JPH01152456A - Silver halide photographic sensitive material having high stability of picture image - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having superior color developability and causing scarce deterioration of dye picture image by incorporating a specified yellow coupler and a bis-type phenol deriv. having one of the phenolic OH groups, being substituted and a substituent in another phenol ring into at least one emulsion layer. CONSTITUTION:A yellow coupler expressed by formula I, and a bis-type phenol deriv. having one of the phenolic OH groups being substituted and a substituent in another phenol ring are incorporated into at least one emulsion layer. In formula I, R1 is an alkyl group; R2 is an aryl group; and Z1 is an eliminable group by coupling bonded to a C atom. with an N atom. Preferred R1 is a t-butyl group, and preferred R2 is a phenyl group. Thus, a silver halide photographic sensitive material having high color reproducibility and causing scarcely deterioration of dye picture image is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material that provides yellow images with excellent storage stability, and more specifically, a silver halide photographic material that has excellent color development properties and
The present invention relates to a silver halide photographic material whose yellow dye image hardly deteriorates even if it is exposed to light for a long period of time or stored in a dark place.

[Background of the Invention] In order to form a dye image using a silver halide color photographic light-sensitive material, an aromatic primary amine color developing agent is usually used to reduce the halogenation in the exposed silver halide photographic light-sensitive material. When silver particles are reduced, they are themselves oxidized, and this oxidized product reacts with a coupler previously contained in the silver halide photographic 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-temperature 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 does not easily precipitate, and excellent spectral absorption characteristics. , clear pigment images with good color tone and wide color reproduction gamut are formed;
In addition, the resulting 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 in order to preserve the record of photographic images. ing. However, improvements in the coupler itself are not sufficient, and various image stabilizers have been researched and developed. Although many image stabilizers can improve stability against light, they also degrade storage stability in dark places, reduce the color development of couplers, and are used in coating solutions used during the production of photosensitive materials. Some coatings may precipitate during stagnation and cause coating failures, so they do not necessarily give satisfactory results in all performances.

[Purpose of the Invention] An object of the present invention is to provide a silver halide photographic material that has excellent color reproducibility and exhibits minimal deterioration of dye images even when exposed to light for long periods of time or stored in a dark place. .

[Structure of the Invention] In view of the above-mentioned circumstances, the present inventors have conducted extensive research, and as a result, the present inventors have developed a method in which a certain combination of a coupler and an image stabilizer can be used without impairing the excellent properties of a silver halide photographic light-sensitive material. The inventors have discovered that the above object can be achieved quickly and have completed the present invention.

That is, the silver halide photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one of the emulsion layers is represented by the following general formula [I]. It is characterized by containing a bis-type phenol derivative in which one of the yellow couplers and one of the phenolic hydroxyl groups is substituted, and at least one of the phenol rings has a substituent.

General Formula [I] In the formula, R□ represents an alkyl group, R2 represents an aryl group, and Zl represents a coupling-off group bonded to a carbon atom through a nitrogen atom.゛Hereinafter, the present invention will be explained in detail.

R1 in the general formula [I] is a linear or branched alkyl group, preferably a t-tutyl group, and R2 is preferably a phenyl group. The aryl group represented includes those having a substituent, and the aryl group of R2 is preferably substituted with a halogen atom, an alkyl group, or the like. As z8, a group represented by the following general formula [■-1] is preferable, and a group represented by the general formula [I-1'] of general formula [I-1] is more preferable.

General formula [I-1] is -N Z,' \.

In the formula, Z and ' represent a group of nonmetallic atoms that can form a 4- to 7-membered ring.

General formula [I-1”] Represents a group of nonmetallic atoms that can form.

In the general formula [I], a preferable yellow coupler according to the present invention is represented by the following general formula [I-2].

In the general formula [■-2], R4 and R8 each represent a hydrogen atom, a halogen atom, or an alkoxy group. R4 is preferably a halogen atom, and R8 is preferably a hydrogen atom. Also R5, R6, R7
are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, carboxy groups,
Represents an alkoxycarbonyl group or a carbamyl amino group. R5 and R6 each represent a hydrogen atom, and R7 is preferably an alkoxycarbonyl group, an acylamido group, or an alkylsulfonamide group. Also z
l represents a group having the same meaning as zl shown in the above general formula [I], preferably represented by the above general formula [I-1], particularly preferably the above general formula [I-1'] Examples include groups represented by:

Further, among the couplers of the present invention represented by the general formula [I], the compound represented by the following general formula [I-3] is particularly preferable because it has excellent coloring properties and is suitable for rapid processing.

General formula [-3] In the formula, R9 represents a halogen atom or an alkoxy group, and R
IG is one NH (:ORIISO2RI2, COO
Rx2.

represents. R11 represents an alkylene group, R□2 represents a diffusion-resistant group, R13 represents an alkyl group, an aralkyl group, or a hydrogen atom; 2. represents a coupling-off group.

The yellow coupler represented by the general formula [I] of the present invention is
Can be used in conjunction with other yellow couplers.

The yellow coupler addition layer may be any silver halide emulsion layer, preferably a blue-sensitive silver halide emulsion layer, and the amount added is 2 x per mole of silver halide.
10-3 to 5 X 10-' mol is preferred, more preferably 1 x 10-2 to 5 X 10-' mol.

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

(Yl) (Y-2) (Y-3) 07C+ U3H7 (Y-’4) rule (Y-5) (Y-6) (Y-7) (Y-8) (Y-9) (Y-10) (Y-11) (Y-1, 2) H3U-L; Go to □■ (Y-13) (Y-14) HCbe, Jilt ゝC' ■ (Y-16) (Y-17) (Y-19) H3 (Y-20) H26'), f:H.

(Y-22) Q (Y-23) (Y-24) (Y-25) (Y-26) (Y-28) CH3 (Y-29) (Y-31) (Y-32) (Y- 33) (Y -34) (Y -35) (Y-36) (Y-37) (Y-38) (Y-39) (Y-40) (Yil) (Y-42) H3 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.

As a substituent for one phenolic hydroxyl group.

Examples include aliphatic hydrocarbons (e.g. alkyl groups, alkenyl groups), alicyclic hydrocarbons (e.g. cycloalkyl groups), aromatic hydrocarbon groups, sulfonyl groups (e.g. arylsulfonyl groups, alkylsulfonyl groups), and acyl groups. , the substituent includes those further having a substituent.

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 alkylidene groups, alkylene groups, sulfonyl groups, and petero atoms (eg, oxygen and sulfur), preferably alkylidene groups and sulfur atoms.

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 the Hensen ring of the phenol ring.

The M ground tea that at least one phenol ring in the bis-type phenol derivative has, 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.

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, etc. It can be obtained by reacting halides, dialkyl sulfates, etc.

The bis-type phenol derivative is preferably added in a particularly high-boiling organic solvent together with the coupler.

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 preferably contained in the silver halide emulsion layer in a state dissolved in oil droplets of a high-boiling point organic solvent. Those that are immiscible with water are preferred, such as phenol derivatives that do not react with oxidized developing agents, phthalates, phosphates, citric esters, benzoic esters, alkylamides, fatty acid nistyl, fatty acid amides, and trimesic acid esters. etc.

Among high boiling point organic solvents, those having 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 represented by the following general formula [II].

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

In the present invention, the alkyl groups represented by R1 and R2 in the general formula [II] may be linear or branched,
Examples include tutyl group, pentyl group, hexyl group, 2-ethylhexyl group, 3,5.5-trimethylhexyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, and the like. R□
The aryl group represented by and R2 is, for example, a phenyl group,
Examples of the alkenyl group include a naphthyl group, a hexenyl group, a heptenyl group, and an octadecenyl group.

These alkyl groups, alkenyl groups and aryl groups are
It also includes those having single or multiple substituents, and examples of substituents for argyl and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, alkoxycarbonyl groups, etc. Examples of substituents for the aryl 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, R1 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 advantageously used in the present invention include those represented by the following general formula [III].

General formula [III] represents a group, alkenyl group or aryl group. However, R3,
The total number of carbon atoms in the groups represented by R1 and R5 is 24 to 54.

The alkyl groups represented by R3, R4 and R5 in the general formula [I[II are, for example, tutyl 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, naphmol group, etc. Examples of the alkenyl group include hexenyl group, heptenyl group, and octadecenyl group.

These alkyl groups, alkenyl groups and aryl groups are
It also includes those having single or multiple substituents. Preferably R3, R4 and R5 are alkyl groups, 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, 5ec-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.

Q Exemplary organic solvent S-1 2H5 2H5 CH3CH3 2H5 0-CH2CH(CH2)3CH3 Complex O C2H5 CiH2 0H (OH2) 3CH32H5 4! -c 0-C9H□9(i) Q=p-Q-Q 9H , 9(i) 0-O gH , 9(i) 0-09H19(Xun 0; P-009H19(Xun oc, nl, (n) 0-C1oH21(i) 0=P-0-C1oH2□(i) View0-C1oH2□(i) ” zoH21(n) 0 = P-0-0 1oH2□(n)0-C1o
H2□(n) 0 -0□1H23(i) 0 = P O 011 H23(i)Q 011
H23(+) :47□ S-18 0-C1□Hzs(i) 0=P-0-01□H25(i) ■ O-C□2H25(i) The amount of high boiling point organic solvent used is It is preferably 0.1 to 10 m sentences, particularly preferably 0.5 to 2 m sentences per 1 g.

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

In the oil-in-water emulsion dispersion method, hydrophobic additives such as couplers are dissolved in a high-boiling organic solvent, if necessary in combination with a low-boiling and/or water-soluble organic solvent, and hydrophilic additives such as gelatin aqueous solution are dissolved. Stirrers, homogenizers, colloid mills, flowchette mixers, using surfactants in the binder.
It may be emulsified and dispersed using a dispersion means such as an ultrasonic device, and then 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 material of the present invention may be, for example, color negative and positive films, color photographic paper, etc., and may be for monochrome use or multicolor use.

In the case of multicolor silver halide photographic light-sensitive materials, there are usually a silver halide emulsion layer containing yellow, magenta, and cyan couplers and a non-light-sensitive layer, or an appropriate number and order of layers on the support. However, the number of layers and the 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 material of the present invention include silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any material used in emulsions can be used, but silver chlorobromide and silver chloride containing a high content of silver chloride are particularly preferred because they facilitate rapid processing.

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 light-sensitive material of the present invention, it is preferable to use ceratin, or other materials such as ceratin derivatives, tallaf polymers of gelatin and other polymers, proteins, sugars, etc. Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as derivatives, cellulose derivatives, 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.

The silver halide photographic material of the present invention can be used to form an image by subjecting it to a color development treatment known in the art.

[Effects of the Invention] According to the silver halide photographic light-sensitive material of the present invention, it is possible to provide a silver halide photographic light-sensitive material in which the preservability of yellow dye images, especially the light fastness, is improved without impairing color development. I can do it.

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

Example 1 0.075 mol of yellow coupler (shown in Table 1) and 0.05 mol of image stabilizer were dissolved in a high boiling point organic solvent (DOP).
) and a solution dissolved in ethyl acetate were added to an 8% gelatin aqueous solution containing a dispersion aid (dodecylbenzenesulfonic acid sodium salt) and dispersed with a homogenizer. The resulting dispersion was made into one sentence and kept at 40°C for 3 hours. This dispersion was mixed with an aqueous gelatin solution for coating and a blue-sensitive silver chlorobromide emulsion to prepare a coating solution for a blue-sensitive emulsion layer.

Coating solutions for a green-sensitive emulsion layer, a red-sensitive emulsion layer and a non-sensitive emulsion layer were prepared by a conventional method and coated on a polyethylene-coated paper support in the following order.

1st layer: blue-sensitive emulsion layer yellow coupler I x 10-5 mol/drn',
Blue-sensitive silver chlorobromide emulsion (containing 20 mol% silver chloride and 80 mol% silver bromide) in terms of silver: 3 mg/dm', high boiling point organic solvent (DOP): 3+ng/dm', image stabilizer 6.
67X 10-6 mol/dm' and gelatin at 16B/dm'
Apply so that the coating amount is dm'.

2nd layer: Intermediate layer hydroquinone derivative (HQ~1) 1, 2+++g
/dm', DOP was applied at a coating amount of 12 mg/drn' and gelatin was applied at a coating amount of 4 mg/drn'.

Third waste green-sensitive emulsion layer macenta coupler (M-1) at 4 mg/drrf, green-sensitive silver chlorobromide emulsion (silver chloride 20 mol%, silver bromide 80 mol%)
Contains) in terms of silver: 4 mg/drn', high boiling point organic solvent (DOP): 4 rng/dm', anti-fading agent AO-1
The coating amount was 2 mg/dm', 1 mg/drn' of AO-2, and 16+ng/drn' of gelatin.

4th layer/intermediate layer ultraviolet absorber (UV-1) at 3mg/dm', (UV-1)
2) at 3 mg/drn', high boiling point organic solvent (DOP) at 4n+g/dm'', hydroquinone derivative (HQ-2)
0, 45+ng/dm' and gelatin 14mg
/dm' coating amount.

5th layer: red-sensitive emulsion layer cyan coupler (C-1) at 4 rng/dm', high boiling point organic solvent (DOP) at 4 mg/drn', red-sensitive silver chlorobromide emulsion (silver chloride 20 mol%, bromide Contains 80 mol% silver) in terms of silver: 3 mg/drn' and gelatin: 14 mg
Apply so that the coating amount is 7 drrf.

6th layer: Interlayer UV absorber (UV-3) 4mg/d, high boiling point organic solvent (DOP) 2mg/drrf and gelatin 6
Apply the coating so that the coating amount is mg/drn'.

7th layer: Protective layer gelatin was coated at a coating amount of 9 mg/drrf.

(Compound used for sample preparation) DOP Ni(2-ethylhexyl)phthalate comparison Y
Coupler e t1 AO-1 AO-2 Q-1 Q-2 V-1 HC,)! , , (t) V-2 HV-3 These samples were subjected to optical wedge exposure with blue light using a photosensitive needle (KS-7 model manufactured by Konica), and then subjected to the following treatments.

Processing process Processing temperature Processing time Color development
Bleach and fix at 32.8℃ for 3 minutes and 30 seconds 3
2.8'C 1 minute 30 seconds water washing 32.8°0
3 minutes 30 seconds [Color developer composition] N-ethyl-N-(β-methanesulfonamidoethyl)
-3-methyl-4-aminoaniline sulfate
4.0g hydroxylamine sulfate 2.0g potassium carbonate
25.0g sodium chloride
0.1g potassium bromide
0.2g anhydrous sodium sulfite 2.0
g Pencil alcohol 10.0 m Polyethylene glycol (average degree of polymerization 40'0) 3.0
Add ml water to make one sentence, use sodium hydroxide,
Adjust the pH to 10.0.

[Bleach-fixing solution composition Coethylenediaminetetraacetate iron (m) Sodium salt 60.0g Sodium thiosulfate 100.0g Sodium bisulfite 20.0g Sodium metabisulfite 5.0g Water was added to make one sentence, and the pH was adjusted to 7 using sulfuric acid. , adjust to 0.

For each sample obtained after processing, bright and dark fading properties of the yellow image were evaluated in the following manner.

[Bright fading test When irradiated with 80 kilolux light for 3 weeks using a coxenone fade meter, the initial density was shown as a residual rate of 1.0.

Residual rate” (D/D,) x 100 (D = density after fading)
[Dark fading test] When stored for 14 days in a high temperature and high humidity atmosphere at 85°C and 60% R), the initial density decreased. The residual rate was -1.0.

Residual rate - (D / Do) x 100 (D = 0 after fading) 'a degree) In addition, for the measurement to evaluate the storage stability of the dye, the blue density was measured using a Konica DPA-65 densitometer. Measurements were taken. The results are shown in Table 1.

Table 1 Bis-type phenol derivative (image stabilizer) according to the present invention
is effective in increasing the stability of yellow images against light regardless of the type of coupler, but it can be seen that this effect is significantly enhanced when the yellow coupler according to the present invention is used. Furthermore, within the scope of the yellow coupler according to the present invention, various compounds (for example, Y-5, Y-26, Y-
38) was also found to have the effect of significantly increasing stability against light.

Example 2 A sample was prepared in the same manner as in Example 1 except that the silver halide emulsion was a silver chlorobromide emulsion containing 99.5 mol % of silver chloride, and was exposed to light wedge light with blue light by a conventional method. After that, the following treatment was performed. The sensitivity (relatively expressed with sample 201 as 100) and shoulder gradation (gradation of density 0.7 to 1.5) were determined for the obtained yellow image, and as in Example 1, light fading was determined. A dark fading test was conducted. The results are shown in Table 2.

Processing process Processing temperature Processing time Color development
34.7±0.3°CSO second bleach fixing 34.7
±0.5℃ 50 seconds stabilization 30~346C9
Drying for 0 seconds, 60 seconds at 60 to 80° C. In the Rakugai process, the composition of the treatment liquid used was as follows.

[Color developer co-triethanolamine 10+n sentence N,
N-diethylhydroxylamine (85% aqueous solution) IDm Potassium chloride 2g Sulfate
5g sodium tetrapolyphosphate 2g potassium sulfite
0.2g potassium carbonate
Add 30g of optical brightener (4,4'-diaminostilbenzsulfonic acid derivative) and 1.0g of pure water to make one sentence, and adjust to polo and oa.

[Bleach-fix solution] Disodium ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 mfl Ammonium sulfite (40% solution) 27.5 ml Add water to make one part, and adjust to pH 5.5 with potassium carbonate or glacial acetic acid.

[Stabilizing liquid 5-Chloro-2-methyl-4-inthiazolin-3-one Add 1 g of water to make one sentence, and adjust to pH 7.0 with sulfuric acid or potassium hydroxide.

Table 2 Bis-type phenol derivative (image stabilizer) according to the present invention
The effects of improving the light stability of the yellow image obtained when using the yellow coupler (especially noticeable in combination with the yellow coupler of the present invention) and the storage stability in the dark are due to the high silver chloride content. It can be seen that similar results can be obtained when rapid processing is performed using a silver halide emulsion. The use of a silver halide emulsion having a high silver chloride content is a preferred embodiment of the present invention because an image can be obtained in a short time without impairing the effects of the present invention. Further, Samples 210 to 212 using couplers represented by the general formula [I-3] are more preferable because they can obtain images with higher sensitivity and higher contrast. In addition, samples 202 and 205 using comparative compound A showed a deterioration in sensitivity gradation compared to samples 201 and 204 in which no image stabilizer was added.
When the bis-type phenol derivative according to the present invention is used, such a problem does not occur, and when rapid processing is performed, the uninvented effects are fully exhibited, which is preferable.

Example 3 A solution in which yellow coupler Y-36 and the image stabilizer shown in Table 3 were dissolved in a high boiling point organic solvent (DOP) and ethyl acetate was mixed with 8 containing dodecylbenzenesulfonic acid sodium salt.
% aqueous gelatin solution and dispersed using a homogenizer. The resulting dispersion was made into one sentence and kept warm at 40°C.
A blue-sensitive emulsion coating solution was prepared by appropriately dividing the sample, and a coating sample was prepared in the same manner as in Example 2.

In this way, a series of coating samples having different heat retention retention times were prepared as dispersions. This sample was subjected to optical wedge exposure with blue light, and then developed according to Example 2, and the blue density and green density of the obtained yellow image were measured and the blue density (DB) was determined.
The green density (DG) at the 2.50 part was determined and color turbidity was evaluated. At the same time, light fading and dark fading were evaluated, and the results are shown in Table 3.

Table 3 Magenta color mixing in high density areas of yellow images tends to increase as the heat retention stagnation time increases, but in the compound according to the present invention, the color mixture after 3 hours is small, and further, the heat retention stagnation time increases. The degree of deterioration was also small and showed good characteristics.

When the bis-type phenol derivative according to the present invention is used, there is less color mixing, so it is possible to reproduce vividly without yellowing or reddish.

Comparative compound B in terms of photostability of yellow images
However, the bis-type phenol derivatives according to the present invention have excellent photostability. It can be seen that the light stabilizing effect is not impaired due to color turbidity or stagnation in heat retention.

Comparative Compound B Example 4 A sample was prepared in the same manner as in Example 2, except that the yellow coupler, image stabilizer, and high-boiling organic solvent were changed as shown in Table 4, and the light fading property and dark fading property were evaluated. .

Table 4 It can be seen that even when various compounds are changed in the combination of the yellow coupler and the bis-type phenol derivative according to the present invention, yellow images with high photostability and improved storage stability in the dark can be obtained. Among them, when a compound with a dielectric constant of 6.0 or less is used as a high boiling point organic solvent, the photostability is significantly improved. It is a preferred embodiment of the present invention to use a compound with a dielectric constant of 6.0 or less as the high boiling point organic solvent.

Also, instead of Y-3 of sample 405, Y-22, Y-24,
The effects of the present invention were also observed when Y-31 and Y-33 were used.

Example 5 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/rn'. However, for silver halide, the coating amount is expressed in terms of silver.

1st layer (gelatin layer) Ceratin 1.40 2nd M
(Antihalation layer) Black colloidal silver 0.10 Seratin 0.60 3rd layer (1st
Red sensitive layer) Cyan coupler C-10,07 Cyan coupler C-20,14 Bis-type phenol derivative (7) 0.20 High-temperature point solvent (S-12) 0.06D,
14 Gelatin 1.0 4th layer (second red-sensitive layer) Cyan coupler C-10,10 Cyan coupler C-20,20 High boiling point solvent (S-12) 0.10
Bis-type phenol derivative (7) 0.300.
16 Gelatin 1.0 5th layer (
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) j O, 150, 15 Seratin 1.0 7th layer (
2nd green-sensitive layer) Bis-type phenol derivative (7) 0.14 Magenta coupler (M-2) 0.14 High boiling point solvent (S-'2)' 0.15 Gelatin l.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-36) 0.40 High clear point solvent (S-2) 0.10 Spectrally sensitized with blue sensitizing dye (D-4) AgBr1 (Ag1
3.0 mol%, average particle size 0.4 JL+n) 0.15 Bis-type phenol derivative (7) 0.40 Gelatin 0.70 10th layer (
Second blue sensitive layer) Yellow coupler (Y-36) 0.80
High clearing point solvent (S-2) 0.20 AgBr1 (A
gl 3.0 mol%, average particle size 0.8 JLm) 0.2
0 Bis-type phenol derivative (7) o, g.

Gelatin 1.3 11th layer (ultraviolet absorbing layer) Ultraviolet absorber U-10,2 Ultraviolet absorber U-20,2 Ultraviolet absorber U-30,2 Ultraviolet absorber U-40,2 Gelatin 2.0 12th layer Layer (protective layer) Ceratin 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.

Ultraviolet absorber 0 ■ R> R2R3 U-1(t)CJs (t)C<H9HU-2Ct
)C4H9CH3' CIU-3(t)Cl3(t
)C4H9CJljU 4 (t)CsHt+
(t) CsH++ 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
100] ux or more 1 second or more Second 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 1.0g Sodium bromide 2.4g Potassium iodide
8.0 mg potassium hydroxide (48%
) 6.2m potassium carbonate
14g sodium bicarbonate
12g1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5g
Hydroquinone monosulfonate 23.3g Add water to make one sentence and adjust the pH to 9.65.

[Color developer Copencyl alcohol 14.6n1 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 Add 5.0g water to make one sentence.

[Bleach-fix solution] 1.56 molar solution of ammonium salt of ethylenediaminetetraacetate diiron complex 115Il
lKL Sodium Metabisulfite 15.4
gAmmonium thiosulfate (58%) 126m
M1.2.4-) Riazole-3-thiol 0.
Add 4g of water to make one layer and adjust the pH to 6.5.

Patent applicant: Konica Co., Ltd. Chief brewer: Nobuaki Sakaguchi, patent attorney

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one layer of the emulsion layer comprises a yellow coupler represented by the following general formula [I] and one phenol. 1. A silver halide photographic light-sensitive material comprising a bis-type phenol derivative having a substituted hydroxyl group and at least one phenol ring having a substituent. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are included▼ In the formula, R_1 represents an alkyl group, R_2 represents an aryl group, and Z_1 represents a coupling-off group bonded to a carbon atom through a nitrogen atom.