JPH04157458A - Silver halide photosensitive material for color photograph - Google Patents

Abstract

PURPOSE:To prevent the deterioration of the photograph performance due to harmful substances and suppress the fogging increase after the storage under the high temperature and high humidity condition by allowing at least one layer of the photosensitive silver halide emulsifier layer to contain at least one kind of specific compounds. CONSTITUTION:At least one layer of the photograph constitution layers contains at least one kind of the compound which reacts with formaldehyde and fixes the product, and at least one layer of the photosensitive silver halide emulsifier layer contains at least one kind of the compounds represented by the formula I. In the formula I, R1 is the nitrogen-containing heterocyclic group, and R2, R3 is a hydrogen atom, alkyl group, or aryl group. R2 and R3 may combine to form the nitrogen-containing heterocyclic ring. Accordingly, the reduction of the coloring concentration and gamma and the deterioration of the photograph characteristic are prevented even after the contact with noxious gas for a long time, and the storage performance under high temperature and high humidity is improved, and the fogging increase and the reduction of sensitivity can be improved.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to silver halide color photographic materials, and more specifically, during storage of photographic materials, deterioration of photographic performance due to harmful substances such as formaldehyde is prevented. The present invention relates to a silver halide color photographic light-sensitive material which prevents the occurrence of oxidation and suppresses an increase in fog after storage, particularly under high temperature and high humidity conditions.

[Conventional technology]

Generally, a silver halide color photographic light-sensitive material has a plurality of silver halide emulsion layers that are sensitive to different regions of the spectrum and contain a coupler that reacts with the oxidation product of a color developing agent to form a dye. It is usually composed of a silver halide emulsion layer that is sensitive to blue light, green light, and red light and contains a yellow coupler, a magenta coupler, and a cyan coupler, respectively, on a support.

After exposure, each of these silver halide emulsion layers is colored yellow, magenta and
A dye image of 77 colors is formed.

In such a multilayer color photographic light-sensitive material, the best color image can be obtained only when each of the silver halide emulsion layers maintains a balance in terms of sensitivity and contrast. It is desirable that the photographic performance does not change even during the long storage period before and after exposure and before development.

However, if a silver halide color photographic light-sensitive material containing a coupler is placed in an atmosphere of a harmful gas such as formaldehyde gas before color development processing, the coupler will react with the harmful gas such as formaldehyde and be consumed, which is undesirable. Reaction products are generated, resulting in serious deterioration of photographic performance, such as lowering color density and gamma, or increasing fog.

On the other hand, toxic gases such as formaldehyde are emitted from new building material furniture, resin-processed products, adhesives, clothing, etc., and as these are frequently used in daily life, for example, photosensitive materials are stored in chests of drawers and resin cabinets. Photographic materials often come into contact with these harmful gases, such as when they are stored for long periods of time.

In order to prevent such deterioration of photographic performance due to the interaction with formaldehyde, it is possible to use, for example, a compound that is reactive with formaldehyde and renders it harmless (hereinafter referred to as a formalin scavenger). Proposed. - For example, U.S. Pat. No. 2,309,492 points out the problem of trace amounts of formaldehyde that interact with pyrazolone color formers to form yellow compounds and cause color fog in photographic elements, and hydroxylamine , hydrazine derivatives, hydrazo derivatives, semicarbazides, dimethylhydroresorcinol or naphthylenediamine.

In addition, Japanese Patent Publication No. 46-34675 discloses that as a scavenger for formaldehyde gas contained in the atmosphere,
N.

N'-ethylene urea, 2,3-dihydroxynaphthalene, dimedone, etc. are proposed. Others, special public service 51-2
No. 3908, No. 63-32378, JP-A-59-19
No. 945, No. 48-39029, No. 57-13345
No. 0, No. 58-150950, No. 62-159145
No. 4,441.987, U.S. Patent No. 3,811.8
No. 91, No. 4,003,748, No. 4,414,30
No. 9, No. 7900.028, Research Disclosure magazine,
Compounds described in Vol. 101, No. 10133, etc. are known.

However, when these compounds are used, the pre-exposure shelf life (hereinafter referred to as raw shelf life) of photographic light-sensitive materials is affected, especially when stored under high temperature and high humidity, resulting in increased fog and decreased sensitivity. I found out that I don't like it.

On the other hand, increased fog leads to decreased sensitivity and deterioration of gradation.
Attempts have been made over the years to add a number of substances to silver halide emulsions for the purpose of preventing fogging, since this significantly impedes image reproducibility.

A typical example is Research Disclosure (mentioned above), Volume 176, December 1978, 1
7643 (■). Particularly effective fog suppressants include "The Theory of the Photographic Process" by T. Hlames.
e Theory of the Photography
hic Pro-cess) 4th edition, Maclili
It is described in Ilan Publishing (1977), pages 393-399, and the mechanism of action is also explained.

However, it is difficult for many of these fog suppression technologies to adequately respond to the recent advances in sensitivity, activation, and rapid processing of photosensitive materials, especially when they are left at high temperatures (approximately 45°C or higher). , under high temperature and high humidity (approximately 50 to 80°C1
The actual situation is that they lack antifogging properties and stability of photographic properties under severe conditions such as storage at relative humidity of about 50 to 90%. That is, when using the effective concentration of t: which adapts the many known compounds mentioned above to the above conditions, the sensitivity decreases and the gradation deteriorates significantly. Key) : Unable to maintain balance in Capri.

Therefore, especially when using a formalin scavenger,
Loss of sensitivity due to fog even under harsh conditions,
There is a strong desire to develop a fog suppression technology that does not deteriorate photographic characteristics such as deterioration of gradation.

[Purpose of the invention]

Therefore, an object of the present invention is to prevent photographic performance from deteriorating, such as a decrease in color density or gamma, or an increase in fog, even if exposed to toxic gases such as formaldehyde for a long period of time during the storage period before color development processing. Another object of the present invention is to provide a silver halide color photographic light-sensitive material which has improved storage stability, particularly under high temperature and high humidity conditions, and is improved in terms of increased fog and decreased sensitivity.

[Failure to solve the problem]

As a result of intensive studies in accordance with the above-mentioned objective, the present inventors have found that the shelf life of a photographic light-sensitive material containing a formalin scavenger is improved when a fog suppressant is selected and used in the constituent layers of the photographic light-sensitive material. We found a phenomenon that was significantly improved.

In particular, when the photographic light-sensitive material was stored under high temperature and high humidity conditions, the improvement in raw shelf life was remarkable.

[Structure of the invention]

The object of the present invention is to form a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer and at least one light-insensitive hydrophilic colloid layer on a support. In a silver halide color photographic light-sensitive material having as a constituent layer, at least one of the photographic constituent layers contains at least one compound capable of reacting with and fixing formaldehyde, and the photosensitivity /・
At least one of the silver halide emulsion layers has the following general formula [■]
This was achieved using a silver halogen color photographic light-sensitive material containing at least one compound represented by the following.

General Formula [I] In the formula, R1 represents a nitrogen-containing heterocyclic group, and R2 and R8 each represent a hydrogen atom, an alkyl group, or an aryl group. R2
and R3 may be bonded together to form a nitrogen-containing heterocycle.

The compound represented by general formula [I] will be explained in more detail.

In general formula CI), the nitrogen-containing heterocyclic group represented by R1 is, for example, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, an indolyl group, an isoindolyl group, a benzimidazolyl group, a benzthiazolyl group, a benzoxane Examples include silyl group, benzselenazolyl group, quinolyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, and examples of the alkyl group represented by R2 and R3 include methyl group, ethyl group, propyl group, butyl group, and cyclohexyl group. Examples of the aryl group include a phenyl group, a naphthyl group, etc., and examples of the nitrogen-containing heterocyclic group formed by bonding R1 and R1 include a pyrrolidine ring, a piperazine ring, a piperidine ring, a morpholine ring, Examples include thiomorpholine rings, and these groups and rings may further have substituents.

Typical specific examples of the compound represented by the general formula CI) used in the present invention are shown below, but the present invention is not limited thereto.

Compound Rr Rz
Rs compound R1R2Rs l C,H.

2Hs C2H.

Compound RI R2R12H5 CH2COOC3H7 CH2α force C,H.

CH2COOC, H.

Compound RI R2R3C0CH.

■ C0CH+ ■ Compound R, R2R.

Compound R, R2RI CHl Compound R+ R+
Rs compound R+ R2R3 compound RI R2R3 compound R
, R2R.

Compound R, RI R5I-77l
-78 I-79l-80 I-81l-82 -83 Although some of these compounds of the present invention are commercially available, they are
l of Organic Chemistry) 1
4.921 (1949), Annalen der Hemie
(Annalen der Chemie) ηυ Engineering,
57 (1912), Doshu, 2 (1913), etc.

In the present invention, the above compound can be used as a fog suppressant, and can be used in silver halide emulsion layers and adjacent hydrophilic colloid layers (intermediate layers, filter layers, antihalation layers, protective layers, undercoat layers, etc.) of photosensitive materials. at least one of
Contained in the layer. A particularly preferred layer is a silver halide emulsion layer.

The amount of the compound of the present invention to be added varies depending on the photosensitive material and the type of compound, but the amount of the compound represented by the general formula [I] is 0.01-1,000 per mole of silver halide.
It is preferable to use it in the range of +sg, more preferably 0
．． 05-500a+g.

The amount added to the hydrophilic colloid layer is 1. 0 per %
．． It is preferably used in the range of 1 to 2,000+ag, more preferably 10 to 1,000 mg.

These compounds are dissolved in water or a hydrophilic organic solvent (eg, methanol, dimethylformamide, etc.) and added to the desired constituent layers. Further, in the case of a silver halide emulsion, it is added during chemical ripening, after chemical ripening, and/or immediately after emulsion coating, but more preferably at the end of chemical ripening of the silver halide emulsion.

Next, compounds capable of reacting with and fixing formaldehydes of the present invention will be explained.

Here, formaldehyde is a general term for formaldehyde gas and substances similar thereto, which have a similar adverse effect on photosensitive materials.

Fixation means to combine with formaldehyde gas to turn it into a substance that does not have an adverse effect on light-sensitive materials such as couplers.

As the compound used in the present invention that reacts with and fixes formaldehyde (hereinafter referred to as formalin scavenger), any compound having such an action can be used.

Preferred formalin scavengers for use in the present invention are:
It is represented by the following formulas (I[) to [■].

General formula (ICE - Formula (I[[) - Formula (IV) - Formula [■] General formula [■]] In general formula [■], R1 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an acylamino group, or It represents an amino group, R1 represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, or an amidino group, and R4 and R6 may be combined to form a ring.

These groups also include those having substituents (eg, hydroxyl group, carboxyl group, amino group, ureido group, nitro group, halogen atom, etc.). X represents -CH- or -N-.

- Formula CnI), R,, R, and R, may be the same or different, and each represents a hydrogen atom, an alkyl group (
methyl, ethyl, propyl, l-propyl, butyl, hydroxymethyl, 2-hydroxyethyl, methoxymethyl, chloromethyl, carboxymethyl, cyanethyl, etc.), alkenyl groups (allyl, 2-butenyl, 2-chloroallyl, etc.), aralkyl Groups (benzyl, phenethyl, p
-methoxybenzyl, etc.), aryl groups (phenyl, p-
tolyl, p-methoxyphenyl, 0-chlorophenyl,
m-hydroxyethyl, etc.) or acyl groups (acetyl, talopionyl, trifluoroacetyl, taloloacetyl,
Acryloyl, methacryloyl, etc.).

R9 and RIO are each a hydrogen atom or an alkyl group (R8
~ Same as described in R8).

The compound represented by the formula [■] includes a polymeric compound bonded to a polymer chain (for example, a polyethylene chain or a polypropylene chain) via the R6-R8 group. Furthermore, in this case, -CO- is used as a linking group.

It also includes those in which -Coo-, -C0NH-, etc. connect the R1-R8 groups and the polymer chain.

In general formula [IV), R11 represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and may form a naphthalene ring together with a phenyl ring. n represents an integer of 2 or more.

In the general formula (V), R12 represents, for example, an alkyl group, an aryl group, a cycloalkyl group, an acyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, etc., and these groups have substituents (for example, a carboxyl group, a sulfo group). , hydroxyl group, amino group, etc.).

Ro represents, for example, hydrogen, an alkyl group, an aryl group, a cyano group, a carbamoyl group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a haloalkyl group, a nitro group, a sulfamoyl group, an alkylsulfonyl group, and the like.

In general formula [VI), R14 and R15 represent a hydrogen atom or a substituent, R16 represents a hydrogen atom or an alkyl group,
Z represents a hydrogen atom, an alkyl group, an aryl group, an aryl group, or a heterocyclic group, and R111 represents the same group as R11l. Rlfi and 2 may be combined to form a ring.

The compound represented by the general formula CVT) will be explained in more detail.

RI4 represents a hydrogen atom or a substituent, and examples of the substituent include a straight chain or branched alkyl group having 1 to 18 carbon atoms (e.g., methyl, etinope dodecyl, etc.), and a cycloalkyl group having 5 to 7 carbon atoms (e.g., cyclopentyl, etc.). , cyclohexyl, etc.), aryl groups (e.g. phenyl, naphthyl, etc.), 5
or 6-membered heterocyclic group (e.g. pyridyl, pyrimidyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, thiazolyl, piperidino, etc.) CQ
OR+s, CON request! l+ Cgu2"<HR□, '
<omrR, (here, R3 represents an alkyl group, an aryl group, or a heterocyclic group, R20 represents a hydrogen atom or an alkyl group, and RZ+ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. ), etc.

The substituent represented by R1 can further have a substituent, and examples of these substituents include an alkyl group, an alkoxy group, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and a nitro group. group, cyano group, hydroxyl group, carboxyl group,
Examples include a sulfo group and a halogen atom, and among these, a sulfo group, a carboxyl group, and a hydroxyl group are most preferred.

R3 is preferably a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an acyl group, a carbamoyl group, or an alkoxycarbonyl group.

R1 represents a hydrogen atom or a substituent, and examples of the substituent include a straight chain or branched alkyl group having 1 to 18 carbon atoms (for example, methyl, ethyl, undecyl, etc.), and a cycloalkyl group having 5 to 7 carbon atoms ( (e.g., cyclopentyl, cyclohexyl, etc.), aryl groups (e.g., phenyl, naphthyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, etc.), aryloxy groups (e.g., phenoxy, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), aryl Oxycarbonyl group (e.g., phenoxycarbonyl, etc.), carbamoyl group (e.g., dimethylcarbamoyl, diethylcarbamoyl, etc.), acyl group (e.g., acetyl, benzoyl, etc.), amino group, alkylamino group (e.g., methylamino, dimethylamino, etc.), arylamino groups (e.g. anilino), acylamino groups (
(e.g., acetylamino, penzamide, etc.), sulfonamide groups (e.g., methanesulfonamide, benzenesulfonamide, etc.), carbamoylamino groups (e.g., dimethylcarbamoylamino, etc.), sulfamoylamine groups (e.g., dimethylsul7amoylamino, etc.), alkoxycarbonylamino groups (e.g. methoxycarbonylamino,
ethoxycarbonylamino, etc.), a cyclic amino group (for example, morpholino, piperidino, pyrrolidino, etc.), a carboxyl group, or a cyan group.

These groups can further have a substituent, and examples of these substituents include those mentioned for R1. As R, a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, an acylamino group, a carbamoylamino group, a sulponamide group, a sul7amoylamino group, an alkoxycarbonylamino group are preferable, and an alkyl group is particularly preferable. , acylamino group, carbamoylamino group, sulponamide group, and alkoxycarbonylamino group.

R11 represents a hydrogen atom or an alkyl group, and the alkyl group represents a linear or branched alkyl group having 1 to 18 carbon atoms, and these may further include a halogen atom, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group. , a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a sulfo group, an amino group, an alkylamino group, a dialkylamino group, or the like.

2 is a hydrogen atom, an alkyl group similar to R, an allyl group,
It represents an aryl group or a heterocyclic group, and R23 represents the same group as R11. ), examples of which include methyl group, ethyl group, butyl group, methoxymethyl group, cyanoethyl group, phenyl group, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, benzenesulfonyl group,
Examples include dimethylsulfamoyl group and diethylsulfamoyl group. 2 is preferably an alkyl group or an alkylsulfonyl group.

Representative examples of compounds represented by the general formulas [■] to (Vl, ) are shown below, but the present invention is not limited thereto.

ll-3 ■ 4 m-5 ■ 6 If-711-8 11-9I [-10 ■ River 3 m-14 n-1511-1,6 11II 1
'CB, CCH, CCH, NH, CNHC2 [(.

It-17m-18 111!1111 CH,CN)ICNH2CH,CNHCNHCH.

n-19If -20 II li
II IC,HIN)ICNHNH2CH,CNH
CNHCCH Yull-21I [-22 II II
11 IINH2CNH(CH2) 2NH
CNH2NH2CNHCH2NHCNH2I[-23l
l-24 II II
II 11CH,CCH,COC,H,C,
H,0CCH,αi z H5111-]
]111-2m-3
m-4m-7■-B I[1-9I[1-10 C■.

IV-11V-21V-3 Shini 13 V-I V-2V-3V-
4 ■5 V-6 y7V-8 V -9V -10 V-11V-12 V -15V -16 y-17V-18 V-21V-22 V-23V-24 V-25V-26 V-27V-28 y -2g V-30V-3
1V-32 V-33V-34 V-35V-36 V-37V-38 y 3g V-40Vl-I
VI-2 Vl -3Vl -4 Vl-5Vl-6 Vl-7VI-8 Vl-9VI-10 V[-11Vl -12 Vl -13VI -14 Vl -19Vl -20 Vl-21VI-22 Vl -23Vl - 24 Many of the above compounds are commonly commercially available compounds, and compounds that are not commercially available can be easily synthesized according to the methods described in the patents, literature, etc. exemplified below.

Compounds I[-7 and I[-8 are listed in Bulletin of...
The Chemical Society of Japan (Bull
etin of the Che+aical 5oi
ety of Japan) Volume 39 1559-156
7, pp. 1734-1738 (1966), Chemische der Berichte
Berichte) 54 volumes, B 1802-18
33, pp. 2441-2479 (1921), Beilstein Handbook der Organissien.
Hemi (Beilstein Handbuch de
r Organischen Chemie) H98
(1921) and others.

Compound I[-13 is an oligomer or polymer with 0 repeat units.

Compound I [-19 is from Peilstein Handbook.
It can be synthesized by the method described in Der Organitschen Hemie (cited above), vol. 4, enlarged edition, p. 354, vol. 3, p. 63.

Compounds I[[-1 to I[I-11 are described in British Patent 717
, 287, U.S. Pat. No. 2,731.472, 3.1
No. 87.004, H, Pauly
, Hemissie der Berichte (Chem, Ber,)
63B, 2063 (1930), F.B. 5lezak, Journal.
Of Organic Chemistry (J, Org, Che
m,) 27.2181 (1962), J, Nematollahl, Journal of Organic Chemistry (J, Org, Chew
) 28.2378 (1963). Furthermore, alkyl, acyl, hydroxymethyl, alkoxymethyl, and halomethyl derivatives can be obtained by subjecting glycoluryl to alkylation, acylation, hydroxymethylation, alkoxymethylation, halomethylation, etc., using conventional methods.

Compounds V-1-V-30 can be easily synthesized according to the methods described in JP-A-51-77327, JP-A-62-273527, British Patent No. 585.780, and the like.

Compounds ■-1 to ■-24 were prepared by Berichte der Deutschen Chemidien Gesellschaft.
der Deutschen Chemischen
Ge5ellschaft) 57.332 (192
4) , Annalen der Chemie
der Chemie) 52.622 (1936
), 397°119 (1913), 568,
227 (1950), Journal of the American Chemical Society
f tbe American Chemical 5
734.664 (1951) and others.

The formalin scavenger according to the present invention is/) In the case of a silver halide color photographic light-sensitive material in which a photographic constituent layer is present above the layer containing the magenta coupler, the layer containing the magenta coupler is used. And/or one type or a combination of two or more of them may be contained in at least one of the photographic constituent layers located above the magenta coupler-containing layer. Further, a known formalin scavenger may be used in combination. The most preferable layer containing these formalin scavengers is the layer closest to the outside air of the photosensitive material, such as the protective layer.

In the present invention, the above-mentioned photographic constituent layers include, for example, optically or chemically sensitized silver halide emulsion layers having photosensitivity forming a photosensitive material, intermediate layers as non-photosensitive layers, It includes an ultraviolet absorbing layer, a yellow filter layer, a protective layer and other auxiliary layers.

In order to add and contain the formalin scavenger according to the present invention in these layers, the formalin scavenger may be dissolved in a suitable solvent such as water or methanol and added to the coating solution for forming the layer. , the addition timing may be at any stage.

For example, when adding it to a silver halide emulsion, it may be added at any time during the manufacturing process, but it is generally preferable to add it immediately before coating.

The amount added is 0.0 per 1e of color photographic material.
1-5.0g is preferable! [, squid, special j: 0.1-2.0
The most favorable results are obtained by adding g (7).

The photosensitive material of the present invention can be applied to the following various types of photosensitive materials.

For example, for general black and white, for X-ray recording, for plate making, for color positive, for color negative, for color paper, for reverse color,
U.S. Patent Nos. 2,996,382 and 3,178,282 using photosensitive materials for direct positive use, heat development use, etc., or surface latent image type silver halide grains and silver halide grains having internal fog nuclei. Although it can be used in photosensitive materials prepared by the method described in the above, it is particularly advantageous to apply it to color photosensitive materials having a multilayer structure.

The silver halide emulsion used in the present invention can be any silver halide used in conventional 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 grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain.

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

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

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. Gelatin is advantageously used as binder for the emulsion.

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

Couplers are used in the emulsion layer of color light-sensitive materials.

Furthermore, the development accelerator,
Photographically useful agents such as bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers. Compounds that release fragments can be used.

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

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

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

As a cyan dye-forming coupler, phenol or
Tall couplers are commonly used.

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, a formalin scavenger-1 ultraviolet absorber, a fluorescent whitening agent, a surfactant, a development accelerator, a development retardant, 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.

A known method can be used to develop the photosensitive material of the present invention. The processing temperature used is between 18°C and 50°C, and depending on the purpose, black and white photographic processing, lithographic development processing, or color photographic processing to form a dye image can be applied. Furthermore, photosensitive materials for thermal development are processed at temperatures of 100° C. or higher.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all the examples below, the amount added in the silver halide photographic material is expressed in grams per 1-2 tons unless otherwise specified. Incidentally, silver halogenide and colloidal silver are expressed in grams in terms of silver. Further, the number of sensitizing dyes is expressed in moles per mole of silver in the same emulsion layer.

Example 1 On a triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare a multilayer color photographic material sample 1.

Sample 1 1st layer: Antihalation layer (HC) Black colloidal silver 0.15 UV absorber (UV-1) 0.20 Colored cyan coupler (CG-1) 0.02 High boiling point solvent (O
il-1) 0.20 high boiling point solvent (Oil
-2) 0.20 gelatin
1.6 2nd layer: Intermediate layer (IL-1) Gelatin 1.3@3 layer: Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (E'm -1) 0.4 Silver iodobromide Emulsion (E m -2) O-3 sensitizing dye (S-1) 2.8x 10-' sensitizing dye (s-2) 3.3x 10" sensitizing dye (S-3>0.2X 10- 'Cyan coupler (C-1) 0.50 cyan coupler (C-2) 0.13 colored cyan coupler (CC-1) 0.07DIR compound
(D-1) 0.006DIR compound
(D-2) 0.01 high boiling point solvent (
Oil-1) 0.55 gelatin
l・0 4th layer: High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (E m -3) 0.9 Sensitizing dye (S-1) 1.7X 10-'
Sensitizing dye (S-2) 1.5X 10
-' Sensitizing dye (S-3) O, 1X10
Light Cyan Coupler CC-2') 0.23
Colored cyan coupler (CC-1) 0.03DI
R compound (D-2) 0.02 High boiling point solvent (Oil-1) 0.25 Gelatin I・0 5th layer: Intermediate layer (
IL-2) Gelatin 0.8 6th layer:
Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.6 Silver iodobromide emulsion (E m-2) 0.2 Sensitizing dye (S-4) 6.6X 10-' Sensitizing dye (S-5) 0.8X 10-' Magenta coupler (M-1) 0.60 colored magenta coupler (CM-1) [110 DIR compound
(D-3) 0.02 high boiling point solvent (
○1l-2) 0.70 gelatin
1.0 7th layer: Highly sensitive green-sensitive emulsion layer (G
H) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (S-6) 1. OX, lO-' Sensitizing dye (S-7) 2.2X 10-
'Sensitizing dye (S-8) 0.3X 1
0-' Magenta coupler (M-1) 0.15 Colored magenta coupler (CM-1) 0.04DI
R compound (D-3) 0.004 High boiling point solvent (Oil-2) 0.35 Gelatin i.

8th layer: yellow filter layer (yc) yellow colloidal silver 0.1 additive (SC-1)
0.12 High boiling point solvent (Oil-2)
0.15 gelatin
1.0 9th layer: Low-speed blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (
S-9) 5.8x 10-' Yellow coupler (Y-1) 0.60 Yellow Kagler (Y-2) 0.32 DIR compound (D-1") 0.003 DIR compound (D-2) 0.006 High boiling point 8 medium (Oil-2) 0.18 gelatin
l・3 1st O layer: High sensitivity blue sensitive emulsion layer (B H) Silver iodobromide emulsion (E m -4)
0.5 sensitizing dye (S-10)
3. OX to-false sensitizing dye (S-11)
1.2X 10-' Yellow Coupler (Y-1)
0.18 yellow coupler (Y-2)
0.10 high boiling point solvent (Oil-2)
0.05 gelatin l・
0 1st t layer: 1st protective layer (PRO-1) Silver iodobromide emulsion (E m -5) 0.3 Ultraviolet absorber (UV-1) 0.07 Ultraviolet absorber (UV-2) 0.1 high boiling point solvent
(Oil-1) 0.07 high boiling point solvent (O
il 3) 0.07 gelatin
0.8 12th layer: 2nd protective layer (PR
O-2) Alkali-soluble matting agent 0.13 (average particle size 2 μm) Polymethyl methacrylate 0.02 (average particle size 3 μl) Gelatin 0.5
．． 4.6, 7.9 and 10 emulsion layers were added with the following compound 1:Z-1) in an amount of 30 mg per mole of silver halide. In addition to the above composition, each layer also contains 5U of coating aid.
2. Dispersion aid 5U-1, hardener H-L dye A I-1
, A I-2 were added as appropriate.

The emulsions used in the above samples are as follows. Both are monodisperse emulsions with high internal iodine content.

Em-1: Average Agl content 7.5 mol% octahedron Average grain size 0.55 μm Em-2: Average Agl content 2.5 mol% octahedron Average grain size 0.36 μm Em-3: Average Agl content 8.0 mol% octahedron Average grain size 0.84 μm Em-4: Average Agl content 8.5 mol% Octahedron Average grain size 1.02 μm Em-5: Average Agl content 2.0 mol% average grain Diameter 0
．． 08μ heavy C-I M-1 MC,H.

I-1 I-2 SUISU-2 c- i ○ i l-1 C2H.

C2H.

Oi! -2 Next, in Sample 1, the general formula [■] of the present invention was substituted for the compound [2-1) used in the sixth and seventh emulsion layers.
The compound represented by is added as shown in Table 1, and the 11th
Samples 2 to 30 were prepared by adding 6 mmoQ/m'' of the formalin scavenger of the present invention to each layer as shown in Table 1.

Four sets of each of the obtained samples 1 to 30 were prepared. 2 of them
After applying wedge exposure to the set according to a conventional method, the following treatment 1 or treatment 2 was performed, respectively.

Those for which Process 1 was performed are group A, and those for Process 2 are group B.

Treatment 1 Add 300II of 35% glycerin aqueous solution to the bottom of a sealed container.
IQ, in air equilibrated with this, at 30℃ for 3 hours.
Retain samples for days.

Treatment 2: Add 35% glycerin aqueous solution 300xQ to the bottom of a sealed container.
A solution containing 5 ml of a 35% formaldehyde aqueous solution was placed per bottle, and the solution was heated at 30°C for 30 minutes in the air kept in equilibrium with this.
Retain samples for days.

One set of the remaining samples was stored for 7 days at 48° C. and 80% relative humidity, and then subjected to wedge exposure according to a conventional method. (Set as set 0) The remaining set was stored at 5° C. for 7 days and then subjected to wedge exposure according to a conventional method (set as D).

The samples of Groups A to D were each subjected to color development processing according to the following processing steps.

Processing process (38℃) Processing time Color development
Bleach for 3 minutes and 15 seconds
Fixed for 4 minutes 20 seconds
6 minutes 30 seconds water
Washing, Stabilization for 3 minutes and 15 seconds, Drying for 1 minute and 30 seconds. The composition of the treatment liquid used in each treatment step is as follows.

Color developer 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g potassium iodide
1.9mg potassium bromide
1.3g nitrilotriacetic acid trisodium salt (l hydrate) 2.5g potassium hydroxide 1.0g Add water to make H. (pH-10,02) Bleaching Liquid ethylenediaminetetraacetic acid iron (m) Ammonium salt 100.0g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 1000 UQ Add water to make IQ, ammonia Adjust pH = 6.0 using water.

Fixing solution Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 112, and adjust pH to 6.0 using acetic acid.

Stabilizing liquid formalin (37% aqueous solution) 1-5ml
2 Konidax (manufactured by Konica Corporation) 7.5m1
2 Add water to make 14.

Among the samples subjected to color development processing as described above, for Group A and Group B, the maximum magenta color density was determined by Konica Corporation.
Measured with green light using an optical densitometer PDA-65 manufactured by Kogyo Co., Ltd., the magenta of the sample of Process-2 that was in contact with formaldehyde gas (Group B) relative to the sample of Process-1 that was not in contact with formaldehyde gas (Group A). The residual rate of the maximum color density area was determined.

The maximum magenta color density was determined by subtracting the green density of the unexposed area from the maximum green density.

Also, if you have trouble with Group 0 and Group D, please refer to the PDA-6 mentioned above.
The fog density and sensitivity of magenta color development using green light were determined from the exposure amount necessary to give an optical density of "fog + 0.3" using 5. It is expressed as a relative value when the sensitivity value of sample 1 of the set is set to 100.

Further, the fog density is shown as the value obtained by subtracting the base density.

As is clear from Table 1, when the formalin scavenger of the present invention is used, even when it comes into contact with formaldehyde gas (treatment-2), the macenta maximum concentration remains high, the fog concentration is low, and the formalin scavenger Although there is little influence, when used in combination with Comparative Compound Z-1, the fog density increases in Group 0 and Group D (Sample 2.3).

When the amount of Z-1 added is increased to suppress the fog density, the sensitivity decreases significantly (Sample 4).

On the other hand, it can be seen that samples 6 to 30 using the compounds of the present invention have high sensitivity and low fog after storage (set 0), and are hardly affected by formaldehyde gas.

〔Effect of the invention〕

As described above, according to the present invention, even if exposed to toxic gases such as formaldehyde for a long period of time during the storage period before color development processing, there will be no decrease in color density or gamma, or increase in fog; It is possible to provide a highly sensitive silver halide color photographic material that does not cause an increase in fog or a decrease in sensitivity even when stored under high humidity.

Claims (1)

[Scope of Claims] A blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and at least one non-light-sensitive hydrophilic colloid layer are formed on a support as photographic constituent layers. In the silver halide color photographic light-sensitive material, at least one of the photographic constituent layers contains at least one compound capable of reacting with and fixing formaldehyde, and the light-sensitive silver halide emulsion A silver halide color photographic material, wherein at least one layer contains at least one compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents a nitrogen-containing heterocyclic group, R_2 and R
Each of _3 represents a hydrogen atom, an alkyl group, or an aryl group. R_2 and R_3 may be bonded together to form a nitrogen-containing heterocycle. ]