensitive layer and green-sensitive layer sharpness without significantly reducing relative sensitivity.

[0212]

[Table 3] Example 2 Samples 201 to 21 which are multilayer color light-sensitive materials of Example 1
After exposing No. 3 in the same manner as in Example 1, the following color development processing was performed to evaluate the relative sensitivity of each color-sensitive layer, the RMS granularity, and the sharpness of the red-sensitive layer and the green-sensitive layer. Similar results were obtained.

Treatment Step Temperature (° C.) Time 1. Pre-bath 27 ± 1 10 seconds 2. Backing removal 27-385 seconds and spray water washing 3. Color development 41.1 ± 0.1 3 minutes 4. Stop 27-38 30 seconds 5. Bleach acceleration 27 ± 1 30 seconds 6. Bleach 38 ± 1 3 minutes 7. Washing with water 27-38 1 minute 8. Stationary 38 ± 12 2 minutes 9. Washing with water 27-38 2 minutes 10. Stability 27-38 10 seconds Prescription of each treatment liquid (1) Pre-bath Prescription value Water at 27-38 ° C 800 ml Borax (10-hydrate) 20.0 g Sodium sulfate (anhydrous) 100 g Sodium hydroxide 1.0 g Water In addition, 1.00 liter pH (27 ° C.) 9.25 (3) Color development Water having a prescribed value of 21 to 38 ° C. 850 ml Kodak anti-calcium No. 4 2.0 ml sodium sulfite (anhydrous) 2.0 g Eastman Antifog No. 9 0.22 g Sodium bromide (anhydrous) 1.20 g Sodium carbonate (anhydrous) 25.6 g Sodium bicarbonate 2.7 g Color developing agent; 4-Amino-3-methyl-N-ethyl-N-4.0 g (β -Methanesulfonamidoethyl) -aniline 1.00 liters by adding water pH (27 ° C) 10.20 (4) Stop water with a prescribed value of 21-38 ° C 900 ml 7.0N sulfuric acid 50 ml Water by adding 1.00 liters pH (27 ° C) 0.9 (5) Bleach accelerating solution Prescription value Water 900 ml Sodium metabisulfite (anhydrous) 10.0 g Glacial acetic acid 25.0 ml Sodium acetate 10.0 g EDTA-4Na 0.7 g PBA 5.5 g Water In addition 1.0 liter pH (27 ° C.) 3.8 ± 0.2 PBA stands for 2-dimethylaminoethylisothiourea dihydrochloride.

(6) Bleaching liquid Prescription value Water at 24-38 ° C. 800 ml Gelatin 0.5 g Sodium persulfate 33.0 g Sodium chloride 15.0 g Sodium monophosphate (anhydrous) 9.0 g Phosphoric acid (85%) 2 0.5 liter pH (27 ° C.) 2.3 ± 0.2 (8) Fixing prescription value water of 20 to 38 ° C. 700 ml Kodak anti-calcium No. 4 2.0 ml 58% antimonium thiosulfate solution 185 ml Sodium sulfite (anhydrous) 10.0 g Sodium bisulfite (anhydrous) 8.4 g Water was added to 1.0 liter pH (27 ° C) 6.5 (10) Stable formulation Water with a value of 21 to 27 ° C. 1.00 liter Kodak Stabilizer Additive 0.14 ml Formalin (37.5% solution) 1.50 ml

[0215]

As described above, the present invention provides a silver halide color photographic light-sensitive material having improved sensitivity graininess and sharpness.

Claims (3)

[Claims] 1. A blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and at least one layer each on a support.
In a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, the average grain size of silver halide grains in each silver halide emulsion contained in each silver halide emulsion layer is 0.4 μm or less. And a silver halide color photographic light-sensitive material, characterized in that at least one of the emulsion layers contains a tellurium-sensitized silver halide emulsion. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide emulsion is subjected to sulfur sensitization and tellurium sensitization. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide emulsion is subjected to sulfur sensitization, selenium sensitization and tellurium sensitization.