JPH01144050A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve resistance to fading in the dark, light fastness and resistance to yellowing due to light by incorporating a specified bisphenol deriv. into at least one of emulsion layers. CONSTITUTION:A 2,5-diacylaminophenol type cyan coupler and a bisphenol deriv. in which one of the phenolic hydroxyl groups has been substd. and at least one of the phenol rings has a substituent are added to oil mist of a high b.p. org. solvent and the mist is incorporated into at least one of the emulsion layers of a silver halide photographic sensitive material. A silver halide photographic sensitive material with improved shelf stability of a cyan dye image, especially resistance to fading in the dark, light fastness and resistance to yellowing due to light can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material in which the image storage stability of cyan dye images is improved.

[Background of the Invention] To form a dye image using a silver halide color photographic light-sensitive material, 1. Usually, an aromatic primary amine color developing agent is used to remove the halogen in the exposed silver halide photographic light-sensitive material. When reducing silver oxide particles.

This is accomplished by oxidizing the silver halide itself and reacting the oxidized product with a coupler previously contained in the silver halide photographic light-sensitive material to form a dye. Generally, three types of couplers are used that form three dyes, yellow, magenta, and cyan, in order to perform color reproduction by the subtractive color method.

Each coupler is usually added to the silver halide emulsion by being dissolved in a substantially water-insoluble high-boiling organic solvent or in this solvent, if necessary, in combination with an auxiliary solvent.

The basic properties required of each coupler are: firstly, high solubility in high-boiling organic solvents, good dispersibility and dispersion stability in silver halide emulsions, and no easy precipitation;1) excellent spectral absorption characteristics; Examples include that a clear dye image is formed in a wide color reproduction range with good one color tone, and that the obtained dye image has fastness to light, heat, moisture, and the like. In particular, for couplers used in color print materials, it is desirable to improve both the light fastness and dark storage stability (dark fading resistance) of the resulting dye image as much as possible due to the mission of preserving photographic images. . In particular, for cyan couplers, it is desired that the storage stability in light and dark places be improved in a well-balanced manner.

As the above-mentioned cyan coupler with improved dark fading property, 2, in which the 2- and 5-positions of the phenol are substituted with acylamino groups,
5-Diacylaminophenol cyan couplers are known, and are described, for example, in U.S. Pat. .

However, although these 2,5-diacylaminophenol-based cyan couplers do significantly improve the dark fading resistance of the cyan dye images obtained, many of them have significantly poor light fastness, and they also produce light yellow stains. (light yellowing) and other inconveniences may occur.

As a technique for improving the image storage stability of this 2,5-diacylaminophenol cyan coupler,
No. 105645, No. 59-124340, q60-2
Examples include the methods described in Japanese Patent Application No. 22853 and No. 62-118344, as well as Japanese Patent Application No. 61-291277 and No. 61-38893, but none of these methods are sufficient, and there is a method for simultaneously improving the above-mentioned drawbacks. has not been found.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic material in which the storage properties of cyan dye images, especially dark fading resistance, light fastness, and light yellowing are simultaneously improved.

[Configuration of the Invention] The above object has been achieved by a silver halide photographic material having the following configuration.

A silver halide photographic material having at least one silver halide emulsion layer on a support.

At least one of the emulsion layers contains a 2,5-diacylaminophenol-based cyan coupler and a bis-type phenol derivative in which one of the phenolic hydroxyl groups is substituted, and at least one of the phenol rings has a substituent in the same high-boiling point organic solvent. A silver halide photographic material characterized by containing oil in droplets.

The present invention will be explained in detail below.

Preferable examples of the 2,5-diacylaminophenol cyan coupler are represented by the following general formula.

General formula [I] Z+ In the formula, R1 represents alkyl 11, an aryl group, a cycloalkyl group, or a heterocyclic group. R2 does not represent an alkyl group or an aryl group. R3 is a hydrogen atom, a halogen atom,
Does not represent an alkyl or alkoxy group. Zl does not represent a hydrogen atom or a group that can be interpreted as #It by reaction with an oxidized product of an aromatic primary amine color developing agent.

1g of alkyl represented by R1 in the general formula [I] is,
Examples include methyl cloud, ethyl group, butyl group, hexyl group, tridecyl group, pecitadecyl group, heptadecyl group, and the like. , R1 is, for example, a phenyl group, a naphthyl group, etc., and preferably a phenyl group.

The heterocyclic group represented by R1 is, for example, pyridyl 1B or a furan group. The cycloalkyl group represented by R1 is, for example, a cyclopropyl group or a cyclohexyl group.

These polygroups represented by R1 include those having single or multiple substituents; for example, typical substituents introduced into the aryl group include a halogen atom, an alkyl group, a hydroxyl group, a cyano group, Nitro group, carboxyl group, alkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkyloxycarbonyl group, aryloxy Examples include carbonyl group, aminosulfonamide group, acylamino group, acyl group, alkylcarbamoyl group, etc. Substituents introduced into the alkyl group, cycloalkyl group, and heterocyclic group represented by R1 are also the same as above. I can list things.

Preferred groups represented by R1 include a fluorinyl group or a halogen atom, an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfonyl moyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and an acyl group. Alternatively, it is a phenyl group having a cyano group as a substituent.

The alkyl group represented by R2 is linear or branched, and includes, for example, a methyl group, ethyl group, propyl group, butyl group, octyl group, tridecyl group, and the like. The aryl group represented by R2 is, for example, a phenyl group or a naphthyl group. These multigroups represented by R2 include those having substituents, and examples of the substituents to be introduced include the same substituents as those for the group represented by R1 above.

The halogen atom represented by R3 is, for example, each atom such as fluorine, chlorine, or bromine, the alkyl group is, for example, a methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc., and the alkoxy group is , for example, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, etc. R
3 is preferably a water M atom or a halogen atom, particularly preferably a hydrogen atom.

Typical examples of the group obtained by reacting with the acid derivative of an aromatic primary amine color developing agent represented by Zl include a halogen atom, an alkoxy group,
Examples include an aryloxy group, an arylazo group, a thioether, a carbamoyloxy group, an acyloxy group, an imide group, a sulfonamide group, a thiocyano group, and a complex ring group. A particularly preferred example of Zl is a hydrogen atom or a chlorine atom.

In the present invention, preferred cyan couplers represented by the general formula [I] are compounds represented by the following general formula [I].

General formula [I'] In the general formula [I'], Rt+ represents an alkyl group or an aryl group, and may be a single or multiple group.

Also includes those having a 1A group. Typical substituents include halogen atoms, hydroxyl groups, carboxyl groups, alkyl groups, cyano groups, nitro groups, alkoxy groups, aryloxy groups, alkylsulfonamide groups, arylsulfonamide groups, and alkylsulfamoyl groups. group, arylsulfamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, aminosulfonamide group, alkylsulfonyl group, arylsulfonyl group, acyl group, aminocarbonylamide group, carbamoyl group,
Examples include sulfinyl group.

Preferred groups represented by R11 are an alkyl group when nj -0 and an aryl group when n1=1 or more. More preferable groups represented by R11 include:
When n1=0, it is an alkyl group having 1 to 22 carbon atoms excluding substituents, and when nl-1 or more, it is a phenyl group, or an alkyl group, an alkylsulfonamide group, an arylsulfonamide group, an aminosulfone It is a phenyl group having an amide group or an alkyloxycarbonyl group as a substituent.

R12 represents an alkylene group, preferably a linear or branched alkylene group having 1 to 20 atoms, more preferably 1 to 12 carbon atoms.

nl is O or a positive integer, preferably 0 or 1.

X represents a divalent group, and examples of this divalent group include -〇-
1-CO-1-COO-1-OCO-1-8O2NR'
-1-NR' 302 NR''-1-S-1-SO-1
-3O2- and the like.

Here, Rl and RLJ represent an alkyl group, R',
Rrr includes those each having an exchange group. X is preferably 10-1-S-1-SO-1-3O2-.

R+', R3' and Z+' have the same meanings as R+, R3 and Zl in the above-mentioned formula [I'], respectively.

Typical specific examples of Z, ``+-5F acylami/7-el cyan couplers are shown below in the margins, but the invention is not limited to these.

GsuC,2H2,So2Nl-I C411, (nl C4Ll, (ul し1□112.tllll C,2II,,, +Il+ shi°e 1--i 9 Also 2,5-diacylaminophenol cyankabu 2
- may be used alone or in combination with other cyan couplers as appropriate, and preferred for use in combination are the following cyan couplers:

-Fukudai[1[] (In the formula, R4 represents an alkyl group, R5 is an alkyl group, a teryl group, an alkoxy group, an awaroxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or an aromatic group. Represents a group that can be separated by reaction with an oxidized product of a primary amine color developing agent. generation [■′]
It is expressed as

-Fukudai [■'] In the formula, R++ and R+2 are the same or different and represent a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group,
propyl group, butyl group, amyl group, octyl group, dodecyl group, etc.), alkoxy I (for example, IrA, me-1-xy 4B,
ethoxy group, etc.).

However, the total number of carbon atoms in PUT and RI2 is 8 to 16. More preferably, R++ and R+2 are each a butyl group or an amyl group.

R13 is a hydrogen atom or an alkyl group (for example, a methyl group,
(ethyl group, propyl group, butyl group, octyl group, etc.).

Preferably a hydrogen atom, a nibble group, or a butyl group, with a blank space below. Ru.

R'5 has the same meaning as R5 in the above-mentioned clothing charge [II].

That is, alkyl M (e.g., methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), aryl group (e.g., phenyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, etc.), aryloxy group (e.g., phenyloxy group, etc.). ), alkylthio groups (e.g. methylthio group, ethylthio group etc.), arylthio group (e.g. phenylthio group etc.), alkylsulfonyl group (e.g. methanesulfonyl group, ethanesulfonyl group etc.) or arylsulfonyl group (e.g. benzenesulfonyl group etc.) ), and R'5 is preferably an alkyl group, more preferably a methyl group or an ethyl group.

m represents an integer of 0 to 2; Z4 represents a hydrogen atom or a group capable of being separated by reaction with an oxidized product of an aromatic primary amine color developing agent;

In the formula [[1, [1], [1'1 and [■'],
f' by reaction with oxidized products of aromatic primary amine color developing agents represented by Z9, Z3, Z1' and Z.
Groups that can be used to modify the reactivity of the coupler or remove I from the coupler are well known to those skilled in the art.
IJI Jul In fact, in the coating layer or other layers containing a coupler in the silver halide color photographic light-sensitive material 1, it works advantageously by exerting functions such as phenomenon suppression, bleaching suppression, and color correction. One representative example is, for example, a 7% lodene atom, an alkoxy group, an aryloxy group, an arylazo group, a 1,000-onythyl group, a carbamoyloxy group, an acyloxy group, an imide group, a sulfonamide group, a thiocyano group, or a polycyclic group ( For example, oxacylyl, diazolyl, triazolyl, tetrazolyl, etc.)
A particularly preferred example represented by Z″C is
It is a hydrogen atom or a chlorine atom.

Typical examples of the cyan coupler IP11 represented by the formula [111] are shown below, but the invention is not limited thereto.

Below is a margin t CL In the present invention, the amount of cyan coupler added is 2X10- per mole of silver halide as the total amount of cyan coupler.
'mol - 1 mol is preferred, more preferably 1 x 10 -
The range is 2 moles - 8X10 moles.

In addition, when the 2,5-diacylaminophenol cyan coupler according to the present invention and the cyan coupler represented by the general formula [111] are used together, the ratio of the cyan coupler of the general formula [■1] to the former cyan coupler is Bow O~9
Preferably 0 mol%, more preferably 20 to 90 mol%
It is.

Next, a bis-type phenol derivative (hereinafter referred to as a bis-type phenol derivative) in which one phenolic hydroxyl group is substituted and at least one phenol ring has a substituent will be described.

Substituents for one phenolic hydroxyl group include, for example, aliphatic hydrocarbons (e.g. alkyl groups, alkenyl groups), alicyclic hydrocarbons (e.g. cycloalkyl groups), aromatic hydrocarbon groups, sulfonyl groups (e.g. arylsulfonyl groups). ,
(alkylsulfonyl group) and acyl group, and the substituents include those having further substituents.

The two phenol rings in the bis-type phenol derivative may be bonded directly or may be bonded via a bonding group. Examples of the bonding group include an alkylidene group, an alkylene group, a sulfonyl group, and a petero atom (eg, oxygen, sulfur), and preferably an alkylidene group and a sulfur atom.

Further, the bonding positions of the two phenol rings are preferably ortho positions relative to the phenolic hydroxyl group and the substituted phenolic hydroxyl group.

The phenol ring in the bis-type phenol derivative also includes a fused ring in which another ring is fused to a phenolic benzene ring.

Examples of substituents on at least one phenol ring in the bis-type phenol derivative include 1, for example, an alkyl group,
Examples include a cycloalkyl group, an alkenyl group, and an aryl group.

The substitution positions of these substituents are preferably the ortho position and/or the rose position of the phenolic hydroxyl group and the substituted phenolic hydroxyl group, and the substituents at the ortho position and the rose position of both groups are the same, respectively. It is preferable that

Next, specific representative examples of bis-type phenol derivatives will be shown, but the present invention is not limited thereto.

CH31-Ha 1; tls CHt-C*H*(t) The bis-type phenol derivative of the present invention is a bis-type phenol compound in which the phenolic hydroxyl group is not substituted, for example, an alkyl halide, a carboxylic acid halide, a sulfonic acid halide. It can be obtained by reacting compounds, dialkyl sulfates, etc.

The bis-type phenol derivative is preferably added to a silver halide emulsion layer containing a coupler or a layer adjacent thereto, and it is particularly preferred that the bis-type phenol derivative coexists with the coupler in a high-boiling organic solvent.

The amount of bis-type phenol derivative added is preferably 0.1 to 2.0 mol, particularly 0.2 to 2.0 mol per mol of coupler.
1.0 mol is preferred.

In the present invention, the bis-type phenol derivative is contained in the silver halide emulsion layer in the same oil droplet of a high-boiling point organic solvent, in coexistence with a 2,5-diacylaminophenol cyan coupler. The solvent is preferably one that is immiscible with water and has a boiling point of 150°C or higher;
Examples include phenol derivatives, phthalate esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, fatty acid amides, trimesic acid esters, and the like, which do not react with the oxidized product of the developing agent.

Among high boiling point organic solvents, those with a dielectric constant of 6.0 or less are preferred.

Examples of high-boiling organic solvents having a dielectric constant of 6.0 or less include esters such as phthalates and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds having a dielectric constant of 6.0 or less. Preferably, the dielectric constant is 6.0 or less and 1.9 or more and 10
It is a high boiling point organic solvent with a vapor pressure of 0.5 mmHg or less at 0°C. Even more preferred are phthalic esters or phosphoric esters in the high-boiling organic solvent. Furthermore, the high boiling point organic solvent may be a mixture of two or more.

Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C.

Examples of phthalic acid esters advantageously used in the present invention include those shown below.

In the general formula [II], R and R2 each represent an alkyl group, an alkenyl group, or an aryl group. However, the total number of carbon atoms in the groups represented by R1 and R2 is 12 to 32. More preferably, the total number of carbon atoms is 16 to 24.

In the present invention, the alkyl group represented by R1 and R2 in the above-mentioned -clothing cost [m] may be linear or branched, such as a butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, 3,5 .5-trimethylhexyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, etc. R8
The aryl group represented by and R2 is, for example, a phenyl group,
Examples of the alkenyl group include a naphthyl group, and examples of the alkenyl group include a hexenyl group, a heptenyl group, and an octadecenyl group.

These alkyl groups, alkenyl groups and aryl groups are
Substituents for alkyl and alkenyl groups include, for example, halogen atoms, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, alkoxycarbonyl groups, etc. Examples of substituents of the group include halogen atoms,
Examples include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group.

In the above, R8 and R2 are preferably alkyl groups, such as 2-ethylhexyl group, 3,5°5-trimethylhexyl group, n-octyl group, n-nonyl group, etc.

Phosphoric esters that are advantageously used in the present invention include those shown below.

General formula [IV] In the formula, R3, R4 and R5 each represent an alkyl group, an alkenyl group or an aryl group, provided that the total number of carbon atoms in the groups represented by R3, R4 and R is 24 to 54. .

The alkyl groups represented by R3, R4 and R in general formula [17] are, for example, butyl group, pentyl group, hexyl group, 2
- Ethylhexyl group, heptyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, nonadecyl group, etc.; examples of the aryl group include phenyl group, naphthyl group, etc., and alkenyl group Examples include hexenyl group, heptenyl group, octadecenyl group, and the like.

These alkyl groups, alkenyl groups and aryl groups are
Preferably R3, R4 and R5 are alkyl groups, including those having single or multiple substituents, such as 1, for example 2
-ethylhexyl group, n-octyl group, 3,5.5-trimethylhexyl group, n-nonyl group, n-decyl group, 5
Examples include ec-decyl group, 5ee-dodecyl group, t-octyl group, and the like.

Typical specific examples of high boiling point organic solvents used in the present invention are shown below, but the present invention is not limited thereto.

Exemplary organic solvent C! 2H5 2H5 S-9 S-10 02H.

0-0H20H(OH2) 30H3 0H20H(OH2)3(3H3 2H5 0-Og HIg(i) 0=P-0-0,H,, (i) 0-09H19(i) 0-C3H+5(II) 0= P-00sH1g(n) 0-CsHxs(n) 001oHzl(i) Wealth o = p oc 10H21(')■ 0 01oH21(i) o-C1oH2□(n) O-COH2□(rl) 0- C1□H23(i) 0=P 0-011H23(1) 0- CoHz3(i) 0-C1zHzs(i) o=po-o-cm2H25(z) 0-C1□H25(i) High boiling point organic solvent The amount used is preferably 0.1 to 10 Il1, particularly 0.5 to 2
mfL is preferred.

The preferred method for adding the coupler and bis-type phenol derivative is an oil-in-ice emulsion dispersion method.

In the oil-in-ice emulsion dispersion method, hydrophobic additives such as couplers are dissolved in a high-boiling organic solvent, if necessary in combination with a low-boiling point and/or water-soluble organic solvent, and a hydrophilic binder such as an aqueous gelatin solution is dissolved. After emulsifying and dispersing the mixture using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device using a surfactant, it can be added to the desired hydrophilic colloid layer. . A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

The silver halide photographic light-sensitive material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., and may be one for monochrome use or one for multicolor use.

In the case of multicolor silver halide photographic light-sensitive materials, silver halide emulsion layers containing magenta, yellow, and cyan couplers and non-light-sensitive layers are usually formed on a support in an appropriate number and layer order. Although it has a laminated structure, the number and order of layers may be changed as appropriate depending on the important performance and purpose of use.

Silver halide emulsions used in the silver halide photographic light-sensitive material of the present invention include silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, and any other commonly used silver halide emulsions. can be used.

The silver halide emulsion used in the present invention can be prepared by sulfur sensitization method,
Chemically sensitized by selenium sensitization, reduction sensitization, noble metal sensitization, etc.

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry.

As the binder (or protective colloid) used in the silver halide photographic material of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugars, etc. Hydrophilic colloids such as derivatives, cellulose derivatives, synthetic hydrophilic polymeric materials such as single or copolymers may also be used.

The silver halide photographic material of the present invention requires additives such as a hardening agent, a color clouding prevention agent, an image stabilizer, a plasticizer, a latex, a surfactant, a matting agent, a lubricant, and an antistatic agent. It can be used depending on the situation.

An image can be formed on the silver halide photographic material of the present invention by subjecting it to color development treatment known in the art.

[Effect of the invention] According to the silver halide photographic material of the present invention.

It is possible to provide a silver halide photographic light-sensitive material in which cyan dye image storage stability, especially dark fading resistance, light fastness, and light yellowing are simultaneously improved.

[Example 7] The present invention will be specifically explained below using Examples, but the embodiments of the present invention are not limited thereto.

Example l 60g8 of cyan coupler (C-1) and 32g of bis-type phenol derivative compound (14) were dissolved in a high boiling point organic solvent (D
A solution of OP) and ethyl acetate was added to an 8% aqueous gelatin solution containing a dispersion aid (dodecylbenzenesulfonic acid sodium salt) and dispersed with a homogenizer. The resulting dispersion was finished into ISOOmi and kept at 40° C. for 3 hours. Apply this dispersion to a 3% aqueous gelatin solution for coating.
In addition to the above, 400 g of a red-sensitive silver chlorobromide emulsion (containing 80 mol % of silver bromide) was added to prepare a coating solution for a red-sensitive emulsion layer.

This coating solution was kept at 40°C for 2 hours.

Coating solutions for each layer were prepared in the same manner, and coated on a polyethylene-coated paper support at a coating speed of 100 m/min to have the following composition.

First calendar: Blue-sensitive emulsion layer Yellow coupler (Y-1) is 8B/dm'', blue-sensitive silver chlorobromide emulsion (containing 20 mol% silver chloride and 80 mol% silver bromide) is 3B in terms of silver. /dm”, high boiling point organic solvent (D
OP) at 3111 g/dm'' and gelatin at 16 B/d.
Apply so that the coating amount is m''.

No. 218 = 0.45 mg/d of middle layer hydroquinone derivative (HQ-1)
The coating amount was 4 mg/d of DOP and 4 mg/d of gelatin.

3rd layer: green-sensitive emulsion layer magenta coupler (M-1) at 4 mg/dm'', green-sensitive silver chlorobromide emulsion (20 mol% silver chloride, 80 mol% bromide)
Contains) in terms of silver, axis g/dm'', high boiling point * mechanical solvent (
DOP) was applied at a coating amount of 4 mg/drn'', antifading agent AO-1 was applied at 2 mg/drrf, AO-2 was applied at 1 mg/dm'', and gelatin was applied at a coating amount of 16 mg/dm''.

4th layer: Intermediate layer ultraviolet absorber (UV-1) at 3H/dm'', (υV-
2) at 3 mg/drn' and high boiling point organic solvent (DOP) at 4 tag/drr? , hydroquinone derivative (HQ-2
) at 0.45mg/dm and gelatin at 14mg/dm
Apply the coating so that the coating amount is '.

5th layer: red-sensitive emulsion layer cyan coupler (C-1) at 411 g/dm'', high boiling point organic solvent (DOP) at 4+1 g/drn', bis-type phenol derivative (14) at 4 B/dm'', red-sensitive salt Silver bromide emulsion (containing 20 mol% silver chloride and 80 mol% bromide) is converted to silver at 3+++ g/dm' and gelatin is 14 mg.
/dm' coating amount.

6th layer: Intermediate layer ultraviolet absorber (UV-3) 4rtrg/drrf,
High boiling point organic solvent (DOP) was applied at a coating amount of 2 mg/drn' and gelatin was applied at a coating amount of 6B/drrr'.

7th layer: Protective layer Gelatin was coated at a coating weight of 91 g/dm''.

(Compound used for sample preparation) DOP Nidioctyl phthalate I2 O-1 O-2 HQ-1 HQ-2 l 2t15 υi tr*-1 H C,H,,(t) V-2 H V-3 H 2H5 This sample was designated as sample 1.

Next, Samples 2 to 16 were prepared in the same manner as Sample 1 except that the 5N bis-type phenol derivative and the high point organic solvent of Sample 1 were changed as shown in Table 1 (the bis-type phenol derivative was used in Sample 1). ), these samples were exposed to red light using a photosensitive needle (Model KS-7, manufactured by Konica), and then subjected to the following treatment.

Processing process Processing temperature Processing time Color development
32.8°03 minutes 30 seconds bleach fixing 32.8
℃ Wash with water for 1 minute and 30 seconds 32.8℃
3 minutes 30 seconds [Color developer composition] Sulfate 4.0g Hydroxylamine sulfate 2.0g Potassium carbonate 25.0g Sodium chloride
0.1g potassium bromide
0.2g anhydrous sodium sulfite
2.0g benzyl alcohol
10.0m polyethylene glycol (average degree of polymerization 400) 3.0m
Add Bunsui to make 1fL, use sodium hydroxide,
Adjust the pH to 10.0.

[Bleach-fix solution composition] Ethylenediaminetetraacetic acid sodium salt 60.0g Sodium thiosulfate 100.0g Sodium bisulfite 20.0g Sodium metabisulfite 5.0g Water was added to make 141, and the pH was adjusted to 7.0 using sulfuric acid. do.

For each sample obtained after processing, the light fastness, light yellowing, and dark fading of the cyan image were evaluated in the following manner.

[Light fastness test] The residual rate was shown as the initial concentration D0 = 1.0 when exposed to sunlight for 30 days using an underglass outdoor sunlight exposure table. (D=density after fading) [Light yellowing test] It was expressed as the difference ΔD between the blue density value in the unexposed area of each sample subjected to the light fastness test and the value before the test.

[Dark Fading Resistance Test] The fading property after being stored for 2 weeks in the dark in 70" C140

Try from the results in Table 1! In samples No. 41 and 2, in combination with the comparative cyan coupler (C-1), although the bis-type phenol derivative of the present invention had a slight improvement effect on dark fading resistance, it was still insufficient, and the light fastness was In sample 3, the cyan coupler of the present invention has excellent performance in terms of dark fading resistance, but has poor light fastness. It can be seen that the properties and optical yellowing were inferior and were at a level that would pose a practical problem. However, sample 4, which is a combination of the present invention,
It can be seen that Samples No. 1 to 11 had good dark fading properties and were sufficiently improved in terms of light fastness and light yellowing. This effect cannot be predicted from conventional knowledge. Further, in Samples 13 to 16, where the cyan couplers [I] and [II] were used in combination, an improvement in dark fading resistance was observed, indicating that they had even better performance.

Example 2 A silver chlorobromide emulsion containing 99.5 mol % of silver chloride was used in place of each silver halide emulsion used in Example 1, and the cyan coupler and bis-type phenol derivative were changed as shown in Table 2. Each sample (Sample 1) was the same as Sample 1 of Example 1 except that
7 to 25) were prepared. Each sample was exposed to red light in a conventional manner and then subjected to the following treatments.

Processing process Processing temperature Processing time Color development
34.7±0.3℃ 50 seconds bleach fixing 3
4.7±0.5℃ Stabilized for 50 seconds 30-34
Dry for 90 seconds at °C 60-80 °C 6
The composition of the treatment liquid used in each treatment step is as follows.

[Color developer coethylene glycol 1. Om sentence N,
N-diethylhydroxylamine 10nl Potassium chloride 2g Sodium tetrapolyphosphate 2g Potassium carbonate
30g optical brightener (4,4'-diaminostilbenzsulfonic acid derivative)
Add 1.0g of pure water to make one sentence, pH 10.0
Adjust to 8.

[Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100mM ammonium sulfite (4
0% solution) 27.5■ Add water to make one sentence,
Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid.

[Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one Add 1 g of water and lfL
and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

The light fastness, light yellowing, and dark fading of each sample after treatment were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Also, instead of the cyan coupler ■-1 of sample 23, n-4
, U-5, ll-8, ll-10, ll-14゜U-1
The effects of the present invention were also observed when 1i, n-19, and U-20 were used.

The results in Table 2 also show that the light fastness, light yellowing and dark fading properties were simultaneously improved in the samples of the present invention.

Example 3 Samples 26 to 33, which were the same as those used in Example 2 except that the cyan coupler, bis-type phenol derivative, and high-boiling organic solvent were changed as shown in Table 3, were prepared, and after the same exposure treatment, the light fastness was Evaluations were made regarding color, yellowing, and fading. The results are shown in Table 3.

From the results in Table 3, the effect of the present invention is that the dielectric constant is low (6,0
(below) It can be seen that the combination with a high boiling point organic solvent results in even better results.

High boiling point organic solvents S-1, S-5, S-6, 5-11, 5-12, 5 instead of high boiling point organic solvent DOP of sample 28
-18, 5-19, 5-22, and sample 3
0 cyan coupler l-42 instead of 1-10, knee 17, l-18, ■-20, l-21° knee 27, knee 28, knee 36, ■-38, knee 43, knee 44, l-
The effect of the present invention was also observed when No. 46 was used.

Example 4 A color reversal photosensitive material sample was prepared by providing the following 1st to 12th layers on a paper support coated with polyethylene on both sides. The coating amount of each component is expressed in g/m'; however, for silver halide, the coating amount is expressed in terms of silver.

1st layer (gelatin layer) Gelatin 1.40 2nd layer (antihalation layer) Black colloidal silver 0.10 Gelatin 0.60 3rd layer (1st layer)
Red-sensitive layer) Cyan coupler ll-10,07 Cyan coupler 1-42 0.14 Bis-type phenol derivative (7) 0.20 High boiling point solvent (S-12) 0.06 Red sensitizing dye (D- 1, AgBr1 spectrally sensitized with D-2)
(Ag 13.0 mol%, average particle size 0.4 pm) 0.1
4 Gelatin 1.0 4th layer (
2nd red sensitive layer) Cyan coupler II -10,10 Cyan coupler l-420,20 High boiling point solvent (S -12) 0.10
Bis-type phenol derivative (7) 0.300.
16 Gelatin 1.0 No. 5ff
(1st intermediate layer) Gelatin 1.0 Color mixing inhibitor (AN-1) 0.08 6th layer (1st
Green-sensitive layer) Bis-type phenol derivative (7) 0.14 Magenta coupler (M-2) 0.14 High boiling point solvent ('S-2) -0.15 Spectral sensitization with green sensitizing dye (D-3) AgBr1 (
Agl 3.0 mol%, average particle size 0.4 gm) 0.1
5 Gelatin 1.0 7th layer (
Second green-sensitive layer) Bis-type phenol derivative (7') 0.14 Magenta coupler (M-2) 0.14 High-boiling solvent (S-2) 0.150.1
5 Gelatin 1.0 8th layer (
2nd intermediate layer) Yellow colloidal silver 0.15 Color mixing inhibitor (AN-1) 0.08 Gelatin
1.0 9th layer (first blue sensitive layer) Yellow coupler (Y-1) 0.40 High boiling point solvent (S-2) 0.100.1
5 Sub-covered phenol derivative (7) 0.40 Gelatin 0.70 10th layer (
Second blue-sensitive M) Yellow coupler (Y-1) 0.80 High boiling point solvent (S-2) 0.200.2
0 Bis-type phenol derivative (7) 0.80 Gelatin 1.3 11th layer (ultraviolet absorption layer) Ultraviolet absorber 1) -10,2 Ultraviolet absorber U+ 2 0.2 Ultraviolet absorber U -30,2 Ultraviolet absorption Agent U-40,2 Gelatin 20 mouths t512
Layer (protective layer) Gelatin 1.0 However, in addition to the above, it contains an anti-fading agent, a surfactant, a hardening agent, and an anti-irradiation dye.

In addition, the third layer, the fourth layer, the sixth layer, the seventh layer, the ninth layer, and the first layer
In the 0 layer, the bis-type phenol derivative was dissolved together with the coupler in a high boiling point solvent and added in a dispersed manner.

Cσ i2 Hardener UV absorber OH RI RI Ri Ri Rs U -1(t)CJs (t)CJs HU
-2(t)C,Hs OH,CIU -3(t)
C4H*, (t)C4H! CIU-4
(t) CsH++ (t) CsHs* H color mixing inhibitor (AN-1) Example 1 except that the following treatment steps were used for the sample.
When evaluated in the same manner as in Example 1, the same effects of the present invention as in Example 1 were confirmed.

1st development (monochrome development) 1 minute 15 seconds (38°C) 1st water wash 1 minute 30 seconds Light fogging
1001ux or more 1 second or more 2nd development (color development)
2 minutes 15 seconds (38℃) 2nd water wash
45 seconds bleach fixing 2 minutes (38
°C) Third water washing 2 minutes and 15 seconds The composition of the treatment solution used is as follows.

[First developer] Potassium sulfite 3.0g Sodium thiocyanate 160g Sodium bromide 2.4g Potassium iodide
8.0mg hydroxide/'IF'
) ') Mu (48%) 6.21f
L Potassium carbonate 14g Sodium hydrogen carbonate 12g Hydroquinone monosulfonate 23.3g Add water to make 1 mixture, pH
9.65.

[Color developer] Benzyl alcohol 14.6mA-
Ethylene glycol 12.6m Potassium carbonate (anhydrous) 26g Sodium hydroxide 1.4g Sodium sulfite 1.6g 3.6-cythiaoctane-1.8-diol 0.24g Hydroxylamine sulfate 2.6g Sesquisulfate 5.0g Add water It is one sentence.

[Bleach-fix solution] 1.56 molar solution of ammonium salt of ethylenediaminetetraacetate diiron rust 115 mJ
l Sodium metabisulfite 15.4g Ammonium thiosulfate (58%) 126iJ1
1.2.4-triazole-3-thiol 0.4
g Add water and l! ;L and pH 5.5.

Patent Applicant Konica Co., Ltd. Representative Patent Attorney Nobuaki Sakaguchi Procedural Amendment Letter January 5, 1988 Mr. Kunio Ogawa, Commissioner of the Patent Office;

l Indication of the case Japanese Patent Application No. 1983-303892 2 Name of the invention Silver halide photographic light-sensitive material 3 Person making the amendment Relationship to the case Applicant name (127) Konica Co., Ltd. 4 Agent Publication 60 Address Shinjuku-ku, Tokyo Nishi-Shinjuku 7-10-11, 2nd Building, 5th floor 6 Number of inventions increased by amendment 7 Specification subject to amendment (detailed description of invention column) 8 Contents of amendment (1) No. 43 in the specification Delete lines 7 to 10 of the page.

(2) In the same book, page 53, line 11, the phrase "flow jet mixer" is corrected to "flow jet mixer."

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers is substituted with a 2,5-diacylaminophenol cyan coupler and one of the phenolic hydroxyl groups. , and a bis-type phenol derivative in which at least one phenol ring has a substituent group is contained in the same high-boiling organic solvent oil droplet.