JPS6275449A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To inhibit yellow staining by incorporating a 3-anilino-5-pyrazolone type magenta coupler, a specified compound and a cyclic ether compound. CONSTITUTION:A 3-anilino-5-pyrazolone type magenta coupler, a compund represented by the formula and a cyclic ether compound are incorporated into a silver halide color photographic sensitive material in the from of drops of oil in the presence or absence of an og. solvent having a high b.p. In the formula, R1 is H, alkyl, alkenyl, aryl or a heterocyclic group, each of R2, R3, R5 and R6 is H, halogen, hydroxy, alkyl, alkenyl, aryl, alkoxy or acylamino and R4 is alkyl, hydroxy, aryl or alkoxy. Thus, yellow staining is inhibited.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material containing a 3-anilino-5-pyrazolone type magenta coupler, a phenol compound or a phenol ether compound, and a cyclic ether compound as oil droplets.

Conventionally, by imagewise exposing a silver halide color photographic light-sensitive material and subjecting it to color-forming fjl, a coupling reaction occurs between the oxidized product of the aromatic primary amine present carrier and the color-forming agent, such as indophenol, It is well known that indoaniline, indamine, azomethine, phenoxazine, phenazine, and similar pigments are produced to form color images. In such photographic systems, a subtractive color reproduction method is usually adopted, and color forming agents having additional colors, namely yellow, magenta and A color silver halide photographic material containing a coupler that develops a cyan color is used.

Among these, magenta color image forming couplers include:
5-pyrazolone, cyanoacetophenone, indashilon, pyrazolobenzimidazole, and pyrazolotriazole couplers are known, but the ones that have been widely used as magenta couplers have been based on the spectral absorption characteristics of the produced dye, heat, and light. Most of the compounds were 5-pyrazolones due to their fastness to UV rays and ease of synthesis of couplers. Among the 5-pyrazolone magenta couplers, 3-anilino-5
- Pyrazolone type magenta couplers are preferable in terms of color reproduction because they cause less unnecessary absorption of dyes formed therefrom, and have been used as magenta couplers in color light-sensitive materials, particularly print-type color light-sensitive materials.

The 3-anilino-5-pyrazolone type magenta coupler is
Although this is an excellent magenta coupler, the light fastness of the resulting dye is still insufficient, and efforts have been made to increase the light fastness of color images by adding certain stabilizer compounds, but this is still not sufficient. There wasn't.

On the other hand, changes in color images due to moist heat and yellow stains are major problems for color photosensitive materials, but US Pat.
No. 540,657 describes a color light-sensitive material in which a magenta coupler is dissolved in a coupler solvent having a terminal epoxy group and dispersed and coated to increase the fastness of color images to moist heat and reduce yellow stain.

However, as is clear from the description in the patent, by using a coupler solvent having an epoxy terminal group,
Although the yellow stain caused by moist heat is improved to some extent, the light fastness of the color image is insufficient even when the stabilizer compound described in the patent is used.

By using a 3-anilino-5-pyrazolone type magenta coupler, a stabilizer compound represented by the above-mentioned general formula [A], and a cyclic ether compound together as oil droplets, we have achieved In addition to increasing fastness and suppressing yellow stain, it has been found that the lightfastness of color images is improved to an extent unexpected from conventionally known techniques.

The present invention provides a silver halide color photosensitive material in which a 3-anilino-5-pyrazolone type magenta coupler, a compound of general formula [A], and a cyclic ether compound are formed as oil droplets in the presence or absence of an appropriate high-boiling organic solvent. It is characterized by being contained in.

As the 3-anilino-5-pyrazolone type magenta coupler used in the present invention, those having the following general formula are preferably used.

Ar Ar: A phenyl group specifically substituted with a phenyl group.

Substituents include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfonamido group, and an acylamino group, and the phenyl group represented by Ar has 2 It may have one or more substituents.

Specific examples of substituents are listed below.

Halogen atom: chlorine, bromine, fluorine Alkyl group: Methyl group, ethyl group, 1so-propyl group, butyl group, t-butyl group, t-pentyl group, etc., but alkyl groups having 1 to 5 carbon atoms are particularly preferred .

Alkoxy group: methoxy group, ethoxy group, butoxy group,
Examples include 5ec-butoxy group, 1so-benpuroxy group, and particularly preferred is an alkoxy group having 1 to 5 carbon atoms.

7-aryloxy group, cophenoxy group, β-isotoxy group, etc., but this aryl moiety may further have a substituent similar to that of the phenyl group represented by Ar.

Alkoxycarbonyl group: Refers to the above-mentioned carbonyl group with an alkoxy group attached, preferably a methoxycarbonyl group or a pentyloxycarbonyl group having 1 to 5 carbon atoms.

Alkylcarbamoyl groups such as carbamoylurbamoyl groups Sulfamoyl groups: Alkylsulfamoyl groups such as sulfamoyl groups, methylsulfamoyl groups, dimethylsulfamoyl groups, ethylsulfamoyl groups Sulfonyl groups: methanesulfonyl groups, ethanesulfonyl groups, Alkylsulfonyl group such as butanesulfonyl group Sulfonamide group: Alkylsulfonamide group such as methanesulfonamide group, toluenesulfonamide group, arylsulfonamide group Acylamino group: Acetamin group, pivaloylamino group, benzamide group, etc. Particularly preferably a halogen atom Of these, chlorine is the most preferred.

Y: represents a hydrogen atom or a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent.

Specifically, for example, a 5- or 6-membered ring is formed with an atom selected from carbon atoms, oxygen atoms, nitrogen atoms, and ionic atoms together with halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, and aryl atoms. represents the atomic group required to do so. ) Specific examples are given below.

Halogen atom, chlorine, bromine, fluorine Alkoxy group: Ethoxy group, benzyloxy group, methoxyethylcarba7ylmethoxy group, tetradecylcarba/lyloxy group: Phenoxy group, 4-methoxyphenoxy group, 4-nitronenoxy group, etc. Acyloxy Groups: acetoxy group, myristoyloxy group, benzoyloxy group, etc. Arylthio group: phenylthio group, 2-butoxy-5-
Alkylthio groups such as octylphenylthio group, 2.5-dihexyloxyphenylthio group: methylthio group, octylthio group, hexadecylthio group, benzylthio group, 2-(diethylamino)ethylthio group, ethoxycarbonylmethylthio group,
Ethoxyethylthio group, phenoxyethylthio group, triazolyl group, tetrazolyl group, etc. X: Halogen atom, alkoxy group, alkyl group Specific examples are listed below.

Halogen atoms: chlorine, bromine, fluorine alkoxy groups: methoxy group, ethoxy group, butoxy group,
Alkoxy groups having 1 to 5 carbon atoms such as sec-butoxy group and iso-pentyloxy group are preferred.

Alkyl group: An alkyl group having 1 to 5 carbon atoms is preferable, such as a methyl group, an ethyl group, an isO-propyl group, a butyl group, a t-butyl group, and a t-pentyl group.

Particularly preferred is a halogen atom, with chlorine being particularly preferred.

R: represents a group capable of substituting Wl on the benzene ring, n represents an integer of 1 or 2, and when n is 2, R may be the same or different. Examples of the group that can be substituted on the benzene ring represented by R include a halogen atom and O R''.

R', R", and R" may be the same or different, and each represents a hydrogen atom or an alkyl group, alkenyl group, or aryl group that may each have a substituent. Among these, R'CONH-1R'5O2 is preferable.
Specific examples of magenta couplers are shown below NH-1, but the invention is not limited thereto.

The following margin is 1 sen Shiba Σ Zeng! pusoto+ 1 1+ 1Σ
Σ Shiba Shiba Shiba M 1
2 -3CI2H25 to 4-13 -3CH2CotCtHsM-14-
3CH2COOH M-16-3CHICONH.

M-17-3CH, CH, OC2Hs M -, t8 -8CH2CH20HM-t9
-8CH, CH2NH8O2CH3(JU)i3 So, C4H.

M-340° or less margin The 3-7nilino-5-pyrazolone type magenta coupler used in the present invention preferably has an arylthio group or an alkylthio group as the leaving component Y.

The color image stabilizer used in the present invention is represented by the general formula [A].

General formula [A] In the formula, R1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R2, ・R3, R
5 and R6 each represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acylamino group, and R4 represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group.

Further, R1 and R2 may be ring-closed with each other to form a 5- or 6-membered ring, in which case R4 represents an alkyl group or an alkoxy group, and when this ring forms spiro ring 1, R4
does not represent a hydroxy group, an alkyl group, or an alkoxy group. Further, R3 may form an ff ring to form a 5-membered hydrocarbon ring, in which case R1 represents an alkyl group, an aryl group, or a heterocyclic group. However, the case where R1 is a hydrogen atom and R-+ is a hydroxy group is excluded.

Further, when R1 represents an alkyl group or an alkenyl group and R4 represents an alkoxy group, two groups among R2, R3, R5, and R6 cannot be an alkoxy group at the same time.

In the general formula [A], R1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Among these, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an n- Octyl group, tert-
Straight chain or branched alkyl groups such as octyl group and hekylydecyl group can be mentioned. Examples of the alkenyl group represented by R1 include allyl, hexenyl, and octenyl groups. Furthermore, examples of the aryl group for R1 include phenyl and naphthyl groups. Further, specific examples of the heterocyclic group represented by R1 include a tetrahydropyranyl group and a pyrimidyl group. Each of these groups can have a substituent, for example, an alkyl group having a substituent such as a benzyl group, an ethoxymethyl group, an aryl group having a substituent such as a methoxyphenyl group, a chlorophenyl group, a 4-hydroxy-3,5-
Examples include dibutylphenyl group.

In general formula [A], R2, R3, R5J5 and R6
represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acylamino group; Examples include the same groups as alkenyl and aryl groups. Examples of the halogen atoms include fluorine, chlorine, and bromine. Furthermore, specific examples of the alkoxy groups include a methoxy group, 11-xy, and the like. Furthermore, the above acylamide is represented by R'CONH-, where R' is an alkyl group (e.g., methyl, ethyl, lopropyl, n-butyl, n-octyl, tert-octyl, benzyl, etc.) , alkenyl groups (e.g., allyl, octenyl, oleyl, etc.), aryl groups (e.g., phenyl, methoxyphenyl, naphthyl, etc.), or hezolocyclic groups (e.g., pyridyl, pyrimidyl). can.

Further, in the general formula [A], R4 represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group.
The same alkyl groups and aryl groups as shown in 1 can be specifically mentioned. As for the alkenyl group of R4, the same alkoxy groups mentioned above for R2, R3, Rs and Rs can be mentioned.

Examples of the ring formed by R1 and R2 together with a benzene ring by closing each other include chroman, coumaran, and methylenedioxybenzene.

Furthermore, examples of the ring formed by R3 and R4 together with a benzene ring include indane. These rings may have substituents (eg, alkyl, alkoxy, aryl).

In addition, a spiro compound may be formed by using the atom in the ring formed by [<1 and R2, or R3 and R4 to close the ring as a spiro atom, or a bis compound may be formed by using R2, R4, etc. as a linking group. It's okay.

Among the phenol compounds or phenyl ether compounds represented by the general formula [A], preferred are:
It is a biindane compound having four R, O- groups (R represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group), and is particularly preferably represented by the following general formula [A-,
1].

Below is the general formula [A-1] in which R is an alkyl group (e.g. methyl, ethyl, propyl, n-octyl, tert-octyl, benzyl, hexadecyl), an alkenyl group (e.g. allyl, octenyl, oleyl), an aryl group (e.g. allyl, octenyl, oleyl), Examples include groups represented by phenyl, naphdylne, or heterocyclic groups (e.g., tetrahydropyranyl, pyrimidyl).R9#
and R+.

are hydrogen atoms, halogen atoms (e.g. fluorine, chlorine,
bromine), an alkyl group (e.g. methyl, ethyl, n-butyl, benzyl), an alkoxy group (e.g. allyl, hexenyl, octenyl), or an alkoxy group (e.g. methoxy, ethoxy, benzyloxy), where R+1 is a hydrogen atom, alkyl groups (e.g. methyl, ethyl, n-butyl, benzyl), alkenyl groups (e.g. 2-propenyl, hexenyl, octenyl), or aryl groups (e.g.
For example, phenyl, methoxyphenyl, chlorphenyl,
(naphthyl).

The compound represented by the general formula [A] is disclosed in U.S. Patent No. 3
, No. 935,016, No. 3,982,944, 14
No. 4.254,216, JP-A-55-21004,
No. 54-145530, British Patent Publication No. 2,077.4
No. 55, No. 2,062,888, U.S. Patent No. 3,76
No. 4,337, No. 3,432,300, No. 3,5
No. 74,627, No. 3,573,050, Japanese Unexamined Patent Publication No. 1973
2-1522254, No. 53-20327, No. 53-
No. 17729, No. 55-6321, British Patent No. 1,
It also includes compounds described in No. 347,556, Publication No. 2,066.975@, Equity [54-12337M, Publication No. 48-31625, U.S. Patent No. 3,700,455, etc.].

The amount of the compound represented by the general formula [A] used is preferably 5 to 300 mol%, more preferably 10 to 200 mol%, based on the magenta coupler.

Typical specific examples of the compound represented by the general formula CA1 are shown below.

Below margin type (1) RI type (2) Name Eve (3) Type (4) Type (5) Type (6) Ri, Eve (7) Type (2) Below margin type (4) Type (5) Type (6) Below Margin A-7 Below Margin The cyclic ether compound in the present invention is preferably 3-6H. Further, the number of oxygen atoms contained in one ring is preferably 1 to 2.

A cyclic ether compound having three members is preferably represented by the following general formula.

In the formula, R+, R2, R3, R4 are selected from the following.

:Hydrogen atom:Halogen atom (e.g. chlorine, bromine, fluorine, etc.) :Light chain or branched alkyl group (preferably one or more carbon atoms)
40, e.g. methyl, ethyl, 1-propyl, 2-ethylhexyl, lauryl, stearyl (8), even if it has a mulberry group. Examples of substituting groups include the above-mentioned halogen atoms, alkoxy groups (such as methoxy, butoxy, stearyl AI', etc.), and aryloxy groups (
(e.g., phenoxy, etc.), aryl groups (e.g., phenyl, etc.), arylthio groups (e.g., phenylthio, etc.), aralkylthio groups (e.g., benzylthio, etc.), amino groups (e.g., piperidino, dimethylamino, etc.), acyloxy groups (e.g., acetoxy, benzoyloxy, etc.). , furanoyloxy, cyclohexanoyloxy, etc.), alkoxycarbonyl groups (e.g., butoxycarbonylnyl, etc.), cycloalkoxycarbonyl groups (e.g., cyclohexyloxycarbonyl, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl, etc.), oxalyloxy groups (e.g., ethoxyoxalyloxy, etc.), carbamoyloxy groups (e.g., hexylcarbamoyloxy, etc.), sulfonyloxy groups (e.g., 1-nylsulfonyloxy, etc.), amide groups (e.g., benzoylamino groups, etc.), ureido groups (e.g., phenylureido, etc.) ), aminosulfamoyl groups (e.g. dimethylaminosulfur/l), etc.

The dichloroalkyl group (preferably having 3 to 6 carbon atoms, such as cyclopropyl, cyclohexyl, etc.) may further have a substituent, and examples thereof include the above-mentioned substituents for the alkyl group.

The neararyl group (eg, phenyl, etc.) may have the same substituents as the alkyl group.

:Alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.), may have the same substituents as in the case of alkyl group.

: Carbamoyl group (for example, l-nylcarbamoyl, etc.) Niacyl group (for example, acetyl, p-methoxybenzoyl, etc.) Nidiano group Furthermore, R1 and R2 and/or R1 and R4 may be bonded to form a ring.

Exemplary compounds are shown next, but the present invention is not limited thereto.

Margin below Margin below 34　　-　・ 0 CH.

(+1″12-hiti(Umon,),C(λ(shihtsu)?
Sushikushimon2-8shin-%mon2(J(CH:)s'-E
l (-1002 or less margin CH.

What is a cyclic ether compound consisting of 4 members?

It is preferably represented by the following general formula.

In the formula, R1, R2, R3, R4, R5, and R6 are selected from the following.

:Hydrogen atom:Halogen atom (e.g. chlorine, bromine, fluorine, etc.) :Light chain or branched alkyl group (preferably one or more carbon atoms)
40, for example methyl, ethyl, i-propyl, 2-ethylhexyl, lauryl, stearyl, etc.), and may further have an exchange group. Examples of the substituent include the above-mentioned halogen atom, alkoxy L! (e.g. methoxy, butoxy, stearyloxy, etc.), aryl group (e.g. lnoxy, etc.), aryl group (e.g. phenyl group, etc.)
, arylthio group (e.g., phenylthio, etc.), aralkylthio M (e.g., benzylthio, etc.), amino group (e.g., piperidino, dimethylamino, etc.), acyloxy group (e.g., acetoxy, benzoyloxy, furanoyloxy, cyclohexanoyloxy, etc.), alkoxy Carbonyl group (e.g., butoxycarbonyl, cyclohexyloxycarbonyl, etc.), aryloxycarbonyl M (e.g., phenoxycarbonyl, etc.), oxalyloxy group (e.g., ethoxyoxalyloxy, etc.), carbamoyloxy group (e.g., hexylcarbamoyloxy, etc.), sulfonyloxy group (e.g. phenylsulfonyloxy etc.), amide group (e.g. benzoylamino group etc.), ureido group (e.g. phenylureido etc.),
Aminosulfamoyl group (eg, dimedylaminosulfamoyl group), etc.

Nijikuro Aruol 2′! (preferably 3 to 6 carbon atoms, such as cyclopropyl, cyclohexyl, etc.), and may further have a substituent, such as the above-mentioned substituents for the alkyl group.

The neararyl group (eg, phenyl, etc.) may have the same substituents as the alkyl group.

:Alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, etc.), device 1 as in the case of alkyl group! ! ! It may have a group.

: Carbamoyl group (eg phenylcarbamoyl etc.) Niacyl group (eg acetyl, p-meth4dibenzoyl etc.) Nidiano group Furthermore, R1 and R2 and/or R1 and R4 may be bonded to form a ring.

Exemplary compounds are shown next, but the present invention is not limited thereto.

Margin below What is a 5-membered cyclic ether compound?

It is preferably represented by the following general formula.

In the formula, R1, R2, R3, R4, R5, R6, Rn, R
a is selected from the following:

:Hydrogen atom:Halogen atom (e.g. chloro, bromine, fluorine, etc.) :Light chain or branched alkyl W (preferably 1 to 1 carbon atoms)
40. For example, methyl, ethyl, i-propyl, 2-ethylhexyl, lauryl, stearyl, etc.), and may further have a substituent. Examples of substituents include 1, for example, the above-mentioned halogen atom, alkoxy V (e.g. methoxy, butoxy, stearyloxy), aryl A4-S, t (
f't' , acyloxy groups (e.g. acetoxy, benzoyloxy, furanoyloxy, cyclohexanoyloxy, etc.), alkoxycarbonyl groups (e.g. butoxycarbonyl, 2-
ethylhexyloxycarbonyl, etc.), cycloalkoxycarbonyl groups (e.g., cyclohexyloxycarbonyl, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl, etc.), oxalyloxy groups (e.g., ethoxyoxalyloxy, etc.), carbamoyloxy groups (e.g., hexyloxycarbonyl, etc.), carbamoyloxy, etc.), sulfonyloxy groups (e.g. phenylsulfonyloxy, etc.), amide groups (
For example, benzoylamino, etc.), ureido groups (eg, phenylureido, etc.), aminosulfamoyl groups (eg, dimethylaminosulfamoyl, etc.), and the like.

Nidicloalkyl group (preferably having 3 to 6 carbon atoms, e.g. cyclopropyl, cyclohexyl, etc.) may further have MmM, examples of which include the above-mentioned examples of substituents for the alkyl group. .

The neararyl group (eg, phenyl, etc.) may have the same substituents as the alkyl group.

:Alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.), may have the same substituents as in the case of alkyl group.

: Carbamoyl group (eg, phenylcarbamoyl, etc.) Niacyl group (eg, acetyl, ρ-methoxybenzoyl, etc.) Nidiano group Furthermore, R1 and R2, R7 and R8, and/or R1 and R4 may be bonded to form a ring.

Exemplary compounds are shown next, but the present invention is not limited thereto.

Cyclic ether compounds having five members are preferably represented by the following general formula.

In the formula R, R+, R2, R3, R4, Rs, Re are selected from the following.

:Hydrogen atom:Halogen atom (e.g. chlorine, bromine, fluorine, etc.) :Light chain or branched alkyl group (preferably one or more carbon atoms)
40. For example, methyl, ethyl, i-propyl, 2-ethylhexyl, lauryl, stearyl, etc.), and may further have a substituent. Examples of the substituent include the above-mentioned halogen atoms, alkoxy groups (e.g. methoxy, butoxy, stearyloxy, etc.), aryloxy groups (e.g. phenoxy etc.), aryl groups (e.g. phenyl group etc.), arylthio groups (e.g. phenylthio etc.), Aralkylthio groups (e.g., benzylthio, etc.), amino groups (e.g., piperidino, dimethylamino, etc.), acyloxy groups (e.g., acetoxy, benzoyloxy, furanoyloxy, cyclohexanoyloxy, etc.), alkoxycarbonyl groups (e.g., butoxycarbonyl, 2- ethylhexyloxycarbonyl, etc.), cycloalkoxycarbonyl groups (e.g., cyclohexyloxycarbonyl, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl, etc.),
Oxalyloxy group (e.g. ethoxyoxalyloxy etc.), carbamoyloxy group (e.g. hexylcarbamoyloxy etc.), sulfonyloxy group (e.g. phenylsulfonyloxy etc.), amide M (e.g. benzoylamino group etc.), ureido group (e.g. phenylureido etc.) ,
Aminosulfamoyl group (eg, 1 moyl dimethylaminosulfate, etc.), etc.

Alkyl (eg, cyclopropyl, hexyl, etc.) may further have a substituent, examples of which include the above-mentioned substituents for the alkyl group.

A neararyl group (eg, phenyl, etc.) may have an exchange group similar to that of an alkyl group.

:Alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.), may have the same substituents as in the case of alkyl group.

: Carbamoyl group (eg, phenylcarbamoyl, etc.) Niacyl group (eg, acetyl, p-methoxybenzoyl, etc.) Nidiano group Furthermore, R1 and R2 may be combined to form a ring.

Exemplary compounds are shown next, but the present invention is not limited thereto.

Below margin CH2-CHR RR'10'l HH l(l CH3H +o'? CH2Cl H1+
o CHzOC, Hs H+++
cH2ca cQ.

In the following cyclic ether compounds, those having 6 members are preferably represented by the following general formula.

In the formula, R1, R2, R3, R4, R5, R6, R? ,
Ra is selected from the following.

:Hydrogen atom:Halogen atom (e.g. chlorine, bromine, fluorine, etc.) :Light chain or branched alkyl group (preferably one or more carbon atoms)
40, for example methyl, ethyl, i-propyl, 2-ethylhexyl, lauryl, stearyl, etc.), and may further have a substituent. Examples of the substituent include the above-mentioned halogen atoms, alkoxy groups (e.g., methoxy, butoxy, suderyloxy, etc.), aryloxy groups (e.g., phenoxy, etc.), aryl groups (e.g., phenyl group, etc.),
Arylthio groups (e.g., phenylthio, etc.), aralkylthio groups (e.g., pendylthio, etc.), amine groups (e.g., piperidino, dimethylamino, etc.), acyloxy groups (e.g., acetoxy, benzoyloxy, furanoyloxy,
cyclohexanoyloxy, etc.), alkoxycarbonyl groups (e.g. butoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), cycloalkoxycarbonyl groups (
For example, cyclohexyloxycarbonyl, etc.), aryloxycarbonyl group (for example, phenoxycarbonyl, etc.)
, oxalyloxy groups (e.g., ethoxyoxalyloxy, etc.), carbamoyloxy groups (e.g., hexylcarbamoyloxy, etc.), sulfonyloxy groups (e.g., phenylsulfonyloxy, etc.), amide groups (e.g., benzoylamino groups, etc.), ureido groups (e.g., phenylureido) etc.), aminosulfamoyl groups (for example, 1 moyl dimethylaminosulfate, etc.), etc.

A dichloroargyl group (preferably a carbon number of 3 to G, such as cyclopropyl, cyclohexyl, etc.) may further have a substituent, examples of which include the above-mentioned substituents for the alkyl group.

The neararyl group (eg, phenyl, etc.) may have the same substituents as the alkyl group.

:Alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.), may have the same substituents as in the case of alkyl group.

: Carbamoyl group (e.g. phenylcarbamoylniacil group (e.g. acetyl, p-methoxybenzoyl, etc.) Nidiano group Furthermore, R+ and R2 and/or R1 and R4 may combine to form a ring. Also, R3 and R4 Double viscosity.

may be formed.

Exemplary compounds are shown next, but the present invention is not limited thereto.

Margin below + + 8 R: (CHz)zl 1'?
(CH2)3+2 o
(CH2) <+21
(CH2)2C=CH2 Below Margin Among the cyclic ether compounds mentioned above, a preferred group includes at least one ether bond, nistyl bond (e.g. -C○-1-3O20-, amide bond (e.g.)).

-802N) or ureido packing (for example, at least one hydrogen atom is bonded to the carbon atom directly bonded to the oxygen atom in the ring) is preferred.

The cyclic ether compound may be purchased as a commercial product. Alternatively, the compound can be obtained by synthesizing a corresponding compound having a double bond in advance, and then oxidizing the double bond with a carbonizing agent (for example, monoarsenic peroxide). Further, the above-mentioned 6-membered cyclic ether compound is described, for example, in JOC Vol. 36 pH76 (1971
), Macromolecules 1980, p2
52, for example, British Patent No. 867918, Ann 6231) 194 (1
40 can be synthesized by the method described in German Patent No. 1021858.

The 3-anilino-5-pyrazolone type magenta coupler used in the present invention is preferably used in the range of 1X10-3 mol to 1 mol, more preferably 1XIO-2 mol, per 1 Tyl silver halide combined with the coupler. -8X1
0-' mol is preferred.

The amount of the cyclic ether compound of the present invention added is preferably 0.1 to 10, more preferably 0.1 to 10, based on weight pressure relative to the 3-anilito-5-pyrazolone type magenta coupler.
It is 2-5.

In the present invention, "containing as oil droplets" means that hydrophobic additives such as couplers are added to a high boiling point paid solvent with a solubility of 10% or less in water with a boiling point of about 150°C or higher, and/or a water-soluble organic compound as necessary. Dissolve using a solvent and emulsify using a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, 70-jit mixer, or ultrasonic device. This means that after being dispersed, it is added to the desired hydrophilic colloid liquid, coated on a support, and contained in the same state as the high boiling point organic solvent in the dried layer. .

In order to incorporate the cyclic ether compound in the present invention into the light-sensitive material as oil droplets, it is preferable to use the oil-in-water emulsion dispersion method described below.

The cyclic ether compound is normally liquid at 1 (20"C),
When it has a boiling point of about 150°C or higher (for example, Exemplary Compound 1
5,24,26,28,44.46°89.98,10
2, etc.) can be incorporated into photosensitive materials as oil droplets by using them as high boiling point paid solvents. In this case, it is not essential that the cyclic ether compound oil droplets contain a hydrophobic photographic additive, and if the cyclic ether compound is solid at room temperature, the cyclic ether compound is added to a high boiling point organic solvent. By dissolving it, it can be incorporated into the photosensitive material as oil droplets.

The silver halide emulsion used in the silver halide color photographic material of the present invention includes conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used in silver emulsions can be used.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling I)H and/or pAg in the mixing pot. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After the formation, a conversion method may be used to change the halogen composition of the particles.

When producing a silver halide emulsion, a silver halide solvent can be used as necessary to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains.

In the process of forming and/or growing the grains, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including lead salts), rhodium salts (tB
Metal ions can be added using at least one selected from iron salts (including complex salts) and iron salts (including complex salts), and these metal ions can be contained inside the particles and/or on the particle surfaces. By placing the particles in a reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (Research D 1s
Closure (hereinafter abbreviated as RD)) No. 17643, Section 2 can be carried out.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. This indicates the diameter when the image is converted into a circular image with the same area.) may be used alone or in combination. Further, a mixture of an ax-dispersed emulsion and a monodispersed emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. Namely, sulfur sensitization method, selenium bottle sensitization method, reduction sensitization method,
Noble metal sensitization methods using gold or other member metal compounds can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemin cyanine dyes, styryl dyes, hemioxanol dyes, and the like are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention can be hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. can.

A hardening agent can be added to the processing solution to harden the photosensitive material to such a degree that it is not necessary to add a hardening agent to the processing solution, but it is also possible to add a hardening agent to the processing solution.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in section XI of RD 17643 [section 8].

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

The emulsion layer of the photosensitive material contains a dye-forming agent that forms a dye through a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer so that a dye is formed that absorbs light in the emulsion layer's sensitive spectrum;
A Yuikoro dye-forming coupler is used, a magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-iso-R, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bipodal is acceptable. Dye-forming couplers include colored couplers that have a color correction effect, and by coupling with oxidized forms of developing agents, they can be used as development inhibitors, development accelerators, bleaching accelerators, toners, silver halide solvents, and toning agents. Compounds that release photographically useful fragments such as agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included.

Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. Instead of the DIR coupler, a DIR compound that undergoes a coupling reaction with the oxidized form of the olfactory image agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction in the makuuchi separated by the coupling reaction (timing DIR couplers, and timing DIR compounds). In addition, the inhibitor is also m
Depending on the purpose, one that is diffusible after removal and one that is not so diffusible can be used alone or in combination. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye may also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, etc. can be used in combination with the 3-anilito-5-pyrazolone coupler of the present invention. .

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers.

yellow dye-forming coupler, cyan dye-forming coupler,
Dye-forming couplers, colored couplers, DIR couplers, DIR compounds used in combination with the magenta dye formation of the invention, image stabilizers used in combination with the image stabilizer of the invention, color antifoggants, ultraviolet absorbers, optical brighteners Among these, hydrophobic compounds can be dispersed using various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc.
This can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsification dispersion method is
Conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, usually by dissolving them in a high-boiling point solvent with a boiling point of approximately 150°C or higher, in combination with a low-boiling point and/or water-soluble organic solvent as necessary. , using a stirrer, homogenization using a surfactant in a hydrophilic binder such as an aqueous gelatin solution,
It may be emulsified and dispersed using a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic device, and then added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included after or simultaneously with the dispersion.

As the high boiling point solvent, organic solvents such as phenol derivatives, phthalic acid alkyl esters, phosphoric esters, citric acid esters, benzoic esters, alkylamides, fatty acid esters, and trimesic esters that do not react with the oxidized form of the developing agent are used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and water-soluble organic solvents include acetone, Medylisobutylkene, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol,
Acetonitrile, dioxane, dimethylformamide,
Examples include dimyl sulfoxide, hexamethylphosphoric triamide, diethylene glycol monophenyl ether, and phenoxyethanol.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. contain MM such as carboxylic acid or sulfonic acid, they are hydrophilic as an alkaline aqueous solution. It can also be incorporated into sex colloids.

Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable.

The anti-fogging agent may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

The photosensitive material may further contain an image stabilizer that prevents deterioration of the dye image.

A hydrophilic colloid layer such as a protective layer or an intermediate layer of a photosensitive material may contain an ultraviolet absorber in order to prevent fogging caused by discharge caused by charging of the photosensitive material due to friction, etc., and deterioration of images due to ultraviolet rays. .

In order to prevent deterioration of Mazenk dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change development properties such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. A compound that can be preferably used as a development accelerator is RD 1
The compound is a compound described in Section XXI B to D of No. 7643, and the phenomenon retardant is a compound described in Section XXI E of No. 17643. Black and white developing crude drugs and/or for the purpose of promoting development and other purposes.
Alternatively, its precursor may be used.

The emulsion layer of the light-sensitive material contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thia ether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urea derivatives, imiguzole derivatives, and the like.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as optical brighteners are described in HD 17643, section V.

The photosensitive material includes a single layer of filter, anti-halation, snow,
Auxiliary layers such as anti-irradiation layers can be provided. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process.

Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes'r:1.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. Preferably used antistatic agents are the compounds described in RD 17643 X■.

The silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material has various properties such as improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and photographic properties (promoting development, hardening, sensitization, etc.). ) Various surfactants can be used for the purpose of improvement.

The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of , flexible supports made of these films with reflective layers, glass, metals, ceramics, etc.

The hydrophilic colloid layer of the photosensitive material can be applied directly or after applying corona discharge, ultraviolet irradiation, flame treatment, etc. to the surface of the support as necessary, or to improve the adhesion, antistatic property, dimensional stability, and abrasion resistance of the support surface. The coating may be coated with a base coat layer of 1B or more to improve properties such as hardness, hardness, antihalation properties, friction properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which have quick reactivity and will cause gelation if added to the coating solution before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

As coating methods, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

The exposure time is not only the 1 millisecond to 1 second exposure time normally used in cameras, but also the exposure shorter than 1 microsecond, for example, 100 nanoseconds to 1 microsecond exposure using a cathode ray tube or xenon flash lamp. However, exposures longer than 1 second are also possible.

The exposure may be performed continuously or intermittently.

Any known method can be used for developing the photosensitive material of the present invention. If an image is to be produced by the reversal method, a black and white negative development step is first carried out, and then a color development process is carried out by applying white exposure or processing with a bath containing a fogging agent.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. In addition, a bleach-fixing process can be performed using a one-bath bleach-fixing solution, or a monobath processing process using a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. You can also do

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activating process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator process may be performed in the monobath process. can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process, or a stabilization process.)・Color development process - Bleaching process Constant fixation process ・Color image processing process - Bleach fixing Processing process/Pre-hardening process - Color development process - Stop fixing process - Water washing process - Bleaching process Constant fixation process - Water washing process - Post hardening process/Color development process - Washing process - Supplementary color development process - Stop process - Bleach process Constant monitoring process/Activator process - Bleach-fix process/Activator process - Bleach process Constant fixation process/Monobath process Processing temperature is usually 10 It is selected in the range of ℃~65℃,
The humidity may exceed 65°C. Preferably from 25°C
Process at 45°C.

A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes amine phenol derivatives and p-phenylenediamine derivatives. These color developing agents can be used as salts of organic acids and amorphous acids, such as salts 81 M, sulfates, p-t-luenesulfonates,
Sulfites, oxalates, benzenesulfonates, etc. can be used.

These compounds generally have a concentration of preferably 0.1 to 30 (J) for the color developer 12, more preferably 1 to 1
Used at a concentration of 5a.

Examples of the above amine phenol developer include 0-aminophenol, p-aminephenol, 5-amino-phenol,
These include 2-hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbenzene, and the like.

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, particularly useful compound examples include N-N-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, and N.

N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline Sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3- Examples include methylaniline-p-toluenesulfonate.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.

In this case, it is also possible to process the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution.

The color developing solution may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaporate, or borax, and various other alkaline agents. additives, such as benzyl alcohol, alkali metal halides, such as potassium bromide or potassium chloride, or development regulators, such as citrazic acid, and preservatives, such as hydroxylamine or sodium chloride.
It may also contain acid salts and the like. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developer is usually 7 or higher, preferably about 9.
~13.

In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or hexose, pyrogallol-1,
3-dimethylnythyl and the like may be contained.

In the color developing solution, various chelating agents can be used in combination as metal ion sequestering agents. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, organic phosphonic acids such as 1-hydroxyethylidene-1,1'-diphosphonic acid, aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, etc. Oxycarboxylic acids such as aminopolyphosphonic acid, citric acid or gluconic acid, 2-
Examples include phosphonocarboxylic acids such as boshoptan-1,2,4-1-licarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately.

As a bleaching agent, a metal complex salt of 11m is used, for example, a polycarboxylic acid, an aminopolycarboxylic acid, or an organic acid such as oxalic acid or citric acid, which is coordinated with a metal ion such as iron, cobalt, or copper. . Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminebenzene, and ethylenediamine-N-(β-oxyethyl).
-N, N', N' -Triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), glycol ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid Examples include acetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, and the like.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

These bleaching agents are preferably used at 5 to 450 Q/l, more preferably 20 to 250 Q/l.

In addition to the above bleaching agents, the bleaching solution may contain a sulfite salt as a preservative, if necessary. In addition, the bleaching solution is ethylenediaminetetraacetate iron (I
[[) It may be a liquid containing a complex salt bleach and containing a large amount of a halide such as ammonium bromide. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide,
Ammonium iodide and the like can also be used.

Bleaching solutions include JP-A No. 46-280 and JP-A No. 45-85.
No. 06, No. 46-556, Belgian Patent No. 770,9
Various bleaching accelerators described in Japanese Patent Publication No. 10, Japanese Patent Publication No. 45-8836, Japanese Patent Publication No. 53-9854, Japanese Patent Application Publication No. 54-71634 and Japanese Patent Publication No. 49-42349, etc. can be added.

The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． It is used between 0 and 9.5, preferably between 4.5 and 8.0, and most preferably between 5.0 and 7.0.

A fixing solution having a commonly used composition can be used. As a fixing agent, compounds that react with silver halide to form an aqueous complex salt, such as those used in ordinary fixing processing, such as thiosulfate MjP such as sodium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, and thiocyanic acid are used. Potassium, thiocyanates such as sodium thiocyanate, ammonium thiocyanate, thiourea,
Typical examples include thioether. These fixing agents are used in a range where they can be dissolved in an amount of 5 g/l or more, but generally they are used in amounts of 70 to 250 a/l. A part of the fixing agent can be contained in the bleaching solution. death,
Conversely, a part of the bleaching agent can also be included in the fixing solution.

In addition, the bleaching solution and fixing solution include m+ acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. 1) H binding agents can be contained alone or in combination of two or more. In addition, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, hardening agents such as water-soluble aluminum salts, Organic solvents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. can be appropriately contained.

The fixer is used with I) H3.0 or higher, but generally it is 4.
．． 5 to 10, preferably 5 to 9.5, most preferably 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the gold scrap complex salts of organic acids described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron (I[[) complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely, an ammonium bromide It is also possible to use a special bleach-fixing solution made by adding a halide to quince.

As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, potassium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may also be used. I can do it.

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the DH buffer and other additives that can be contained in the bleach-fixing solution are the same as in the above-mentioned fixing process.

The pH of the bleach-fix solution is 4. Used on OLX, generally 5.0 to 9.5, preferably 6.0 to 8
．． 5, most preferably 6.5 to 8.5.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these.

Example 1 0.05 mol of the magenta coupler according to the present invention listed in Table 1 below, and 0.015 mol each of the stabilizer compound or comparative compound represented by the general formula [A] were added to the same amount as the coupler. A mixed solution of 100 d of cyclic ether compound and 100 d of ethyl acetate or a mixed solution of 100 d of ethyl acetate (hI2) and a comparatively high boiling point solvent of 7J Blur and the same boat was dissolved, respectively, and this solution was dissolved in 2.0 d of sodium dodecylbenzenesulfonate. 5% gelatin aqueous solution containing 5g
0-, the resulting dispersion was dispersed using a homogenizer, and the resulting dispersion was mixed with green-sensitive silver chlorobromide (emulsion 7 containing 40 mol% silver chloride).
000v (2s containing 60p of silver and N as a hardener)
.

Add 10n12 of a 2% methanol solution of N',N''-1-lyacroyl-6H-8-triazine and coat it on a polyethylene coated paper support so that the coated silver m is 0.4 fJ/1'. A geladine retention layer was applied on this H to obtain samples F11 to F14.

After exposing each of the above samples to light through an optical beam,
The following treatments were performed.

Processing process (33℃) Processing time Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Water washing 2 minutes stabilization
Dry for 1 minute (color developing solution composition) 4-Amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline 6A acid salt 5.0 g Benzyl alcohol 15.0 mN Sodium hexametaphosphate 2 .5g anhydrous sodium sulfite 1.9g sodium bromide
1.4g potassium bromide
0.50 borax (N82B+07 ・10H
20) Add 39.1 g of water to make 12, and adjust to p) -110,30 using sodium hydroxide.

(Bleach-fix solution composition) Iron ammonium ethylenediaminetetraacetate 61.0 g Ethylenediaminetetraacetate diammonium s, o g Ammonium thiosulfate 124.5 (1 Ammonium metabiTa 13.3 () Anhydrous sodium sulfite 2.1 g Water 11, and adjusted to p)l 6.5 using aqueous ammonia.

(Stabilizing liquid composition) Wood vinegar M20d Add 800tR of water, add sodium acetate to pH 3,
After adjusting to 5 to 4.0, add water to the colander to make it 12.

The following tests were conducted on each of the treated samples.

The results are shown in Table-1.

Light resistance> Dye residual rate (initial concentration 1. OD = density after test) and uncolored color when exposed for 200 hours using a xenon fade meter Department Y
-Stin (difference between before and after the test of blue Ill a Da)
was measured.

Comparative Stabilizer A' In the section of high-boiling organic solvents in the margin below, DBP represents dibutyl phthalate and TCP represents tricresyl phosphate. As is clear from Table 1, the 3-anilino-5-
It was found that by using a pyrazolone-type magenta coupler, a stabilizer compound of general formula [A], and a cyclic ether compound together as oil droplets, the light resistance of magenta images was significantly improved, and the occurrence of yellow stain was also suppressed. Ta. This was completely unexpected from known compound combinations.

Example 2 The following m was placed on a polyethylene resin-coated support.
One color paper material was created.

First layer, blue-sensitive emulsion layer α-pivaloyl-α-(2,4
-dioxo-1-benzylimidazolidin-3-yl)
-2-chloro-5-[γ-(2゜4-di-t-amylphenoxy)butyramide J-7 cetanilide 1,5X
Weighed 1Q-2 mol and dispersed it in a usual emulsion using dibutyl phthalate to make a blue-sensitive silver chlorobromide emulsion (silver bromide 80 mol%) 5
Photographic emulsion 200 containing 10-2 moles of X and 109 gelatin
i) and applied. (Coated silver m 400mg/l
') 2nd H, Interlayer 2. Gelatin layer containing 5-di-t-octylhydroquinone Third layer, green-sensitive emulsion layer Exemplary coupler M-4 IX 10. -2 moles and 2,5
Weigh out 5 x 10-4 moles of di-t-octylhydroquinone and 3 x 10-3 moles of 1,4-di-octyloxy-2,5-di-monoamylbenzene (general formula A-8), and Emulsification and dispersion were carried out using phthalate in a conventional manner. This was mixed into a green-sensitive silver chlorobromide emulsion (silver bromide 80 mol%) 5
200 photographic emulsions containing ×10−2 moles and 10 g of gelatin
g and applied. (Coated silver amount 300mG/1'
) Fourth layer, intermediate layer 2.5-di monooctylhydroquinone and UV absorber 2-(penztriazol-2-yl)-4,
Gelatin layer containing 6-di-t-butylphenol and 2-(penztriazol-2-yl)-4-t-butylphenol (coated film thickness 2μ) Fifth Leopard, red-sensitive emulsion layer 2-[α- (2,4-di(-amylphenoxy)-butyramide]-4゜6-dichloro-5-methyl-phenol was weighed out in 1.5 x 10-2 moles, emulsified and dispersed in the usual manner with dibutyl phthalate, and red-sensitive chlorobromide. It was mixed with 200 g of a photographic emulsion containing silver emulsion (80 mol % silver bromide > 5 x 10 -2 mol %) and 10 g of gelatin and coated.

(Coating silver fa 400 mL/12) Sixth layer, protective layer A 2% aqueous solution of 1,2-bis(vinylsulfonyl)ethane was added as a hardening agent to an aqueous gelatin solution and coated. (Coating film thickness: 1 μm) The sample thus prepared was designated as (15).

Further, samples (16) to (18) were prepared in the same manner as above except that the stabilizer compound A-8 in the third layer and the high boiling point organic solvent dibutyl phthalate were changed as shown in Table 2.

In this manner, the sample was wedge-exposed through a green filter and developed in the same manner as in Example 1, and a light fastness test of the magenta image was conducted.

As is clear from Table 2 below, even in multilayer color light-sensitive materials, the light fastness of the magenta color image of the sample of the present invention, which is a combination of the coupler of the present invention, a stabilizer compound, and a cyclic ether compound, is higher than that of other materials. I found it to be excellent.

Example 3 A cyclic etherified compound was further added to the oil droplets of coupler A-8 and DBP of sample 2 used in Example 1 so that the weight ratio to the coupler was 0.3, and samples 19 to 19 were added. No. 27 was prepared, and exposure, development, and light resistance experiments were conducted in the same manner as in Example 1. The results are shown in Table 3.

As is clear from Table 3 in the margin below, the 3-anilino-5-
By using a pyrazolone type magenta coupler together with a stabilizer compound of general formula [A] and a cyclic ether compound as oil droplets, the light resistance of the magenta color image is greatly improved even in the presence of a high boiling point organic solvent. The occurrence of yellow stain can also be suppressed.

Patent Applicant Roku Konishi Shasan Kogyo Co., Ltd. Agent Patent Attorney Ichinose Miyao Procedural Amendments November 12, 1985 1, Indication of Case 1985 Waiting FfM No. 21594 (3 No. 2, Name of Invention Halogen Silver Chemical Color Photographic Luminous Material 3, Relationship with the Amendment Person Case Patent Applicant Address 1-2692 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1)
27) Konishi Roku Photo Industry Co., Ltd. Kinsha Representative Director Sou Benko, 4th grade, agent 102

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material containing a 3-anilino-5-pyrazolone type magenta coupler, a compound represented by the following general formula [A], and a cyclic ether compound as oil droplets. . General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 is a hydrogen atom, an alkyl group, an alkenyl group,
Represents an aryl group or a heterocyclic group, R_2, R_3,
R_5 and R_6 are each a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group,
It represents an alkoxy group or an acylamino group, and R_4 represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group. Furthermore, R_1 and R_2 may be closed together to form a 5- or 6-membered ring, in which case R_4 represents an alkyl group or an alkoxy group, and when this ring forms a spiro ring, R_4 represents a hydroxy group or Represents an alkyl group or an alkoxy group. Further, R_3 and R_4 may be ring-closed to form a 5-membered hydrocarbon ring, in which R_1 represents an alkyl group, an aryl group, or a heterocyclic group. However, R_
Except when 1 is a hydrogen atom and R_4 is a hydroxy group. Furthermore, R_1 represents an alkyl group or an alkenyl group, and R_1 represents an alkyl group or an alkenyl group;
When 4 represents an alkoxy group, R_2, R_3, R_5
, R_6 never become an alkoxy group at the same time.