JPS63128336A - Silver halide photographic sensitive material having improved preservative property - Google Patents

Abstract

PURPOSE:To prevent deterioration of photographic property of the titled material during a lapse of preservation of the titled material contg. an alkylene oxide compd., and especially, to prevent generation of fogging in the titled material by incorporating at least one kind of a nonionic surfactant and/or an anionic surfactant having polyoxyethylene group and a specific compd. to the titled material. CONSTITUTION:The titled material comprises at least one kind of the nonionic surfactant and/or at least one kind of the anionic surfactant having polyoxyethylene group and at least one kind of the compd. shown by formula I wherein R is hydroxyalkyl, hydroxyalkoxy, hydroxyiminoalkyl or aralkyl group, etc., R' is halogen atom, acyl, amino or acylamino group, etc., Q is an atomic group which may form a benzene ring, (n) is an integer of 0-2. In case that R' is hydroxy group, (n) is not zero, and at least one of R' is a group except the hydroxy group. Thus, the generation of fogging in the titled material during the lapse of the preservation thereof is remarkably reduced.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a highly sensitive silver halide photographic light-sensitive material, and more specifically, to a silver halide photographic light-sensitive material that has high sensitivity, high contrast, and prevents fogging during storage of the light-sensitive material over time. This invention relates to a silver halide photographic material in which generation is prevented.

[Conventional technology]

There are various demands for improving the performance of silver halide photographic materials (hereinafter referred to as "photosensitive materials"), and in particular, there is a demand for highly sensitive materials with stable photographic properties.

In light-sensitive materials, high sensitivity is generally achieved by increasing the size of silver halide emulsion grains.

However, according to this method, the blackening density per unit of developed silver decreases, and the gamma (the slope of the linear portion of the characteristic curve) decreases. In order to improve these problems, it is necessary to increase the amount of silver per unit area of the photosensitive material.

On the other hand, for the purpose of accelerating development to increase sensitivity, the exposed photosensitive material is preferably developed in the presence of a development accelerator. The development accelerator can be used either in the silver halide emulsion layer, in an adjacent layer or in the development bath. They include various types of alkylene oxide compounds, such as U.S. Pat.
No. 2,423,549, No. 2,441゜389, No. 2,531.83'2, No. 2,533,990, British Patent No. 920,637, No. 940.051, British Patent No. No. 945,340, No. 991゜608, No. 1,015
Alkylene oxide condensation products or polymers such as those described in US Pat.

In addition, since photosensitive materials generally consist of an electrically insulating support and photographic constituent layers, they are easily charged by friction or peeling under low humidity, and the photosensitive emulsion layer is sensitized by this discharge, resulting in static It has the property of producing dendritic or feather-like fog called marks.

As a means to prevent such charging, it is known to use surfactants similar to coating aids, and polyalkylene oxide surfactants are particularly useful.

However, when these compounds are used in photosensitive materials like the development accelerators mentioned above, they may cause a decrease in sensitivity or deterioration of gradation (deterioration of gamma) due to the occurrence of fog during storage over time.
It has disadvantages such as inviting

Since it is desirable to minimize such undesirable phenomena, it has been known to add antifoggants or stabilizers to silver halide emulsions. For example, U.S. Patent No. 2.403.927;
1-phenyl-5-mercaptotetrazoles, or 4-hydroxy-6-methyl-1,3,3a, described in No. 804,633, Japanese Patent Publication No. 39-2825, etc.

7-chitrazaindene and the like have been used as antifoggants.

However, these compounds do not necessarily have a sufficient fog-inhibiting effect during storage over time, and have drawbacks such as a decrease in sensitivity and softening of gradation, so that they have not yet reached a level of satisfaction.

In addition, in the case of color light-sensitive materials, fog suppressants used with the intention of improving storage stability over time may adsorb to the silver halide emulsion more strongly than necessary, thereby inhibiting spectral sensitization. This has had many disadvantages such as delaying desilvering properties during the development process.

[Purpose of the invention]

Therefore, the present invention has been made in view of the above-mentioned circumstances, and its first object is to prevent the deterioration of the photographic performance of a photographic material containing an alkylene oxide compound during storage over time, and in particular to suppress the occurrence of fog. The purpose of the present invention is to provide a highly sensitive photosensitive material with high sensitivity.

A second object of the present invention is to provide a highly sensitive photosensitive material containing a fog inhibitor that is less likely to cause a decrease in sensitivity or softening of gradation due to development inhibition.

A third object is to provide a highly sensitive photosensitive material in which the occurrence of fog is significantly suppressed when subjected to high-temperature development processing, particularly at 30 DEG C. or higher.

[Structure of the invention]

The above object is achieved by a photosensitive material containing at least one nonionic surfactant and/or at least one anionic surfactant having a polyoxyethylene group and at least one compound represented by the following general formula (l). be done.

General formula (r) n In the sweet formula, R is a hydroxyalkyl group, a hydroxyalkoxy group, a hydroxyiminoalkyl group, a hydroxyalkylcarbamoyl group, an aralkyl group, an acyl group, a carboxyalkenyl group, a carbohydroxamic acid group, a carbamoyl group, or a hydroxyl group. R' represents a halogen atom, an acyl group, an amino group, an acylamino group, a nitro group, an alkoxy group, a cyano group, a hydroxyl group, a carboxyl group or a salt thereof, or a sulfo group or a salt thereof.

Q represents an atomic group that may form a benzene ring, and n is 0
Represents an integer between ~2. However, when R is a hydroxyl group, n is not O and at least one of R' is a group other than a hydroxyl group.

The present invention will be explained in more detail below.

Examples of the nonionic surfactant used in the present invention include compounds represented by the following general formula [11a], (lb) or (Ilc).

General formula (TIa) R, -A(CH,C1,O)n, I [General formula Cl1lb) General formula [IIc) In the formula, R0 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an alkenyl group, or The aryl group, A is 10- group, -8- group, -C00- group, -NR,. group, (1) CON Rho group, -802N-RIo group (where RIo represents a hydrogen atom or a substituted or unsubstituted alkyl group).

Rt, R3, R7 and R= represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkoxy group, halogen atom, acyl group, amide group, sulfonamide group, carbamoyl group or sulfamoyl group.

Moreover, Re and R8 represent a substituted or unsubstituted alkyl group, aryl group, alkoxy group, halogen group, acyl group, amide group, sulfonamide group, carbamoyl group, or sulfamoyl group.

In the general formula C11c), the substituents on the phenyl ring may be asymmetrical.

R4 and R5 represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. R4 and R5, Re
and R7, and R6 and R8 may be linked to each other to form a substituted or unsubstituted ring. n I + n t + n
3 and R4 are the average degree of polymerization of ethylene oxide, and are 2 to
The number is 50.

Moreover, m is an average degree of polymerization, and is a number from 2 to 50.

Preferred examples of the present invention are described below. RI is preferably an alkyl group, alkenyl group, or alkylaryl group having 4 to 24 carbon atoms, particularly preferably hexyl, dodecyl,
Isostearyl, oleyl, L-butylphenyl, 2.
Groups such as 4-di-t-butylphenyl, 2.4-di-L-pentylphenyl, p-dodecylphenyl, m-pentadecylphenyl, t-octylphenyl, 2.4-dinonylphenyl, octylnaphthyl, etc. .

Rp, Rs, RB, R? , Re and R9 are preferably methyl, ethyl, i-propyl, t-
Substituted or unsubstituted carbon atoms such as butyl, t-amyl, t-hexyl, t-octyl, nonyl, decyl, dodecyl, trichloromethyl, trichloromethyl, 1-phenylethyl, 2-phenyl-2-propyl, etc. an alkyl group, a phenyl group, a substituted or unsubstituted aryl group such as a p-chlorophenyl group, -OR, (here, RI represents a substituted or unsubstituted alkyl group or aryl group having 1 to 20 carbon atoms). The same applies hereinafter), a substituted or unsubstituted alkoxy group, a halogen atom such as a chlorine atom or a bromine atom, an acyl group represented by -COR, -, NR,
,COR,, (where R12 is a hydrogen atom or a carbon number 1
~20 alkyl groups.

amide group represented by (the same applies hereinafter), NRItSO-RI
, and R7.
R3.

R? , RQ may be a hydrogen atom. Of these, R
e and Ra are preferably an alkyl group or a halogen atom, particularly preferably a bulky tertiary alkyl group such as t-butyl, t-amyl, or t-octyl. R7,R
a is particularly preferably a hydrogen atom.

That is, a compound of the general formula [■c] synthesized from a 2,4-disubstituted phenol is particularly preferred.

R,, R1, is preferably a hydrogen atom, methyl, ethyl,
Substituted or unsubstituted alkyl groups such as n-propyl, i-propyl, n-hebutyl, 1-ethylamyl, n-undecyl, trichloromethyl, tribromomethyl, α-
furyl, phenyl, naphthyl, p-chlorophenyl, p
-Substituted or unsubstituted aryl group such as -methoxyphenyl and m-nitrophenyl. Also, R4 and R5, Re
and R7, and R6 and R8 may be linked to each other to form a substituted or unsubstituted ring, such as a cyclohexyl ring. Among these, R4 and R5 are particularly preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group,
It is a frill group. 11. , "2+ R3 and I4 are particularly preferably numbers from 5 to 30. R3 and I4 may be the same or different.

These compounds are disclosed in, for example, U.S. Pat. No. 2,982,651, U.S. Pat.
3,454,625, 3,552,972, 3,655,387, Japanese Patent Publication No. 51-9610, Japanese Patent Publication No. 53-29715, 54-89626, 58
No. 203435, No. 5g-208743, and written by Masaru Horiguchi [New Surfactant-1 (Sankyo Publishing, 1975), etc.].

Next, specific examples of nonionic surfactants preferably used in the present invention will be shown.

H-I C,,113,C00(C112CH20)
. 11I-2C,? 1i33C00 (C112CH20
)IJIT-3C,IJ,,0(C1,C1(,0),
HU 4 CadL5Q(C112CI12)ts
l+n-8C,,+123cON11(C112CII
ffiO), 11n-9C, 3112? C0N(C11
, ClI20), 211■ 1l- If -11, C, 2H25S (CH2Cl, 0) 3J
Tl 12 C4He0(CHCHpO)3(C
HzCHzO) IJCH3 CH2CH20 (CH-CH20) 12H■-15 ■-16 ■-17 ■-18 ■-27 ■-28 1111+9 U
lh The anionic surfactant having a polyoxyethylene group used in the present invention is represented by the general formula (111).

In the general formula CI) R, -A(C)12CH20)15B-D, R1 and A have the same meanings as in the above general formula (IIa). B represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and D represents an anion group. Moreover, n5 is the average degree of polymerization of ethylene oxide, and is a number from 1 to 50.

As a preferable example of general formula (III), R,, A are the same as in general formula (IIa), and n5 is preferably 2 to 1
0, and B is preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably groups such as methylene, ethylene, propylene, and butylene.

D is preferably ill knee C00M, -303M, -
0-303M.

Here, M represents an inorganic or organic cation, preferably a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or a lower alkylamine.

These compounds are described in U.S. Pat. No. 3,026,202, U.S. Pat.
, 201,252, 3゜415.649, JP 54-98235, JP 40-23747, British Patent No. 1,178,546, JP 1,344,987,
U.S. Patent No. 3,264,108, U.S. Patent No. 2,600,831
It is stated in the number etc.

Specific examples of the anionic surfactant containing polyoxyethylene of the present invention are shown below.

Compound example Cstl+70(C)12cH20)z(CHJ4SO
JaC+ rH250(CH2CH2O)t(Cut)
4SOJaI[[-3 C+sH3,0(CHtCHzO)e(CH2)ssO
Ja111=4 C+ J25S(CHzCLO)3 (CH2)480
3 Na■-9'CHs C+ +Ht3CON(CHtCHtO)2(CI(2
)+5OJa■-10CeH+. 0(CI, CH20)4S03■-13 c+5u33o(cnzcn2o)<5o3Na■-1
5 C1tH2aO(CH2CH20)4CH2COONa
General formulas Cl1a) , CIIb) , (l1c) and [
The amount of the surfactant represented by (2) varies depending on the form, type, coating method, etc. of the photographic material used, but generally it is 1 to 1,000 m9 per 1 m' of the photographic material, and especially 5 to 200 mg is preferred. The method of applying these surfactants of the present invention into the layer of a photographic light-sensitive material is to dissolve them in water, an organic solvent such as methanol, ethanol, acetone, or a mixed solvent of water and the organic solvent;
It can be contained in a light-sensitive emulsion layer, a non-light-sensitive auxiliary layer (for example, a backing layer, an antihalation layer, an intermediate layer, a protective layer, etc.) on a support, or it can be sprayed or coated on the surface of a support, or it can be contained in a solution. Just soak it in and dry it.

At this time, two or more of the nonionic surfactants and anionic surfactants of the present invention may be used as a mixture.

Next, the fog suppressant represented by the general formula [I] used in the present invention will be explained.

In general formula (I) n+1 general formula CI), the alkyl or alkenyl moiety contained in each group of hydroxyalkyl, hydroxyalkoxy, hydroxyiminoalkyl, hydroxyalkylcarbamoyl, aralkyl or carboxyalkenyl represented by R has 4 or less carbon atoms. Those are preferable, and groups such as methyl, ethyl, and vinyl are particularly preferable.

Examples of the acyl group represented by R include an acetyl group, a propanoyl group, a butanoyl group, a benzoyl group, and a 2-hydroxybenzoyl group.

The carbamoyl group represented by R may be substituted, and examples include groups such as alkylcarbamoyl and arylcarbamoyl.

The compound of general formula [1) is characterized by having a specific group at the ortho position of the hydroxyl group, and there are no restrictions on the substituent represented by R', but when R is a hydroxyl group, R' must be a specific group represented by R.

Typical specific examples of the compound represented by the general formula CI (hereinafter referred to as the fog suppressant of the present invention) are shown below.

u These compounds are manufactured by Beilstein Handboot der Organischen Hemie (Beilste-4n
s Handbuch der Organische
n Chemie), Chemical Berichte (Chem,
Ber, ), Annalen der Hemie (Ann, C
hem, ), Chemical Abstracts (Chem, A
bstr, ), Journal of the American Chemical Society (J, Am, ChemSoc,
), Mona-t
sch, chem), Journal der Ru5sischen P
hysikalisch-Che-mischen G
There have been many reports in abstracts and journals such as E5ellschaft, and it can be easily synthesized by the methods described in these publications.

Layers of silver halide photographic light-sensitive materials to which the compound of the present invention can be added include silver halide emulsion layers, protective layers, interlayers, filter layers, antihalation layers, undercoat layers, and other conventional light-sensitive materials. It is added to the constituent layers provided in the. Particularly preferred layers are a silver halide emulsion layer and a hydrophilic colloid layer adjacent to the emulsion layer.

The amount of the fog suppressant of the present invention to be added varies depending on the photosensitive material and the type of compound, but it is preferably 1XIO3 to 10' mol, more preferably 1X10' to 1X10' mol, per 1 mol of silver halide. .

1 m” for the hydrophilic colloid layer adjacent to the emulsion layer.
The amount used is preferably 10 to 1000n+9, more preferably 100 to 700mg.

In addition, known antifoggants can also be used in combination within a range that does not impede the effects of the present invention.

In addition, in the case of a silver halide emulsion, the addition time is preferably during chemical ripening, after chemical ripening, and/or before emulsion coating after chemical ripening, and more preferably at the end of chemical ripening of the silver halide emulsion. be.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
- Any commonly used silver halide can be used. Further, the grain size distribution of the silver halide grains in the photographic emulsion is arbitrary, and may be polydisperse or monodisperse.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
It may have a regular crystal shape such as a tetrahedron or a dodecahedron, or it may have an irregular crystal shape such as a spherical shape or a plate shape, or a composite of these crystal shapes. It can also be something that has a shape. It may also consist of a mixture of particles of various crystalline forms.

In addition, for example, a junction type silver halide crystal that combines an oxide crystal such as PbO and a silver halide crystal such as silver chloride, and an epitaxially grown silver halide crystal (
For example, silver chloride, silver iodobromide, silver iodide, etc. are grown epitaxially on silver bromide. ), a hexagonal crystal, a crystal in which a regular hexahedral silver chloride is aligned over a regular octahedral silver iodide, etc. may be used.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of 5 times or more the grain thickness occupy 50% or more of the total projected area. For details, see JP-A-58-127.
It is described in specifications such as No. 921 and No. 58-113927.

It is also possible to use a combination of internal latent image type silver halide grains and surface latent image type silver halide grains described in Japanese Patent Publication No. 41-2086.

In carrying out the present invention, the silver halide grains used in the silver halide emulsion may be prepared by the neutral method, acidic method, ammonia method, forward mixing method, back mixing method, double jet method, etc., which are well known in the photographic field. Chondrold double jet method,
It can be manufactured by applying a method such as a congersion method or a core/shell method.

Further, as another form of the double jet method, a triple jet method in which soluble halogen salts of different compositions are added independently (for example, soluble silver salt, soluble bromine salt, and soluble iodine salt) can also be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which pΔg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

Two or more types of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion may or may not be chemically sensitized.

That is, a sulfur sensitization method using sulfur-containing compounds that can react with active gelatin silver (e.g., diosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., silver-tin salts, Amines, hydrazine derivatives,
Reduction sensitization method using formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts, P
(complex salts of metals in group II of the periodic table, such as t, lr, and pd)
A noble metal sensitization method using a sensitizer can be used alone or in combination.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. Sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

The photographic emulsion used in the present invention contains various stabilizers and fog suppressants for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or to stabilize photographic performance. be able to.

The photosensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

The photographic material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer.

The photographic light-sensitive material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability.

Although the photosensitive material of the present invention is preferably provided with a protective layer,
This protective layer is a layer made of a hydrophilic colloid, and the hydrophilic colloid used is one described above. Further, the protective layer may be a single layer or a multilayer.

A matting agent and/or a smoothing agent may be added to the emulsion layer or protective layer of the light-sensitive material of the present invention, preferably to the protective layer.

Various other additives may be used in the photosensitive material of the present invention, if necessary. For example, dyes, development accelerators,
These include optical brighteners, color formers, color antifoggants, and ultraviolet absorbers. Specifically, research disclosure (
RESBARC)IDISCLO3tlRE)176
No., pages 22 to 31 (RD-17643, 1978) can be used.

In the light-sensitive material of the present invention, the photographic emulsion layer and other layers can be embodied by being coated on one or both sides of a flexible support commonly used in light-sensitive materials.

Specifically, the photosensitive material of the present invention includes an X-ray photosensitive material, a Lith photosensitive material, a black and white photographic photosensitive material, a color negative photosensitive material,
It can be used in color reversal photosensitive materials, color photographic papers, colloid transfer processes, silver salt diffusion transfer processes, gui transfer processes, silver dye bleaching methods, printout photosensitive materials, photosensitive materials for heat development, etc.

Exposure to obtain a photographic image may be performed using a conventional method.

For example, Research Disclosure No. 176, pp. 25-30 (RD-1
Any of the various methods and various treatment liquids can be applied, such as those described in US Pat. No. 7,643.

This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose.

The processing temperature is usually chosen between 18°C and 50°C, but 1
The temperature may be lower than 8°C or higher than 50°C.

Surfactants that can be used in the practice of the present invention include, for example, nonionic surfactants such as zaponin (steroids), glycidol derivatives, fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. In addition, alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, etc. Examples include anionic surfactants containing acidic groups such as a carboxyl group, a sulfo group, a phosphor group, a sulfuric acid ester group, and a phosphoric acid ester group. Further examples include amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, and amine oxides. Cationic surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles are also used. Can be mentioned. Furthermore, a fluorine-containing surfactant or the like can be used.

Examples of fluorine-containing surfactants include Japanese Patent Publication No. 47-930
3, 48-43130, 52-25087, 57
-1230, JP-A-49-46733, JP-A-50-165
25, 50-34233, 51-32322, 5
4-14224, 54-111330, 55-55
7762, 56-19042, 56-41093,
56-34856, 57-11341, 57-2
9691, 57-64228, 57-146248
, 56-114944, 56-114945, 5
8-196544, 58-200235, 60-1
09548, 57-136534, US-358
9906, same 3775126, same 4292402,
Examples include compounds disclosed in RD-16630 and the like, and compounds exemplified in JP-A-60-164738.

As an antistatic agent, for example, U.S. Patent No. 2,882,15
No. 7, No. 2,972,535, No. 3,062,785
No. 3,262,807, No. 3,514,291, No. 3,615,531, No. 3,753゜716,
No. 3,938,999, No. 4,070,189, No. 4,147゜550, German Patent No. 2,800,466, Japanese Patent Application Publication No. 48-91165, No. 4g-9443:1, No. 49-46733, No. 50-54672, No. 5
No. 0-94053, No. 52-129520, etc., such as those described in U.S. Pat. No. 2,982,6
No. 51, No. 3 428.456, No. 3,457,07
No. 6, No. 3,454,625, No. 3゜552.972
Surfactants such as those described in U.S. Pat. No. 3,655,387, etc., for example, those described in U.S. Pat. Examples of matting agents include metal oxides such as barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymers, colloidal silica, powdered silica, and the like.

In addition, propylene glycol, 1,1.1-)limethylolpropane, etc. can be added to the layer containing the nonionic surfactant and anionic surfactant of the present invention or to other layers, and by doing so, A favorable antistatic effect can be obtained.

The layers containing the nonionic surfactant and anionic surfactant of the present invention include an emulsion layer, an undercoat layer on the same side as the emulsion layer, an intermediate layer, a surface protection layer, an overcoat layer, and a back layer on the opposite side to the emulsion layer. etc. Among these, surface layers such as a surface protective layer, an overcoat layer, and a back layer are particularly preferred.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Example 1 A high-sensitivity negative silver iodobromide emulsion with an average grain size of 1.2 μl was chemically ripened with gold and sulfur sensitizers to the highest sensitivity.

Next, as a green-sensitive sensitizing dye, anhydro-5,5'
An appropriate amount of -diphenyl-9-ethyl-3,3'-di-γ-sulfopropyloxacarbocyanine hydroxide sodium salt was added to prepare a green-sensitive silver halide emulsion.

1-(2,4,6-)lichlorophenyl)-3- as magenta coupler per mole of silver halide.
80 g of [3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone, 1-(2,4,6-)lichlorophenyl)-4-(1-naphthylazo) as a colored magenta coupler. )-3-(2
-Chloro-57 octadecenyl succinimide anilino)-5-pyrazolone were weighed respectively, 120 g of tricresyl phosphate and 240 g of ethyl acetate.
were mixed and dissolved by heating, and then a coupler solution emulsified and dispersed in a solution of 59 ml of sodium triisopropylnaphthalene sulfonate and 550 ml of a 7.5% aqueous gelatin solution was added to the above emulsion.

Divide the emulsion into 25 parts and use one part as a blank sample.
In addition, as shown in Table 1 below, comparative compounds and compounds according to the present invention were added, respectively, and an appropriate amount of 2-hydroxy-4,6-dichlorotriazine sodium was uniformly added as a gelatin hardener. It was made into a silver oxide emulsion.

This emulsion was uniformly coated and dried on a subbed triacetate film so that the silver content was 3.0 g/m 2 to prepare samples (Nos. 1 to 25).

The obtained film sample was subjected to a forced deterioration test at a temperature of 65°C.
After being left at 7% relative humidity for 3 days, it was wedge exposed in the usual manner and color developed according to the color processing steps described below.

The color sensitometry results obtained from the obtained pieces are shown in Table 1 below.

The fog in the table is the value after subtracting the base concentration, and the sensitivity is based on the blank sample left for 3 days (sample No. 1).
This is the relative sensitivity when expressed as 100. Also, gamma is expressed by the slope of the straight line.

Processing process [Processing temperature 38℃] Processing time Color development
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
3 minutes 15 seconds 36 seconds Arrival 6 minutes 30 seconds Wednesday
Washing Stabilize for 3 minutes and 15 seconds
Drying for 1930 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

4-amino-3methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75g
Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate z, og Anhydrous potassium carbonate 31.59 Sodium bromide
1.39 Nitrilotriacetic acid trisodium salt (l hydrate) 2.59 Potassium hydroxide Add 1.0 g of water to make one volume, and use sodium hydroxide to make pl (10,
Adjust to 6.

[Bleach solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.09 Ammonium bromide 150.09 Glacial acetic acid 10.09 Add water to make IC, and adjust to pH = 6.0 using aqueous ammonia. do.

[Fixer]

Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.69 Sodium metasulfite 2.39 Add water to make lρ, and adjust to pH = 6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5m
ρConidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5m
12 Add water to make 112.

Jtl Comparative surfactant HO(CH2CH20)n
H (a) n-3 (b) n-13MW=600 (c) n-90MW=4000 As is clear from Table 1 above, the samples according to the present invention are:
It can be seen that, despite the harsh storage conditions, fogging and gamma deterioration are suppressed, and the stability of the film during storage is improved.

Example 2 A monodispersed silver chloroiodobromide core containing 2 mol% iodine and 0.2 mol% chlorine with an average grain size of 0.3 μm and the outside thereof,
A silver iodobromide layer is formed with a ratio of 40 mol% iodine and 60 mol% bromine, grown to a grain size of 0.5 μm, and then iodobromated to 0.85 μm with a ratio of 1 mol% iodine and 99 mol% bromine. A silver layer was grown to obtain slightly rounded tetradecahedral silver halide grains.

Chloroauric acid salts, rhodanammonium, sodium thiosulfate, and thiourea compounds were added to these particles, and the particles were chemically ripened.

An emulsion preparation solution was prepared by adding 11 g of tomelytyolpropane and 2 g of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene per 70 g of the particles, and also containing the compounds shown in Table 2.

This milk preparation liquid, the protective layer liquid described below, and the compounds shown in Table 2 were contained in the protective layer liquid, and the emulsion liquid had a silver content of 4.8 g/m'', and the protective layer liquid had a gelatin content of 1.8 g/m''. 0
Coating speed 150m so that g/m'
/mil+ was simultaneously coated on a subbed polyethylene terephthalate support-L and dried for 2 minutes and 30 seconds to obtain 22 types of X-ray film samples (Nos. 26 to 47).

[Protective layer liquid]

・Gelatin 100g・N
a03S -CHC00CH7(CF, CFp)3HC
I(-, C00CH, (CP, CF,)3)1
0.5gC11,-C00C,,H,.

・NaO+S 'CHC00CsH++
2.09 Polymethyl methacrylate particles with an average particle size of 2.5 μm 3
g. Colloidal silica (Dupont Ludox AM)
Convert it to solid content and add 5g, a vinyl sulfonyl hardener, and water to make it 1.2a.

Each sample prepared as above was left at room temperature for 3 days as a fresh sample, and a sample was prepared at a temperature of 55°C and a relative humidity of 7.
% for 3 days, and forced deterioration aging samples that were left at a temperature of 50° C. and a relative humidity of 80% for 3 days.

Then, sensitometric exposure was applied and an automatic processor GX-
300 (manufactured by Konishiroku Photo Industry Co., Ltd.) using XD-90.
After processing with a developer (manufactured by the same company) for 90 seconds, photographic performance was measured and the results shown in Table 2 were obtained.

Note that the sensitivity in Table 2 is for the comparison sample (No. 26).
It is expressed as a relative value when the value after 3 days of natural storage is set as 100. The sensitivity is the reciprocal of the amount of exposure required to obtain a transmitted light blackening density of 1 fog value + 1.0.

Table 2 shows that the samples of the present invention all have high sensitivity, and increase in fog and deterioration in gamma are suppressed despite severe storage conditions.

In addition, each sample was conditioned for 12 hours at 25°C and 20%RH.
After rubbing a neoprene rubber roll and a nylon roll with different charge series under the same conditions, the development process described above was performed and the degree of static mark generation was examined, but no generation was observed in the sample of the present invention. The antistatic performance was also extremely good.

Applicant: Konishiroku Photo Industry Co., Ltd. -4 et al-

Claims (1)

[Scope of Claims] Contains at least one nonionic surfactant and/or at least one anionic surfactant having a polyoxyethylene group and at least one compound represented by the following general formula [I] A silver halide photographic material characterized by: General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a hydroxamic acid group, carbamoyl group or hydroxyl group, R' is a halogen atom, acyl group, amino group, acylamino group, nitro group,
Represents an alkoxy group, cyano group, hydroxyl group, carboxyl group or a salt thereof, or a sulfo group or a salt thereof. Q represents an atomic group that may form a benzene ring, and n is 0
Represents an integer between ~2. However, when R is a hydroxyl group, n is not 0 and at least one of R' is a group other than a hydroxyl group. ]