JPS6275447A - Photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the shelf life of an image by incorporating a specific cyan coupler and cyclic ether compd. in the form of oil drops into an emulsion layer. CONSTITUTION:The cyan coupler expressed by the formula and the cyclic ether compd. are incorporated in the form of oil drops into the emulsion layer. The incorporation thereof in the form of oil drops is executed by dissolving a hydrophobic additive such as coupler into a high boiling org. solvent having >=150 deg.C b.p. and <=10% solubility with water in combination use, if necessary, with a low boiling and/or water soluble org. solvent and emulsifying and dispersing the same into a hydrophilic binder such as aq. gelation soln. by using a surface active agent, then adding the same into an intended hydrophilic colloid liquid, coating the liquid on a base and maintaining the same state as the state in which the high boiling org. solvent is incorporated into the dry layer. The cyclic ether compd. is preferably 3-6-membered compd. and the number of the oxygen atoms to be incorporated within one ring is preferably 1-2 pieces. The shelf life of the image is thereby improved.

Description

Detailed Description of the Invention [Industrial Application Valve JJ'] The present invention relates to a silver halide photographic light-sensitive material, and particularly relates to a silver halide photographic material that has hydrophilic properties by dispersing photographic additives that are sparingly soluble in water using epoxies. This invention relates to a silver halide color light-sensitive material containing V in a shell colloid layer.

[Background of the Invention] Conventionally, photographic additives that are poorly soluble in water (for example, oil-soluble couplers), antioxidants used to prevent color fogging or color mixing,
Antifading agents (e.g., alkylhydroquinones, alkylphenols, chromans, etc.), hardeners, oil bath filter paints, oil-soluble ultraviolet absorbers, Dl, R compounds, etc. are dissolved in suitable high-boiling point organic solvents to make them hydrophilic. Hydrophilic colloids (e.g., photosensitive emulsion layer, filter layer, antihalation layer, intermediate layer, protective layer, etc.)
It is used by containing it in. As high boiling point organic solvents, phthalate ester compounds and phosphoric ester compounds are particularly used.

In particular, most of the solvents for oil-soluble internal couplers used in color photographic materials are of this type.

For example, U.S. Patent Nos. 2,322,027 and 2,533
, No. 514, 3,287.134@, 3.748.
No. 141, No. 3,779°765, West German Patent No. 1,
No. 152,610, British Patent No. 1.272,561, etc.

Phthalate ester compounds and phosphate ester compounds, which are high boiling point organic solvents, have an effect on coupler dispersibility, affinity with gelatin and colloid layers, and stability of colored dye images.
They have been widely used because of their influence on the hue of color-forming dye images, their chemical stability in photosensitive materials, and their low cost.

However, such high boiling point organic solvents affect the dispersibility of photographic additives that are poorly soluble in water, the affinity with the hydrophilic stone layer colloid layer, and the chemical stability in photosensitive materials. In terms of performance, etc., the performance was not completely satisfactory.

For example, some high-boiling point organic solvents have good dispersibility, but may have a negative effect on the storage stability of color images obtained through development, and vice versa. It had the performance of

In particular, cyan images have good fastness to heat and moist heat, and water has good dispersibility! Although there were no high-boiling point organic solvents for i-soluble photographic additives,
7, U.S.P.-4,540,657 states that a cyan dye is produced by oxidative coupling with a female agent in a high-boiling organic solvent having at least one of an epoxy group, an epoxy group and an ester group, or an amide group. It has been described that by dispersing the coupler to be formed, the poorly water-soluble cyan coupler is dispersed in a hydrophilic colloid in a stable state, and the fastness to heat and humidity of the resulting dye image is improved. However, even in this method, the fastness of the color image under high temperature and high humidity is not fully satisfied.

[Object of the Invention] The first object of the present invention is to form a dye image that has improved light resistance, heat resistance, and moisture resistance, and exhibits excellent image storage stability even at high temperatures and high humidity. An object of the present invention is to provide a silver halide photographic material.

A second object of the present invention is to provide a silver halide photographic material capable of forming a dye image with improved image storage stability without adversely affecting photographic properties.

[Structure of the Invention] The above-mentioned object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which a cyan compound represented by the following general formula [I] is provided. This is achieved by a photographic material containing a coupler and a cyclic ether compound as oil droplets.

The following margin general formula [I] R2 represents an alkyl group, a substituted alkyl group, an alkenyl group,
Substituted alkenyl group, cycloalkyl group, substituted cycloalkyl group, aryl group, substituted aryl group, heterocyclic group, substituted heterocyclic group, R1 is alkenyl group, substituted alkenyl group, cycloalkyl group, substituted cycloalkyl group, Aryl group, substituted aryl group, hetero radical, substituted hetero 1″;
4 groups, 2 groups are separated by reaction with a hydrogen atom, a halogen atom, or an oxidized product of an aromatic primary amine color developing agent.

In the present invention, "containing as oil droplets" means that a hydrophobic additive such as a coupler is added to a high boiling point sensitive solvent having a boiling point of about 150° C. or higher and a solubility of 10% or less in water, as necessary, to a low boiling point and/or water soluble additive. It is dissolved in a hydrophilic binder such as an aqueous gelatin solution using a surfactant and a dispersion means such as a stirrer, a homogenizer, a colloid mill, a flow jet mixer, and an ultrasonic device. This means that after emulsification and dispersion, 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 contained in the dried layer. do.

The cyclic ether compound used in the present invention is preferably 3 to 6 cm. 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, for example methyl, ethyl, 1-propyl, 2-ethylhexyl, lauryl, stearyl, etc.), and may further have a substituent. Examples of substituents 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 (
For example, cyclohexyloxycarbonyl, etc.), aryloxycarbonyl group (for example, cyclohexylcarbonyl, 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 group (e.g. dimethylaminosulfamoyl), rfu dichloroalkyl group (preferably 3 to 6 carbon atoms, e.g. cyclopropyl, cyclohexyl, etc.), which may further have a substituent, Examples include the above-mentioned examples of substituents on 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, 1-nylcarbamoyl, etc.) Niacyl group (for example, acetyl, p-methoxybenzoyl, etc.) Nidiano group Furthermore, R+ and R2 and/or R1 and R4 may be bonded to form a ring.

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

Margin below COC)i:CHC, Hs 0 C2Hs Margin below QC day.

Nice ti2 (J (,; (ni M2 H Fl-Sil
"12su (C; H2), ni l-1-(,1" 12 or less margin COCHC, H.

+1 1 0 C2H5 and h2- to 1-1 (to l-12]5 to b U 21N
(2CH to shi M 215 shi + 1- shi.

CH.

(-〇(J is 285) A 4-membered cyclic ether compound is preferably represented by the following general formula.

I 2 R4 where R+, R2, R3, R4, Rs, Rs are selected from the following.

: Hydrogen atom : Halogen atom (e.g. chloro, bromine, fluorine, etc.) : Straight 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 substituents include the above-mentioned halogen atoms, alkoxy groups (e.g., methoxy, butoxy, stearyloxy, etc.), aryl groups (e.g., phenyl groups, etc.), aryl groups (e.g., phenyl groups, etc.),
Aryldio groups (e.g., phenylthio, etc.), aralkylbo groups (e.g., benzylthio, etc.), amino groups (e.g., piperidino, dimethylamine, 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., phenyl ureido, etc.), aminosulfamoyl groups (e.g., dimedylaminosulfamoyl, etc.).

Nidicloalyl group (preferably 3 to 6 carbon acids, such as cyclopropyl, cyclohexyl, etc.) may further have a substituent, examples of which include the above-mentioned examples of substituents for alkyl groups. Can be mentioned.

Niaryl M (for example, phenyl, etc.) may have the same substituent as in the case of an alkyl group.

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

: Carbamoyl group (for example, phenylcarbamoyl, etc.) Niacyl group (for example, 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 below, but the present invention is not limited thereto.

Below is a blank space 8. A cyclic ether compound having five members is preferably represented by the following general formula.

In the formula, R1, R2, R3, R4, Rs, R7,
Ra is selected from the following.

:Hydrogen atom:Halogen atom (for example, hydrogen atom, bromine, fluorine, etc.) :Light chain or. is a branched alkyl M (preferably 1 carbon number)
to 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., me-1-xy, butoxy, stearyloxy, etc.), aryloxy groups (e.g., J-nogishi, 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, dimedylamino, etc.), acyloxy groups (e.g., acetoxy, benzoyloxy, furanoyloxy,
cyclohexanoyloxy, etc.), alkoxycarbonyl groups (e.g., butoxycarbonyl, 2-ethylhexyloxycarbonyl, cyclohexyloxycarbonyl, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl, etc.), oxalyloxy M (e.g., ethoxyoxalyloxy, etc.) , carbamoyloxy (e.g. hexylcarbamoyloxy), sulfonyloxy group (e.g. phenylsulfonyloxy), amide group (e.g. benzoylaminokuzu etc.), ureido group (e.g. phenylureido etc.), aminosulfayl group (e.g. dimethylaminosulfamoyl etc.) 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 (e.g. phenylcarbamoyl etc.) Niacyl group (e.g. acetyl, p-methoxybenzoyl etc.) Nidiano group Furthermore, R1 and R2, R7 and R8 and/or R1 and R4
may be combined 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, R1, R2, R3, R4, R5, R6 are selected from the following.

: Hydrogen atom: Halogen atom (e.g. chloro, bromine, fluorine, etc.) ° : Straight chain or branched alkyl group (preferably 1 to 40 carbon atoms, e.g. methyl, ethyl, i-propyl, 2-
ethylhexyl, lauryl, stearyl, etc.), which may further have a substituent. Examples of substituents include the above-mentioned halogen atoms, alkoxy groups (e.g., meth]hexy, butoxy, sudearyloxy, etc.), 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, furanoyloxy, cyclohexanoyloxy, etc.), alkoxycarbonyl groups (e.g., butoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), cycloalkoxycarbonyl groups (e.g., cyclohexyloxycarbonyl, etc.), aryl Oxycarbonyl group (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) groups), ureido groups (e.g., phenylureido, etc.), aminosulfamoyl groups (e.g., dimethylaminosulfamoyl, etc.) @.

° Cycloal4 group (Good J・L, < kl charcoal Song late 3~
6. (rIJ: 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 (for example, phenylcarbamoyl, etc.) Niacyl group (for example, acedel, p-methoxybenzoyl, etc.) Nidiano group Furthermore, R+ and R2 may be combined to form a ring.

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

Margin below CH2-CHR RR'10'lH)"1 1o8 CH) H+o9
CH2 (JI H+ + o
CH20C6Hs HIll
CH2Ct' Cα and below are preferably 6-membered cyclic ether compounds represented by the following general formula.

In the formula, R1, R2, R3, R4, R5, R6, R7, R
a 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. Substituents include, for example, the above-mentioned halogen atoms, alkoxy groups (such as methoxy, butoxy,
(sudearyloxy, etc.), aryl quaternary-cy group (for example)
1noxy, etc.), aryl groups (e.g., phenyl, etc.), arylthio groups (e.g., phenylthio, etc.), aralkylthio groups (e.g., pendylthio, etc.), amino groups (e.g., piperidino, dimethylamino, etc.), acyloxy groups (e.g., acetoxy, benzoyloxy, etc.) , furanoyloxy, cyclohexanoyloxy, etc.), alkoxycarbonyl groups (e.g., but-1-xycarbonyl, 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, dimethylaminosulfamoyl, etc.), etc.

The dichloroargyl group (preferably having 3 to G carbon atoms, 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 (eg, phenylcarbamoyl, etc.) Niacyl group (eg, acetyl, p-methoxybenzoyl, etc.) Nidiano group Furthermore, R+ and R2 and/or R1 and R4 may be bonded to form a ring. Further, R3 and R4 may form a double bond.

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

Below margin + l 8 R: (CHz)z11'l
(CH2)3+ l o
(CH2) tl 21
(CH2) 2 C'' CH2Among the above-mentioned cyclic ether compounds, a preferable group has at least one ether bond, nistyl bond (for example, -CO-
1-8O20-, amide bond (e.g.

-3O2N) or a ureido bond (for example, at least 51 hydrogen atoms are preferably bonded to the carbon atom directly bonded to the oxygen atom in the ring).

The cyclic ether compound may be purchased as a commercial product. Alternatively, it can be obtained by synthesizing a corresponding compound having a double bond in advance and then oxidizing the double bond with an oxidizing agent (for example, hydrogen peroxide). Further, the above-mentioned 6-membered cyclic ether compound is described, for example, in JOC Vol., 36 p., 1176 (19
11), lvlacromolecules1980
, p. 252, for example, British Patent No. 867918, Ann 623 p.
191 (1959), and the four-membered one can be synthesized by the method described in German Patent No. 1021858.

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.

When the cyclic ether compound is liquid at room temperature (20°C) and has a boiling point of about 150°C or higher (for example, Exemplified Compound 15
,24.26.28,44,46°89.98.102
etc.) can be incorporated into photosensitive materials as oil droplets by using them as high-boiling organic 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 cyclic ether compound is preferably added in the same layer as the coupler of the present invention or in an adjacent layer, and the same layer is particularly preferred. Among these, the most preferred is the case where a cyclic ether compound is added to the oil droplets containing the coupler of the present invention.

The additive can of the cyclic ether compound of the present invention has a weight Q ratio relative to the hydrophobic photographic additive, preferably from 0.1 to 10, more preferably from 0.2 to 5.

The cyan coupler in the present invention has the following general formula.

The alkenyl group represented by the general formula [I] as R1 or R2 in the general formula is preferably an alkenyl group having 2 to 20 carbon atoms (allyl group, heptadecenyl group, etc.), and the cycloalkyl group is preferably is a 5- to 7-membered ring (for example, cyclohexyl, etc.), the aryl group is, for example, phenyl group, tolyl group, naphthyl group, etc., and the heterocyclic group preferably has 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms.
It is a 5- to 6-membered ring group containing (eg, furyl group, chenyl group, pensinaazolyl group, etc.). Further, the alkyl group as R2 is preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, butyl, dodecyl, etc.). Note that any substituent can be introduced into R+ and R2, such as an alkyl group having 1 to 10 carbon atoms (for example, methyl, i-propyl, i-butyl, t-butyl, [-octyl, etc.), aryl groups (e.g. phenyl, naphthyl, etc.), halogen atoms (fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide groups (e.g. methanesulfonamide, butanesulfonamide, p-toluenesulfonamide moyl group (methylsulfamoyl) , phenylsulfamoyl, etc.), sulfonyl groups (e.g. methanesulfonyl, p
-t-luenesulfonyl, etc.), fluorosulfonyl group,
Carbamoyl group (e.g. dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl group (e.g. ethoxycarbonyl, phenoxycarbonyl, etc.), acyl group (e.g. acetyl, benzoyl, etc.), heterocycle (e.g. pyridyl group, pyrazolyl group, etc.), alkoxy group, Examples include an aryloxy group and an acyloxy group.

It is preferable that at least one of R1 and R2 is a ballast group necessary for imparting diffusion resistance to the cyan coupler and the cyan dye formed from the cyan coupler, and preferably carbon JiJ. 4 to 30 alkyl groups, allyl groups, alkenyl groups (, Schif[1 alkyl groups or heterocyclic groups; for example, straight chain or branched alkyl groups (
For example, s-butyl, n-octyl, t-octyl, n-
dodecyl, etc.), 5-membered bb< is a 6-membered heterocyclic group, and the like.

In the general formula [T], examples of the group that can be separated during the coupling reaction with the oxidized product of the aromatic primary amine color developing agent represented by Z include a substituted or unsubstituted alkoxy group, an aryloxy group, Examples include a heterolfioxy group, an acyloxy group, a carbamoyloxy group, a sulfonyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, and a sulfonamide group.

In the present invention, preferred compounds have the following general formula % [where R3, R4, R5, R6 and R7 are each a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkoxy group, aryl group,
aryloxy group, alkylsulfamoyl group, arylsulfamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonamide group,
Represents a group selected from an arylsulfonamide group, an alkylsulfonyl group, and an arylsulfonyl group.

However, when R3 is a group selected from alkylsulfonamide groups, R7 is also a group selected from alkylsulfonamide groups. Z represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. ] R2 has the same meaning as in the general formula [I] above, but is preferably a group represented by the following general formula [I11].

General formula [I11] %Formula % In formula [I11], R9 is an alkyl group (e.g., n-ethyl group, n-pentyl group, 0-off square group, n-nonyl group, n-decyl group, n-undecyl group). group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, sec-pentadecyl group, sec-tridecyl group, shi-octyl group, [
-nonyl group, etc.) or phenyl group. The phenyl group may have a single or multiple substituents, and this substituent and a nitro group, an alkyl group (for example, a methyl group, an ethyl group, a butyl group, a pentyl group, an octyl group, a dodecyl group, etc.), an alkoxy groups (e.g. methoxy, ethoxy, butoxy, octoxy, etc.), alkylsulfamoyl groups (e.g. butylsulfamoyl, octylsulfamoyl, etc.), arylsulfamoyl groups (e.g. phenylsulfamoyl) , xylylsulfamoyl group, tolylsulfomyl group, mesitylsulfamoyl group, etc.), alkyloxycarbonyl group (e.g., butyloxycarbonyl group, butyloxycarbonyl group, etc.), or aryloxycarbonyl group (e.g., phenyloxycarbonyl group, xylyloxycarbonyl group, tolyloxycarbonyl group, etc.). Two or more of these substituents may be introduced into the phenyl group. Preferred groups represented by R9 include phenyl group,
Hydroxyl group, alkyl group, halogen as a substituent,
Examples include phenyl groups having an alkyloxycarbonyl group, particularly phenyl groups having a branched alkyl group and/or a chlorine atom at the 2- and 4-positions.

RIO represents an alkylene group. It preferably represents a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably 2 to 14 carbon atoms (for example, α-butylmethylene group, α-ebrenemethylene group, α-dodecylmegulene group).

× (represents a divalent group such as yo-0-1-S-1-8〇- or -3O2- group).

General formula [1B in Ill, R3, [1, R5, RI
J' and R7 are a hydrogen atom and a halogen atom (
For example, (3 [fluorine, inline, bromine, etc.), hydroxyl group, nitro group, cyano group, alkyl q ((pl) methyl group, ethyl group, propyl group, 1 tyl group, octyl group, decyl group, dodecyl group, etc. ), alkoxy groups (e.g., methoxy, ethoxy, octoxy, etc.), aryl groups (e.g., phenyl, etc.), aryloxy groups (e.g., phenoxy, etc.), alkylsulfamoyl groups (e.g., butylsulfonyl group, octylsulfonyl group, etc.) moyl group, N,
N-dimethylsulfatyl, etc.), arylsulfamoyl groups (e.g., phenylsulfamoyl, xylylsulfamoyl, tolylsulfamoyl, mesitylsulfamoyl), alkyloxycarbonyl groups (e.g., methyloxycarbonyl), group, butyloxycarbonyl group, octyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g. phenyloxycarbonyl group,
xylyloxycarbonyl group, tolyloxycarbonyl group, mesityloxycarbonyl group, etc.), alkylsulfonamide group (e.g. methyloxysulfonamide group, butylsulfonamide group, octylsulfonamide group, etc.)
, and arylsulfonamide groups (e.g., phenylsulfonamide group, 2,4-di-t-butylphenylsulfonamide group, etc.), alkylsulfonyl groups (e.g., butylsulfonyl group, etc.), and arylsulfonyl groups (e.g., phenylsulfonyl M, etc.) Represents the percentage selected.

Preferred groups represented by R3, R4, Rs, Re and R7 are hydrogen atoms, halogen atoms, alkyl groups, and alkoxy groups, and preferred groups represented by R4, R5 and R6 are Examples of the group include a hydrogen atom, a halogen atom, an alkyl group, an alkylsulfonamido group, a cyano group, a hydroxyl group, an alkyloxycarbonyl group, an alkylsulfonyl group, and the like.

More preferred are compounds represented by the following general formula [TV].

General formula [IVl (R.,).

[In the formula, Y represents a halogen atom. m is an integer from 1 to 5. R++ represents an alkyl group, a hydroxy group, an alkylsulfonamide group, an arylsulfonamide group, a halogen atom, or an (aminosulfonamide group).R
+o represents an alkylene group. Z represents a hydrogen atom, a halogen atom, or a group capable of being separated in a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. n represents an integer from 0 to 5. When n is 2 or more, R
++ may be the same or different. 1 In the present invention, the alkyl group represented by R1+ in the general formula [IVl is linear or branched, such as a methyl group,
Ethyl group, propyl group, (-butyl group, sec-butyl group, (-pendel group, sec-pentyl group, t-octyl group, n-nonyl group, n-dodecyl group, n-pentadecyl group, etc.), preferably is a straight chain or branched alkyl group having 1 to 20 carbon atoms.

Examples of the alkylsulfonamide group represented by R11 include a methanesulfonamide group, an ethanesulfonamide group, a propanesulfonamide group, a butanesulfonamide group, a pentanesulfonamide group, an octanesulfonamide group, a dodecanesulfonamide group, and a hexadecanesulfonamide group. Examples include an amide group, a methoxyethanesulfonamide group, a butane (N-benzyl)sulfonamide group, and the like.

As the arylsulfonamide group represented by RH,
Examples include benzenesulfonamide group, phenolsulfonamide group, and toluenesulfonamide group.

The aminosulfonamide group represented by R++ is
N-methylaminosulfonamide group, dimethylaminosulfonamide group, N-nibruaminosulfonamide group,
Examples include alkylsulfonamide groups such as N,N-diethylaminosulfonamide groups, and phenylaminosulfonamide groups.

Examples of the halogen atom represented by R++ include chlorine and fluorine.

A particularly preferable group as R11 is 2,4-G t
-butyl group, 2,4-di-t-pendel group, N, N-
Examples include dimethylaminosulfonamide group, n-do group, n-octylsulfonamide group, n-dodecylsulfonamide group, and chlorine atom.

n is preferably an integer of 1 to 3.

Among the halogens represented by Y, C2 or F is particularly preferred.

Specific compounds of the cyan coupler according to the present invention are listed below, but the invention is not limited thereto.

Margin below [Ia “I Indication Case Prevention” C-34 C-37 1　　　　〇 C.I. C-70 CH.

-is -1 6-1
”l QQ
QCJ - B I - The coupler used in the present invention has a concentration of 1 x 10-3 mol to 1 mol per mol of silver halide combined with the coupler.
It is preferable to use it in a molar range, more preferably 1 x 1
0-2 mol to 8X10-1 mol is preferred.

The silver halide emulsion used in the sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, which are commonly used in silver halide emulsions. Any one 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. Alternatively, it may be generated by sequentially and simultaneously adding halide ions and silver ions while controlling the pH and/or I)A() in the mixing pot while controlling the critical growth rate of silver halide crystals. By this method, 1q of silver halide grains having a regular crystal shape and nearly uniform grain noise can be obtained.After growth, a conversion method may be used to change the halogen composition of the grains.

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.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( By adding metal ions using at least one selected from the group consisting of complex salts), these golden horse elements can be contained inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere. Inside the particle and.

/Or reduction sensitizing nuclei can be provided on the particle surface.

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) may be used.

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). When divided by the average grain size, the value is 0.20 or less.Here, the grain size is the diameter for spherical silver halide, and for grains with shapes other than spherical, the value is 0.20 or less. , which indicates the diameter when the projected image is converted into a circular image of the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse 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. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble 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, boropolar cyanine dyes, hemin cyanine dyes, sudyryl dyes, hemiogisanol 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 keeping photographic performance stable, photographs may be taken during chemical ripening, at the end of chemical ripening, and/or before the silver halide emulsion is applied. 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 are 1. Hardening can be achieved by using one or more hardening agents that crosslink binder (or protective colloid) molecules and increase film strength.

A hardening agent can be added to the processing solution to the extent that it is possible to harden the photosensitive material to the extent that it is not necessary to add a hardening agent, 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 RD 17643 Section XII A
It is a compound described in .

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 such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the 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. Furthermore, even though these dye-forming couplers are 4-isomer, in which 4 molecules of silver and ions must be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions are reduced. Either good 2-isomerism is fine. Dye-forming couplers have the effect of color correction, and can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning by coupling with oxidized forms of developing agents. Compounds that release photographically useful fragments such as agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, DIR is a coupler that releases a development inhibitor during development and improves image sharpness and image graininess.
called a coupler. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing 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 the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction within the group separated by the coupling reaction, an intramolecular electron transfer reaction, etc. (referred to as timing DIR couplers and timing DIR compounds). Also, depending on the purpose, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can 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 piparoylacetanilide compounds are advantageous.

As magenta dye-forming couplers, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

Phenolic or naphthol couplers may also be used in conjunction with cyan dye-forming couplers.

These dye-forming couplers, colored couplers, DIR
Among couplers, DIR compounds, image stabilizers, color cast inhibitors, ultraviolet absorbers, optical brighteners, etc., hydrophobic compounds can be processed using various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc. The dispersion method can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water type emulsification dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers. Usually, a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low boiling point and/or water soluble one as necessary. and a hydrophilic binder such as an aqueous gelatin solution using a surfactant and dispersing means such as a stirrer, homogenizer, colloid mill, flow jet mixer, and ultrasonic device. After being emulsified and dispersed, it may be 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 a high boiling point solvent, organic solvents such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, trimesic acid esters, etc. that do not react with the oxidized form of the 1.1 developing agent are used. It will be done.

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, Methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonyl-1-lyl, dioxane, dimethylformamide,
dimethyl sulfoxide, hexymethyl phosphoric]
- Examples include lyamide, 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. have acid groups such as carboxylic acid or sulfonic acid, they may be mixed with an alkaline aqueous solution. , and can also be introduced into hydrophilic 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 color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

An image stabilizer can be used in the photosensitive material to prevent 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 magenta 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 the developability, such as development accelerators and development retarders, 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 17
The compound is a compound described in Section XXI B-D of No. 643, and the development retardant is a compound described in Section XXI E of No. 17643. A black-and-white developing agent and/or a precursor fogging agent may be used to accelerate development or for other purposes.

The emulsion layer of the light-sensitive material contains polyalkylene oxide or derivatives thereof such as ethers, esters, and amines 1, thioether compounds, thiomorpholines, quaternary ammonium compounds, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development.
It may also contain urethane derivatives, urea derivatives, imidazole 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 section V of RD 17643.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. 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.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

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. It may also be used in -. Preferably used antistatic agents are the compounds described in RD 17643 X■.

The silver halide hole M layer and/or other hydrophilic colloid layers of light-sensitive materials have the following properties: improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and photographic properties (promoting development, hardening, sensitization, etc.). etc.) Various surfactants can be used for the purpose of improvement.

The support used in the photosensitive material of the present invention includes paper laminated with an α-olefin polymer (e.g., polyethylene, polypropylene, ethylene/butene copolymer), etc.
Flexible reflective supports such as synthetic paper, films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and reflective layers provided on these films. flexible support, glass, metal,
Includes pottery 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. properties, hardness, anti-halation properties, f! It may be coated via one or more subbing layers to improve lj 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 Kylenon 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 produced by the reversal method, a black-and-white negative development step is first carried out, followed by exposure to white light or treatment with a bath containing a fogging agent, followed by color development.

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.

However, instead of the processing step using a bleaching solution and the processing step using a fixing solution, a bleach-fixing processing step can be performed using a one-bath bleach-fixing solution, or color development, bleaching, and fixing can be carried out in one step. It is also possible to carry out a monobath processing step using a one-bath developing, bleach-fixing solution that can be carried out in a bath.

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 processes, instead of the color development process, an activator 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 which the monobath process is performed using an activator solution. Processing 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 - Bleach process Constant fixation process - Color development process - Bleach-fixing process Processes: Pre-hardening process - Color development process - Stopping and holding process - Washing process - Bleaching process Constant fixation process - Washing process - Post-hardening process - Color development process - Washing process - Supplementary color development treatment process - Stop treatment process - Bleach treatment process Constant fixation treatment process / activator treatment process - Bleach-fix treatment process / activator treatment process - Bleaching treatment process Constant fixation treatment process / Monobath treatment process Processing temperature is normal , is selected in the range of 10°C to 65°C,
The temperature may exceed 65°C. Preferably from 25°C
Processed 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 aminophenol derivatives and p-phenylenediamine derivatives. These color developing agents can be used as salts of organic and inorganic acids, such as salt mM, sulfate, o-toluenesulfonate,
iIt salts, oxalates, benzenesulfonates, etc. can be used. - These compounds are generally used at a concentration of preferably 0.1 to 30 g, more preferably 1 to 15 g, for color developer 1i.
Use at a concentration of a.

Examples of the above amine phenol developer include 0-amine phenol, p-aminophenol, 5-amino-2
- and droxytoluene, 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, examples of particularly useful compounds include N-N-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, 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-1(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate and the like.

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

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 contains alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, rum, and Ial.
It may contain sodium, thorium metaborate, borax, etc., and may further contain various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or development regulators such as citradinic acid. , hydroxyamine or VA-nitrate may be contained as a preservative. Furthermore, various antifoaming agents, surfactants, and solvents such as methanol, dimethylformamide or dimethyl sulfoxide can be appropriately contained.

The pl-1 of the color developing solution is usually 7 or more, preferably about 9-13.

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

In the color developing solution, various chelating agents can be used in combination as metal ion sequestering agents. For example, the Kiri-1
As agents, ethylenediamine 41Vt M, diethylenetriamine 51ffi' M W amine polycarboxylic acid, 1-hydroxyethylidene-1,1'-diphosphonic M aH Mizawa phosphonic acid, amine 1-(methylene phosphonic acid) or nib- Aminopolyphosphophones DIi, Ri1-N (1!2-like), L-glucones, Δxycarboxylic acids such as Kutsu, phosphono-polyphosphones such as 2-phosphonobutane-1,2,i-trical ribbons, etc. Examples of carboxylic acids and tripolyphosphoric acids include polyphosphoric acids such as hexametaphosphoric acid, and polyhydroxy compounds.

The bleaching process is performed using the same aN as the treatment process determined as described above.
It may be carried out separately, or it may be carried out separately.

As a bleaching agent, a metal complex salt of an organic acid is used, such as polycarboxylic acid, aminopolycarboxylic acid, L61 acid,
An acidic acid such as citric acid coordinated with a metal ion such as iron, cobalt, or copper is used. Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminebencacetic acid, ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid, propylenediaminetetra-waveproof, Nitri[ItriII! , cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxydiethylglycine citric acid (or tartaric acid), ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, phenylenediaminetetraacetic acid, etc.

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

These bleaches are preferably 5-450Q/ffi
, more preferably 20 to 250 l/ffi.

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
II) A liquid containing a complex salt bleaching agent and a large amount of a halide such as ammonium bromide may be used. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, putrium iodide, potassium iodide,
Ammonium iodide and the like can also be used.

1 for bleach solution! Kaimei, IG-230, Special Publication Showa 4, '+-f3! r O6, 46-55 (i
F;, Bell V-Holding No. 770. ! '110%;, 11j
Kimiaki) No. 15-f11R3G, 53-98! +4 issue,
L#3 hearing 1! p, : 14-71634 and 49-
It is possible to add the bleaching accelerator of Seed Noah, which is described and published in 42349.

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

A fixer having a commonly used composition can be used. As the fixing agent, compounds that react to form water-soluble DI salts, such as silver halide used in the usual fixing process P41, such as potassium thiosulfate, sodium thiosulfate, and ammonium thioacid, are used. acid salt,
Potassium thiocyanate, 1-lium thiocyanate, ammonium thiocyanate.

Typical examples include thiocyanates such as rum, thioureas, and thioethers. These fixatives are 5a
The fixing agent is used at a q range of 70 to 250(]/ffi or more, but is generally used at a q of 70 to 250(]/ffi).A part of the fixing agent can be contained in the bleaching solution, or conversely, the fixing agent can be contained in the bleaching solution. A portion of the agent can also be included in the fixer.

In addition, various pH buffering agents such as i1M% borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide are added to the bleaching solution and fixing solution. Alone or 2f! ! A combination of the above can be contained. In addition, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, and bicarbonate fiM adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, and hardening agents such as water-soluble aluminum salts. , methanol, dimethylsulfamide, dimethylsulfamide, etc.! 5i solvent etc. may be included as appropriate.

Fixed ↑ 1 Hiroshi (j, 111 (used in 3,0 and above,
- ■ 2 to 1 is used in 4.5 to 10, preferably 5
~9.5, preferably 6 to 9 from 2.

Bleach fixing solution, 2. Used TFFI whitening agent and 1. Is there any frozen metal mentioned in the above bleaching process? i1 salts can be mentioned, and DJ in preferable i1 salts and treatment solutions.
This is exactly the same as in the above bleaching treatment step.

The bleach-fixing solution B contains a silver halide fixing agent in addition to a bleaching agent such as Makoto, and if necessary, a solution containing sulfite as a preservative is applied. In addition, a bleach-fix solution consisting of an ethylenediamine quadruple rJIi iron<DI) complex salt bleach and a silver halide fixer such as ammonium bromide containing a small amount of silver halide (M1), or conversely, A special bleach-fixing solution containing a halide such as ammonium chloride may also be used.

As the halides, in addition to ammonium bromide, hydrochloric acid, odors (hydonic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc.) are also used. be able to.

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 OH slowing agent 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 used at 4.0 or higher, generally 5.0 to 9.5, preferably 6.0 to 8.5.
5, most preferably 6.5 to 8.5.

[Example-1] Monochromatic photographic elements were prepared with the layer configurations shown in Table 1.

The application port was expressed in mg/100cf.

<'L-Use it in the first layer, dicyan coupler'J> 1st attack;:l(YU, VF: completed/,:.

(a) Shown in Table 2/r example cyan) J Blur 33
9゜2.5-G (-Okburu completed the draw with a non-0.
45Q, cyclic ether compound 26.4 (
1. Mix 60g of RSV Egil (heat to 30°C to dissolve).

(b,) 40 g of photographic gelatin and 500112 pure water were mixed at room temperature and allowed to swell for 20 minutes. Next, after heating to 60°C and stirring, Alkanol B (manufactured by DuPont)
Add 50112 ml of 5% aqueous solution of and stir uniformly.

(C) The solutions obtained in (a) and (b) were mixed and dispersed for 30 minutes using ultrasonic dispersion to obtain a dispersion liquid.

The sample thus obtained was exposed to white light through a sensitometry light wedge and then processed according to the following processing steps.

(Processing process) Processing time Temperature color development 3.5 minutes 33℃ bleach fixing
1.5 minutes 33℃ water washing
3 minutes 33℃ drying 80℃ (color developer composition) Pure water
700. Q Benzyl alcohol
151g diethylene glycol 15.
12 hydroxylamine sulfate 2gN-
Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.4Q Potassium carbonate 30 (Potassium monobromide 0.4g Potassium chloride
o5@! If! I dat6 odor potassium 29 Add pure water and 1! (+)l-1=10.2) (bleach-fix solution ηr
J', ) Ethylenediaminedetrar1 ferric anneptinium 61g] - Masu
1 non the horn comin tetra r'f
:lta 2 ammonium
5g thiosulfate 7tontium 125 rimetafil! I Sodium 13 i
ll sulfite order natri cum 2.1g
Water was added to make the film 11 (DI-1 = 7.2).The obtained film was evaluated for photographic performance such as relative sensitivity, maximum reflection density, and gamma (γ), but there were no significant differences. The combination of coupler/cyclic ether compound as high-boiling solvent of the present invention has no adverse effects on photographic performance.

Next, a dye image storage test was conducted as described in (a) and (b) below. Note that the dye image storage stability is determined by the initial density (Do
) = 1.0, expressed as a percentage of the concentration after the test (D>).

As is clear from the results in Table 2, the combination of the ()-shaped ether compound and cyan coupler of the present invention containing U significantly improves the light chromaticity of color images and the fading resistance under high temperature and high humidity. .

(A) Light chromaticity A Kuff-Ra (1), CI Supporter Kuff-Ra (2) Below margin [Example-2] Multicolor photograph of the layer structure shown in Table 4? V element was created.

The following margins (UV-1) (UV-2) The following margin coupler dispersions were prepared according to the method used in Example-1.

The samples prepared by the above method were exposed to blue light, green light, and red light, respectively, and then subjected to the same treatment as in Example 1 to produce yellow (Y), magenta (M) t'j.
19 is a three-color separation sample of cyan and cyan (C). These samples were subjected to the same dye image storage test as in Example-1. The results are shown in Table 5.

As is clear from the results in Table 5, the combination of the cyclic ether compound and cyan coupler of the present invention significantly improves the light chromaticity of color images and the fading resistance under high temperature and high humidity conditions.

Note that the color balance was also good.

The following margin sample 21 is an exemplary compound = DBP as a high boiling point organic solvent.
They were mixed at a ratio of 1:1.

Patent applicant Konishiroku Photo Industry Co., Ltd. Immediate patent attorney Miyao Ichinose Procedural amendment (own opinion) November 8, 1985 sound

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the emulsion layer contains a cyan coupler represented by the following general formula [I] and a cyclic ether compound. A photographic material characterized in that it is contained in the form of oil droplets. General formula [I] ▲ Numerical formula, chemical formula, table, etc. ▼ R_2 is an alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, cycloalkyl group, substituted cycloalkyl group, aryl group, substituted aryl group, heterocycle basis,
Substituted heterocyclic group, R_1 is alkenyl group, substituted alkenyl group, cycloalkyl group, substituted cycloalkyl group, aryl group, substituted aryl group, heterocyclic group, substituted heterocyclic group, Z is hydrogen atom, halogen atom, aromatic Represents a group that can be separated by reaction with an oxidized product of a primary amine color developing agent.