JPH05142723A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance fastness of a cyan color-developed image and color developing performance and further storage stability of a raw sample by incorporating a specified cyan coupler, a specified compound, and a silver halide emulsion layer high in silver salt content in the same layer. CONSTITUTION:At least one of the photosensitive silver halide emulsion layers formed on a paper base contains at least one kind of cyan dye forming coupler represented by formula I and at least one kind of compound selected from formulae II, II, and IV and an silver halide emulsion containing silver chloride in an amount of >=90mol % and the raw paper of the film base has a pH of 5. In formulae I-IV, each of R1 and R2 is alkyl; L is absent or a divalent bond; Z is H or the like; each of R21 and R22 is an aliphatic group or the like; each of X1 and A is a group to be released by reaction with a developing agent; n is 1 or 0; B is H or the like; Y1 is a group for promoting addition of the developing agent to the compound of formula III; R30 is an aliphatic group or the like; and Z1 is a nucleophilic group or a group to be allowed to release by decomposition.

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 particularly to a silver halide multi-layer color photographic light-sensitive material having improved storability of color images. More specifically, the present invention relates to a rapid-processing type silver halide color photographic light-sensitive material in which the fastness of a cyan color image and the raw storability of the light-sensitive material are improved.

[0002]

2. Description of the Related Art A silver halide light-sensitive material is exposed to light and then color-developed, whereby an aromatic primary amine developing agent oxidized by silver halide reacts with a dye-forming coupler to form a color image. It In this way,
A color reproduction method using a subtractive color method is often used, and in order to reproduce blue, green, and reddish colors, yellow, which has a complementary color relationship with each other,
A magenta and cyan color image is formed.

Conventionally, phenols or naphthols have been widely used as cyan image forming couplers. However, some problems remain in the storability of color images obtained from conventional phenols and naphthols. For example, U.S. Patent Nos. 2,367,531 and 2,
No. 369,929, No. 2,423,730 and No. 3,772,002 disclose color images obtained from 2-acylaminophenol cyan couplers, but they generally have poor thermal fastness and U.S. Pat. Ibid 2,89
The color image obtained from the 2,5-diacylaminophenol cyan coupler described in No. 5,826 generally has a drawback that light fastness is poor. Further, the color images obtained from the 2-ureidophenol cyan couplers described in U.S. Pat.Nos. 3,446,622 and 4,333,999 generally have poor light fastness, and 1-hydroxy-2-naphthamide cyan couplers generally have light and heat (Especially wet heat) It was insufficient in terms of both fastness.

A color image obtained from a phenolic coupler having a chain or branched alkyl group as a ballast group described in JP-A-61-39045 has excellent fastness to light and heat, There was a defect that the unexposed portion was colored cyan after the treatment.

On the other hand, attempts to improve the fastness of a color image obtained from a cyan coupler by using an epoxy coupler solvent have been made in US Pat. Nos. 4,239,851 and 4,540,657.
JP-A-62-75447 and JP-A-64-21447, the improvement of the fastness is certainly seen but not sufficient.

In recent years, in order to satisfy the demand for rapid development processing, a silver halide emulsion containing a high content of silver chloride in a light-sensitive material, a so-called high silver chloride emulsion, is used to achieve a rapid processing step. A new system is being developed and introduced, but in such a rapid processing system, there is a problem that the unexposed portion is colored cyan after the above processing, or when the photosensitive material is stored raw. It was necessary to solve the rising wear.

[0007]

SUMMARY OF THE INVENTION Accordingly, the first object of the present invention is to provide a silver halide color photographic light-sensitive material capable of forming a cyan dye image having excellent fastness to light and heat. The second objective is a silver halide color photograph that can be processed quickly without side effects such as fog increase or desensitization that can occur during the life of the light-sensitive material, and that the unexposed areas are not colored after processing. To provide a light-sensitive material.

[0008]

[Means for Solving the Problems] As a result of intensive studies on the above-mentioned problems, it was found that the problems can be solved by the following methods. That is, at least one photosensitive silver halide emulsion layer coated on a paper support comprises at least one cyan dye-forming coupler represented by the following general formula (I) and the following general formulas (II) and (III Or at least one compound selected from (IV) and a silver halide emulsion having a silver chloride content of 90 mol% or more, and the pH of the base paper of the support.
The problem has been solved by a silver halide color photographic light-sensitive material characterized in that the ratio is 5 or more and 9 or less.

[0009]

[Chemical 2]

In the above general formula (I), R ₁ represents an alkyl group having at least 7 carbon atoms, R ₂ represents an alkyl group having 2 to 15 carbon atoms, and L represents a simple bond or a divalent linking group. And Z represents a hydrogen atom or a group or atom capable of splitting off upon coupling with a developing agent.

General formula (II) R ₂₁ -(-A _n -)-X ₁

General formula (III)

In the general formulas (II) and (III), R ₂₁ and R ₂₂
Each represents an aliphatic group, an aromatic group or a heterocyclic group. X ₁ represents a group which reacts with an aromatic amine developing agent to leave, and A represents a group which reacts with an aromatic amine developing agent to form a chemical bond. The reaction product with the aromatic amine developing agent is a substantially colorless compound. n is 1 or 0
Represents. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group, and Y ₁ promotes addition of the aromatic amine developing agent to the compound of the general formula (III). Represents a group. Where R ₂₁ and X ₁ , Y ₁ and R
₂₂ or B may combine with each other to form a ring structure.

General formula (IV) R ₃₀ -Z ₁

In the formula, R ₃₀ represents an aliphatic group, an aromatic group or a heterocyclic group. Z ₁ represents a nucleophilic group or a group which decomposes in the photosensitive material to release a nucleophilic group.

The cyan coupler represented by formula (I) of the present invention will be described in more detail. R ₁ represents an alkyl group having at least 7 carbon atoms (octyl, tert-octyl, tridecyl, pentadecyl, eicosyl, etc.), preferably a linear unsubstituted alkyl group having 10 to 22 carbon atoms. L represents a simple bond or a divalent linking group. Here, the divalent linking group represents an alkylene group, a phenylene group, an ether bond, a carbonamide bond, a sulfonamide bond, an ester bond, a urethane bond, and the like, and a divalent group formed by combining these groups. Are as follows.

[0017]

[Chemical 3]

R ₂ in the general formula (I) has 2 to 2 carbon atoms.
It represents an alkyl group of 15 (ethyl, butyl, tert-butyl, cyclohexyl, pentadecyl, etc.), preferably an alkyl group having 2 to 4 carbon atoms, and most preferably an ethyl group. Z represents a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom (fluorine, chlorine, bromine, etc.), an alkoxy group (ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonyl, ethoxy). Etc.), aryloxy groups (4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, etc.), acyloxy groups (acetoxy, tetradecanoyloxy, benzoyloxy, etc.), sulfonyloxy groups (methanesulfonyloxy, toluenesulfonyloxy) Etc.), amide group (dichloroacetylamino, heptafluorobutyrylamino, methanesulfonylamino, toluenesulfonylamino, etc.), alkoxycarbonyloxy group (ethoxycarbonyloxy, benzyloxy) Carbonyloxy, etc.), aryloxycarbonyloxy groups (phenoxycarbonyloxy, etc.), aliphatic or aromatic thio groups (ethylthio, phenylthio, tetrazolylthio, etc.), imide groups (succinimide, hydantoinyl, etc.), aromatic azo groups (phenylazo, etc.) and so on.
These leaving groups may include photographically useful groups. Z in the general formula (I) is preferably a hydrogen atom or a halogen atom, with chlorine and fluorine being most preferred.

In the present specification, the "aliphatic group" means a linear, branched or cyclic aliphatic hydrocarbon group, alkyl,
It is meant to include saturated and unsaturated alkenyl and alkynyl groups. Typical examples are methyl, ethyl, butyl, dodecyl, octadecyl, eicosenyl, iso-propyl, tert-butyl, tert-octyl, te.
rt- Dodecyl, cyclohexyl, cyclopentyl, allyl, vinyl, 2-hexadecenyl, propargyl, etc.

The alkyl group, aliphatic group and substitutable linking group (alkylene, phenylene amide bond, etc.) in the general formula (I) further include an alkyl group, aryl group, heterocyclic group, alkoxy group (methoxy group, 2-methoxyethoxy, etc.), aryloxy groups (2,4-di-tert-amylphenoxy, 4-cyanophenoxy, etc.), alkenyloxy groups (2-propenyloxy, etc.), acyl groups (acetyl group,
Benzoyl), ester groups (butoxycarbonyl,
Phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy, etc.), amide group (acetylamino, ethylcarbamoyl, dimethylcarbamoyl, methanesulfonamide, butylsulfamoyl, etc.), sulfamide group (dipropylsulfamoylamino, etc.) , Imide group (succinimide, hydantoinyl, etc.), ureido group (phenylureido group, dimethylureido, etc.), aliphatic or aromatic sulfonyl group (methanesulfonyl, phenylsulfonyl, etc.), aliphatic or aromatic thio group (ethylthio, phenylthio, etc.) ), A hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom and the like.

Specific examples of the compound of the present invention represented by formula (I) are shown below, but the present invention is not limited thereto.

[0022]

[Chemical 4]

Two or more cyan couplers of the general formula (I) used in the present invention may be used, and other cyan couplers may be used in combination. A cyan coupler containing the general formula (I) which can be particularly preferably used is represented by the following general formula (CI)
Can be shown as

[0024]

[Chemical 5]

In the general formula (C-I), R ₁₁ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₁₂ represents an aliphatic group,
R ₁₃ represents an aromatic group or an acylamino group, R ₁₃ represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, an aliphatic or aromatic oxy group, or an acylamino group, and Z ₁₁
Represents a hydrogen atom or a group or atom capable of splitting off by an oxidative coupling reaction with a developing agent, and n is 0 or 1.
And R ₁₂ and R ₁₃ may combine with each other to form a 5- to 7-membered ring. Typical examples of the cyan coupler represented by the general formula (CI) are shown below.

[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

[Chemical 8]

The coupler used in the present invention can be incorporated into the silver halide emulsion layer by a known method. At that time, a coupler solvent which can be introduced together with the coupler, an ultraviolet absorber, a protective colloid, a binder, an antifoggant, a color mixing inhibitor, an antifading agent, a sensitizing dye, a dye, a bleaching agent, and a method for forming a silver halide photosensitive material. , (The method of forming photographic emulsion, the method of introducing couplers, the support, the layer structure of each photosensitive layer, etc.) and the photographic processing, etc.
ch Disclosure), December 1978, item 17643 (Industria
Opportunies Ltd., UK), JP-A-56-65134 and JP-A-56-104333, and the substances and methods described in the cited documents can be used. The amount of the coupler of the present invention to be added is usually 0.1 to 1.0 mol, preferably 0.1 to 0.5 mol per mol of silver halide in the silver halide emulsion layer constituting the photosensitive layer.

Next, the compounds represented by formulas (II), (III) and (IV) will be described in more detail. The compounds represented by the general formulas (II) and (III) are the second-order reaction rate constant k with p-anisidine measured by the method described in JP-A-63-158545.
Compounds having a ₂ (80 ° C.) of 1.0 liter / mol · sec to 1 × 10 ⁻⁵ liter / mol · sec are preferable. On the other hand, in the compound represented by the general formula (IV), Z ₁ is Pearson's nucleophilic CH ₃ I value (RG Pearson, et al., J. Am. Chem. S.
oc., 90,319 (1968)) is preferably a group derived from a nucleophilic functional group of 5 or more.

Among the compounds of the general formulas (II) to (IV), it is preferable to use the compound of the formula (II) or (III) and the compound of the formula (IV) in combination. Each group of the compounds represented by formulas (II), (III) and (IV) will be described in more detail.

R_{twenty one}, R_{twenty two}, B and R₃₀Aliphatic group
Is a linear, branched or cyclic alkyl group,
Represents a alkenyl group, which may be further substituted with a substituent.
Yes. R _{twenty one}, R_{twenty two}, B and R₃₀Aromatic group is carbon
Ring aromatic groups (eg phenyl, naphthyl) and hetero
Ring aromatic groups (eg furyl, thienyl, pyrazolyl,
(Pyridyl, indolyl), monocyclic
The system is also a condensed ring system (eg benzofuryl, phenanthridinini)
Le) In addition, these aromatic rings have substituents
You may stay. R_{twenty one}, R_{twenty two}, B and R₃₀Heterocycle
The group is a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or
Of a 3-membered to 10-membered ring structure composed of hydrogen atoms
Group is preferred, even if the heterocycle itself is a saturated ring, it is unsaturated
It may be a ring and may be further substituted with a substituent.
(Eg chromanyl, pyrrolinyl, morpholinyl).

X _{1 in the} general formula (II) represents a group which is released by reacting with an aromatic amine type developing agent, and is a group which is bonded to A through an oxygen atom, a sulfur atom or a nitrogen atom (for example, 2-pyridyloxy). , 2-pyrimidyloxy, 4-pyrimidyloxy,
2- (1,2,3-triazine) oxy, 2-benzimidazolyl, 2-imidazolyl, 2-thiazolyl, 2-benzthiazolyl, 2-furyloxy, 2-thiophenyloxy, 4-pyridyloxy, 3-isooxa Zolyloxy, 3-pyrazolidinyloxy, 3-oxo-2-pyrazolonyl, 2-oxo-1-pyridinyl, 4-oxo-1-pyridinyl, 1-benzimidazolyl, 3-pyrazolyloxy, 3H-1,2 , 4-Oxadiazoline-5-oxy, aryloxy, alkoxy, alkylthio, arylthio, substituted N-oxy) or halogen atoms are preferred.

A in the general formula (II) represents a group which reacts with an aromatic amine type developer and forms a chemical bond, and contains a group containing an atom having a low electron density, for example, the following group.

[Chemical 9]

When X ₁ is a halogen atom, n represents 0. Where L is

[0036]

[Chemical 10]

Represents (For example, a carbonyl group, a sulfinyl group, an oxycarbonyl group, a phosphonyl group, a thiocarbonyl group, an aminocarbonyl group, a silyloxy group, etc.).
Y ₁ has the same meaning as Y _{1 in} formula (III), and Y ₁ 'is Y
Represents the same meaning as ₁ .

R'and R "may be the same or different,
Each represents an -L '''-R _21. R '''is a hydrogen atom, an aliphatic group (eg, methyl, isobutyl, t-butyl, vinyl, benzyl, octadecyl, cyclohexyl), an aromatic group (eg, phenyl, pyridyl, naphthyl), a heterocyclic group (eg, piperidinyl, pyranyl) , Furanyl, chromanyl), acyl groups (eg acetyl, benzoyl),
And a sulfonyl group (eg, methanesulfonyl, benzenesulfonyl).

[0039] Preferred are divalent radicals. Among the compounds represented by the general formula (II), more preferable compounds are the general formula (II-a),
It is represented by (II-b), (II-c) or (II-d) and has a second-order reaction rate constant k2 (80 ° C) of 1 with p-anisidine.
x10 ^-1 liter / mol · sec ~ 1x10 ^-5 liter / mol
・ A compound that reacts in the range of sec.

[0040]

[Chemical 11]

In the formula, R ₂₁ has the same meaning as R _{21 in} formula (II). Link represents a single bond and -O-. Ar represents an aromatic group having the same meaning as defined for R ₂₁ , R ₂₂ and B. However, it is preferable that the one released as a result of the reaction with the aromatic amine-based developer is not a group useful as a photographic reducing agent such as a hydroquinone derivative. Ra, Rb and R
c may be the same or different and each is a hydrogen atom,
It represents an aliphatic group, an aromatic group or a heterocyclic group having the same meanings as defined for R ₂₁ , R ₂₂ and B. Ra, Rb and R
c is further an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an acyl group, an amide group, a sulfonamide group, a sulfonyl group, an alkoxycarbonyl group, It represents a sulfo group, a carboxyl group, a hydroxy group, an acyloxy group, a ureido group, a urethane group, a carbamoyl group and a sulfamoyl group. Where Ra and R
b or Rb and Rc may be bonded to each other to form a 5- to 7-membered heterocycle, which is further substituted with a substituent, forms a spiro ring, a bicyclo ring, or an aromatic ring. May be condensed with. Z ₁ and Z ₂ are 5 to 7
Represents a group of non-metal atoms necessary to form a member heterocycle,
This heterocycle may be further substituted with a substituent, may form a spiro ring, a bicyclo ring or the like, or may be condensed with an aromatic ring.

In the general formula (II-a) among the general formulas (II-a) to (II-d), the second-order reaction rate constant k 2 (80 ° C.) with p-anisidine is ¹ × 10 ^-1 liter / mol. sec ~
To adjust to the range of 1 × 10 ^-5 liter / mol · sec A
When r is a carbocyclic aromatic group, it can be adjusted by a substituent. At this time, depending on the type of R ₂₁ group, the Hammet of each substituent is
The sum of the σ values of t is preferably 0.2 or more, more preferably 0.4 or more, still more preferably 0.6 or more. Note that the above σ
In calculating the value, the ortho σ value is substituted by the para σ value. General formulas (II-a) to (II-d)
When the compound represented by the formula (3) is added during the production of the light-sensitive material, the compound preferably has a total carbon number of 13 or more. The compound of the present invention also has the meaning of achieving the object of the present invention,
Those that decompose during development are not preferred.

Y _{1 in the} general formula (III) is an oxygen atom, a sulfur atom, Here, R ₂₄ , R ₂₅ and R ₂₆ are hydrogen atoms, aliphatic groups (eg methyl, isopropyl, t-butyl, vinyl, benzyl, octadecyl, cyclohexyl), aromatic groups (eg phenyl, pyridyl, naphthyl), heterocycles. Represents a group (for example, piperidyl, pyranyl, furanyl, chromanyl), an acyl group (for example, acetyl, benzoyl), a sulfonyl group (for example, methanesulfonyl, benzenesulfonyl), and R ₂₅ and R ₂₆ may be bonded to each other to form a cyclic structure. Good.

Among the compounds represented by the general formulas (II) and (III), the particularly preferred compound is the general formula (II). Among them, the more preferable compound is a compound represented by the general formula (II-a) or the general formula (II-c), and a compound represented by the general formula (II-a) is particularly preferable.

Z _{1 in the} general formula (IV) represents a nucleophilic group or a group which decomposes in a light-sensitive material to release a nucleophilic group. The compound of general formula (IV) chemically bonds with the oxidant of an aromatic amine developing agent to form a substantially colorless compound.
Here, for example, a nucleophilic group in which an atom directly chemically bonded to an oxidant of an aromatic amine developing agent is an oxygen atom, a sulfur atom, or a nitrogen atom (for example, an amine compound, an azide compound, a hydrazine compound, a mercapto compound, a sulfide compound ,
Sulfinic acid compounds, cyano compounds, thiocyano compounds, thiosulfate compounds, seleno compounds, halide compounds,
(Carboxy compounds, hydroxamic acid compounds, active methylene compounds, phenol compounds, nitrogen heterocyclic compounds, etc.)
Can be given. Among the compounds of general formula (IV), more preferred compounds can be represented by the following general formula (IV-a).

[0046]

[Chemical 12]

In the formula, M is an inorganic material (eg, Li, Na, K,
Ca, Mg, etc.) or organic (eg triethylamine,
Methylamine, ammonia, etc.) forming an atom or group of atoms and

[0048]

[Chemical 13]

And hydrogen atom. Where R _15a and R
_16a may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R
_15a and R _16a may combine with each other to form a 5- to 7-membered ring. R _17a , R _18a , R _20a and R _21a may be the same or different and each is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group,
Represents a sulfonyl group, a ureido group and a urethane group. However, at least one of R _17a and R _18a and at least one of R _20a and R _21a are hydrogen atoms. R _19a
And R _22a represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R _19a further represents an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. Here, at least two groups out of R _17a , R _18a , and R _19a may combine with each other to form a 5- to 7-membered ring. R _23a represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R _24a represents a hydrogen atom, an aliphatic group,
It represents an aromatic group, a halogen atom, an acyloxy group or a sulfonyl group.

R _10a , R _11a , R _12a , R _13a and R
_14a may be the same or different and each is a hydrogen atom, an aliphatic group (eg methyl, isopropyl, t-butyl, vinyl, benzyl, octadecyl, cyclohexyl), an aromatic group (eg phenyl, pyridyl, naphthyl), a heterocycle. A group (for example, piperidyl, pyranyl, furanyl, chromanyl), a halogen atom (for example, chloro atom, bromine atom), -SR _26a , Xycarbonyl group (eg, methoxycarbonyl, butoxycarbonyl, cyclohexylcarbonyl, octyloxycarbonyl), aryloxycarbonyl group (eg, phenyloxycarbonyl, naphthyloxycarbonyl), sulfonyl group (eg, methanesulfonyl, benzenesulfonyl), sulfonamide group (Eg, methanesulfonamide, benzenesulfonamide), sulfamoyl group, ureido group, urethane group, carbamoyl group,
Sulfo group, carboxyl group, nitro group, cyano group, alcoxalyl group (for example, methoxallyl, isobutoxalyl, octyloxalyl, benzoyloxalyl), aryloxalyl group (for example, phenoxalyl, naphthoxalyl), sulfonyloxy group (for example, methanesulfonyloxy, benzene) Sulfonyloxy),

Here, R _26a and R _{27a, which} may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group or a sulfonyl group. R _28a and R
_29a may be the same or different and each is a hydrogen atom,
It represents an aliphatic group, an aromatic group, an alkoxy group and an aryloxy group. Of these, the sum of Hammett's σ values of the benzene substituents with respect to the —SO ₂ M group is preferably 0.5 or more from the viewpoint of the effect of the present invention. In calculating the σ value, the ortho σ value is replaced with the para σ value. Representative examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby.

[0052]

[Chemical 14]

[0053]

[Chemical 15]

[0054]

[Chemical 16]

[0055]

[Chemical 17]

[0056]

[Chemical 18]

[0057]

[Chemical 19]

[0058]

[Chemical 20]

[0059]

[Chemical 21]

[0060]

[Chemical formula 22]

[0061]

[Chemical formula 23]

[0062]

[Chemical formula 24]

[0063]

[Chemical 25]

[0064]

[Chemical formula 26]

[0065]

[Chemical 27]

[0066]

[Chemical 28]

[0067]

[Chemical 29]

[0068]

[Chemical 30]

[0069]

[Chemical 31]

[0070]

[Chemical 32]

[0071]

[Chemical 33]

[0072]

[Chemical 34]

[0073]

[Chemical 35]

[0074]

[Chemical 36]

[0075]

[Chemical 37]

These compounds are disclosed in JP-A-62-143048,
63-115855, 63-115866, 63-158545, and European Patent Publication No. 255722, and methods analogous thereto. The preferred compounds of the present invention also include the compounds specifically exemplified in the above-mentioned patents and JP-A Nos. 62-283338 and 62-229145.

The compounds represented by the general formulas (II), (III) and (IV) are preferably those which can be dissolved in a high boiling organic solvent, and 1 mol of the cyan dye-forming coupler of the general formula (I) used in the present invention. It is preferably 3 × 10 ^{-2 to} 10 mol,
More preferably, it is added in an amount of 3 × 10 ^-2 or more and 5 mol or less. These compounds are preferably coemulsified with the coupler.

The pH value of the base paper of the paper support used in the light-sensitive material of the present invention must be 5 or more and 9 or less, and preferably 5.5 or more and 8.5 or less. Conventionally, acid paper has generally been used as a base paper for a paper support of a light-sensitive material, but in the present invention, it is necessary to regulate the pH as described above. In the present specification, the pH value of the base paper is a value measured according to the hot water extraction method of JIS-P-8133. The outline of the hot water extraction method of JIS-P-8133 is described below.

About 1.0 g of the test piece was weighed and placed in an Erlenmeyer flask.
In a 100 ml volume, add 20 ml of distilled water and soak it with a flat stir bar until the test piece is evenly moistened to soften it. Next, add 50 ml of distilled water and stir, and attach a condenser to the flask. Then, without boiling water, mix the contents of the flask with 95
Place the flask in a water bath to maintain ~ 100 ° C. Heat at this temperature for 1 hour with occasional shaking, then 20
Cool to ± 5 deg. C and measure the pH value of the extract as it is using a glass electrode pH meter. Details of the above measurement method and the equipment used for the measurement shall comply with the Japanese Industrial Standards of 1963.

The constitution of the paper support used in the present invention and specific means for adjusting the pH value of the base paper to 5 to 9 will be described below. The base paper used for the paper support is produced by making wood pulp as a main raw material and making paper. As wood pulp,
Although both softwood pulp and hardwood pulp can be used, it is preferable to use a large amount of short fiber hardwood pulp in the present invention. Specifically, it is preferable that 60% by weight or more of the pulp constituting the base paper is hardwood pulp. If necessary, part of the wood pulp may be replaced with synthetic pulp made of polyethylene, polypropylene or the like, or synthetic fiber made of polyester, polyvinyl alcohol, nylon or the like. The freeness of the pulp used is preferably 150 to 500 cc, more preferably 200 to 400 cc according to the CSF regulations. Further, regarding the fiber length after beating, it is preferable that the 24 + 42 mesh residue defined by JIS-P-8207 is 40% by weight or less. In general, a sizing agent is internally added to the base paper, but in the present invention, the pH value of the paper support is 5 to 5.
Therefore, it is necessary to use a neutral sizing agent such as epoxidized fatty acid amide, fatty acid anhydride, rosin acid anhydride, alkenyl succinic anhydride, succinic acid amide, isopropenyl stearate, aziridine compound, and alkyl ketene dimer. It is preferably used as an additive sizing agent. In addition, a sizing agent is generally added internally to the base paper,
In the present invention, it is necessary to set the pH value of the base paper to 5 to 9, so that instead of the sulfuric acid band (aluminum sulfate) usually used as a fixing agent, cationized starch, polyamide polyamine epichlorohydrin, polyacrylamide, polyacrylamide derivative It is preferable to use a neutral or weakly alkaline compound such as the above, or to add a sulfuric acid band and then neutralize with an alkali. Further, a filler such as calcium carbonate, talc, clay, kaolin, titanium dioxide or urea resin fine particles may be internally added to the base paper for the purpose of improving smoothness.

As internal additives other than the above-mentioned internally added sizing agent, fixing agent, and filler, paper strength agents such as polyacrylamide, starch, polyvinyl alcohol, etc .; a reaction product of a maleic anhydride copolymer and a polyalkylene polyamine, a higher grade A softening agent such as a quaternary ammonium salt of a fatty acid; a colored dye; a fluorescent dye or the like may be added to the base paper if necessary. These internal additives also have a pH value of the base paper of 5 to 9, and therefore it is preferable in principle to select and use a drug having a pH value close to neutral. Further, it is preferable to use as little acidic or alkaline chemical as possible.

The raw paper used for the paper support can be produced by using the raw materials described above and using a Fourdrinier paper machine or a cylinder paper machine. Preferably the basis weight of the base paper is 20 to 300 g / m ^2, and particularly preferably 50 to 200 g / m ^2. The thickness of the base paper is preferably 25 to 350 μm, particularly preferably 40 to 250 μm. The base paper is preferably subjected to a calendering treatment such as an on-machine calender in a paper machine or a super calender after paper making for the purpose of improving smoothness. By the calendering treatment, the density of the base paper is preferably 0.7 to 1.2 g / m ² according to JIS-P-8118, and 0.85 to 1.
It is particularly preferable that the amount is 10 g / m ² .

The pH value of the base paper to be produced is adjusted to 5 to 9 by the method for producing the base paper as described above, particularly by selecting the internal additive chemicals (internal additive sizing agent, fixing agent, etc.) and surface sizing agent. You can In the light-sensitive material of the present invention, the base paper as described above can be used as it is as a paper support. A surface sizing agent may be applied to the surface of the raw paper.
Examples of the surface sizing agent include polyvinyl alcohol, starch, polyacrylamide, gelatin, casein, styrene maleic anhydride copolymer, alkyl ketene dimer, polyurethane, and epoxidized fatty acid amide.

A coating layer may be further provided on one or both surfaces of the above-mentioned base paper (including those coated with a surface sizing agent). There is no particular limitation on the structure of the coating layer,
It preferably comprises a hydrophobic polymer. By providing the coating layer containing the hydrophobic polymer, the water absorption of the paper support is lowered, and the strain of the support which occurs during the coating of the photosensitive layer can be reduced. The hydrophobic polymer may be a homopolymer or a copolymer. Further, in the case of the copolymer, even if it partially has a hydrophilic repeating unit, it may be hydrophobic as a whole. Examples of the hydrophobic polymer include polyethylene, polypropylene, polyvinylidene chloride, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-acrylic acid ester copolymer, and styrene-methacrylate-acrylic acid ester copolymer. be able to.

A pigment may be added to the coating layer for the purpose of improving resolution. As the pigment, a known pigment used for coated paper can be used. Examples of pigments include inorganic pigments such as titanium dioxide, barium sulfate, talc, clay, kaolin, calcined kaolin, aluminum hydroxide, amorphous silica, crystalline silica and synthetic alumina silica;
And organic pigments such as polystyrene resin, acrylic resin and urea formalin resin. The amount of the pigment added is suitably 5 to 60% by weight in the hydrophobic polymer, preferably 8 to 30% by weight, more preferably 14 to 30% by weight. As a method for providing the coating layer, an extrusion coating method, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a doctor coating method, a gravure coating method, or the like can be used. For the purpose of improving the smoothness of the paper support, it is preferable to carry out a calender treatment such as a gloss calender or a super calender during or after coating.

Next, the silver halide emulsion of the present invention will be described in detail. The silver halide emulsion of the present invention requires a so-called high silver chloride emulsion having a silver chloride content of 90 mol% or more, and further, silver bromide is present in the vicinity of at least one apex of the silver halide grains. It is preferable that the average silver bromide content of the grain surface is 15 mol% or less.
Here, the "vicinity of the apex" is preferably about 1/3 (more preferably 1/5) of the diameter of a circle having the same area as the projected cubic or cubic crystal-like cubic silver chlorobromide grains. It is within the area of a square whose length is one side and whose vertex is a cube or the intersection of the edges of normal crystal grains regarded as a cube. The content ratio of silver chlorobromide grains having a silver bromide-rich region to all silver halide grains contained in the same emulsion layer is preferably 70 mol% or more.

The host silver halide crystals used to make the emulsions of the present invention are cubic or tetradecahedral crystal grains having substantially (100) faces (these have rounded corners and higher-order faces). The halogen composition is silver chlorobromide or silver chloride containing silver iodide in an amount of 2 mol% or less or having a silver chloride content of 90 mol% or more, and preferably 95%. A silver halide or pure silver chloride crystal containing at least 99 mol% of silver chloride, particularly preferably at least 99 mol%. The average grain size of the host silver halide grains is preferably 0.2 μm to 2 μm, and the distribution state thereof is preferably monodisperse. The monodisperse emulsion relating to the present invention means
Coefficient of variation (S / r) for grain size of silver halide grains
Is an emulsion having a grain size distribution of 0.25 or less. Where r
Is the average particle size, and S is the standard deviation for the particle size. That is, when the grain size of each emulsion grain is ri and the number is ni, the average grain size r is defined by r = (Σni · ri) / (Σni), and its standard deviation S is S = [{ Σ (r-ri) ² · ni} / {Σni}] ^1/2 is defined.

The grain size in the present invention means a silver halide emulsion as described in "The Theory of the Photographic Pr" by TH Jams et al.
ocess ", 3rd edition, pages 36-39, published by Macmillan (1966
(Year), which is the diameter equivalent to the projected area corresponding to the area projected when microscopically photographed by a method well known in the art (usually electron microscope photographing) as described in (1). Here, the diameter equivalent to the projected area of a silver halide grain is defined by the diameter of a circle having an area equal to the projected area of a silver halide grain as described in the above-mentioned book. Therefore, the shape of silver halide grains is not spherical (eg, cubic, octahedral, 14
The average particle size r and its deviation S can be obtained as described above even in the case of a face, a flat plate, a potato, etc. The coefficient of variation with respect to the particle size of the silver halide grains is 0.25 or less, preferably 0.20 or less, more preferably 0.15
Hereafter, it is most preferably 0.10.

Next, bromine ions or fine silver bromide grains are supplied to the host silver halide grains to deposit a new silver halide phase richer in silver bromide on the surface of the host silver halide grains. .. This process proceeds by a so-called "halogen conversion" process due to the exchange reaction of the bromide ion with the halogen ion on the surface of the host silver halide grain. The other process using high silver bromide fine particles proceeds due to the reaction between the host silver halide grains and the high silver bromide grains to form a crystal with a more stable composition, and it can be considered separately from the conversion reaction. Is. Despite these two different types of reactions, the effect of selecting the vicinity of the apex of the host grain as the formation site of a new silver bromide-rich phase can be similarly obtained in both reactions.

In order to more effectively achieve the purpose of obtaining a very high sensitivity by concentrating latent images or development nuclei, a compound (CR) which suppresses or blocks the initiation of halogen conversion.
Compound) can be used. A CR compound is a substance that functions to retard or completely prevent the initiation of halogen conversion and recrystallization by selectively adsorbing to a specific crystal plane as compared with the case where the compound is not adsorbed. , Especially in the present invention (100)
It is a substance that is mainly (selectively) adsorbed on the surface and acts to suppress the initiation of conversion and recrystallization on the (100) surface.

The CR compound used in the present invention includes
Cyanine dye, merocyanine dye, mercaptoazoles (specific examples thereof include compounds represented by the general formulas (XXI), (XXII) and (XXIII) described in detail in EP 0273430), nucleic acid degradation (For example, deoxyribonucleic acid, a product in the process of decomposing ribonucleic acid, adenine, guanine, uracil, cytosyl, thymine, etc.). In particular, the following general formulas (Is), (IIs) or
The compound represented by (IIIs) is preferable.

[0092]

[Chemical 38]

In the formula, Z ₁₀₁ and Z ₁₀₂ each represent an atomic group necessary for forming a heterocyclic nucleus. As a heterocyclic nucleus,
A 5- to 6-membered ring nucleus containing a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom as a hetero atom (a condensed ring may be further bound to these rings, or a substituent is further bound thereto). May be used) is preferred. Specific examples of the heterocyclic nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus,
Imidazole nucleus, naphthoimidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenine nucleus, indole nucleus, tellurazole nucleus, benzoterrazole nucleus, naphthoterrazole nucleus, etc. it can.

R ₁₀₁ and R ₁₀₂ each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group.
Each of these groups and the groups described below is used in the meaning including the substituted form. For example, when an alkyl group is taken as an example, it includes an unsubstituted alkyl group and a substituted alkyl group, and these groups may be linear, branched or cyclic. The alkyl group preferably has 1 to 8 carbon atoms. Specific examples of the substituent of the substituted alkyl group include a halogen atom (chlorine, bromine, fluorine, etc.), a cyano group, an alkoxy group,
Examples thereof include a substituted or unsubstituted amino group, a carboxylic acid group, a sulfonic acid group and a hydroxyl group, and one or more of these may be substituted together. A specific example of the alkenyl group is a vinylmethyl group. Specific examples of the aralkyl group include a benzyl group and a phenethyl group.

M₁₀₁ Is an integer of 0 or 1, 2 or 3
Represent m₁₀₁ Is 1 then R₁₀₃ Is a hydrogen atom, low
It represents a primary alkyl group, an aralkyl group or an aryl group. The above
Specific examples of the aryl group of are a substituted or unsubstituted phenyl group.
A nyl group can be mentioned. R₁₀₄ Represents a hydrogen atom
You m₁₀₁ Is 2 or 3, then R₁₀₃ Is a hydrogen atom
Represents R₁₀₄ Is a hydrogen atom, lower alkyl group, aralkyl
In addition to R₁₀₂ To form a 5- to 6-membered ring
You can Also m₁₀₁ Represents 2 or 3, and R
₁₀₄ Is a hydrogen atom, R₁₀₃ Is another R₁₀₃ Connected with
To form a hydrocarbon ring or a heterocycle. these
The ring is preferably a 5- or 6-membered ring. j₁₀₁ , K_{Ten 1} Is 0 or
Represents 1 and X^- ₁₀₁Represents an acid anion, n₁₀₁ Is 0 or
Represents 1.

[0096]

[Chemical Formula 39]

In the formula, Z₂₀₁ , Z₂₀₂ Is the above Z₁₀₁ Or
Z₁₀₂ Is synonymous with. R₂₀₁ , R_{20 2} Is R₁₀₁ Or R
₁₀₂ Is synonymous with R₂₀₃ Is alkyl, alkenyl, ar
Quinyl or aryl group (substituted or unsubstituted phenyl group
Etc.) m₂₀₁ Represents 0, 1 or 2. R₂₀₄ 
Represents a hydrogen atom, a lower alkyl group, an aryl group,
m₂₀₁ When R represents 2 R₂₀₄ And R₂₀₄ Carbonated water
A prime ring or a heterocycle may be formed. These rings are 5
A 6-membered ring is preferred. Q₂₀₁ Is sulfur atom, oxygen atom, selenium
Atom or> N-R₂₀₅ Represents R₂₀₅ Is R₂₀₃ Same as
Represents righteousness. j_{20 1} , R₂₀₁ , X^- ₂₀₁And n₂₀₁ Is it
Each j₁₀₁ , K₁₀₁ , X^- ₁₀₁And n_{Ten 1} Synonymous with
You

[0098]

[Chemical 40]

In the formula, Z₃₀₁ Is necessary to form a heterocycle
Represents an atomic group. As this heterocycle, Z₁₀₁ And Z₁₀₂ To
And other specific examples of thiazo.
Lysine, thiazoline, benzothiazoline, naphthothiazo
Phosphorus, selenazolidine, selenazoline, benzoselenazo
Phosphorus, naphthoselenazoline, benzoxazoline, naphth
Toxazoline, dihydropyridine, benzimidazole
Nuclei such as naphthoimidazole and naphthoimidazoline
It Q₃₀₁ Is Q₂₀₁ Is synonymous with. R₃₀₁Is R_{Ten 1} Also
Is R₁₀₂ And R₃₀₂ Is R₂₀₃ Is synonymous with. m₃₀₁ Is m
₂₀₁Is synonymous with. R₃₀₃ Is R₂₀₄ Synonymous with, m₃₀₁
 R is 2 or 3₃₀₃ And other R₃₀₃ Is connected
To form a hydrocarbon ring or a heterocycle. j₃₀₁
Is j₁₀₁ Is synonymous with.

In addition to increasing the selectivity of the initial formation site of the new silver bromide-rich phase over the host grains, the CR compound also allows the newly formed new phase to recrystallize with the surface of the host grains. It is possible to prevent the reaction that causes the formation of a uniform new layer on the entire surface of the host grain by repeating the crystallization, and to grow epitaxially in the vicinity of the apex of the host grain. To form and retain. Then, by forming a new phase limited to this place, a very high sensitivity is achieved. This increase in sensitivity also tends to give pressure desensitization. Pressure desensitization is a phenomenon in which the sensitivity of a photosensitive material decreases when pressure is applied before exposure, but the content of silver bromide in a new phase richer in silver bromide than the host grains increases. The silver bromide content of this phase is preferably higher than that of the host grains and 90 mol% or less. It is more preferably 60 mol% or less.

The silver halide grains in the present invention contain 90 mol% or more of silver chloride as an average value in the same emulsion,
A new phase that is richer in silver bromide than the host particles has grown epitaxially near the apex of the host particles, and there is a transition region with a gradual halogen composition between the new phase and the host particles. There is. The structure of such particles is observed by various analytical methods. First, by observation with an electron microscope, it is observed that a new phase is bonded near the apex of the particle due to the morphological change of the particle.
Further, the halogen composition of the host particle and a new phase can be obtained by the X-ray diffraction method. For the average halogen composition of the surface, see XPS (X-ray Phtoelectron Spectrosc
opy) method, for example, using an ESCA750 spectrometer manufactured by Shimadzu-du Pont. About this measuring method, please refer to Someno / Yasumorii "Surface Analysis" Kodansha (Published in 1977).
It is described in. By knowing the halogen composition of the host grain and the new phase by the X-ray diffraction method, and by knowing the average halogen composition of the surface by the XPS method, the proportion of the new phase rich in silver bromide from the host grain on the entire surface can be determined. It can be roughly estimated whether it occupies. Further, in order to identify the existence position of a new phase richer in silver bromide than the host grains and to measure how much it occupies in the vicinity of the apex of the grains, the method by observation with the electron microscope is used. Besides, ED
It can be measured by an X (Enegy Dispersive X-ray analysis) method using an EDX spectrometer equipped in a transmission electron microscope. This measuring method is specifically described in "Electron beam microanalysis" by Keiyoshi Soejima, Nikkan Kogyo Shimbun (issued in 1987). The new phase in the present invention is preferably localized near the apex of the host grain, and the average halogen composition of the surface is preferably 15 mol% or less of silver bromide, more preferably 10 mol% or less. .. The increase in the average silver bromide content on the surface means that the degree of localization of the new phase near the apex decreases, and at the same time, the sensitivity decreases. It has been observed by an electron microscope that, in the preferred production method of the present invention, the new phase formed is in the form of being epitaxially bonded and grown at the corner portion of the host grain.

The preferred grain size of the fine grain high silver bromide emulsion used in the present invention may vary depending on the size of the host grain and the halogen composition, but a grain size of 0.3 μm or less is usually used. It is more preferably 0.1 μm or less. It is essential that the halogen composition of the fine grain high silver bromide emulsion has a higher silver bromide content than the host grains, and a bromide concentration of 50 mol% or more is preferable. More preferably 70 mol%
It is desired to contain the above bromide. The fine grain high silver bromide emulsion may contain iodide if necessary. It is also possible to include ions or compounds of heavy metals such as iridium, rhodium and platinum. Fine grain high silver bromide emulsions have a silver content of 50% relative to the host silver halide.
It is mixed in the range of 0.1%. More preferably 0.2 to 20
%, Particularly preferably in the range of 0.2 to 8%. The mixing temperature can be freely selected between 30 ° C and 80 ° C.

In the silver chlorobromide emulsion of the present invention, latent images or development centers are concentrated, very high sensitivity is achieved, and fogging can be suppressed without impairing rapid developability. Further, there are advantages that the gradation is hard and the pressure desensitization is small.

The CR compound in the present invention can be selected from sensitizing dyes. Especially useful C for (100) plane
The R compound has the above general formula (Is), (IIs) or (I
It can be selected from the compounds represented by IIs), and it can also function as a sensitizing dye, and therefore it is also useful for increasing the spectral sensitivity. In particular, partial recrystallization of the surface can also increase the stability of spectral sensitivity. Further, it may be used in combination with other sensitizing dyes for the purpose of further sensitization and stabilization, and may also be used in combination with a supersensitizer. For example, a substituted aminostilbenzene compound having a nitrogen-containing heterocyclic nucleus group (for example, the general formula described in JP-A-62-174738 filed on September 30, 1986 by Fuji Photo Film Co., Ltd.) A compound of (I),
Particularly, specific compound examples (I-1) to (I-17) and the like, those described in US Pat. Nos. 2,933,390 and 3,635,721), and aromatic organic acid formaldehyde condensates (for example, described in US Pat. No. 3,743,510) Stuff), cadmium salt,
An azaindene compound or the like may be included. U.S. Patent No. 3,
615,613, 3,615,641, 3,617,295, 3,63
The combination described in 5,721 is particularly useful. General formula (I
s), (IIs) and (IIIs), specific examples of the CR compound are described in the above-mentioned European Patent EP0273430.
CR-1 to 55 can be mentioned. Various polyvalent metal ion impurities can be introduced into the high silver chloride grains having a silver bromide-rich region used in the present invention in the process of emulsion grain formation or physical ripening. Examples of compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or Group VIII elements iron, ruthenium,
Examples thereof include salts or complex salts of rhodium, palladium, platinum and the like. Particularly, the above Group VIII elements can be preferably used. The polyvalent metal ion most preferably used in the present invention is 10 ⁻⁸ to 10 ⁻⁵ mol of iridium compound and 10 ⁻⁹ to 10 ⁻⁴ mol of iron compound per mol of silver.
It is preferable to contain the same in order to further enhance the effect of the present invention.

In the present invention, the use of the cyan dye-forming coupler represented by formula (I) exerts a remarkable effect in improving the fastness of a cyan color image and improving the color forming property. However, there arises a problem that the sensitization is lowered or the fog is increased during long-term storage of the photographic material. When various possible factors were examined in order to investigate the cause, it was revealed by adding at least one compound selected from the general formulas (II), (III) and (IV) to the cyan coupler-containing emulsion layer. Improved effect was obtained. Further, by setting the pH of the base paper of the paper support to 5 to 9 by the method according to the present invention, the above-mentioned improvement effect is further enhanced, and the performance almost equal to the above problem can be reached in practical use. did it.

Further, a high-silver chloride emulsion having a silver chloride content of 90 mol% or more, particularly an emulsion having a silver bromide-rich region in the vicinity of the apex of grains (referred to as apex-type emulsion) used in the present invention is used. It has been found that the improvement effect of the present invention is effectively exhibited when applied to each emulsion layer. It is preferable that this emulsion is further applied to another magenta or cyan coupler-containing emulsion layer in order to improve rapid processing property or color reproducibility.

Other silver halides used in the present invention include silver chloride, silver bromide, and silver bromide.
Although (iodo) silver chlorobromide, silver iodobromide, etc. can be used, especially for the purpose of rapid processing, the content of silver chloride substantially free of silver iodide is 90 mol% or more, and further 95%. It is preferable to use a silver chlorobromide or silver chloride emulsion of 98% or more.

In the light-sensitive material of the present invention, a hydrophilic colloid layer for the purpose of improving image sharpness and the like, a dye decolorizable by treatment described in European Patent EP0,337,490A2, pages 27-76. (Among others, an oxonol dye) is added so that the optical reflection density of the light-sensitive material at 680 nm is 0.70 or more, and dihydric alcohols (for example, trimethylol) are added to the water-resistant resin layer of the support. It is preferable to contain 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with ethane or the like.

High boiling organic solvents for photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention are water-immiscible compounds having a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher, and are good couplers. Any solvent can be used. The melting point of the high boiling point organic solvent is preferably 80 ° C. or lower. The boiling point of the high-boiling organic solvent is preferably 160 ° C or higher, more preferably 170 ° C or higher.

Details of these high-boiling point organic solvents are described in JP-A-62-215272, page 137, lower right column.
See page 144, upper right column.

Cyan, magenta or yellow couplers are also loadable latex polymers in the presence or absence of the above-mentioned high boiling organic solvents (see, for example, US Pat.
No. 4,203,716) or dissolved with a water-insoluble polymer and an organic solvent-soluble polymer, and emulsified and dispersed in a hydrophilic colloid aqueous solution.

The homopolymers or copolymers described on pages 12 to 30 of US Pat. No. 4,857,449 and International Publication WO88 / 00723 are preferably used, more preferably a methacrylate-based or acrylamide-based polymer, particularly Use of an acrylamide polymer is preferable in terms of color image stabilization and the like.

Further, in the light-sensitive material according to the present invention, a magenta dye coupler and a compound represented by the general formula (II) or (III) of the present invention can be used.
It is preferable to use a compound selected from and (IV). In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, the compound (F) which chemically bonds to the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or after the color development processing. It is possible to use the compound (G), which is chemically bonded to the remaining oxidant of the aromatic amine color developing agent to form a chemically inactive and substantially colorless compound, simultaneously or alone, for example, after processing. Is preferable in preventing stain generation and other side effects due to the formation of a coloring dye by the reaction of the coupler with the color developing agent remaining in the film or the oxidant thereof during storage.

Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention has an anti-mold property as described in JP-A-63-271247. It is preferable to add an agent.

As a support used in the light-sensitive material of the present invention, a white polyester support or a layer containing a white pigment for a display is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to further improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. Especially, the transmission density of the support is 0.35 ~ so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set it in the range of 0.8.

The light-sensitive material of the present invention may be exposed to visible light or infrared light. The exposure method may be low illuminance exposure or high illuminance short time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 −4 seconds is preferable.

Further, upon exposure, US Pat. No. 4,880,72
It is preferable to use the band stop filter described in No. 6. As a result, the light color mixture is removed, and the color reproducibility is significantly improved.

The exposed light-sensitive material may be subjected to a conventional color developing process, but for the purpose of rapid processing, it is preferable to carry out a bleach-fixing process after color developing. In particular, since the high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering.

Silver halide emulsions and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied to the light-sensitive material according to the present invention, and processing methods applied to process the light-sensitive material. The following patent publications, particularly European Patent EP0,355,660A2 (JP-A-2-395)
Those described in No. 44) are preferably used.

[0121]

[Table 1]

[0122]

[Table 2]

[0123]

[Table 3]

[0124]

[Table 4]

[0125]

[Table 5]

As the cyan coupler, the cyan coupler represented by formula (I) of the present invention and the diphenylimidazole type cyan coupler described in JP-A-2-33144, European Patent
3-Hydroxypyridine cyan couplers described in EP0,333,185A2 (among others, couplers (42) listed as specific examples are 4-equivalent couplers with a chlorine-releasing group to make them 2-equivalent, and couplers (6)). And (9) are particularly preferable) and the cyclic active methylene cyan couplers described in JP-A No. 64-32260 (coupler examples 3, 8, and 34 listed as specific examples are particularly preferable). May be.

A method for processing a silver halide color light-sensitive material using a high silver chloride emulsion having a silver chloride content of 90 mol% or more is described in JP-A-2-207250, page 27, upper left column to page 34, upper right. The method described in the section is preferably applied.

[0128]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these.

(Preparation of emulsion) 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added.
Was added. An aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.15 mol of sodium chloride and 0.05 mol of potassium bromide were added and mixed at 66 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.80 mol of silver nitrate and an aqueous solution containing 0.60 mol of sodium chloride and 0.20 mol of potassium bromide were added and mixed at 66 ° C. with vigorous stirring. After the addition of the aqueous solution of silver nitrate and the aqueous solution of alkali halide was completed, the temperature was lowered to 40 ° C. for desalting and washing with water. Furthermore, 90.0 g of lime-processed gelatin was added, and p was added using sodium chloride.
After adjusting Ag to 7.2, 60.0 mg of the red-sensitive sensitizing dye shown in Table 8
And 4.0 mg of triethylthiourea were added for optimum chemical sensitization at 50 ° C. The silver chlorobromide emulsion thus obtained was designated as Emulsion A.

Next, 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added. To this aqueous solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride were added and mixed at 66 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.78 mol of silver nitrate and an aqueous solution containing 0.78 mol of sodium chloride were added and mixed at 66 ° C. with vigorous stirring. After the addition of the silver nitrate aqueous solution and the alkali halide aqueous solution is completed, 40 ° C
The temperature was lowered to desalination and washing with water. Furthermore, 90.0 g of lime-processed gelatin was added, and pAg was adjusted to 7. with sodium chloride.
After adjusting to 2, the same red-sensitive sensitizing dye as Emulsion A 6 mg
And 4.0 mg of triethylthiourea were added for optimum chemical sensitization at 50 ° C. The silver chloride emulsion thus obtained was designated as Emulsion B.

Next, 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added.
While stirring vigorously, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride were added to this aqueous solution.
The mixture was added and mixed at 0 ° C. Subsequently, an aqueous solution containing 0.78 mol of silver nitrate and an aqueous solution containing 0.78 mol of sodium chloride were added and mixed at 66 ° C. with vigorous stirring. One minute after the addition of the aqueous silver nitrate solution and the aqueous alkali halide solution was completed, 60.0 mg of the same red-sensitive sensitizing dye as in Emulsion A was added. After keeping at 56 ° C for 10 minutes, the temperature was lowered to 40 ° C, and desalting and washing were performed. After further adding 90.0 g of lime-processed gelatin and dissolving at 50 ° C, a silver chlorobromide fine grain emulsion (silver bromide content: 75 mol%, silver content:
0.02 mol, average particle size 0.05 μm) and added for about 20 minutes, then adjust the pAg to 7.2 with sodium chloride,
Optimal chemical sensitization was performed at 50 ° C by adding 4.0 mg of triethylthiourea. The thus obtained silver chlorobromide emulsion (silver bromide content: 1.5 mol%) was designated as emulsion C.

Next, 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added.
The aqueous solution containing 0.2 mol of silver nitrate and the aqueous solution containing 0.2 mol of sodium chloride were stirred vigorously.
The mixture was added and mixed at 0 ° C. Subsequently, an aqueous solution containing 0.78 mol of silver nitrate and an aqueous solution containing 0.78 mol of sodium chloride and 4.2 mg of potassium ferrocyanide are stirred vigorously at 66 ° C.
Was added and mixed. One minute after the addition of the aqueous silver nitrate solution and the aqueous alkali halide solution was completed, 60.0 mg of the same red-sensitive sensitizing dye as in Emulsion A was added. After keeping at 56 ℃ for 10 minutes, 40 ℃
The temperature was lowered to desalination and washing with water. Further, 90.0 g of lime-processed gelatin was added and dissolved at 50 ° C., and then a silver chlorobromide fine grain emulsion (silver bromide content: 75 mol%, silver amount: 0.02 mol, average grain size: 0.05 μm, iridium ion was converted to hexachloroiridium ( VI) equivalent to potassium acid, containing 0.91 mg)
After 20 minutes, the pAg was adjusted to 7.2 with sodium chloride, 4.0 mg of triethylthiourea was added, and optimal chemical sensitization was performed at 50 ° C. The thus obtained silver chlorobromide emulsion (silver bromide content: 1.5 mol%) was designated as Emulsion D.

With respect to the silver halide emulsions A to D thus obtained, the grain shape, grain size and grain size distribution were determined from electron micrographs. All of these silver halide grains are cubic and have a grain size of 0.
The 72 μm coefficient of variation was 0.08. The particle size is represented by the average value of the diameter of the circle equivalent to the projected area of the particle, and the particle size distribution is the standard deviation of the particle size divided by the average particle size.

Then, the halogen composition of the emulsion grains was determined by measuring the X-ray diffraction from the silver halide crystals. The diffraction angle from the (200) plane was measured in detail using a monochromatic CuKα ray as the radiation source. A diffraction line from a crystal having a uniform halogen composition gives a single peak, whereas a diffraction line from a crystal having a localized phase having a different composition gives a plurality of peaks corresponding to those compositions. The halogen composition of the silver halide constituting the crystal can be determined by calculating the lattice constant from the diffraction angle of the measured peak. The average silver bromide content on the surface of emulsion grains was measured by the XPS method. As a result, the halogen composition of Emulsion A was a uniform grain with a silver chloride content of 75% and the surface silver bromide content was 25%.
Met. The halogen composition of emulsion B was 100% uniform grains of AgCl, and the silver bromide content on the surface was 0%. In addition, in each of emulsions C and D, a broad diffraction pattern in which the center is at 30% of silver bromide and the skirt is extended to around 40% of silver bromide in addition to the main peak at 100% of AgCl can be observed. The average silver bromide content on the surface was 3%.

(Preparation of paper support) 70 parts LBKP and LBS
P30 parts of wood pulp using a disc refiner C
Alketene dimer (made by Dick Hercules, Accorpel 1 as a neutral sizing agent, beaten to SF290cc
2) 1.0 part, anionic polyacrylamide (Polystron 194-7 manufactured by Arakawa Chemical Industry Co., Ltd.) 1.0 part, cationic polyacrylamide (Polystron 705 manufactured by Arakawa Chemical Industry Co., Ltd.) 0.5
And 0.3 parts of polyamide polyamine epichlorohydrin (Kaimen 557, manufactured by Dick Hercules) were added at an absolutely dry weight ratio to the pulp. Then, using a Fourdrinier paper machine, paper was made into a base paper having a basis weight of 170 g / m ² and a thickness of 165 μm. The base paper prepared as described above is referred to as (A).
The pH value of the base paper (A) was 6.4 when measured by the hot water extraction method of JIS-P-8133.

0.6 part of an epoxidized fatty acid amide (manufactured by Modern Chemical Industry Co., Ltd., NS-715) as a neutral sizing agent on the same beaten pulp as that of the base paper (A), anionic polyacrylamide (Polystron 194-7 manufactured by Arakawa Chemical Industry Co., Ltd.) ) 1.2 parts, aluminum sulfate 1.0 part, NaOH 0.9 part, cationized starch
All 1.0 parts were added in an absolutely dry weight ratio to pulp. Then, the same as the base paper (A), the basis weight 170g / m ² , thickness
A 165 μm base paper (B) was produced. The pH value of the base paper (B) was 7.3.

Next, using the same beaten pulp as the base paper (A), 1.0 part of sodium stearate and anionic polyacrylamide (manufactured by Arakawa Chemical Industry Co., Ltd., Polystron 194-7)
1.0 part and 1.5 parts of aluminum sulfate were added in an absolutely dry weight ratio to the pulp. Then, in the same manner as the base paper (A), a base paper having a basis weight of 170 g / m ² and a thickness of 166 μm was made into a paper, and used as the base paper (C). The pH value by the hot water extraction method was 3.8. After adding aluminum sulfate to the base paper (C), a base paper (D) was prepared in the same manner as the base paper (C) except that 0.5 part of sodium aluminate was added. The pH value by the hot water extraction method is
It was 4.7.

Polyethylene with a density of 0.94 / cm ² containing 10% by weight of titanium oxide was extruded and coated on the surface (the surface on which the light-sensitive material is coated) of each of the above-mentioned base papers (A) to (D) by a thickness of 35 μm, Paper supports (A) to (D) were prepared.

(Preparation of Photosensitive Material) After the surface of the paper support (A) prepared as described above was subjected to corona discharge treatment, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constitutions were prepared. The layers were applied to prepare a multilayer color photographic paper having the layer constitution shown below. The coating liquid was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.
0 g, color image stabilizer (Cpd-2) 7.5 g, color image stabilizer (Cpd-3) 16.0 g
Is dissolved in 25.0 g of solvent (Solv-1), 25.0 g of solvent (Solv-2) and 180 cc of ethyl acetate, and this solution is added to 1000 g of a 10% gelatin aqueous solution containing 60 cc of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid. Emulsified and dispersed to prepare an emulsified dispersion A. On the other hand, a silver chlorobromide emulsion (cubic, a 3: 7 mixture of a large size emulsion having an average grain size of 0.88 μm and a small size emulsion of 0.70 μm (silver molar ratio). The variation counts of the grain size distribution were 0.08 and 0.10, respectively. , Each emulsion 0.3 silver bromide
(Containing mol% localized on a part of the particle surface) was prepared. The blue-sensitive sensitizing dyes A and B shown below were added to the emulsion in an amount of 2.0 × 1 for each large-sized emulsion per mol of silver.
^0-4 , or 2.5 × for small emulsions
10 ⁻⁴ mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution for the first layer having the composition shown below.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Further, Cpd-14 and Cpd-15 were added to each layer so that the total amount was 25.0 mg / m ² and 50.0 mg / m ² , respectively. The following spectral sensitizing dyes were used in each photosensitive emulsion layer.

[0142]

[Table 6]

[0143]

[Table 7]

[0144]

[Table 8]

Blue-sensitive emulsion layers, green-sensitive emulsion layers, red-sensitive emulsion layers
1- (5-methylureidophenyl) -5-mel for the emulsion layer
Captotetrazole was applied to 1 mol of each silver halide
8.5 x 10^-FiveMole, 7.7 × 10^-FourMole, 2.5x
10^-FourMol added. In addition, a blue-sensitive emulsion layer and a green-sensitive emulsion
For the layers, 4-hydroxy-6-methyl-1,3,3a, 7-tetraza
1 x 1 of indene per mol of silver halide
0^-Four2 x 10 with moles^-Four Mol added. Irradiation
In order to prevent this, the following dyes are added to the emulsion layer
Represented) was added.

[0146]

[Chemical 41]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

[0148]

[Table 9]

[0149]

[Table 10]

[0150]

[Table 11]

[0151]

[Table 12]

[0152]

[Chemical 42]

[0153]

[Chemical 43]

[0154]

[Chemical 44]

[0155]

[Chemical 45]

[0156]

[Chemical 46]

[0157]

[Chemical 47]

[0158]

[Chemical 48]

[0159]

[Chemical 49]

Based on the above layer constitution, an emulsion of the fifth layer (red sensitive emulsion layer), a cyan coupler, and general formulas (II) to (IV)
Samples 101 to 113 in which the compound of Example 1 and the paper support were changed as shown in Table 13 were prepared.

Cyan couplers and general formulas (II) to
The emulsion dispersion containing the compound of (IV) contained 10 g of a cyan coupler, 5.5 g of an ultraviolet absorber (UV-2), and a color image stabilizer (C
pd-1) 9.0 g, the same (Cpd-10) 4.5 g, the same (Cpd-11) 4.
5 g, the same (Cpd-12) 0.3 g, compounds of the general formulas (II) to (IV) 0.3 g, solvent (Solv-1) 0.3 g, solvent (Solv-6)
A solution obtained by heating 6.7 g and 20 ml of ethyl acetate to 50 ° C. was prepared by emulsifying and dispersing in 80 g of a gelatin solution containing 8 ml of a 1% sodium dodecylbenzenesulfonate aqueous solution.

Samples 101 to 103 containing no compounds of the general formulas (II) to (IV) were also prepared by emulsifying and dispersing in the same manner as above.

[0163]

[Table 13]

A sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) was used for each sample, and a three-color separation filter for sensitometry (SP-1, SP-2, manufactured by the same company).
The gradation exposure of SP-3) was applied. The exposure at this time was performed so that the exposure amount was 250 CMS with the exposure time of 0.1 seconds. The exposed sample was subjected to continuous processing (running test) using a paper processor using a liquid having the following processing steps and processing compositions until the tank was replenished with twice the tank capacity for color development.

[0165]

[Table 14]

The composition of each processing liquid is as follows.

[0167]

[Table 15]

[0168]

[Table 16]

The reflection density of each of the B, G and R colors was measured for the samples which had undergone the treatment, and their characteristic curves were obtained. From this characteristic curve, the logarithmic value of the reciprocal of the exposure amount at which the density of the minimum density (Dmin) +0.5 is obtained, is taken as the sensitivity, and is shown as a difference from each sample with respect to the sensitivity of the sample 101 for the red sensitive layer as a reference. .. A + value means a high feeling and a − value means a low feeling.
In addition, using a sample obtained by separately performing the above-mentioned treatment,
The sample was stored for 6 months under the dark condition of 60 ° C. and 70% RH, and the change in stain (cyan density) and the density of the red filter exposed area (cyan color density) from the initial density D _R = 2.0 were reduced Δ.
D _R was measured.

Further, the long-term raw storage stability of the prepared sample before the exposure treatment was evaluated by the same sensitivity value as described above after the change of fog and the sensitivity change after 3 months under the storage condition of 25 ° C. and 55% after the preparation of the sample. It showed with. These results are summarized in Table 1
7 shows.

[0171]

[Table 17]

From these results, it is understood that by using the cyan coupler of the present invention, the robustness of the cyan color image is enhanced, and at the same time, the sensitivity is increased and the cyan color developability is improved. However, as seen in Samples 103 to 104, the fog change after long-term storage of the raw sample remains somewhat inferior. In this respect, the emulsions, compounds according to the invention,
Samples 105 to 111 in which the supports were combined at the same time unexpectedly solved these problems all at once. In particular, Samples 106 to 111 containing the compound of the general formula (II) have the largest degree of improvement in stain among the color image storability and are preferable. In addition, Samples 108 to 110 of the present invention using the silver halide emulsion D having a silver bromide-rich phase and Sample 112 using the same emulsion D but not using the support of the present invention (for comparison).
Comparing the door, it can be seen that the direction of the sample of the present invention is excellent for raw stock storability (fogging change) and dye stability ([Delta] D _R and stain).

[0173]

INDUSTRIAL APPLICABILITY The silver halide color photographic light-sensitive material of the present invention forms a dye image which is excellent in color image fastness and long-term storage after processing and is excellent in color development. Further, it is possible to provide a silver halide color photographic light-sensitive material in which the long-term storage stability of a raw sample is further improved even before processing.

Claims (1)

[Claims] 1. At least one light-sensitive silver halide emulsion layer coated on a paper support comprises at least one cyan dye forming coupler represented by the following general formula (I) and the following general formula (II): ), (III) or (IV) and at least one compound and a silver halide emulsion having a silver chloride content of 90 mol% or more, and the pH of the base paper of the paper support is 5 or more and 9 or less. A silver halide color photographic light-sensitive material characterized by the above. [Chemical 1] In the general formula (I), R ₁ has at least 7 carbon atoms.
Represents an alkyl group having R ₂ , R ₂ represents an alkyl group having 2 to 15 carbon atoms, L represents a simple bond or a divalent linking group, and Z is a hydrogen atom or is removable upon coupling with a developing agent. Represents a group or atom. General formula (II) R ₂₁ -(-A _n -)-X ₁ General formula (III) In formulas (II) and (III), R ₂₁ and R ₂₂ each represent an aliphatic group, an aromatic group or a heterocyclic group. X ₁ represents a group which reacts with an aromatic amine developing agent to leave, and A represents a group which reacts with an aromatic amine developing agent to form a chemical bond. n represents 1 or 0. B is a hydrogen atom, an aliphatic group,
It represents an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group, and Y ₁ represents a group which promotes the addition of the aromatic amine developing agent to the compound of the general formula (III). Where R
₂₁ and X ₁ , Y ₁ and R ₂₂ or B may be bonded to each other to form a cyclic structure. In the general formula (IV) R ₃₀ -Z ₁ formula, R ₃₀ represents an aliphatic group, an aromatic group or a heterocyclic group. Z ₁ represents a nucleophilic group or a group which decomposes in the photosensitive material to release a nucleophilic group.