JPH03140952A - Silver halide photographic sensitive material having excellent formalin resistance - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material which is improved in formalin resistance and is less deteriorated in fragility by incorporating a 4 equiv. yellow coupler into the nonphotosensitive layer of the position further from a base than photosensitive silver halide emulsion layers. CONSTITUTION:This photosensitive material has at least one layer of the photosensitive silver halide emulsion layers on the base and has at least one layer of the nonphotosensitive layers in the position furtherer from the base than at least any one layer of the emulsion layers, i.e. on the outer side. At least any one layer of the nonphotosensitive layers contain the 4 equiv. yellow coupler. The 4 equiv. yellow coupler functions as a formalin scavenger. The nonphotosensitive layers to be incorporated with the 4 equiv. yellow coupler are preferably a protective layer or the intermediate layer adjacent to the protective layer, etc. The silver halide photographic sensitive material which is less deteriorated in the fragility and is highly resistant to formalin is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material having excellent resistance to pomarin. The present invention can be particularly suitably used as a silver halide color photographic light-sensitive material having excellent resistance to formalin gas.

[Prior Art] It is well known that the performance of silver halide photographic materials is affected by the effects of various harmful gases.

Among them, formalin (formaldehyde) is used in furniture, building materials, clothing, etc. as a resin raw material, bactericidal agent, curing agent adhesive, etc., and is used in silver halide photographic materials, especially silver halide color photographic materials. When stored for a long time in such an environment, various constituent compounds including couplers react with formalin, resulting in undesirable changes such as a decrease in color density, staining, and an increase in fog density.

In order to prevent such deterioration of photographic performance, a technique has been developed in which a compound (formalin scavenger) that reacts with formalin and converts it into a harmless substance is contained in a photosensitive material.

Examples of such techniques are Japanese Patent Publications No. 46-34675, No. 48-38418, No. 51-23908, and Japanese Patent Publication No. 51-23908.
No. 0-87023, No. 57-133450, No. 58-
No. 150950, No. 58-79248, U.S. Patent No. 2
．． 895.827, 3.652.278, 3゜770.431, 3,811,891, 4.0
No. 03,748, No. 4,411.987, No. 4,41
No. 4,309, No. 4,418,142, No. 4,464
．． 463, US Defense Patent No. 900,028, West German Patent No. 3,223,699, West German Patent No. 3,227.961,
3゜227, No. 962, Research Disclosure No. 10.133, etc.

However, these compounds have the disadvantage that when added to a photosensitive material in an amount necessary to obtain a sufficient effect, they deteriorate film properties such as brittleness and film hardness.

Furthermore, it is known that pyrazolone-based 4-equivalent magenta couplers are particularly susceptible to formalin, and it is clear that it is preferable to contain a large amount in the layer containing the magenta coupler and/or the layer above it. However, all of these formalin scavengers have a problem in that they are highly water-soluble and diffuse uniformly into photosensitive materials, so that they do not function effectively.

If a lipophilic group (ballast group) is introduced into these formalin scavengers and added by oil protection dispersion, diffusion in the photosensitive material can be suppressed, but this will weaken the formalin scavenging effect.

Further, due to problems with the film properties, it is not possible to add a large amount, and in the end it is not possible to use an amount that will provide a sufficient effect.

As described above, although the conventional techniques have a certain effect on improving formalin resistance, they also have drawbacks, and improvements are desired.

On the other hand, JP-A-62-159145 discloses a technique for improving formalin resistance by adding a magenta coupler to a protective layer or a layer adjacent thereto.

Although this technique is also effective in improving formalin resistance, strong color turbidity inevitably occurs due to its structure, so measures must be taken to prevent this. This publication discloses a technique for preventing color turbidity using a scavenger of an oxidized developing agent or a non-color-forming coupler. However, this results in problems such as desensitization, deterioration of storage stability, and an increase in the oil component of the protective layer.

[Purpose of the invention]

An object of the present invention is to provide a silver halide photographic material that has improved formalin resistance and exhibits no or little deterioration in brittleness.

[Structure of the invention]

The above-mentioned object of the present invention is to have at least one photosensitive silver halide emulsion layer on a support, and at least one photosensitive silver halide emulsion layer is located at a position farther from the support than at least one of the photosensitive silver halide emulsion layers. Achieved by a silver halide photographic material having one non-photosensitive layer, characterized in that at least one of the non-photosensitive layers contains 4 equivalents of a yellow coupler. It was done.

The present invention will be explained in more detail below.

In the photosensitive material of the present invention, at least one of the non-photosensitive layers contains 4 equivalents of a yellow coupler. This 4-equivalent yellow coupler functions as a formalin scavenger.

The light-sensitive material of the present invention has at least one photosensitive silver halide emulsion layer on a support, and at least one layer is located further away from the support (outside) than at least one of the emulsion layers. It has a non-photosensitive layer. When two or more silver halide emulsion layers are present, in a preferred embodiment of the present invention, one or more non-photosensitive layers are provided at a position farther from the support than all of these emulsion layers; It is preferable that this non-photosensitive layer (at least one layer in the case of two or more layers) located at a position farther from all the emulsion layers contains a 4-equivalent yellow coupler.

Specifically, a preferable example of the non-photosensitive layer containing 4 equivalents of yellow coupler is a protective layer or an intermediate layer adjacent to the protective layer.

In the case of ordinary negative light-sensitive materials for photography, an emulsion layer consisting of a combination of blue-sensitive silver halide and a yellow coupler is generally coated as the top layer (the layer farthest from the support) as the light-sensitive layer. Therefore, when the present invention is applied in such a manner that the protective layer or the intermediate layer adjacent thereto contains the 4-equivalent yellow coupler as a formalin scavenger, no particular measures are required to prevent color turbidity. It's advantageous.

However, of course, it is not necessarily essential that the non-photosensitive layer to be included be located further from the support than all the emulsion layers, and the non-photosensitive layer that is further away from the support than the emulsion layer to be focused on as a layer to have an effect. The desired effect can be obtained by containing 4 equivalents of yellow coupler in the sexual layer.

For example, a layer that is located far from the support relative to the magenta coupler-containing emulsion layer that is most affected by formalin gas and is not a protective layer, such as a yellow filter layer and/or a non-photosensitive layer adjacent thereto, may be The present invention can also be applied in an embodiment in which an equivalent amount of yellow coupler is contained, and this is also a preferred embodiment of the present invention.

In this case, usually the emulsion layer containing the magenta coupler combined with green-sensitive silver halide and the non-light-sensitive layer containing the above-mentioned 4-equivalent yellow coupler are in contact with each other. In order to suppress color development of the yellow coupler, a known technique such as adding a scavenger of a color developing agent to the non-photosensitive layer may be used to prevent color turbidity.

Further, by applying the present invention in such a manner that a 4-equivalent yellow coupler is contained in a non-photosensitive layer that is not adjacent to the green-sensitive layer, color turbidity can be prevented.

As described above, when applying the present invention, a new layer other than the layer formed in a normal photosensitive material may be provided as a non-photosensitive layer containing a 4-equivalent yellow coupler, but -i
There is no such need, and a 4-equivalent yellow coupler can be added to a non-light-sensitive layer that is usually incorporated into a light-sensitive material.

In the present invention, the amount of the 4-equivalent yellow coupler used in the non-photosensitive layer is usually preferably in the range of 5XlO-5 mol-5X10-'' mol, more preferably 5X10-'mol-1Xl0-'' mol per square meter. be.

Various known photographic additives can be used in the non-photosensitive layer containing the 4-equivalent yellow coupler. In particular, when the non-photosensitive layer containing the above-mentioned 4-equivalent yellow coupler also serves as a layer with a special function such as a protective layer or a yellow filter layer, photographic additives that are normally added to the layer may be added. is preferred.

Examples of such additives include matting agents, ultraviolet absorbers, antistatic agents, fine-grained silver halides with virtually no photosensitivity, slipping agents, dyes, colloidal silver, high-boiling solvents,
Antioxidants, scavengers of oxidized color developing agents, development accelerators, optical brighteners, bleach accelerators, surfactants, hardeners, polymer latex, etc. can be mentioned.

Next, preferred 4-equivalent yellow couplers to be contained in the non-photosensitive layer in the present invention will be described. Such a preferred 4-equivalent yellow coupler has the following general formula (
1), (II:1. (III) or (IV)
It is a compound represented by

(II) (III) (IV) 0 R1 to R in each formula will be explained.

In the general formulas (1) to (IV), RI represents a hydrogen atom, a halogen atom, or an alkoxy group.

When RI represents an alkoxy group, the alkoxy group represented by R1 may have a substituent, such as a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, etc. base,
Examples include an acylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, and a hydroxy group.

RI is preferably a hydrogen atom, a chlorine atom, or an unsubstituted alkoxy group.

Next, Rt may be the same or different when l, m, and n are 2 or more.

Preferred examples of R2 include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group,
Aryloxy group, heterocyclic oxy group, acyloxy group,
Carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group , sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, and aryoloxycarbonyl group. More specifically, R2 represents a halogen atom (e.g., chlorine atom, bromine atom, etc.), a substituted or unsubstituted alkyl group (e.g., methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group, 3- (2,4-di-t-amylphenoxy)propyl group, allyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-hexysulfonylethyl group, cyclopentyl group, benzyl group, etc.),
Substituted or unsubstituted aryl groups (e.g. phenyl group, 4
-t-butylphenyl group, 2.4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group 1 (5- to 7-membered ring group containing 0, N, S, etc., e.g. 2 furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group) group), aryloxy group (e.g. phenoxy group, etc.), aryloxy group (e.g. phenoxy group,
2-methylphenoxy group, 4-t-butylphenoxy group, etc.), heterocyclic oxy group (e.g., 2-benzimidazolyloxy group, etc.), acyloxy group (e.g., acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy group (e.g., acetoxy group, hexadecanoyloxy group, etc.), For example, N-phenylcarbamoyloxyl, N
-ethylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.),
Acylamino group (e.g. acetamido group, benzamide group, tetradecanamide group, α-(2,4-di-t-amylphenoxy)butyramide group, T(3-t-butyl-
(4-hydroxyphenoxy)2 butylamide group, α-(4-(4-hydroxyphenylsulfonyl)phenoxy)decaneamide group, etc.), anilino group (e.g. phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamide group) Reno group,
2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5-(α-(
(3-L-butyl-4-hydroxyphenoxy)dodecanamido)anilino group, etc.), ureido groups (e.g., phenylureido group, methylureido group, N,N-dibutylureido group, etc.), imide groups (e.g., N-succinimide group, -penzylhydantoynyl group, 4-(2-ethylhexanoylamino)phthalimide group, etc.), sulfamoylamino group (e.g. N,N-dipropylsulfamoylamino/group, N-methyl-N-decis rufamoylamino group), alkylthio group (e.g. methylthio group,
Octylthio group, Tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-(
4-t-butylphenoxy) butylthio group), arylthio group (e.g. phenylthio group, 2-butoxy-5-1-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-te1-ladecanamidophenylthio group, etc.), heterocyclic thio group (e.g., 2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), Aryloxycarbonylamino group (e.g. phenoxycarbonylamino group, 2.4
-G and monobutylphenoxycarbonylamino groups, etc.)
, sulfonamide group (e.g. methanesulfonamide group,
hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-t-butylbenzenesulfonamide group, etc.), carbamoyl group (e.g. N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-
(3-(24-di-t-amylphenoxy)propyl)
carbamoyl group), acyl group (e.g. acetyl group,
(2,4-di-amylphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl group (e.g., N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group, N-(2-dodecyloxyethyl) Sulfamoyl group, N-ethyl-N-dodecylfumoyl group, N, N
-diethylsulfamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (e.g. octanesulfinyl group, dodecanesulfinyl group, benzenesulfinyl group, etc.), alkoxy Carbonyl groups (e.g. methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g. phenoxycarbonyl group, 3
-pentadecyloxycarbonyl group, etc.).

Rs, Rh, Ry, and Rs represent a hydrogen atom, an optionally substituted alkyl group, and an optionally substituted aryl group.

R,, R, or R7 and RIl may jointly form a ring.

Examples of the rings formed together include a piperidino group, a piperazinyl group, a morpholino group, a pyrrolidinyl group, and the like.

At least one of R3-R8 is 6 (e.g., methylene group, ethylene group, 1,1o-decylene group, CH2CH20CH2CH2-, etc.), a substituted or unsubstituted phenylene group (e.g., 14-phenylene group,
It is preferable that it is an aryol group represented by 1.3-phenylene group.

Here, R,, R2, f have the same meaning as R,, R2, n described above.

R2 becomes a divalent group and can form a bis body. Similarly, a trimer or more multimer may be formed.

Taking the case of a screw body as an example, a more detailed explanation is as follows.

R2 is a substituent or unsubstituted alkylene group NHCOR
3C0NH- group (R3 represents a substituted or unsubstituted alkyl group or phenylene group, for example N) ICOCHzC
HzCONFI H3 NHCOCH, CCH2C0NII CH3 S-R4-5 group (R4 represents a substituted or unsubstituted alkylene group, and can be, for example, S CILgCHz S7 CL.

When vinyl monomers include those represented by general formulas (1) to (■), the vinyl group may have substituents other than those represented by general formulas (1) to (IV). A preferred substituent is a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group).

Monomers including those represented by general formulas (1) to (IV) may be copolymerized with non-color-forming ethylene-like monomers that do not couple with the oxidized color developing agent.

Non-color-forming ethylene-like monomers that do not couple with oxidized color developing agents include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid (such as methacrylic acid), and esters or esters derived from these acrylic acids. amides, (e.g. acrylamide, butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate,
Ethyl acrylate, propyl acrylate, butyl acrylate, t-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl acrylate, butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide , vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene,
divinibenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid, maleic anhydride,
Maleic acid ester, N-vinyl-2-pyrrolidone, N
-vinylpyridine and 2- and 4-vinylpyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together.

For example, butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide,
These include methyl acrylate and diacetone acrylamide.

As is well known in the polymer color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers are dependent on the physical and/or chemical properties of the copolymer formed. For example, the solubility, compatibility with the binder of the photographic colloid composition, such as gelatin, its cyclicity, thermal stability, etc. can be selected to be most suitable.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred.

Among the above yellow couplers, especially the general formula (IF)
Compounds represented by are preferred.

Representative examples of yellow couplers represented by the above general formulas [I] to (IV) and other specific examples of 4-equivalent yellow couplers that can be used in the present invention are shown below. The 4-equivalent yellow coupler used in the non-photosensitive layer is 1 2 (Y-1 1) (Y ■ 2) (Y ■-3) 3 [Y ■ 7) (Y ■ 8) (Y I-9) 5 (Y-I 4) (Y ■ 5) (Y ■ 6) ShitI3 4 (Y-1 10) (Y I -11) (Y-1-12) 6 (Y-I-13) (Y- 1-14) 7 (Y-1-19) (Y I-20) (Y-I-21) 9 (Y ■ 16) (Y 1-17) (Y-1-18) 8 (Y-1- 22) (Y-1-23) (Y-1-24) 1) 0 (Y-1-25) (Y 1-26) (Y ■ 27) 1 (Y ■ 31) (Y-1 32) ( Y 1-33) (Y ■ 34) 3 (Y ■ 28) (Y-I -29) (Y-1-30) 2 (Y ■ 35) (Y-1 36) (Y ■ 37) (Y 1 -38) 4 (Y-I-39) (Y-I 40) (Y-1-41) 5 (Y-1-45) (Y ■ 46) (Y-I -47) 7 (Y-I-42 ) (Y 1-43) (Y-1-44) 6 (Y-1 48) (Y-1-49) (Y-1-50) (Y-1-51) 8 (Y ■ 52) (Y ■ 53) (Y-1 54) Shii3 9 (Y 1-58) (Y ■ 59) (Y ■ 60) 1 (Y 55) (Y ■ 56) (Y-1-57) Shifl.

0 (Y ■-1) (Y ■ 2) (Y ■ 3) 2 (Y-I[-4) (Y-n-5) (Y-11 6) (Y ■-7) υzL++tnzs 3 (Y -11-11) (Y-n-12) (Y-If-13) Hs (Y-11-14) 5 (Y-n-8) (Y-11-9) (Y-11-10) 4 (Y-11-15) Hs (Y-11-17) 6 (Y-n 18) (Y-n-19) (Y ■ 20) 7 (Y II-24) (Y-n 25) (Y ■ 26) 9 (Y-11-21) (Y-11 22) (Y-11 23) 8 (Y-11-27) (Y II-28) (Y ■ 29) (Y II-30) 0 (Y -n-31) (Y-If-32) (Y-I[-33) (Y-11-34) (Y-IV (Y-V-1) (Y-II-35) (Y-111- 1) (Y-mV-1) 2 In the present invention, the method of adding the 4-equivalent yellow coupler to be contained in the non-photosensitive layer includes the solid dispersion method, the latex method, as well as the method of adding a hydrophobic compound. dispersion method,
Various methods can be used, such as an oil-in-water emulsion dispersion method, and can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsion dispersion method can be applied to a method of dispersing a hydrophobic compound such as a coupler. Usually, a high boiling point organic solvent with a boiling point of about 150°C or higher is used, and if necessary, a low boiling point and/or water soluble compound is used. Using a stirrer, a homogenizer, and a surfactant in a hydrophilic binder such as an aqueous gelatin solution,
It may be emulsified and dispersed by a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic device, and then added to the desired hydrophilic colloid layer. A step of removing the low-boiling organic solvent may be included after or simultaneously with the dispersion.

Examples of high-boiling organic solvents include phenol derivatives that do not react with oxidized developing agents, phthalates, phosphates, citric esters, 4-benzoates, alkylamides, fatty acid esters,
An organic solvent having a boiling point of 150°C or higher, such as trimesic acid ester, is used.

High boiling point organic solvents that can be preferably used include:
A compound with a dielectric constant of 3.5 or more, for example, a dielectric constant of 3.
．． These include 5 or more esters such as phthalic esters and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds. More preferably, it is a high boiling point organic solvent with a dielectric constant of 4.0 or more and 8.5 or less and a vapor pressure of 0.5 mmHg or less at 100°C.

Furthermore, the high boiling point organic solvent may be a mixture of two or more types, and in this case, it can be preferably used if the dielectric constant of the mixture is 3.5 or more.

The silver halide photographic light-sensitive material of the present invention can be applied to the following various types of light-sensitive materials.

For example, photosensitive materials for general photography in black and white, X-ray recording, plate making, color positive, color negative, color paper, reverse color, direct positive, heat development, or surface latent image type silver halide. U.S. Patent No. 2,996,382 using grains and silver halide grains having internal fog nuclei
No. 3,178,282. It is particularly advantageous to apply the method to color photosensitive materials having a multilayer structure.

In the present invention, the silver halide emulsion includes any silver halide used in ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used.

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

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

Silver halide emulsions having any grain size distribution may be used. Emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of the (100) plane to the (111) plane can be used.

These silver halide grains can be prepared by known methods commonly used in the art.

It is preferable that soluble salts be removed from the silver halide emulsions used in the light-sensitive materials of the present invention, but those in which soluble salts have not been removed can also be used.

It is also possible to use a mixture of two or more silver halide emulsions prepared separately.

The emulsion can be chemically sensitized by conventional methods, or optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder for the emulsion.

6. The emulsion layer and other hydrophilic colloid layers can be hardened, and can also contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

When applying the photosensitive material of the present invention to a color photosensitive material, -
A coupler is used in the emulsion layer of a. Furthermore, by coupling with a competing coupler having a color correction effect and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, and a fogging agent are produced. Compounds that release photographically useful fragments can be used, such as antifoggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers.

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

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

In the present invention, a 4-equivalent yellow coupler is used in the non-photosensitive layer, but a 2-equivalent yellow coupler is more preferable for the dye-forming yellow coupler.

As the magenta dye coupler, 5-pyrazolone couplers, pyrazoloazole couplers, pyrazolobenzimidazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, etc. can be used.

The effects of the present invention are particularly noticeable when a 5-pyrazolone coupler is used.

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

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layers may contain dyes that are leached from the light-sensitive material or bleached during the development process.

A matting agent, a lubricant, an image stabilizer, an ultraviolet absorber, a fluorescent whitening agent, a surfactant, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

Furthermore, in the present invention, a known formalin scavenger can be used in combination. By using these compounds in combination, formalin resistance can be further increased.

The addition amount of the known formalin scavenger can be smaller than when it is used alone, and therefore deterioration of the film properties can be suppressed to a small level.

Examples of known formalin scavengers are as described in the description of the prior art examples above.

Any means can be used to develop the photosensitive material of the present invention, such as known methods. The treatment temperature is preferably used between 18°C and 50°C;
Depending on the purpose, any of a variety of color photographic processes for forming dye images can be applied.

9 [Example] The present invention will be explained in more detail with reference to Examples below.
This is an example for explaining the present invention, and the present invention is not limited thereto.

Prior to specific explanation of each example, the production of silver halide emulsions used in the examples will be explained.

A monodisperse gelatin aqueous solution was charged into a reaction vessel, and the pH in the reaction vessel was
While controlling Ag and pH, silver nitrate aqueous solution,
After adding an aqueous potassium iodide solution and an aqueous potassium bromide solution simultaneously while controlling the addition time, precipitation and desalination were performed using pH-coagulating gelatin, and gelatin was added to form seed emulsion N.
E-1 was prepared.

The average grain size of seed emulsion NE-1 was 0.093 μm.

Put the above seed emulsion and gelatin aqueous solution into a reaction pot.
While controlling pAg and T)H in the reaction vessel,
An ammoniacal silver nitrate aqueous solution, a zero iodide aqueous solution, and a potassium bromide aqueous solution were added in proportion to the surface area at the time of particle growth, and at an appropriate particle size, the solution was changed to a potassium bromide solution and subsequently added. As with the seed emulsion, precipitate and desalt, add gelatin and redisperse, and
An emulsion with Ag7.8 and pH 6.0 was obtained.

In this way, the silver iodobromide emulsion E, which has a high yoma content inside the grains,
M-1 to EM-2 were prepared.

Table 1 shows each emulsion and its contents.

Table-1 1 2 Next, examples will be explained in detail.

Example 1 A multilayer color photosensitive material sample No. 1 having a multilayer structure having the composition shown in Table 2 below was prepared on a cellulose acetate support which had been subjected to a +1 subbing process using the iHNα process.

Coating amounts are expressed in g/m2 in terms of silver for silver halides and colloidal silver, g/m'' in terms of additives and gelatin, and sensitizing dyes. , couplers and DIR compounds are expressed in moles per 1 mole of silver halide in the same layer.
The emulsion contained in each color-sensitive emulsion layer was optimally sensitized using sodium thiosulfate and chloroauric acid.

Sensitizing dye ■ ■ -1 9 Sensitizing dye ■ -1 M 0 C V-1 2 U AS FS FS FS 5 (D 3) 4 Hereinafter, each layer of the above composition was formed using the above HG rLl, R
-1, R-2, TL-2, G-1, G2, YC, B-
1, B-2, Pro-1, and Pro-2.

In addition to the above components, a surfactant was added to each layer as a coating aid.

No, 2 to 5 -) G-1, G-2, YC, B-1, B-2, Pr.

1. Comparative formalin scavenger-F to Pro-2
S-1 to FS-4 were added. Otherwise, sample No.
Samples Nos. 2 to 5 were prepared in the same manner as in Example 1.

The distribution of formalin scavenger to each additive layer is as follows:
The solubility of each scavenger was determined as appropriate depending on ease of use.

That is, for example, a scavenger that is difficult to dissolve may be added in many layers, whereas a scavenger that is easily soluble may be added in a small number of layers.

These comparative formalin scavengers diffuse into each layer after sample formation and become contained in all layers.

The amount of formalin scavenger added for comparison was 6. The total amount added for each layer was 5 x 10-3 mol per 1 m''.The types of formalin scavenger used for comparison are shown in Table 3. Formalinth No. 6-1
6 - Sample No. 1 Pro-2
No, except adding 4 equivalents of yellow coupler to the layer.
Sample Nos. 6 to 16 according to the present invention in the same manner as 1
It was created.

The type and amount of the yellow coupler added are shown in Table 3.

The yellow coupler was added as oil-protected dispersed particles. The dispersion recipe is as follows.

(contains 1.0 g of sodium) Mix both A and B above and use an ultrasonic homogenizer to
Dispersed for minutes.

The above dispersion was added to the coating solution for the Pro-2 layer so that the yellow coupler was attached as shown in Table 3.

7 The amount of gelatin was adjusted to be as shown in Table 2.

Each sample of Wipe 1'j was cut and the deterioration of the maximum concentration under formalin gas atmosphere was evaluated.

Each sample was subjected to Treatment-2 as a formalin treatment and Treatment-1 as a reference treatment.

Treatment-1 A liquid containing 300 cc of 35% glycerin aqueous solution was placed at the bottom, and the sample was held at 30''C for 3 days in a closed container filled with air equilibrated with this.

Treatment-2 A liquid containing 6 cc of a 40% formaldehyde aqueous solution per 300 cc of a 35% glycerin aqueous solution was placed at the bottom, and the sample was held at 30°C for 3 days in a closed container filled with air equilibrated with this.

Thereafter, wedge exposure was performed according to a conventional method, and the following development treatment was performed.

8 Treatment process (38°C) Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixed arrival time: 6 minutes 30 seconds Water wash 3 minutes 15 seconds Stabilization 1 minute 30 seconds drying The composition of the treatment liquid used in each treatment step is shown below.

<Color developer> 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate
4.75 g anhydrous sodium sulfite
4.25g hydroxylamine each sulfate 2.0
g Anhydrous potassium carbonate 37.5 g Potassium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g9 0 Potassium hydroxide i, o g Add water to make 12. (pH=10.02) <Bleach solution> Ethylenediaminetetraacetic acid iron (I [I) ammonium salt 100.0 g Ethylenediaminetetraacetic acid 2 ammonium salt io, o g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Add water to adjust to 11, and use ammonia water to pH 6.0.
Adjust to.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous ammonium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to 11
and adjust the pH to 6.0 using acetic acid.

<Stabilizing liquid> Formalin (37% aqueous solution) 1.5mf
Konidax (manufactured by Konica Corporation) Add 7.5mf water and 1! shall be.

In this way, changes in performance of the sample (reference) subjected to Treatment 1 (treatment without contact with formalin gas) and the sample subjected to Treatment 2 (treatment in contact with formalin gas) were evaluated in terms of survival rate.

The results for the green photosensitive layer are shown in Table 3.

As the residual rate, the percentage of the maximum concentration of the sample subjected to treatment-2 relative to the maximum concentration of the sample subjected to treatment-1 was used.

That is, the larger the value, the better the resistance to formalin gas.

In addition, the fragility of each sample was evaluated by the following method.

Cut each sample into a size of 3.5 cm x 80 cm,
After conditioning the humidity at 23°C and a relative concentration of 20% for 3 days, it was evaluated by the method using a wedge-shaped tester described in Photographic Science and Engineering, Vol. 1, page 63 (1957). did.

Note that this test is shown in terms of the length of breakage (c+n), and the longer the length of breakage, the poorer the brittleness.

2 3 As shown in Table 3, sample No. according to the present invention in which a 4-equivalent yellow coupler was added to the second protective layer (Pro 2)
, 6 to 16 have excellent formalin resistance.

Moreover, although the addition of conventional formalin scavengers is effective, it deteriorates the fragility, but in the samples according to the present invention, there is almost no deterioration in the fragility.

Example-2 A 4-equivalent yellow coupler was added to Pro-1 and Pro-2, and a comparative formalin scavenger -FS-
1 to FS-4 were used together. Samples Nos. 17 to 32 according to the present invention were produced in the same manner as in Example-1 except for the above. In addition, sample No. 1 without formalin scavenger and comparative formalin scavenger FS
Sample No. 4 to which Sample No.-3 was added is the same as Sample No. 1 and No. 4 in Example-1.

For each sample obtained, Process-3 and Process-4 were performed,
The survival rate was calculated in the same manner as in Example-1.

Process-3 and Process-4 here refer to Process-1 of Example-1.
, the retention time in the sealed container in treatment-2 was changed from 3 days to 5 days, and otherwise treatment-1 of Example-1,
This was done in the same way as Process-2. Furthermore, the fragility of each sample was investigated in the same manner as in Example-1, and the results are shown in Table-4.

5 6 Table 4 shows that the structure of Example 2 can improve formalin resistance even more effectively.

In this example, Pro-1 and Pr.

2. An example was given in which the same 4-equivalent yellow coupler was added to YC, but similar results were obtained even when different 4-equivalent yellow couplers were combined.

(Effects of the Invention) As described above, the silver halide photographic light-sensitive material of the present invention has the effect that formalin resistance is improved and deterioration of brittleness can be prevented or suppressed.

Claims (1)

[Scope of Claims] 1. At least one photosensitive silver halide emulsion layer is provided on a support, and at least one photosensitive silver halide emulsion layer is provided at a position farther from the support than at least one of the photosensitive silver halide emulsion layers. 1
A silver halide photographic material having a non-photosensitive layer, characterized in that at least one of the non-photosensitive layers contains 4 equivalents of a yellow coupler.