JPS62173456A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the titled material which has high sensitivity and excellent granular characteristic and sharpness and decreases the fluctuation of performance with heat and temp. by incorporating a cyclic ether compd. into an emulsion layer and incorporating a platy silver halide emulsion having a specific average aspect ratio therein. CONSTITUTION:At least one layer of the emulsion layers contains the cyclic ether compd. and at least one layer of the emulsion layers contains the platy silver halide emulsion having >=5:1 average aspect ratio. The preferable aspect ratio of the silver halide emulsion is >=6:1 <=100, more particularly >=8:1 <=20. The 3-6-membered cyclic ether compd. is more preferable and the number of the oxygen atoms incorporated into one ring is preferably 1-2 pieces. The cyclic ether compd. consisting of the 3-membered ring is more preferably the compd. expressed by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a silver halide photosensitive material of the present invention, and more particularly to a silver halide photographic material that has high image quality and excellent stability over time.

[Conventional technology]

In recent years, there have been two major trends in photosensitive materials for photography, due to the large-medium increase in photography opportunities due to the spread of Funbakuto cameras, and the diversification of user needs.

One is the need for higher sensitivity as typified by the 1500-1000 and 1600, and the other is the demand for higher image quality for small 7-automatic cameras. On the other hand, with the spread of funpact labs and short-time finishing, there is a growing demand in the US for higher sensitivity, higher image quality, and more stable quality.

In order to meet these requirements, research on silver halide emulsions has been actively conducted in recent years.

One of the trends is JP-A-55-142329, JP-A No. 58.
-95337, 58-108526, 58-1
No. 13927, No. 59-55426, No. 58-127
This is a tabular silver halide emulsion technology described in No. 921 and others.

Tabular silver halide emulsions have the usual hexahedral, octahedral, and 14
Because the particle surface area is large for the same amount of silver on the grains such as face pieces, it is advantageous for increasing sensitivity.Furthermore, by adsorbing more sensitizing dye, it is especially possible to increase sensitivity and improve graininess in color sensitizing systems. It is expected. Furthermore, by reducing the I'7 of the particles, light scattering can be prevented and sharpness can be improved.

Although such excellent characteristics are expected, there is an increase in fog due to heat and sensitivity to humidity. Many problems remain to be overcome for practical use, such as increased gamma reduction, increased latent image variation after exposure, and increased fog due to pressure, and solutions are desired.

[Object of the present invention]

A first object of the present invention is to provide a silver halide photographic light-sensitive material which is highly sensitive, has excellent graininess and sharpness, and has improved deformation fluctuations due to heat and humidity.

A second object of the present invention is to provide a silver halide photographic material which is highly sensitive, has excellent graininess and sharpness, and has improved latent image fluctuations after exposure.

A third object of the present invention is to provide a silver halide photographic material which is highly sensitive, has excellent graininess and sharpness, and has improved fogging increase due to pressure.

[Structure of the invention]

The object of the present invention is to provide a silver halide photographic material comprising a plurality of photosensitive silver halide emulsion layers coated on a support, at least 61 of the emulsion layers containing a cyclic ether compound, Emulsion 1 (at least one layer of the emulsion has an average vector ratio of 7.
: achieved by a silver halide photographic material characterized by containing one or more tabular silver halide emulsions.

The silver halide emulsion of the present invention has an average 7 subvecto ratio of 5.
: Contains one or more tabular halide particles. The aspect ratio refers to the ratio of grain diameter to thickness, and the diameter of a silver halide grain refers to the diameter of a circle with an area equal to the projected area of the grain.0 The preferred 7-spectral ratio of the silver halide emulsion of the present invention is 6:1. 100 or less, preferably 7: 1 or more and 50 or less, particularly preferably 8:
It is 1 or more and 20 or less.

The average 1.gamma. size of the silver halide grains contained in the tabular silver halide emulsion of the present invention is preferably 0.5 to 0.01 .mu.l, particularly preferably 0.3 to 0.05 .mu.l.

The average grain size of the silver halide grains contained in the tabular silver halide emulsion of the present invention is preferably 0.5 to 30 μm, more preferably 1.0 to 20 μuA″C.

The tabular silver halide emulsion of the present invention is preferably silver iodobromide or silver chloroiodobromide.

The tabular silver halide emulsion is disclosed in JP-A-52-153428,
54-155827, 54-118823, 58
It can be obtained by known methods disclosed in JP-A-127921 and JP-A-58-113928.

The silver halide emulsion of the present invention has a form in which the silver iodide content in the central part of the tabular grain is lower than that in the disc-shaped outer peripheral part surrounding it, that is, silver iodide is in the central part. Preferably, it consists of localized particles.

The high iodine content phase in the center preferably accounts for 80% or less of the total volume of the particles, particularly preferably 60% to 10%.

The silver iodide content in the center is preferably 5 to 40 mol%, particularly preferably 10 to 30 mol%.

Low iodine content phase surrounding the central high iodine content phase (peripheral g)
The silver iodide content is preferably 0 to 10 mol%, preferably 0.
Preferably it consists of 1 to 6.0 mole percent silver iodobromide.

A tabular silver halide emulsion in which silver iodide is localized in the center can be obtained by a known method such as that disclosed in JP-A-59-99433.

The average silver iodide content of the tabular silver halide emulsion of the present invention is preferably from 3 to 20 mol%, more preferably from 4 to 20 mol%.
15 mol%, particularly preferably 6 to 12 mol%.

In the tabular silver halide emulsion 1 of the present invention, the ratio of the silver iodide content of the center to the periphery is preferably 4 times or more, particularly preferably 5 times or more 6. Boundary between the center and the periphery It may change continuously or it may have a clear boundary.

In the layer containing the tabular silver halide emulsion of the present invention, the tabular grains preferably exist in a weight ratio of 40% or more, particularly 60% or more, based on the total silver halide grains in the layer.

J, 1. As a method for confirming the intragrain halogen composition vI structure of the silver halide grains of the present invention. Goldstein (
Fio l da Le i n) and B, WillLavls rTIEH/^T
``X-ray analysis in the former chamber'', Scanning Electron Microscope (1977), Volume 1, IIT
Research Institute, March 1977, P.
651. The particles to be examined were placed on a grid and cooled to the temperature of liquid nitrogen. A focused beam of electrons is to be examined on the particle of 0.2 mic a/-
) hit the spot. Test the sample at a 75 kilovolt accelerating voltage. By measuring the intensity and energy of the X-rays produced by the electron beam, the ratio of iodide to bromide in the particles at the spot struck by the electrons can be determined.

As the cyclic ether compound in the present invention, 3 to 6 compounds are preferred. Further, the number of oxygen atoms contained in one ring is preferably 1 to 2. Among the cyclic ether compounds, those consisting of three shells are preferably represented by the following general formula.

Margin below R, -C-C-R.

2 L In the formula, R1, R2, R1, and R4 are selected from the following.

:Hydrogen atom:Halogen III (e.g. chlorine, bromine, fluorine?P) :Light chain or branched alkyl group (preferably one or more carbon atoms)
40, for example methyl, ethyl, 1-propyl, 2-ethylhexyl, lauryl, stearyl, etc.), and may further have a substituent. Examples of substituents include the above-mentioned halogen atoms, alkoxy groups (e.g., methoxy, butoxy, stearyloxy, etc.), aryloxy groups (e.g., phenoxy, etc.), and 7-aryl groups (e.g., phenyl group'\?).
, arylthio groups (e.g., phenylthio'!4), aralkylthio groups (e.g., pennorthio, etc.), ami7 groups (e.g., piperidino, dimethylami7, etc.), acyloxy groups (e.g., acetoxy, benzoyloxy, 7/yloxy, cyclohexaphyloxy, etc.) ), alkyl dicarbonyl groups (e.g. butoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), cycloalkoxycarbonyl groups (e.g. cyclohexyloxycarbonyl, etc.), aryloquinecarbonyl groups (e.g. 7E/xycarbonylh!F) ), oxalyloxy groups (e.g. ethoxyoxalyloxy'$), carbamoyloxy groups (e.g. hequinyloxy, etc.), sulfonyloxy groups (
For example, phenylsulfonyloxy, etc.), amide groups (for example, benzoylami 7 groups, etc.), ureido groups (for example, phenylureido, etc.), ami/sulfamoyl gi, (for example, trimethylamino/sulfamoyl, etc.), and the like.

: Cycloalkyl group (preferably 3 to 6 carbon atoms, e.g. cyclopropyl, cyclohexyl, etc.), which may further have a substituent, such as (n
Examples of substituents include.

Niaryl groups (eg, phenyl, etc.) may have an alkyl group and a substituent such as i1.

: Alfkidicarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, etc.) may have the same substituent as in the case of an alkyl group.

: Carbamoyl group (e.g., phenylcarbamoyl, etc.) : Anru group (e.g., acetyl, 11-/l quinbenzoyl, etc.) : Anno J1 (In history, R1 and 1./or R1 and R4 combine to form a ring. It's okay.

Next: Examples of compounds are shown below, but the present invention is not limited thereto.

j? J, bottom margin It) UllUlhU (ulhlJ12U) 2
Ul12 Lll L, l+2 th u
lltH2U(Ulh)5L;If LJh11
7-Lll (Ul12), LJhノ) LtJ (L
Jh 几し11- (:112CIl, C11
゜C2I+ 5 ■ COCl12CIIC, 11゜0 C2115 11. (L; 112 nof 11-L; [L, H2) 7
uUL;+al12+H2-Ull(L;1I2J@
Uu(u1127zU Shiki+-1+2J@Ltl-L,
l12(1(LlhJ, L:HL; 112 II 1 C285) A cyclic ether compound consisting of four shells is preferably represented by the following general formula.

R6 ■ In the formula, R1, R2, R5, R1, R5, and R6 are selected from the following.

:Hydrogen atom:Halogen atom (e.g. chloro, bromine, 7), etc.) :Light chain or branched alkyl group (preferably 1 to 1 carbon atoms)
40, for example methyl, ethyl, I-propyl, 2-ethylhexyl, lauryl, stearyl, etc.), and may further have a substituent. Examples of the substituent include the above-mentioned halogen atom, flufoxy group (e.g. methoxy, butoxy, stearyloxy*), aryloxy group (e.g. 7
), aryl groups (e.g., phenyl groups, etc.), arylthio groups (e.g., phenylthio, etc.), 7-ralkylthio groups (e.g., benzylthio, etc.), ami7 groups (e.g., piperite, trimethylamino), acyloxy groups ( For example, acetoxy, benzoyloxy, 7-raphyloxy,
cyclohexanoyloxy, etc.), alkyl dicarbonyl groups (e.g. butoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), cycloalkoxycarbonyl groups (
For example, cyclohexyloxycarbonyl, etc.), aryloxycarbonyl group (for example, 7E/xycarbonyl, etc.)
, oxalyloxy groups (e.g., ethoxyoxalyloxy, etc.), carbamoyloxy groups (e.g., hexylcarbamoyloxy, etc.), sulfonyloxy groups (e.g., phenylsulfonyloxy, etc.), amide groups (e.g., benzoylamide 7 groups, etc.), ureido groups (e.g., phenyl ureido, etc.), ami7sul77moyl group (e.g. dimethylamino/sulfamoyl, etc.) ￥? .

A dichloroalkyl group (preferably having 3 to 6 carbon atoms, e.g. evacycloprovir, cyclohexyl, etc.) may further have a substituent, examples of which include the above-mentioned examples of substituents for the alkyl group. .

=7 A lyl group (for example, phenyl, etc.) may have the same substituents as in the case of an alkyl group.

:Alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl*), may have the same substituents as in the case of alkyl group.

: Carbamoyl group (e.g., phenylcarbamoyl, etc.) Niacyl group (e.g., acetyl, p-7 toxybenzoyl, etc.) : N'ano group Furthermore, R7 and R2 and/or R7 and R1 may be combined to form a ring.

Exemplary compounds are shown next, but the present invention is not limited thereto.

The cyclic ether compound consisting of 5R is preferably represented by the following general formula.

In the formula, R1, R2%R2%R,, R1, R6, R1, R
, is selected from the following:

Diatomic: /1a Den atom (e.g. ral, pam, heptadon, etc.): Straight chain or branched furkyl group (preferably 1 to 1 carbon atoms)
40, for example methyl, ethyl, i-propyl, 2-ethylhexyl, lauryl, stearyl wP), which may further have substituents, 2! Examples of the substituent include the above herodene atom, flucoquine group (e.g. /doquine, butoxy, stearyloxy, etc.), 7lyloxy group (e.g. 71noquine, etc.), aryl group (e.g. phenylIti), etc.
etc.), 7-arylthio group (e.g. 7x nylthio etc.), aralkylthio group (e.g. bennorthio etc.), 7.mino group (
For example, piperite, trimethylamino, etc.), acyloxy groups (for example, 7cetoxy, benzoyloxy, 7)/yloxy, cyclohex/yloxy, etc.), flucoquine carbonyl groups (e.g., butoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), Schiffflukoxylponyl group (e.g. Schiff sigma hexyloxycarbonyl, etc.)
, aryloquinecarbonyl: & (e.g. phenododicarbonyl, etc.), oxalyloxy group (e.g. ethoxyoxalyloxy etc.), carbamoyloxy group (e.g. hekylerylpamoyloxy etc.), sulfonyloxy group (
For example, phenylsulfonyloxy, etc.), 7 mil/group (eg, benzoyl 7-moyl, etc.), ureido group (eg, phenylureido, etc.), 7-mil/sulf 1 moyl J & (eg, dimethyl 7-minosulf 7-moyl, etc.), and the like.

The dichloroalkyl group (preferably having 3 to 6 carbon atoms, such as cyclopropyl, cyclohexyl, etc.) may further have a substituent, such as the above-mentioned examples of the substituent for the furkyl group.

=7 Ryl i& (for example, phenyl, etc.) may have the same r11 substituent as in the case of a furkyl group.

: Flucoquinyl group (for example, nodoxycarbonyl, ethoxycarbonyl l, may have the same substituent as in the case of alkyl group).

: Carbamoyl M (if phenylcarbamoyl 9
I? ) : Anru group (e.g. 7 cetyl, p-/)xybenzoyl, etc.) : Anru group (7/ group) Furthermore, R1 and R2, R, and R1, and/or R3 and R1 may be combined to form a ring. .

Exemplary compounds are shown next, but the present invention is not limited thereto.

Among the cyclic ether compounds below, those consisting of five shells are preferably represented by the following general formula.

R2 In the formula, proceed from R1, R2, Ro, R, 111, R611 and the following.

Diatomic atom: Halogen G (example: Provil, 2-
ethylhexyl, lauryl, stearyl, etc.), which may further have a substituent. Examples of the substituent include the above-mentioned halogen atom, Alfuki/JI; (for the i row, metquin, butquin, stearylleoquin, etc.), an aryloquine group ((for the i row, 7E/quin, etc.), and an aryl-Jl!8 ( For example, phenyl group, etc.), arylthio group (for example, phenylthio, etc.), aralkylthio group (for example, pennorthio, etc.),
Amino 7 group (e.g. piperite, trimethylamino, etc.),
Acyloxy group (e.g. acetoquine, benzoyloxy, 7-yloxy, ncrohexa/ylluoquine, etc.)
, alkyloxycarbonyl groups (e.g., butoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), cycloalfkidicarbonyl groups (e.g., cyclohexyloxycarbonyl, etc.), aryloxycarbonyl groups (e.g., 7
(e/xycarbonyl, etc.), oxalyloxy groups (e.g., ethoxyoxalyloxy, etc.), carbamoyloxy groups (e.g., hexylcarbamoyloxy, etc.), sulfonyloxy groups (e.g., phenylsulfonyloxy, etc.), amide groups (e.g., benzoylamide 7 groups, etc.) , freido group (e.g., phenylureido, etc.), ami7sul7amoyl group (
For example, tsumethyl 7 mi 7 sul 7 amoyl, etc.).

Nidiclofurkyl JJi (preferably 3 to 6 carbon atoms,
(for example, cyclopropyl, cyclohexyl, etc.), and may further include a substituent, such as furkyl J in 111f, 1. Examples of substituents include =\.

The nearyl group (for example, phenyl!?) may have the same substituent as the alkyl group.

: Alfkidicarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.), which may have the same substituent as an alkyl group.

: Carbamoyl group (for example, phenylcarbamoyl, etc.) Niacyl group (for example, acetyl, l]-methquinbenzoyl, etc.) Nidiano group Furthermore, R7 and R2 may be combined to form a ring.

Exemplary compounds are shown below, but the present invention is not limited thereto.

Margin below CH2-C1h 108 C1l, l11
o 9 Cll2C&Ill
] OC1l, 0C6H5Il l 11 C112CIC1 or less Margin Cyclic ether compounds consisting of six shells are preferably represented by the following general formula.

In the formula, R1, R2, R2, R, SR1, R,, R,, R
8 is selected from the following:

:Hydrogen atom:Halogen atom (e.g. chloro, bromine, heptadone, etc.) :Light chain or branched alkyl group (preferably one or more carbon atoms)
40, for example methyl, ethyl, i-propyl, 2-ethylhexyl, lauryl, stearyl, etc.), and may further have a substituent. Examples of the substituent include the above-mentioned halogen atom, alkoxy group (e.g. methoxy, butoxy, steryloxy, etc.), 7lyloxy group (e.g. 7lyloxy),
(e/xy, etc.), aryl groups (e.g., phenyl, etc.), arylthio groups (e.g., phenylthio, etc.), aralkylthio groups (e.g., pennorthio, etc.), ami7 groups (e.g., vivelino/, trimethylami7, etc.), alkoxy groups (e.g., acetoxy , benzoyloxy, 7-raphayloxy, cyclohexanoyloxy, etc.), alkoxycarbonyl group (
(e.g., butoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), cycloalkoxycarbonyl groups (e.g., cyclohexyloxycarbonyl, etc.), aryloxycarbonyl groups (e.g., 7ethyloxycarbonyl, etc.), oxalyloxy groups (e.g., ethoxyoxa+ fluoroxy, etc.), carbamoyloxy groups (e.g., hexylcarbamoyloxy, etc.), sulfonyloxy groups (e.g., phenylsulfonyloxy, etc.), amide groups (e.g., benzoylamide 7 groups, etc.), ureido groups (e.g., phenylureido, etc.), ami/sulfamoyl groups (eg, trimethylaminosulfamoyl'4P), etc.

The dichloroalkyl group (preferably having 3 to 6 carbon atoms, such as cyclopropyl, cyclohexyl, etc.) may further have a substituent, and examples thereof include the above-mentioned substituents for the alkyl group.

The neararyl group (eg, phenyl, etc.) may have the same substituents as the alkyl group.

:Alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.), may have the same substituents as in the case of alkyl group.

: Carbamoyl group (eg, phenylcarbamoyl, etc.) Niacyl group (eg, acetyl, p-methoxybenzoyl, etc.) : Cia/group Furthermore, R1 and R2 and/or R1 and R may be bonded to form a ring. Further, R1 and R1 may form double adhesion.

Exemplary compounds are shown next, but the present invention is not limited thereto.

Below, j-white 118 It: (CI+□)2
] 19 (CI+.).

120 (C112).

121 (C112)2C=CI
I□1O-CH2X Among the above-mentioned cyclic ether compounds, a preferred group includes at least one ether bond, nistyl bond (e.g., -CO-1-SO2-17 mido bond (e.g., -8O2N) or ureido bond (e.g. Further, it is preferable that at least one hydrogen atom is bonded to the carbon atom directly bonded to the oxygen atom in the ring.

The cyclic ether compound may be purchased as a commercial product. Alternatively, it can be obtained by synthesizing a corresponding compound having a double bond in advance and then oxidizing the double bond with an oxidizing agent (for example, hydrogen peroxide). Further, the above-mentioned six-shell cyclic ether compound is, for example, JOC Vol.

36 p, 1176 (197t), Macromol
ecules 1980, p. 252, for example, British Patent No.
The four-shell type can be synthesized by the method described in German Patent No. 1,021,858.

In the present invention, the amount of the cyclic ether compound added to the photosensitive material is determined by the addition amount of the cyclic ether compound in the layer containing the cyclic ether compound.
The object of the present invention can be achieved if the amount is o, oot parts by weight or more.

The cyclic ether compound may be contained in at least one layer of the photosensitive material, but 'Tt contained in the photosensitive silver halide-containing layer is preferred.

In the cyclic ether compound of the present invention, +H■ contained as oil droplets is essential. It is preferred that the oil droplets contain hydrophobic photographic additives, but it is not essential that the oil droplets contain hydrophobic photographic additives. When a hydrophobic photographic additive is contained in the oil droplets, the amount of the cyclic ether compound of the present invention added is as follows in weight ratio to the hydrophobic photographic additive:
Preferably it is 0.1-10, more preferably 0.
It is 2-5.

As a hydrophobic photographic additive, the solubility in water is 10
Photographic additives are not particularly limited as long as they are less than % by weight, but include dye-forming couplers, colored couplers, DIR couplers, DII+ compounds, image stabilizers, color capri inhibitors, ultraviolet absorbers, and optical brighteners. preferable. In particular, dye-forming couplers are preferred.

In order to incorporate the cyclic ether compound in the present invention into the light-sensitive material as oil droplets, it is preferable to use the oil-in-water emulsion dispersion method described below.

When the cyclic ether compound is liquid at room temperature (20°C) and has a boiling point of about 150°C or higher (for example, Exemplary Compound 1
5.24.26.28.44.46.89.98.10
2r? ) can be incorporated into light-sensitive materials as oil droplets by using them as high-boiling, rg, organic solvents.

Further, when the cyclic ether compound is solid at room temperature, it can be incorporated into the photosensitive material as oil droplets by dissolving the cyclic ether compound in a high boiling point organic solvent.

The present invention can be preferably applied to color film, color reversal film, and the like.

Color reversal films generally consist of blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers and non-light-sensitive colloid layers, and the present invention is not subject to any restrictions on the arrangement of these layers on the support. It's not a thing.

The effect of the present invention can be particularly exhibited/I structure is sequentially from the support to colloidal silver antihalation M (intermediate layer) red-sensitive layer (intermediate layer) green-sensitive layer (intermediate layer) colloidal silver yellow filter layer, blue-sensitive layer ( Intermediate layer) Preservation w1 layer coated and further colloidal silver antihalation dust applied to the support.
(Intermediate layer) Red-sensitive layer (middle rv1ffi) Green-sensitive layer (intermediate layer) Blue-sensitive layer (intermediate layer) Red-sensitive layer (middle M) Green-sensitive layer (One layer of colloidal silver yellow filter) Blue-sensitive layer (intermediate layer)
It has an N configuration with a protective layer applied.

Note that the layers in parentheses may be omitted, and the red-sensitive layer, green-sensitive layer, and blue-sensitive layer may be divided into low-sensitivity and high-sensitivity layers, respectively. In addition, at least one of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer as seen in Japanese Patent Publication No. 49-15495.
R4 structure divided into two parts or layers; N structure in which high-sensitivity emulsion layer units and low-sensitivity emulsion layer units are separated as seen in JP-A-51-49027;
, No. 622.923, No. 2,622゜924, No. 2,
Examples include Ifil vt configurations found in No. 704.826 and No. 2,704,797.

The silver halide grains used in the silver halide emulsion in the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the present invention, in the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the liquid in which the other is present.

Also, while considering the critical growth rate of halogenated kite crystal,
pHr p of the mixing pot of halide ions and silver ions
It may be produced by sequentially and simultaneously adding Ag while stirring. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. Conversion methods may be used at any step in the formation of 8gX to change the halogen composition of the particles.

In the present invention, a known silver halide solvent such as ammonia, 1,000-onythyl, thiourea, etc. can be present during the growth of the silver halide emulsion.

In the present invention, silver halide emulsions contain cadmium salts, zinc salts, lead salts, thallium salts, ilinium salts (including & salts), rhodium salts (including complex salts) during the process of grain formation and/or growth process. Metal ions can be added using at least one selected from iron salts (including complex salts) and iron salts (including complex salts) to contain these metal elements inside the particles and/or on the particle surfaces. By placing the particles in an atmosphere, reduction sensitizing nuclei can be produced inside the particles and/or on the surfaces of the particles.

In the present invention, unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, use Research Dischrono + - (Resea
rcl+ Disclosure (hereinafter abbreviated as RD)
This can be carried out based on the method described in Section 1 of No. 17643.

In the present invention, the other silver halide grains may have a regular crystal shape such as a cube, an octahedron, or a dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. It can be anything. In these particles, 11001 faces and [
Any ratio of the 11 sides can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. The silver halide grains used may have a size of 0.05 to 30 microns, preferably 0.1 to 20 microns.

In the present invention, even if the silver halide emulsion has a rough grain size distribution, it will not be uneven.

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). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. (This shows the diameter when the image is converted into a circular image with the same area.)
These emulsions may be used alone or as a mixture of several kinds, or a polydisperse emulsion and a monodisperse emulsion may be mixed together.

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

The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. Sensitizing dyes may be used alone, but
You may use two or more types in combination. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes, and hemioxal-7yl dyes are included II.

1.? Dyes useful for are cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Or, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, during chemical ripening, at the end of chemical ripening, and/or after the end of chemical ripening and before coating the silver halide emulsion. Compounds known in the photographic industry as antifoggants or stabilizers can be added.

Binder (or protective colloid) for silver halide emulsions
Although it is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymeric substances such as single or copolymers may also be used.

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention may contain one or two types of hardening agent to bind binder (or protective colloid) molecules and increase film strength. By using the above, hardening can be achieved. The hardening agent can be added in an amount capable of hardening the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

For example, aldehydes, (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylolurea, methylolnomethylhyguntoin, etc.), nooxane derivatives, (2,3-nohydroxyoxane, etc.), activated vinyl compounds. (1, 3, 5
, -) lyacryloyl-hexahydro-S) rhianone,
1,3-vinylsulfonyl-2-prop/-l etc. L?
ll, -lodene compounds (2,4-fuchloro-6-hydroxy, -trianone, etc.), muco/10 denacic acids (mucochloric acid, muco7e/oxychloroic acid, etc.), and the like can be used alone or in combination.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in item ♦^ of R017643.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (late nox) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycityl (meth)acrylate, (meth)acrylamide, vinyl ester (
(e.g. vinyl acetate), acrylonitrile, olefins,
Styrene, etc. or a combination thereof, or a combination thereof with acrylic acid, methacrylic acid, α, β-unsaturated nocarboxylic acid, hydroxyalkyl (meth)acrylate, sulfofurkyl (meth)acrylate, styrene sulfonic acid, etc. A polymer as a polymer component can be used.

Emulsion M4 of the photosensitive material undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p7z nylennoamine derivative, amino 7 ether derivative, etc.) during color development processing to form a dye. Dye-forming couplers are used. The dye-forming couplers are selected for each emulsion layer so that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, and a yellow dye-forming coupler is selected for the blue-sensitive emulsion layer. A magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

It is desirable that these dye-forming couplers have in their molecules a group called a ballast group, which makes the coupler non-diffusive and has carbon rlL8 or more. Also, these dye-forming couplers are 1
Either 4-isomerism, in which one molecule of silver ion needs to be reduced to form a molecule of dye, or 2-isomerism, in which only 2 molecules of silver ion need to be reduced, are acceptable. .

The dye-forming coupler has a color correction effect, and by cambling with the oxidized form of the developing agent, it can be used as a development inhibitor, a development accelerator, a bleaching agent, a developer,
Releases 7 photographically useful fragments such as silver halide B-shaving, toning agent, hardening agent, fog-shaving, anti-fog+H-shaving, chemical sensitizer, spectral sensitizer, and sensitizer. Compounds are included. Among these, couplers that release a development suppressant during development to improve image sharpness and image graininess are called DIR couplers. Dll (instead of a coupler, cuff-pulling reaction occurs with the oxidized form of the developing agent)
, (When a color compound is produced, a development inhibitor is released in the same manner as 11, ?). It is also possible to use a R compound.

The DIl+ couplers and Dlll compounds used include:
161 with an inhibitor directly attached to the coupling position;
The 1i11 agent is bonded to the coupling position via a divalent group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction, which is released by the coupling reaction. (referred to as timing DIl'l couplers and timing DIR compounds). Furthermore, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination depending on the purpose.

A colorless coupler that performs a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye <21
! (also referred to as couplers) can also be used in combination with dye-forming couplers.

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

Among these, benzoylacetanilide and pivaloyl 7ceto7nilide compounds are right-handed. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Patent No. Z, 87
51o57, 3.265,508, 3.4
08. +94, No. 3.551.155, No. 3.
No. 5112.322, fi 3,725,071, No. 891,445, West German Patent No. 1,547.86
! No. 3, West German Application No. 1212.219,917, No. 2
, 261,361+7, No. 2.414.006,゛
British Patent No. 1.425.020% Special Publication 1977
No. 83, JP-A-47-26133, JP-A No. 4B-7314
No. 7, 5O-t3341, 1.150-87650
4'f, l1150-123342, 1ijI50-
No. 130442, No. 51/21827, No. 51-10
No. 2636, No. 52-82424, No. 52-1152
No. 19, No. 58-95346, etc. As a magenta dye-forming coupler, known 5-
Specific examples of magenta color-forming couplers that can be used include pyrazolone couplers, birazolobenlimigsol-based Kabufu, pyrazolotriazole couplers, open-chain 7syl-7cetonitrile couplers, and ingzolone couplers. US patent tj%2,600,78
No. 8, No. 2.983.608, No. 3.082, 6
No. 53, No. 3,127.269, No. 3.311.
No. 476, No. 3,419.391, No. 3.519
．． No. 429, No. 3,558,319, No. 3,58
2.322, 3.615.506, 3.8
No. 34,908, No. 3.891.445, West German Patent No. 1,810.464 seconds, West German Patent No. 1* (OLS)
No. 2,408.865, No. 2,417.945, No. 2
, 418.959, 2,424.467, JP 40-6031, JP 49-74027, JP 49
・No. 74028, No. 49-129538, No. 50-8
No. 0233, No. 50-159336, No. 51.208
No. 26, No. 51-26541, No. 52-42121, No. 52-58922, No. 53-55122, Japanese Patent Application No. 55-110943, and the like.

As the cyan dye-forming coupler, a 7-er/- or 7-tole coupler is generally used. An example of a cyan coupler that can be used is U.S. Pat. No. 1,423.
, No. 730, No. 12,474,2939, No. 2.80
1.171, 2.895,826, 3 and 4
No. 76.583, No. 3.737.326, No. 3,
No. 758.308, Specification No. 3.893,044,
JP-A No. 47-37425, No. 50-10135, No. 50-25228, No. 50-112038, No. 50
Couplers described in Japanese Patent Laid-open No. 117422 and No. 50-130441, and couplers described in Japanese Patent Application Laid-Open No. 58-98731 are preferred.

Dye-forming couplers, colored couplers, DIR couplers, DI that do not need to be adsorbed on the silver halide crystal surface
R compounds, image stabilizers, various anti-glare agents, etc. Hydrophobic compounds such as external radiation absorbers and optical brighteners can be treated using various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. Appropriate 'ff and ij can be selected depending on the chemical structure and the like. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and usually, a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a boiling point of f and Or, dissolve it in combination with a water-soluble organic solvent and use a surfactant in an aqueous gelatin solution or other aqueous solution using a stirrer, homozonizer, colloid mill, or 7Cy.
After emulsifying and dispersing using a mixer or ultrasonic dispersion means W1￥P, add it to the desired hydrophilic colloid liquid at the same time as A step of removing the solvent may be included.

As a high-boiling single-point solvent, it does not react with the oxidized form of the developing agent7
Engineering 7-ru JW form, 7-tar acid furkyl ester, phosphoric acid ester, citric acid ester, rest tl'l ester,
An organic solvent having a boiling temperature of 150° C. or higher is used, such as alkyl 7amide, fatty acid ester, trinonate ester, etc.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of low boiling point substantially water-insoluble solvents include ethyl acetate, probyl acetate, butyl acetate, butyl acetate, chloroform, carbon tetrachloride, nitrolthane, nitroethane, benzene and the like.

When dye-forming couplers, DIR couplers, colored couplers, 011 compounds, image stabilizers, various types of antibacterial agents, ultraviolet absorbers, fluorescent brighteners, etc. have acid groups such as carboxylic acid and sulft'/acid, , can also be introduced into the woody colloid as an alkaline aqueous solution. 7 Anionic surfactant as a dispersion aid when a hydrophobic compound is dissolved in a low boiling point, 9 solvent alone or in combination with a high boiling point solvent and dispersed in water using mechanical or ifi sound waves.
Nonionic surfactants, cationic surfactants and amphoteric surfactants can be used.

7. Between color-sensitive layers of photosensitive material (between color-sensitive layers and/or)
Prevents color fogging to prevent color turbidity, deterioration of sharpness, and conspicuous graininess due to movement of oxidized developing agent or electron transfer agent between color-sensitive layers Agents can be used.

The color antifoggant may be contained in the emulsion layer itself, or
An intermediate layer is provided between adjacent emulsion layers, and the intermediate layer is provided with an intermediate layer between adjacent emulsion layers. ￥ (You can let me do it.)

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in RD17643 No.

Protection of photosensitive materials: Hydrophilic colloid layers such as intermediate layers may contain an ultraviolet absorber to prevent fogging due to discharge caused by charging of the material due to friction, etc., and to prevent deterioration of images due to ultraviolet rays. .

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material. When dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer of a photosensitive material, they may be dyed with a mordant such as a kanaonic polymer. Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. Compounds that can be preferably used as development accelerators are the compounds described in Section XXI B to D of No. 8017643, and development retardants are those described in Section XXI of No. 17643.
It is a compound described in Section E. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The emulsion layer of photographic light-sensitive materials is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, and urethane derivatives for the purpose of increasing sensitivity, increasing cloud stability, or promoting development. , urea derivatives, imiguzol derivatives, etc. In the light-sensitive material, a fluorescent whitening agent can be used for the purpose of emphasizing the whiteness of the white background and making the coloring of the white areas less noticeable. Compounds that can be preferably used as optical brighteners are described in Section 1 of No. 1'1D17643.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiilanoation layer, and the like. These layers and/or the emulsion layer may contain dyes that are leached from the light-sensitive material during the development process. Examples of such dyes include oxonol dyes, hemioxol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes.

The silver halide emulsion layer of the light-sensitive material and/or the hydrophilic colloid layer of the light-sensitive material may be used to reduce the gloss of the light-sensitive material, improve the ease of writing,
A mantle agent can be added for the purpose of preventing photosensitive materials from sticking to each other. For the cloak wound, II':, 0; Norano is used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid, and their esters, Examples include polyvinyl resin, polycarbonate, and styrene polymers and copolymers thereof. The particle size of the matting agent is 0.05μ~
Preferably, the thickness is 10μ. The amount to add is 1 to 300zf
f/'+++' is preferred.

A lubricant can be added to the photosensitive material to reduce sliding friction.

Antistatic material can be added to photosensitive materials for the purpose of preventing static electricity. An antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated. It may be used in a protective colloid layer other than the L agent layer and/or the emulsion layer on the side where the emulsion layer is laminated with respect to the support. Preferably used (
i''! The antistatic agent is a compound described in HD17643 No.

The hydrophilic colloid layer of the photographic emulsion JM and/or Pond of the light-sensitive material has the following properties: improved coating properties, anti-static properties (1), improved slipperiness (1), anti-static properties (1), anti-static dispersion (7), adhesion prevention, (11) properties (promotion of development, hardening film). Various surfactants can be used for the purpose of improving (sensitizing agent, sensitization, etc.).

Supports used in the photosensitive material of the present invention include flexible reflective supports such as paper and synthetic paper laminated with α-threaded fin polymers (e.g., polyethylene, polypropylene, ethylene/butene copolymers), etc.; Films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene teretate, polycarbonate, polyamide, flexible supports with reflective layers provided on these films, glass, metal,
Includes pottery etc.

After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
It may be coated through one or more subbing layers to improve antihalation properties, frictional properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. In addition, for example, hardeners, which are so reactive that if added to the coating solution in advance, will cause delification before coating, mix them using a static mixer or the like just before coating. is preferable.

As coating methods, extra roots coating and curtain coating, which allow two or more types of layers to be coated at the same time, are particularly useful, but Bakken F coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

Examples of the surfactant include, but are not limited to, natural surfactants such as saponin, 7-ion surfactants such as alkylene oxide type, glycerin type, and glycidol type, higher alkyl heptamines, quaternary ammonium salts, and birinone. Sono g, cationic surfactants such as elementary rings, phosphoniums or sulfoniums, anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, phosphoric esters, etc., 7mi/acids , aminosulfonic acids, sulfuric acid or phosphoric acid esters of 7-minoalcohols, and the like may be added.

Moreover, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. In addition, a bleach-fixing process can be carried out using a one-bath bleach-fixing solution, or a monobath process using a one-bath developing, bleach-fixing solution can perform color development, bleaching, and fixing in one bath. Treatment steps may also be performed.

In combination with these processing steps, a mo-hardening process, its neutralization process, a stop-fixing process, and a post-hardening process may be performed. In these treatments, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed with a 72 activator solution, or a 72 activator solution may be used for the monobath process. Depends on how you apply the process. Among these locations, representative locations J+p are shown for dogs. (These treatments include, as the final step, one of the following steps: washing with water, washing with water, and stabilizing treatment (?). Color development process - Bleach-fixing process Constant fixation process - Color development process - Bleach-fixing process/Moe hardening process - Color development process - Stop fixing process - Washing process - Bleach process Constant fixation process - Washing process - Post hardening I back process/Color development process - Washing process - Supplementary color development process - Stopping % Process - Bleach process constant, γj process/activator process - Bleach-fixing process/activator process - Bleach process ('1', constant The treatment temperature in the deposition process and monobath treatment process is usually selected in the range of 10°C to 65°C, but it may also be a temperature exceeding 65°C.
Processed at 5°C to 15°C.

The color developing solution generally consists of 18 alkaline water solutions containing a color developing agent. The color developing agent is a primary amine color developing agent, and includes amino 7 ether/- and p-phenylenone amine type yJ conductors. These color developing agents can be used as salts of organic acids and inorganic acids; for example, salts of salts, sulfates, 1)-toluenesulfonates, sulfites, oxalates, benzenesulfonates, etc. can be used. I can do it.

These compounds are generally used in color developer 1i! about 0
, 1 to 30, more preferably a color developing solution]l
It is used at a concentration of about 1 to 15 g. o, 1. ?
A sufficient color density cannot be obtained if the amount added is less than .

Examples of the above aminophenol-based developer include 0-amino7er/-, p-amino77er, 5-amino7er/-
2-oxy-toluene, 2-ami/-3-oxy-toluene, 2-oxy-3-ami/-1+・1-tmethyl-
Contains benzene, etc.

1. The primary aromatic amine color developing abrasion useful for TE is N,
It is an N-noahokyl-11-phenylenenoamine compound, and even if the alkyl group and phenyl group are substituted,
Alternatively, it may not be replaced. Among them, particularly useful examples include N-N-methyl-1]-phenylenenoamine;'salt MuiN-methyl-1)-phenylenenoamine hydrochloride, N+N-E//f' rou 1]
-722lennoamine hydrochloride, 2-ami/-5-(:4
-Ethyl-N=dodenruami/)-) Luene, toethyl+1-β-7tansulfonamidoethyl-3-methyl-4-ami/aniline sulfate, N-ethyl-N-β-hydroxyethylami7aniline, 4 -7mi/-3-methyl-N, N-2'ethylaniline, 4-ami/-N
-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-)luenesulfonate and the like can be mentioned.

Further, the color developing agents mentioned above may be used alone or in combination of two or more kinds. Furthermore, the color developing agents mentioned above may be incorporated into the color photographic material.

In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. It also contains various additives such as pennone alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citranonic acid, and preservatives such as hydroxylamine or sulfites. You may. In addition, various foam removers and surfactants may be added, such as methanol, trimethylformamide or trimethylsulfoxide. Q- IT
It is possible to appropriately contain a TFI solvent or the like.

In the color developer used in the present invention, 11 is usually 7 or more, preferably about 9 to 13.

In addition, the color developing solution used in the present invention may optionally contain antioxidants such as ethylhydroquinamine, tetronic acid, tetronimylamine, 2-aniso/ethanol, hydroxyacelin, etc. 6k '52 alcohol, h)! Loxamic acid, benzose or hexose, pyrobrol-1,3-methyl ether, etc. may also be contained.

In the color developing solution used in the present invention, various chelating agents can be used in combination as metal ion sequestering agents. For example, as the chelating agent, amine polycarboxylic acids such as ethylenenoaminetetraacetic acid and noethylenetriami7pentaacetic acid,
Various phosphonic acids such as 1-hydroxyethylidene-1,1'-nophosphonic acid, 7-minoboriphosphonic acids such as ethylenenoaminetitraphosphonic acid, citric acid or gluconic acid, etc. Oxycarboxylic acid, 2-phospho7butane 1,2,4. - Phospho/carboxylic acids such as tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

The bleaching process is: As mentioned above, the fixing process (“
? They may be performed simultaneously or individually.

As bleaching agents (metal l'h salts of sulfuric acid are used, for example polycarboxylic acids, amyl/polycarboxylic acids or oxalic acid,
Organic acids such as citric acid coordinated with gold sulfur ions such as iron, cobalt, and copper are used. The most preferable organic acids among the organic acids described in ``2'' include polycarboxylic acids and 7/polycarboxylic acids. Specific examples of these include ethylenenoamine thitraacetic acid, noethylenetri7minebentaacetic acid, ethylenenoamine-N-(β-okynethyl)-N,N',N'-) diacetic acid, propylenenoamine thitraacetic acid, and nitrilotriacetic acid. , cyclohexanecyaminetetraacetic acid, imi-7-acetic acid, 7-hydroxyl glycine quinone I1%! (or tartaric acid, ethyl ethernoamine thitraacetic acid, glycol ethernoamine thitraacetic acid, ethylene 7minetetraprobionic acid, phenylenedi7minetetraacetic acid, etc.).These polycarboxylic acids are alkaline They may be metal salts, ammonium salts or water-soluble 7-mine salts.
~250g#! Use with.

In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenenoaminetitraacetate ([11) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

The bleaching solution used in the present invention includes vf
No., Special Publication No. 45-8506, No. 46-558, Belgian Patent No. fjS770.910, Special Publication No. 45-883
Various bleaching accelerators described in JP-A-54-71634 and JP-A-49-42349 can be added.

It is used at a bleach solution p of 2.0 or higher, but generally it is 4.
．． 0 to 9.5, preferably 4.5 to 8.0, most preferably 5.0 to 7.0.

A fixer having a commonly used composition can be used. As fixing agents, compounds that react with silver halide to form water-soluble complex salts, such as those used in ordinary fixing processes, such as periosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, and thiocyanic acid are used. Typical examples thereof include potassium, thousocyanate salts such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixing agents are used in an amount of 5 g/l or more, within the range that can be dissolved, but are generally used in an amount of 70 to 250 g/l. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

In addition, the bleaching solution and/or fixing solution includes boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,! I! Sodium carbonate, potassium bicarbonate, acetic acid,
Various PTL such as sodium acetate, ammonium hydroxide, etc.
Relaxation cutting may be contained alone or in combination of two or more types. Furthermore, various optical brighteners and TL
It is also possible to contain Y foam or a surfactant. In addition, preservatives such as hydroxylamine, hydranone, sulfite adducts of aldehyde compounds, organic chelation-resistant agents such as 7/polycarboxylic acids, stabilizers such as nitrofurfur, nitrates, hardeners such as water-soluble aluminum salts, etc. membrane agent,
An organic solvent such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. can be contained as appropriate.

l)H of the fixer is used at 3.0 or more, generally from 4.5 to IO, preferably from 5 to 9.5, most preferably from 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

The bleach-fix solution contains a silver halide fixer in addition to the above bleaching agent, and if desired, a solution containing sulfite as a preservative is applied. In addition, a bleach-fix solution containing a small amount of a halide such as ammonium bromide in the silver halide fixer described in ethylenenoaminetetraacetate complex bleaching solution 1 and 111f, or conversely, A bleach-fix solution containing a large amount of a halide such as ammonium, and a composition containing a combination of ethylene-7minetetraacetic iron (■) f3 salt) whitening solution and a large amount of a halide such as ammonium bromide. A special bleach-fix solution or the like can be used. In addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may also be used as halides. I can do it.

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the +1 II fl abrasion and other additives that can be contained in the bleach-fixing solution are the same as in the fixing process described above.

)1 The pl+ of self-sufficient liquid is used at 4.0 or more, but generally it is used at 5.0 to 9.5, preferably 6.0 to 9.5.
8.5, most preferably 6.5 to 8.5
It is.

[Example-1] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all of the following Examples, additions in silver halide photographic materials are 1, lIO2 unless otherwise specified in TE.
Show the winning one. In addition, silver halide and colloidal silver are shown in terms of silver.

A multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample-1 (comparison) 1st MII; Halation prevention/fl <lIC-
1) Gelatin layer containing black colloidal silver.

21st Threat; Intermediate Layer (+, L,) Gelatin layer containing an emulsified dispersion of 2.5-no-1-octylhydroquinone.

No.: Jl: Low sensitivity red-sensitive silver halide emulsion WJ (RL-
1) Emulsion (emulsion 1) consisting of 8 g Brl containing 6 mol % of average grain size, 0.65 μm - silver coverage 1.8 y/If12 sensitizing dye I.
... f3X10-5 mol sensitizing dye for 11 mol ff
... 1 mole of silver. OX 10-5 Morcian coupler (C-1)...! 0.0 per t1 mole
6 mole colored cyan coupler (CC-1)...f
0.003 mol DIl + compound (D-1) for f11 mol 0.0015 mol DIl compound (D-2) for 1 mol silver 0.002 mol oil droplet additive Comparative compound-1... Coupler c-
Same weight as 1st J Symphony; Highly sensitive red-sensitive silver halide emulsion layer (R1+
-1) il' average particle diameter 1.02μ+n, Δg I 6.0
7L cutting consisting of Δ) (1) r l (including mol%) (breast flattening ■ )... Silver coating m 1.3:I
/+lT” sensitizing dye L... 3 X IQ-5 mol sensitizing dye H...
...Light 1 mole of silver and 1. OX 10-'Morsian coupler (C-1)...0.02 per mole of silver
Mol colored cyan coupler (CC-1)...self...1i
0.0015 mol Dlfl compound per 1 mol of t (
1)-2)...0.001 mol oil droplet additive per 1 mol silver Comparative compound-1...Coupler M-
5th Jη, same weight as 1: Intermediate layer (+, L,) 2nd Same as IC1, gelatin layer.

6th layer: Low sensitivity green sensitive silver halide! ? L abrasion (C,
L-1) Emulsion-1... Coated silver amount 1.5g/
J sensitizing dye ■・・・・・・ 2,5X 10-5 moles per 1 mole of ff Sensitizing dye ■・・・・・・ 1,2X 10 moles magenta coupler (M -1)... 1 mole of silver is 0,
050 molar colored magenta coupler (CM-1)...
1 mole of silver equals 0.009 mole DI+? Compound (D-1)...1 mole of silver is 0,
0010 mol DII+compound (D-3)...
Comparative compound-1 7th layer with the same weight as coupler M-1; high-sensitivity green-sensitive halogenated emulsion layer (to I+-1
) Emulsion -■... Coated silver amount 1.4g/II+
2 sensitizing dye ■・・・・・・ per mole of silver], 5X 10-' mol sensitizing dye ■・
... 1 mole of silver. OX 10-5 mole magenta coupler (M-1)...@0.0 per mole
20 mole colored magenta coupler (CM-1)...
1 mol of silver = Q, OQZ mol DIR compound (D -3)...O, OOl per mol of silver
, O mol oil droplet additive Comparative compound-1...Coupler M-1
Yellow Filter M (YC-1) A gelatin layer containing a yellow colloid and a 7L dispersion of 2.5-note-octylhydroquinone.

9th W; low sensitivity) tooth-sensitive silver halide emulsion layer (13
L-1) Emulsion consisting of Snake Brl with an average grain size of 0.75 μIfl and containing 18 mol% of A3 (emulsion ■)... Silver coating amount 0.927+a2 Sensitizing dye ■... For 1 mole of silver 1,3X 10-5 mole yellow coupler (Y-1)...! 0.0 per mole of a.
29 moles to1a; High sensitivity blue sensitive milking Jf4 (1111-
1) Emulsion (emulsion ■) consisting of 8 g B "I" containing an average grain size of 1.10 μIll and Δg 110 mol %...silver coating amount 0.5 g/+++2 sensitizing dye V...... for ff11 mole 1.OX 10-5 moles Yellow coupler (Y-1)... 1 mole of silver and 0.08 mole DIR compound (D-2)... 1 mole of silver 0.0015 mol 1st+/il; 1st Ill11F4(Pro-1)7
Silver human bromide (Snake 11 mol% average particle size 0.07μl11)
Silver coated io, 59/+o2 Gelatin layer 12 containing ultraviolet absorbers UV-1, [IV-2] Second protective layer (Pro 2) Polymethyl methacrylate particles (diameter 1° 5μ+n) and formalin scavenger (lIS-1) In addition to the composition described above, each gelatin layer contains a gelatin hardening agent CI.
+-1) and a surfactant were added.

Comparative compound-1 Comparative crop-2 The oil droplet additive of the present invention and the comparative oil droplet additive were weighed in the same weight as the coupler of each layer, dissolved in ethyl acetate together with the coupler, colored coupler and DIR compound, and dodecylbenzenesulfone After addition to a 5% gelatin aqueous solution containing sodium chloride, the dispersion obtained by dispersing with a homonizer was added to an emulsion.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; Anhydro 5.5'-nochloro-9-ethyl 3,3'-no (3-sulfopropyl)thiacarbocyanine hydroxide Sensitizing dye II; Anhydro 9-ethyl 3,3-no (''
3-sulfopropyl) -4,',), 4'', 5'
-nobenzothiacarbocyanine hydroquine sensitizing dye III; anhydro 5,5'-nophenyl-9-ethyl-3,3'-no (3-sulfopropyl)oxacarbonanine hydroxide sensitizing dye ■; anhydro 9-ethyl- 3,3'-no
(3-sulfopropyl) 5,6+5', 6
'-Nobenzoxacarbocyanine hydrokind sensitizing dye ■; Anhydro 3,3'-no (3-sulfopropyl) 4,5-benzo-5'-methoxythiacyanine Below margin C, 11.

C-1 M M-1 I C! Y-] UV-] C, 11, (L) UV-2 Next, in Sample 1, the silver halide emulsions and oil droplet additives of the 3rd layer, fjrJ4 layer, 6th layer, and 7th layer were added to &- 1
Samples 1 to 16 were created with the following changes.

Each of Samples 1 to 16 thus prepared was exposed to sea urchin horn using white light, and then subjected to the following development treatment.

Processing process (38℃) Color development 3 minutes 15 seconds) White paper 6 minutes 30 seconds washing with water
3 minutes 15 seconds fixed time 6 minutes 30 seconds washing
Stabilization for 3 minutes and 15 seconds and drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

4-7mi/-3-methyl-N-ethyl-N-(β-hydroxylethyl)-aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine 1/2 sulfate 2.0g anhydrous carbonate Potassium 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 11.

[)Vote white liquid]

Ethylenenoaminetetraacetic acid iron ammonium salt ioo, yethylenenominetetraacetic acid diammonium salt 10,0.

Ammonium bromide 150.0.

Glacial acetic acid 10. Add 1 oz of water to make 11, and use ammonium water to make p11=6.
．． Adjust to 0.

[Fixer]

Ammonium 1,000 sulfate 175.0 g)
1 ((water dish Sodium sulfate 8.5g Sodium metasulfite 2.3g Add water to make 11, and adjust to pH=6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5 shoulders! Konigunkus (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5#Z Add water and I
I! shall be.

For each sample obtained, the relative sensitivity (S) and sharpness (MTF) and +<
MS was measured. The results are shown in Table 2.

Note that the phase N sensitivity (S) is a relative value of the reciprocal of the exposure amount that gives a Capri density of +0.1, and is expressed as a value with wSl and degree of sample No. 1 as 100. The sharpness improvement effect is due to the M TF (Modulation Tran) of the dye image.
:;fer Function) was determined and expressed as a relative value of MTF at 10 pieces/I (Sample No. 091 is taken as 100).

8MS value is the minimum density + 1.2 density with aperture scanning area 25
It is expressed as a value 1000 times the standard deviation of the variation in density value that occurs when scanning with a 0μ12 microdecitometer.

As can be seen from Table 2, the 7% silver lodenide photographic emulsion containing the cyclic ether compound and tabular silver halide emulsion of the present invention was found to have significant improvements in sensitivity, graininess, and sharpness.

It has also been found that the effect of the present invention is particularly great when the silver halide 7L grain consists of grains in which silver iodide is localized in the center.

It has also been found that the effect of the present invention is that the strength of silver iodide contained in the outer periphery of the silver halide emulsion is greater than that of pure silver bromide.

In addition, the frequency of pressure fog occurrence in the developed samples was investigated, and as shown in the right column of Table 2, the frequency of pressure fog occurrence was found in samples containing the cyclic ether compound and tabular silver halide emulsion of the present invention. Significant improvements were observed in (
10 Frequency of occurrence is low - 11 Frequency of occurrence is high).

[Example 2] Tests 11 to 16 of Example 1 were subjected to the strength deterioration treatment shown below. °↓
The stability of the sensitive material over time was evaluated.

Strength deterioration treatment A Strength deterioration treatment B Ij-degree 65℃ 4
0'C relative 78 degrees 20% 80% processing number of openings 10 7 days Also, using another sample No. 1 to 16 of Example 1, 1 after exposure (now exposed at room temperature for 2 months to test image stability).
After standing under normal humidity, the same development treatment and sensitometry as in Example 1 were performed.

The results are shown in Table-3. Table 3 shows the fluctuation range or fluctuation rate based on the sensitometric characteristics of each sample of Example 1.

As can be seen from Table 3 below, the silver halide photographic emulsion containing the cyclic ether compound and the tabular silver halide emulsion of the present invention has significantly improved capri increase at high temperatures and density decrease under high lj degree conditions. It can also be seen that the latent image stability after 'M' is also improved. It has also been found that the effect of the present invention is greater when a silver halide emulsion consisting of silver halide grains in which silver iodide is localized in the center is used.

It has also been found that the effect of the present invention is greater when silver iodide is contained in the outer periphery of the silver halide emulsion than when pure silver bromide is contained.

1.i Patent Applicant Konishi Roku Photo Industry Co., Ltd. Teku ■Kan T Shoji (Method) % Formula % 2 Name of the invention Silver halide photographic light-sensitive material 3 Person making the amendment 1 [Relationship with the matter Patent Applicant Address 1-chome Nishi-Shinjuku, Shinjuku-ku, Tokyo] 26-2 (12
7) Name: Konishi Roku Shai Kogyo Shikisha Company Contact: Publication 91 1 Sakura-cho, Hino City, Tokyo Konishi Roku Shai Kogyo Sister Shiki Company (0425-83-1521)
Patent Department 5, hltilE;''ノ2[1(self1ljl Jll +!J

Claims (1)

[Claims] In a silver halide photographic material comprising a plurality of light-sensitive silver halide emulsion layers coated on a support, at least one of the emulsion layers contains a cyclic ether compound, and at least one of the emulsion layers contains a cyclic ether compound. Layers have an average aspect ratio of 5:1
A silver halide photographic material comprising the tabular silver halide emulsion as described above.