JPS63187240A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce the discoloration and decoloration of a cyan dye image at the time of preserving it by incorporating a specified cyan coupler in a silver halide emulsion layer, and incorporating a UV absorber which is liquid at a normal temperature and a high boiling point org. solvent in a prescribed layer, respectively. CONSTITUTION:One or more kinds of the cyan coupler shown by formula I are incorporated in the silver halide emulsion layer. And, the UV absorber (for example, the compd. shown by formula II) which is the liquid at the normal temperature, and the high boiling point org. solvent such as phthalic acid ester which has <=6.0 dielectric constant and contains 0.65-0wt. ratio on the weight basis of the absorber, are incorporated in the emulsion layer or a nonphotosensitive layer adjacent to the emulsion layer at the opposite side to the substrate of the emulsion layer or the nonphotosensitive layers which exist at the both sides of the substrate and are adjacent to the emulsion layers, etc. In formula I, R1 is 2-6C alkyl group, R2 is a ballast group, Z is hydrogen atom or an atom or a group which is capable of releasing by reacting with the oxidant of a color developing agent. In formula II, R1-R3 are each hydrogen atom. or a halogen atom.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide photographic material in which the dye images formed have good storage stability.

[Background of the invention]

It is generally known that dye images formed in hacl5/silver chloride color photographic light-sensitive materials change color and fade under various storage conditions. For example, when color prints are exposed to light for long periods of time and stored, such as in photo studio window displays, the color changes and fades, a phenomenon known as chronological fading. In addition, when color prints are stored in albums, they are exposed to light for a short period of time, but if they are stored in a dark place with high temperature and humidity for a long period of time, there is discoloration and fading, which is called darkening and fading. When a photographic product containing an image is viewed as a recording material, in order for the dye image carried to have semi-permanent preservation, it is desirable that the above-mentioned discoloration and fading be as small as possible under any storage conditions, and in recent years this demand has increased. It's only going to increase. Furthermore, it is generally desired that the occurrence of yellow stain due to light, heat, and humidity in uncolored areas is as small as possible, as is the case with fading. In particular, cyan couplers are required to have a well-balanced improvement in bright discoloration, clear discoloration, and occurrence of yellow stain. Furthermore, in the case of cyan couplers, in bleaching or bleach-fixing baths in which the oxidizing agent is exhausted or the reducing agent brought in by the photosensitive material has accumulated, the concentration of the cyan coloring dye decreases due to leuco conversion (hereinafter referred to as cyan recoloring property). ) is known to easily occur, and similar improvements are desired. For this reason, many improvement measures have been proposed in the past as techniques for preventing discoloration and fading of cyan couplers. To improve fading in the dark, sterically hindered P-hydroxybenzoic acid phenyl esters, sterically hindered amines, etc. are used, and to improve fading in the light, hydroxy722benz) 1
7Azole ultraviolet absorbers have been proposed as discoloration and fading improvers. Furthermore, as the ultraviolet absorber, liquid ultraviolet absorbers described, for example, in US Pat. No. 4,587,346 and European Patent No. 57,160 have also been proposed recently. On the other hand, a 2-7 sylami 7 phenolic cyan coupler which has a specific purchase price as a means to improve the resistance of cyan couplers is disclosed in, for example, JP-A-60-117249.
In addition, 2,5-diacylamide/phenolic cyan couplers are described in, for example, US Pat. No. 2,895,826, and are found to be effective to some extent against fading in the dark. Furthermore, several improvement techniques have been proposed for the purpose of improving the drawbacks and resistance of the cyan coupler having the above-mentioned specific structure.
No. 550 discloses a combination of a specific 2-7-sylaminophenol-based cyan coupler and an ultraviolet absorber; A combination with an E/L cyan coupler is described.However, in the methods mentioned above, although some effects on darkening and light discoloration, yellow stain, and cyan color restoration are recognized, all of them are effective. At present, satisfactory results have not been obtained in terms of performance, and improvements have been greatly desired.

Problem 1 to be Solved by the Invention In order to solve the above-mentioned problems, the object of the present invention is to provide a cyan dye image with excellent resistance to discoloration and fading during storage, and to reduce leuco formation of the cyan dye in the development process. The purpose of the present invention is to provide a silver halide photographic light-sensitive material. Other objects of the invention will become apparent from the description below. [Means for Solving the Problems] The above object of the present invention is to provide a silver halide photograph having, on a support, photographic constituent layers including at least one silver halide emulsion layer and at least one light-insensitive layer. In the photographic material, the silver halide emulsion layer contains at least one cyan coupler represented by the following general formula [I], and at least one of the photographic constituent layers contains at least one ultraviolet absorber that is liquid at room temperature. The layer containing the seeds and the ultraviolet absorber contains a high boiling point organic solvent with a dielectric constant of 6.0 or less at a weight ratio of 0.6 to the total amount of the ultraviolet absorber that is liquid at room temperature.
This was achieved using a silver halide photographic light-sensitive material having a silver halide content in the range of 5 to 0. The following is a blank general formula [1] In the formula, RI represents an alkyl group having 2 to 6 carbon atoms. R2 represents a ballast group, and Z represents a hydrogen atom or an atom capable of being eliminated by reaction with an oxidized product of the color developing herbal medicine, or a staking group. The alkyl group represented by R2 may be linear or branched, and includes those having a substituent. The ballast group represented by R2 is an organic group having a size and shape that imparts sufficient bulk to the coupler molecule to substantially prevent the coupler from diffusing from the layer to which it is applied to other layers. be. Preferred ballast groups are those represented by the following general formula. -ell-0-^r R R1 represents an alkyl group having 1 to 12 carbon atoms,
represents an aryl group such as a phenyl group, and this aryl group includes those having a substituent. Next, specific examples of the coupler represented by the general formula [1,] will be shown, but the coupler is not limited thereto. Specific examples of cyan couplers that can be used in the present invention, including these, include JP-B No. 49-11572, JP-A-61-3142, JP-A-61-9F352, and JP-A-61-9F.
No. 9853, No. 61-39045, No. 61-501:
No. 116, No. 61-99141, No. 116 (II-1055)
45 etc., it is written as 1m. The cyan dye-forming coupler of the present invention represented by the general formula [1] is usually 7% LX per mole of silver lodenide.
10-' mol - 1 mol, preferably 1X10-'' mol ~
A range of 8×10-' moles can be used. The cyan coupler represented by the general formula [, I] below can be used in combination with other cyan couplers within the scope of the purpose of the present invention. In particular, the following general formula [11]
A combination with a cyan coupler represented by can be preferably used. General formula ['■] n+1 In the formula, R4 represents an alkyl group or an aryl group, R
5 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R6 represents a hydrogen atom, a halogen atom, an alkyl group or a flukoxy group, and R@ may be combined with R4 to form a ring. Z represents a hydrogen atom or a group or atom which can be separated by reaction with an oxidized product of a color developing agent. Typical specific examples of cyan couplers represented by general formula (n) are shown below. The cyan coupler according to the present invention is usually silver halide 1
It is used in the range of about 0.05 to 2 moles per mole, preferably 0.1 to 1 mole. The cyan coupler according to the present invention is usually contained in a red-sensitive silver halide emulsion layer, but it may also be contained in a non-sensitized emulsion or an emulsion layer sensitive to the three primary color regions of the spectrum other than red. In the present invention, an ultraviolet absorber that is liquid at room temperature (hereinafter referred to as the liquid ultraviolet absorbent of the present invention) is used. In the present invention, "liquid at room temperature" means at 25°C,
As defined in ``Chemistry Encyclopedia (1963), Tsuzuma Publishing,'' it refers to something that does not have a fixed shape, is fluid, and has a nearly constant volume. Therefore, as long as it has the above properties, the melting point is not limited, but compounds with a melting point of 30'C or lower, particularly preferably 15C or lower, are preferred. The liquid ultraviolet absorber of the present invention may be a single compound or a mixture, and as a mixture, one composed of a group of structural isomers can be preferably used. (Structural isomers are described in U.S. Patent No. 4,587,346, etc.) The liquid ultraviolet absorber of the present invention can have any structure as long as it satisfies the above requirements. From the viewpoint of light fastness, 2-(2'-hydroxyphenyl)benzotriazole compounds represented by the following general formula [a] are preferred. General formula [a] 11゜In the above general formula [a], J3, R+, R2 and R
3 each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group, or a hydroxyl group. Examples of the halogen J represented by R+, R2 and R3 include fluorine atom, chlorine atom, fresh water atom, etc., with chlorine atom being particularly preferred. The alkyl group and alkoxy group represented by R+, R2 and R3 preferably have 1 to 30 carbon atoms,
The alkenyl group preferably has 2 to 30 carbon atoms, and these groups may be linear or branched. Moreover, these alkyl groups, alkenyl groups, and alkoxy groups may further have a substituent. Specific examples of alkyl groups, alkenyl groups, and alkoxy groups include methyl groups, ethyl groups, isopropyl groups, [
-Butyl M, 5ec-butyl group, n-butyl group, n-amyl group, 5ec-amyl group, t-amyl group, octyl group, nonyl group, dodecyl group, eicosyl group, α, α-dimethylbenzyl group, octyl group Examples include oxycarbonylethyl ethoxy group, octyloxy group, and allyl group. The aryl group and aryloxy group represented by R1, R2 and R3 are particularly preferably, for example, a phenyl group or a phenyloxy group, which may have a substituent. Specific examples include phenyl group, 4-t-butylphenyl group, 2,4-di-t-amylphenyl group, and the like. Among the groups represented by R1 and R2, a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group are preferred, and a hydrogen atom, an alkyl group, and an alkoxy group are particularly preferred. Among the groups represented by R3, hydrogen atoms, halogen atoms, alkyl groups, and alkoxy groups are particularly preferred, and hydrogen atoms, alkyl groups, and alkoxy groups are even more preferred from the viewpoint of light fading. Among the groups represented by R+, R2 and R3, at least one is preferably an alkyl group, and more preferably at least two are alkyl groups in order to become liquid at room temperature. The alkyl groups represented by R1, R2 and R3 can be any alkyl group, but preferably at least one is a tertiary alkyl group or a secondary alkyl group. In particular, it is preferred that at least one of the alkyl groups represented by R1 and R2 is a tertiary alkyl group or a secondary alkyl group. Below are representative examples of the liquid ultraviolet absorber according to the present invention. 0.1~ by weight compared to banhgu
It can be used in the range of 300%, preferably 1 to 2
00%, more preferably in the range of 5 to 100%. Also, the coating amount is 0.01-100++
+g/100cm", and more preferably 0.1 to 501I1g/100cL112, especially 0
．． It is preferable to use it at 5 to 30 mg/100c+a2. In the present invention, the cyan coupler according to the crime prevention invention is contained in the silver halide emulsion layer, and the liquid ultraviolet absorber according to the present invention is contained in the cyan coupler-containing silver halide emulsion layer and the non-photosensitive layer adjacent to this layer. The liquid ultraviolet absorber according to the present invention is preferably contained in at least one layer selected from the layers, and the liquid ultraviolet absorber according to the present invention is preferably contained in at least one layer adjacent to the silver halide emulsion layer on the side opposite to the support when viewed from the support. This is the case where it is contained in a non-photosensitive layer, and more preferably the case where it is contained in both non-photosensitive layers adjacent to the silver ha 1175/N emulsion layer. When the cyan coupler-containing silver halide emulsion layer according to the present invention contains the liquid ultraviolet absorber according to the present invention,
As for the addition method, since the liquid ultraviolet absorber according to the present invention is liquid at room temperature and can be used as a solvent for the cyan coupler according to the present invention, the liquid ultraviolet absorber according to the present invention and the cyan coupler are simply mixed together. It can be finely dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant or, if necessary, a low boiling point solvent such as ethyl acetate. In addition, high boiling point solvents such as phenol derivatives, phthalic esters, phosphoric esters, citric esters, benzoic esters, alkylamides, fatty acid esters, and trimesic esters may be used in combination, if necessary. When adding the liquid ultraviolet absorber according to the present invention to a non-photosensitive layer adjacent to a cyan coupler-containing silver halide emulsion,
The liquid ultraviolet absorber according to the present invention can be used as it is, or if necessary, it can be finely dispersed in a hydrophilic binder such as an aqueous gelatin solution using a low boiling point solvent such as ethyl acetate using a surfactant. Further, if necessary, a high FED point solvent similar to the above may be used in combination. Furthermore, the liquid ultraviolet absorber according to the present invention may be used in combination with a solid ultraviolet absorber at room temperature, and the above-described addition method can also be applied in this case. When the silver halide photographic light-sensitive material of the present invention is a multicolor light-sensitive material, the specific layer structure includes:
Sequentially from the support side: a yellow coupler-containing silver halide emulsion layer, a first intermediate layer, a magenta coupler-containing silver halide emulsion layer, a second intermediate layer, a cyan coupler-containing silver halide emulsion layer according to the present invention, and a third intermediate layer. , and those arranged with a protective layer are particularly preferred. In particular, when the silver halide photographic light-sensitive material of the present invention has the above-mentioned layer structure, the liquid ultraviolet absorber of the present invention is preferably contained in at least the third intermediate layer, more preferably the second intermediate layer and It is preferably contained in the third intermediate layer. In addition, in the present invention, in the layer containing the liquid ultraviolet absorber, a high boiling point organic solvent with a dielectric constant of 6.0 or less is added to
．． It exists in the range of 65 to 0, preferably in the range of 0.30 to 0. The high boiling point paid solvent according to the present invention may be any compound having a dielectric constant of 6.0 or less. The lower limit is not particularly limited, but the dielectric constant is preferably 1.9 or more. Examples include esters such as phthalic esters and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds having a dielectric constant of 6.0 or less. More preferred are phthalic acid esters or phosphoric acid esters. A 1a solvent with a high temperature point and a vapor pressure of 0.5 mm1-1n or less at 100°C is preferred. The organic solvent may be a mixture of two or more types, and in this case, the dielectric constant of the mixture is 6.
It is sufficient if it is 0 or less. The Xff1 rate in the present invention is 3
It shows the Li ffi rate at 0°C. Below, the blank phthalate esters are JP-A-59-1056.
Examples of the phosphoric acid ester include the compounds described in the general formula [ff] of No. 45;
Examples include the compound described in the general formula [11] of No. 646. Furthermore, in the present invention, a high boiling point organic solvent with a dielectric constant of over 6.0 may be included simultaneously with a high boiling point organic solvent with a dielectric constant of 6.0 or less, and the weight ratio of the high boiling point organic solvent with a dielectric constant of 6.0 or less to the total amount of the high boiling point organic solvent is 0.5 or less, preferably 0.5 or less, preferably 0.
It is 25 or less, more preferably 0.1 or less. The silver halide photographic light-sensitive material of the present invention having the above structure can be, for example, color negative and positive films, color photographic paper, etc., but in particular color photographic paper used for direct viewing can be used. In such cases, the effects of the method of the present invention are effectively exhibited. The dye image-forming couplers used in the present invention are particularly limited other than the cyan couplers according to the present invention, and include 1゛,: F
Although various couplers can be used without limitation, the compounds described in 1 below are included as typical examples 2. Yellow dye image-forming couplers include acylacetamide type and benzoylmethane type couplers. Examples of magenta dye image-forming couplers include 5-lazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indacilone type, and cyanoacetyl type magenta dye image-forming couplers. The silver halide used in the silver halide photographic light-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 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. It is advantageous to use gelatin as the binder (or protective colloid) used in the silver halide photographic material of the present invention, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugars, etc. Hydrophilic colloids such as derivatives, cellulose derivatives, synthetic hydrophilic polymeric substances such as single or copolymers can also be used. The silver halide photographic light-sensitive material of the present invention contains a hardening agent, a color clouding preventive agent, an image stabilizer, a plasticizer, latex,
Additives such as surfactants, matting agents, lubricants, and antistatic agents can be used as necessary. An image can be formed using the silver halide photographic material of the present invention by subjecting it to a color development treatment known in the art. [Specific Effects of the Invention] As explained above, the silver halide photographic light-sensitive material of the present invention has improved brightness fading resistance of cyan dye images, particularly eliminates discoloration in low density areas, and can be stored for a long period of time. This silver halide photographic material is capable of forming cyan images that are stable against light, heat, and humidity even when exposed to light, heat, and humidity, and in which conversion of cyan dye to leuco form is reduced in the development process.

[Specific embodiments of the invention]

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto. Margin magenta coupler below M-1 I OP C, 11゜嘱C! I+. As-1D, S-1, Y-1, and M-1 used here are compounds having the structures shown below. Anti-stinting agent ΔS-1 Anti-fading agent O8-1 Yellow coupler Y-1 [Example 1] A multilayer silver halide photographic light-sensitive material prepared under the H4M composition shown in Table 1 was prepared. Created. Table 1 The numbers in parentheses indicate the application port or amount added. Table 1 (continued) Umbrellas are shown in Table 2. BP IDP EHP (OCH2CH(CH2)zcHs): +P○C2Hs After performing optical wedge exposure on these samples 1 to 16 with white light using a photosensitive needle (KS-7 type manufactured by Konishiroku Photo Industry Co., Ltd.), The following treatments were performed. Standard processing steps (processing temperature and processing time) [1 color development 38°C 3 minutes 30 seconds [2] Bleaching layer 33°C 1 minute 30 seconds [3 washing with water 2
5-30℃ 3 minutes [4] Drying 75-80℃
About 2 minutes or less Margin processing solution composition (color developer) Benzyl alcohol 15v12 ethylene glycol 15vN potassium sulfite 2.0g potassium bromide
0.70 Sodium Chloride
0.2G potassium carbonate 3
0.00 Hydroxylamine lll salt 3.00 Polyphosphoric acid (TPPS) 2.503-
Methyl-4amylyN-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5. ．． 5 (1 Fluorescent brightener (4,4'-diaminostilbene di-4 resulfonic acid derivative) 1. QQ potassium hydroxide 2.00 Add water to make total ff11ffi and adjust to DH10.20. (Bleach-fix solution - A) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 (J ethylenediaminetetraacetic acid lj 3g ammonium thiosulfate (70% solution) 1001 + Q ammonium sulfite (40% solution) 27.5% pi-17,1 with potassium carbonate or glacial acetic acid The following margin (bleach-fix solution-B) The composition was the same as that of bleach-fix solution A, except that 300 cc of the color developing solution was added to bleach-fix solution A. Obtained after processing. Various tests were conducted on the sample using the following methods: (1) Dark fading test 20 minutes in a dark, high-temperature, high-humidity atmosphere at 70°C and 80% RH.
Dye residual concentration (%) at initial concentration 1.0 after storage for days
) was measured. (2) Light fading test Using a xenon fade meter (100,000 lux), the residual dye density (%) at an initial density of 1.0 was measured after irradiation for 200 hours. (3) Optical yellow stain (hereinafter referred to as optical YS) of the uncolored area of the sample after irradiation for 200 hours in optical yellow stain (2) was evaluated as follows. Light YS: 80B = DB-D, B DB = Blue density after irradiation, B = Seihaku Utsuhiko before irradiation (4) Cyan rechromatic color developer, bleach-fix solution A and bleach-fix solution B The maximum color density of cyan treated with each was evaluated as follows. Cyan recolorability (%) = DRB/DRA DRA: Light color density of bleach-fix solution treated with bleach-fix solution A DRB: Maximum color density of cyan treated with bleach-fix solution B. These densities are measured using an optical densitometer (Konishi The measurement was carried out using a PDA-65 model (manufactured by Rokusha Kogyo Co., Ltd.). The results obtained in (1) to 4) are shown in Table-2.
Further, the dielectric constant of the high boiling point organic solvent of the present invention used in the examples is shown. High boiling point organic solvent No., dielectric constant DOP
5. I D N P 4.6D I D
P 4.4D B P
8.5TE HP 4
．． The results of 6 and above are summarized in Table 2. - From the results in Margin Table 2 below, it can be seen that Samples 2 to 4 using an ultraviolet absorber for the cyan coupler of the present invention are somewhat effective against bright fading and optical yellow stain compared to Sample 1. , there is almost no effect on dark fading and cyan recoloring. It can also be seen that sample 5, in which a cyan coupler other than the present invention was combined with the constituent requirements of the present invention, had particularly poor dark fading properties. In contrast, Samples 6 to 16 of the present invention exhibited excellent performance in all evaluations, indicating that the effects of the present invention were fully exhibited. Furthermore, the samples of the present invention will be examined in detail. It can be seen that among the liquid ultraviolet absorbers represented by the general formula [, ], Samples 6 to 11 and 13 to 16, which do not contain a halogen atom in R2, are more preferable in terms of optical yellow stain. Furthermore, it can be seen that among the high-boiling point organic solvents, Samples 6 to 14 using phthalate ester solvents or Sample 16 not using any high-boiling point organic solvent showed particularly favorable results in terms of bright room fading resistance. . [Example-2] Samples 21 to 34 were prepared and evaluated in the same manner as in Example-1, with the contents and layers of each ultraviolet absorber and high-boiling organic solvent changed as shown in Table-3. did. The ultraviolet absorber, the high boiling point organic solvent, and the above weight ratio are the same as in Example-1, and the contents are indicated by the sample number of Example-1. However, for the evaluation of color reversibility, instead of the bleach-fix solution B used in Example-1, a fatigue solution of a solution processed using an automatic color vapor processor was used. The results obtained are shown in Table 3. From the results in Table 3, even when the constituent features of the present invention are applied to two or more of the photographic constituent layers, also in sample 32,
Even when different constituent requirements are applied to each photographic constituent layer, the effects of the present invention are fully exhibited. Furthermore, Samples 23, 26 to 32, and 34, which contain the constituent elements of the present invention in the non-photosensitive layer (sixth layer) on the opposite side of the support from the cyan coupler-containing layer when viewed from the support, are light fading, ζ. It can be seen that particularly favorable results are shown. On the other hand, it can be seen that Samples 27, 28, and 31, in which the cyan coupler represented by the general formula [■] and the cyan coupler of the present invention were used in combination, showed favorable results with further improvement in dark fading and color recovery properties. [Example-31 In the two samples used in Example 2 and 31, instead of the cyan coupler I-4 of the present invention, I-8, I-9, ■-
Samples using No. 12, ■-14, ■-16 and ■-17 were prepared and evaluated in the same manner as in Example 2.
The effects of the present invention were fully demonstrated and good results were shown.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having a photographic constituent layer including at least one silver halide emulsion layer and at least one non-photosensitive layer on a support, wherein the silver halide emulsion layer contains at least one cyan coupler represented by the following general formula [I], at least one of the photographic constituent layers contains at least one ultraviolet absorber that is liquid at room temperature, and the ultraviolet absorber The layer containing silver halide is characterized in that a high boiling point organic solvent having a dielectric constant of 6.0 or less is present in a weight ratio of 0.65 to 0 with respect to the total amount of ultraviolet absorber that is liquid at room temperature. Photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents an alkyl group having 2 to 6 carbon atoms. R_2 represents a ballast group. Z is a hydrogen atom or oxidation of a color developing agent. (Represents an atom or group that can be separated by reaction with a body.)