JPS63239435A - Silver halide photographic sensitive material having rapid processing property and less change of sensitivity and gradient against temperature change at exposure - Google Patents

Abstract

PURPOSE:To improve the rapid processing property of the titled material and to reduce the changes of the sensitivity and the gradient of the titled material caused by the temperature change at the time of exposing said material by incorporating a silver halide particle having a prescribed high chloride content and a specified org. compd. in an emulsion layer. CONSTITUTION:One or more layers of silver halide emulsion layers contd. in the titled material contain the silver halide particle (A) having the high chloride content and the org. compd. (B) having solubility product against a silver ion of <=1X10<-11.0>. The compd. B is incorporated in the silver halide emulsion layer during the period from the formation of the silver halide particle to the end of the chemical sensitization of said particle. The particle A is composed of the silver halide which has >=90mol.% silver chloride and is chemically sensitized in the presence of an unstable sulfur compd. and a gold compd. And, the compd. (B) is exemplified by the mercapto compd. shown by formula I wherein Q is 5-6 membered heterocyclic ring group, etc., M is hydrogen atom. The concrete example of the compd. shown by formula I is exemplified by the compd. shown by formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention has excellent rapid processing properties, high sensitivity, and low sensitivity and gradation iI! with respect to temperature changes during exposure. This invention relates to a silver halide photographic material with little I fluctuation.

[Background of the invention]

In recent years, there has been an increasing demand for speeding up color development for various purposes including improving the productivity of photographic prints, and various measures have been taken for this purpose. As one method, it is known to use a color development accelerator when developing an exposed silver halide photographic light-sensitive material using an aromatic primary amine color developing agent. For example, such color development accelerators are described in US Pat. No. 2,950.
No. 970, No. 2,515,147, No. 2,496
．． No. 903, No. 4,038゜075, No. 4,11
No. 9,462, British Patent No. 1,430,998, fJS No. 1.455,413, Special Patent No. 1j11@53-15
No. 831, No. 55-62450, No. 55-624! d
No. 55-62452, No. 55-82453, No. 51-12422, Special Publication No. 51-12422, No. 5
Compounds described in No. 5-49728, etc. have been investigated, but most of these compounds have insufficient development accelerating effects, and even among these compounds, even those that exhibit sufficient development accelerating effects often have It had the disadvantage of generating capri and was not practical.

In addition, various penetrants have been studied in order to promote the penetration of color developing agents into silver halide photosensitive materials, and among these, a method of accelerating color development by adding benzyl alcohol to a color developer is widely used ( It is used.

However, this method has some difficulties in rapid processing because, for example, at a processing temperature of 33° C., a sufficiently high color density cannot be obtained unless the processing is carried out for 3 minutes or more. In addition to the processing temperature, a method has also been proposed in which color development is carried out by increasing the PL+ concentration of the color developer; for example, the pH is increased to 1085
If the temperature is higher than that, the oxidation of the color developing agent will be significantly accelerated, or the pH of the color developing agent will be lowered due to lack of a suitable warm solution.
It is susceptible to changes, which makes it difficult to obtain stable photographic performance and increases the dependence on processing time.

On the other hand, in order to speed up color development, a method is also known in which a color developing agent is incorporated into a light-sensitive material in advance, as described in US Pat. No. 3,719.492, for example.

However, this method has the drawback that the raw storage stability of the silver halide photographic light-sensitive material is poor, that capri occurs in the songs used, and that capri is likely to occur during color development processing.

Furthermore, in order to inactivate the amine moiety of the color developing agent, there is a method of incorporating the color developing agent in the form of ship salt, for example, as disclosed in US Patent No. 53°342.559.
No., Research Disclosure - 1976 No.
15159. However, in these methods, color development does not start until after the color developing agent has been alkaline-hydrolyzed, so that the problem is that color development is rather delayed.

In addition, Japanese Patent Laid-Open No. 57-144547 and Japanese Patent Application Laid-open No. 58-1987 disclose a method of adding 1-7-ly-3-pyrazolidone having a specific structure to a silver halide color photographic material. No. 50532, 58
-5053: No. 1, No. 58-50534, No. 58-5
0535 and 5B-50536, 1-7
It has been disclosed that a reelvirazolidone is added to a silver halide color photographic light-sensitive material and processed within an extremely short development time.

However, the techniques described in these publications are not necessarily satisfactory in terms of obtaining dye images with sufficient color development speed and high color density, and there is still room for improvement. .

Furthermore, it is known that color development can be accelerated by using a silver chloride emulsion or a silver chlorobromide emulsion with a high silver chloride content as a silver halide emulsion. No. 183,756, No. 4,225,6
No. 66, JP-A-55-28589, JP-A No. 58-9144
No. 4, No. 58-95339, No. 58-94340,
No. 58-95736, No. 58-106538, No. 5
No. 8-107531, No. 58-107532, No. 58
-107533, 58-108533, 58-
No. 125612 and the like have descriptions regarding the above technology. From the viewpoint of rapid processing, the techniques described in these documents are
Although the results were quite satisfactory, the sensitivity was still insufficient, and there were further problems in that the sensitivity and gradation fluctuated significantly, especially with respect to temperature changes during exposure of the photosensitive material.

In addition, for the purpose of increasing the sensitivity of emulsions containing high silver chloride, when an unstable sulfur compound and a gold compound are used in chemical sensitization of emulsions containing high silver chloride, the sensitivity to temperature changes during exposure and It became clear that f1 would cause even greater fluctuations in key, which would pose a major problem in practical use.

As a result of intensive studies to eliminate the above drawbacks, the present inventors have discovered that when chemically sensitizing a specific high silver chloride containing emulsion using the above unstable sulfur compound or gold compound, It is expected that by applying this type of compound, it will be possible to obtain a silver halide photographic material that is highly sensitive, has excellent rapid processing properties, and is stable with less fluctuation in sensitivity and gradation due to temperature changes during exposure. Discover external facts,
This has led to the present invention.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a silver halide photographic material that has excellent rapid processability, high sensitivity, and exhibits less sensitivity and gradation fluctuations even with temperature changes during exposure.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a silver lodenide photographic material having at least one silver halide emulsion layer on a support, in which a small amount (one layer of the 710 silver denide emulsion layer) contains unstable sulfur compounds. High chloride with a silver chloride content of 90 mol% or more chemically sensitized in the presence of a gold compound))
Solubility product between silver lodenide particles and silver ions (K=+p
) is selected from organic compounds having a physical property value of 1×10-11・0 or less. This was achieved by using a silver halide photographic material that is added before the end of chemical sensitization of the grains.

[Specific structure of the invention]

In the silver halide photographic light-sensitive material of the present invention, the silver halide grains contained in at least one of the silver halide emulsion layers are high chloride silver halide grains having a silver chloride content of 90 mol% or more. The silver chloride content is preferably from 99.0 mol% to 99.9 mol% for the effect of the present invention.
This range satisfies the effects of the present invention and rapid processability at the same time.

The silver halide grains according to the present invention may be any of silver chlorobromide, silver iodochloride, silver chloroiodobromide, and silver chloride, and silver iodide may be contained, but the content is , preferably 1
mol% or less, more preferably 0.5 mol% or less,
Silver halide grains which are most preferably free of silver iodide and are therefore preferred in the present invention include silver chlorobromide and silver chloride, and the most preferred grains are silver halide grains having the above-mentioned silver chloride content. It is silver.

The silver halide grains according to the present invention may be used in combination with silver halide grains other than the present invention, but in that case, all the halides in the silver halide emulsion layer containing the silver halide grains according to the present invention The ratio of the projected area occupied by the silver halide grains of the present invention to the projected area occupied by the silver halide grains is preferably 50% or more, more preferably 75% or more.

The silver halide grains of the present invention can be used, for example, in JP-A-59-16
No. 2540, No. 59-48755, No. 60-
It can be formed according to the methods described in JP-A No. 222844, JP-A No. 60-222845, JP-A No. 60-136735, and the like.

The grain size of the silver halide grains according to the present invention is particularly preferably II7
There is no limit, but considering other photographic performance such as rapid processing and V sensitivity, preferably 0.2 μl to 1.6 μl,
More preferably, the amount is in the range of 0.25 μl to 1.2 μl. The particle diameter can be measured by various methods commonly used in the technical field. A representative method is Loveland's "Particle Size Analysis Method JA, S, ToM.

Symposium on Light Microscopy 195
5, pp. 94-122 or ``Theory of the Photographic Process'' co-published by Mies and Noames, 1133 edition, published by Macmillan (1966)! It is described in Chapter 52.

The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The grain size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse.

Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 22% or less, more preferably 15% or less in the grain size distribution. Here, the coefficient of variation is the standard deviation of the particle size distribution, the average particle size (arithmetic mean value of particle sizes)
It is the amount expressed as a percentage.

The grain size here refers to the diameter in the case of spherical silver halide grains, and in the case of grains with shapes other than cubic or spherical, the diameter when the projected image is converted to a circular image of the same area. .

The silver halide grains according to the present invention can be produced by an acid method, a neutral method, 7
The particles may be obtained by any of the 7 methods. The particles may be grown all at once, or after forming seed particles, the ti
The method for producing and growing the zero-species particles may be the same or different.

Further, the method of reacting the soluble silver salt and the soluble halogen salt may be any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but it is preferable to use a method obtained by a simultaneous mixing method. 4 forms of law
It is also possible to use the p/Ig-controlled Dawg pull jet method described in No. 48521 and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a compound having a crystal habit such as a mercapto group-containing compound or a sensitizing dye may be used.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having 11001 planes as the crystal surface.

Also, U.S. Patent Nos. 4,183,756 and 4,22
No. 5,686, JP-A-55-26589, JP-A-55
-42737, etc., and The Tsuyaru Op. 7r) Graphic Science (J, Pbotg
r, 5ci) 21.39 (1973), particles having shapes such as octahedron, tetradecahedron, dodecahedron, etc. can also be used. Particles having an irregular shape or particles having an irregular shape may also be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

The silver halide grains according to the present invention can be prepared by adding cadmium salt, zinc salt,
Metal ions can be added using lead salts, thallium salts, iridine salts or complex salts, rhodium salts or complex salts, iron salts or complex salts, and incorporated into the interior of the particles and/or on the particle surfaces. By placing the particles in a reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method of Research Disclosure No. 17G43.

The silver halide grains according to the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is formed mainly in the interior of the grain. These are particles that are mainly formed on the surface.

In the present invention, the silver halide emulsion containing the silver halide grains according to the present invention is chemically sensitized in the presence of an unstable sulfur compound and a VLk compound, and further contains the silver halide grains. From the time of formation to the end of chemical sensitization, the solubility product (Ksp) with silver ions is 1×10-”
- At least one compound selected from organic compounds having a physical property value of 0 or less is added.

The solubility product with silver ions other than the present invention is 1×10-1+・0
The desired effect cannot be expected for compounds that have a solubility product that exceeds 18, that is, compounds that have a smaller ability to form salts with silver ions. (Published) pages 233 to 250 can be referred to. .

In the present invention, the solubility product with the silver ion is 1×10
The organic compound (hereinafter referred to as the organic compound of the present invention) having a physical property value of ``■・O or less preferably has the following general formula [S
] It is a mercapto compound shown by.

The following is a blank general formula (S) (wherein, Q represents a 5-shell or 6-chain heterocycle, or an atomic group necessary to form a 5-shell or 6J:1 heterocycle in which benzene rings are condensed, and M represents a hydrogen atom or cation.) The mercapto compound represented by the general formula [81] which is preferably used as the organic compound of the present invention will be described below.

In the general formula [S], Q represents an atomic group necessary to form a 5-shell or 6-shell heterocycle, or a 5-shell or 6-shell true heterocycle with benzene rings condensed; Examples of the bicyclic ring include an imidazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a selenazole ring, a pencyimiguzole ring, a naphthoselenazole ring, a benzothiazole ring, a tothiazole ring, a benzoselenazole ring, and a naphthoselenazole ring. ring, penzoxazole ring, etc.

Examples of cations represented by M include alkali metal ions (e.g., sodium ions, kawaram ions, etc.)
, ammonium group, etc.

The mercapto compound represented by the general formula [S] can be further synthesized by the following general formula [SAI, [SB], [SC]
Preferred are norcapto compounds represented by the following formulas.

General formula (SAI) In the formula, RA represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or a amide group, and Z represents -N11-1 -〇-1 or -8-, M
is synonymous with M in the general formula [S].

General formula (SB) ^r In the formula, A represents , and R is an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amine 7 group, an acylami 7 group, a carbamoyl group or represents a sulfonamide group, n represents an integer of θ to 2. M has the same meaning as M in general formula [S].

In the general formula [S^1 Ascend [S[I], examples of the alkyl group represented by RA and Re include methyl group, ethyl group, butyl group, etc., and examples of the alkoxy group include methoxy group, ethoxy group, etc. Examples of salts of carboxyl or sulfo groups include sodium salts and ammonium salts.

Examples of the aryl group represented by %RA in the general formula [S^1 include phenyl group, Na7. Examples include chill group, etc.
Examples of the halogen atom include a chlorine atom and a bromine atom.

Examples of the acylami 7 group represented by R@ in the general formula [SD] include a methylcarbonylamino group and a benzoylami 7 group, and examples of the cal/zumoyl group include an ethylcarbamoyl group and a 7-enylcarbamoyl group. Examples of the soufflephonamide group include a methylsulfonamide group and a phenylsulfonamide group.

The above-mentioned alkyl groups, alkoxy groups, aryl groups, ami7 groups, acylami7 groups, carbamoyl groups, sulfone 7mide groups, etc. further include those having substituents.

Represented by the general formula (SC), R is a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, -SR^1, -NtlS
OJAs or a heterocyclic group, RAI represents a hydrogen atom, a furkyl group, an alkenyl group, a cycloalkyl group, an aryl group, -CORA4, or -5OJxs,
RA2 and RAW are a hydrogen atom, a furkyl group,
or represents an aryl group, and RA4 and RAS each represent an alkyl group or a 7-aryl group. 1M is the same as M in general formula (S).

R AT RAl l RA2 in general formula (SC)
Examples of the furkyl group represented by 1RA31R□ and RA include a methyl group, pencil group, ethyl group, and propyl' group, and examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the alkenyl group represented by RA and C/RAI include a propenyl group, and examples of the cycloalkyl group include a cyclohexyl group.

Examples of the heterocyclic group represented by RA include furyl group,
Examples include bilinonyl group.

Above R^・RA-・RA2・RA3・RA4・and R
The alkyl group and aryl group represented by A, RA and R
The alkenyl group and the cycloalkyl group represented by AI and the heterocyclic group represented by RA further include those having a substituent.

General formula (SD) ■ In the formula, RA and M represent the same groups as RA and M in the general formula (SC), respectively, and RBI and V
R132 represents a group having the same meaning as RAI and VRA2 in general formula (SC), respectively.

Furthermore, RBI and R82 may be bonded to each other to form a ring.

Specific examples of the compound represented by the general formula [S] are shown below, but the present invention is not limited thereto.

S^-1s^-2 S^-3s^-4 S^-5s^-6 S^-75A-8 SB-I SB-2SB-5
3B-6 The compound represented by the above general formula (S) is, for example,
No. 0-28496, JP-A-50-89034, Journal of Chemical Science (J, CI+em
, Soc, ) 49, 1748 (1927), 49
2378 (1952), Journal of Opening Chemistry (J, OrH.

Chew+, ) 39.2469 (1965), U.S. Patent No. 2,824,001, Tsuyanal Op Chemical Society.

1723 (1951), Japanese Patent Application Publication No. 56-111846, British Patent No. 1t275w701, U.S. Patent No. 3,2
66.897, 2,403,927, etc., and can be synthesized according to the methods described in these documents.

In order to incorporate the compound represented by the general formula (S) according to the present invention (hereinafter referred to as compound C3) into the silver halide holes MM containing the silver halide grains according to the present invention, water or water and optionally organic solvents miscible with (e.g. meta/-
The compound (S) can be added after being dissolved in a solution of the general formula [S].
A combination of two or more compounds represented by the formula (S
) may be used in combination with other stabilizers or capri inhibitors other than those shown.

Compound [S] may be added at any time between after the formation of silver halide grains and before the end of chemical sensitization, but preferably after the formation of the grains and before the end of chemical sensitization. It's been a while since it started.

Compound (S) may be added in its entirety at one time, or
It may be added in several portions.

There is no particular restriction on the amount added, but it is usually added in the range of 1 x 10-' mol to 1 x 10'' 1 mol, preferably 1 x 10-' mol to 1 x 10-'' mol, per 1 mol of silver halide. be done.

The silver halide grains according to the present invention are chemically sensitized in the presence of an unstable sulfur compound and a gold compound, and the unstable sulfur compound and gold compound used in the present invention will be explained below.

The unstable sulfur compound used in the present invention is a sulfur-containing compound that has the property of forming a silver salt when reacting with silver halide, and further forming silver sulfide under conditions such as strong alkalinity, Examples include thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate,
Mention may be made of sulfur sensitizers such as cystine.

The amount of the sulfur sensitizer, which is an unstable sulfur compound, used in the present invention varies depending on various conditions, but is used in the range of 1 x 10-' mol to IX 10-' mol per 1 mol of silver halide. is preferable, more preferably 1×
10-' mol to 1 x 10-' mol, particularly preferably 2
X 10'' mole to 8X10'' mole. When the above sulfur sensitizer is added to an emulsion, it should be dissolved in water or an alcohol such as methanol or ethanol. Bye.

Examples of the gold compound used in the silver halide emulsion layer of the present invention include Jk chloride acid and 4tll! chloride! ! ! ! Examples include sodium, potassium gold periosulfate, and the like.

However, it is not limited to these.

The amount of the gold compound added according to the present invention is preferably 5X101 to 5X10-' moles per mole of silver halide, more preferably 2X10-' to 1xio-' moles, and even more preferably 2.6X10-' moles. 10-'~4 X 1
0-' moles, most preferably 2,6X 10-' to 9
X 10-' moles.

The gold compound according to the present invention may be added from the time when the formation of silver halide grains according to the present invention ends until the end of chemical sensitization.

The unstable sulfur compound and the gold compound according to the present invention only need to be present during chemical sensitization of the high chloride silver halide grains according to the present invention, and specifically, the unstable sulfur compound and the gold compound according to the present invention may be present from the completion of the formation of the grains to T sensitization. Add and allow to exist until the end.

As described above, the present invention provides a silver halide emulsion containing high chloride silver halide grains according to the present invention in the presence of an unstable sulfur compound and a gold compound according to the present invention, as well as an organic compound according to the present invention. Regarding only the latter chemical sensitization method, for example, British Patent fjSl, No. 315.755, JP-A-58-1265
26, JP-A No. 60-232545, and other publications, the contents described in the above publications are not related to silver chlorobromide or silver iodobromide with a high silver bromide content. However, the effect of the present invention, that is, the specific effect obtained in a silver halide emulsion with a high silver chloride content, was completely unexpected.

On the other hand, the organic compound of the present invention is added to a silver halide emulsion at the end of chemical ripening or at a later stage for the purpose of preventing fog and improving the stability or storage stability over time of the silver halide photosensitive material. Although it is well known in the art that the compound is added after chemical sensitization, it is not possible to obtain the effects of the present invention by adding it after chemical sensitization, which is outside the scope of the present invention.

The emulsion according to the present invention can be spectrally sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dye may be used alone or in combination of two or more, and together with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light, A supersensitizer that enhances the sensitizing effect of the sensitizing dye may be included in the emulsion.

When the silver halide emulsion according to the present invention is used as a blue-sensitive emulsion, it is preferable to spectrally sensitize it with a sensitizing dye represented by the following general formula (A).

General Formula (A) In General Formula (A), Z11 and Z12 are respectively a benzoxazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a bencyimiguzole nucleus, Represents the atomic group necessary to form a naphthimidazole nucleus, a pyridine nucleus, or a quinoline nucleus, and these heterocycles include those with substituents.
Examples of substituents on the heterocycle formed by 2 include a halogen atom, a Schiff/group, a methyl group, an ethyl group, a methoxy group, and an ethoxy group.

Ra + R22 each represents a furkyl group, an alkenyl group, or an aryl group, preferably an alkyl group, more preferably an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably a carbon atom number. 1 to 4 sulfoalkyl groups. Also R2
3 is selected from a hydrogen atom, a methyl group and an ethyl group.

Xe represents an anion, and l represents 0 or 1.

Among the sensitizing dyes represented by the general formula [A], the most useful dyes are the sensitizing dyes represented by the following general formula [A'].

General Formula [A'] Here, Y and Y2 each represent an atomic group necessary to complete a benzene ring or a 7talene ring which may be substituted. The benzene ring and the 7-talene ring may have a substituent, and the substituent is preferably a halogen atom, a sia group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.

R21, R22, R2s, X et(J: (/ j!
It -1/1 Formula (A]t' is the same as shown.

Specific examples of the sensitizing dye represented by the general formula (A) used in the present invention are shown below.

A-5 C11°-1O When the silver halide emulsion according to the present invention is used as a green-sensitive emulsion, it is preferable to perform spectral sensitization with a sensitizing dye represented by the following general formula (B).

In the following margin general formula (t3) general formula CB), Z. and Z12 each represent an atomic group necessary to form a benzene ring or a 7talene ring fused to an oxazole ring. The heterocyclic nucleus formed may be substituted with various substituents, and these preferred substituents are halogen atoms, aryl groups, alkyl groups, or alkoxy groups. More preferred substituents are a halogen atom, a phenyl group or a methoxy group,
The most preferred substituent is phenyl.

The preferred size of the present invention! ! l! I! According to the above, Z I+ and 21□ are both benzene rings fused to an oxazole ring, and at least one of these benzene rings is substituted with a phenyl group at the 5-position, or the 5-position of one benzene ring is substituted with a phenyl group. Phenyl group at position, 5 of other benzene ring
The position is substituted with a halogen atom.

R21 and R22 each represent an alkyl group, an alkenyl group or an aryl group, preferably an alkyl group. More preferably, R2 and R21 are each an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably a sulfoalkyl group having 1 to 4 carbon atoms. Most preferred is a sulfoethyl group.

R23 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an ethyl group.

X and θ represent anions, such as chlorine, odor C1l,
Examples include anions of So, -, cz++sso, and -5. n represents 1 or 0, provided that n represents 0 when the compound forms an inner salt.

Specific examples of the sensitizing dye represented by the general formula CB) preferably used in the present invention are shown below.

Margin below - I When the silver halide emulsion according to the present invention is used together with a red-sensitive emulsion, a sensitizing dye represented by the following general formula (C) or a thickening dye represented by the following general formula CD) can be used for spectroscopy. Sensitization is preferred.

General formula (C) (Xe　)1-1 General formula (D) R, I+.

(xe)1-i In general formula (C) and general formula (D), R represents a hydrogen atom or an alkyl group, R1 and R1 each represent an alkyl group or an aryl group, and 2. ．． 22, Z
4 and Z each represent an atomic group necessary to form a benzene ring or a 7-talene ring fused to a thiazole ring or selenazole ring, and Z represents a hydrocarbon atom necessary to form a 6-shell ring. represents a group, l represents 1 or 2,
Z represents a sulfur atom or a selenium atom, and Xe represents an anion.

In the above general formula, examples of the alkyl group represented by R include a methyl group, an ethyl group, and a propyl group, and R is preferably a hydrogen atom, a methyl group, or an ethyl group. Most preferably a hydrogen atom or an ethyl group.

Further, R,, R,, R3 and VRl are each a linear or branched alkyl group (this alkyl group may have a substituent, for example, methyl, ethyl, propyl, chloroethyl,
Hydroxyethyl, methoxyethyl, 7 setquinethyl, carboxymethyl, carboxyethyl, ethoxycarbonylmethyl, sulfoethyl, sulfopropyl, kulfoptyl, β-hydroxy-γ-sulfopropyl, monkey 7
Z represents a group selected from Z
The polychoric ring nucleus formed by Z 2, Z- or Z may have a substituent, and the preferred substituent is a halogen atom, an aryl group, an alkyl group or an alkoxy group, and further is a halogen atom (e.g. chlorine atom)
, phenyl group or methoxy group are preferred.

Xe is an anion (for example, C1-1[1r-11-1r
represents 1 earth or 2.

However, if the compound forms an inner salt,! represents 1.

Typical specific examples of the sensitizing dye represented by the general formula (C) or CD) preferably used in the present invention are shown below.

Below is the margin re Bre C21 amount, L. , l15 e Below margin D・-1 C211s (L
:lhJ4blhSeD-6 I-Safe The amount of the sensitizing dye represented by the above general formula [Al, [Bl, [C1, or [I)1] is not particularly limited, but is generally 1 mol of silver halide. 1 x 10-' to 1 x 10-3 per
It is preferably used in a molar range, more preferably 5
X 10-'' to 5X10-' moles.

As a method for adding the sensitizing dye, a method well known in the art can be used.

For example, these sensitizing dyes can be dissolved in water-soluble solvents such as pyrinone, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or mixtures of such solvents), in some cases diluted with water, and in other cases can be dissolved in water and added in the form of these solutions. It is also advantageous to use 11 sonic vibrations for this dissolution.

Further, the sensitizing dye used in the present invention is disclosed in U.S. Patent No. 3.4.
89,987, in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added, as described in Japanese Patent Publication No. 46-24185, etc. Alternatively, a method may be used in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added. Furthermore, the sensitizing dye used in the present invention can be added to the emulsion in the form of a dispersion by an acid dissolution and dispersion method, and the addition method is described in U.S. Pat.
Methods described in Ibid. No. 3,342,605, Ibid. No. 2.996.287, Ibid. No. 13,425,835, etc. can also be used.

The sensitizing dyes contained in the silver halide emulsion according to the present invention can be dissolved in the same or different solvents, and these solutions can be mixed or added separately before being added to the silver halide emulsion. Good too.

When adding them separately, the order, time and interval can be arbitrarily determined depending on the purpose.

The timing of adding the sensitizing dye used in the present invention to the emulsion is as follows:
It may be added at any time during the emulsion manufacturing process, but it is preferably added during or after chemical ripening, and more preferably during chemical ripening.

The silver halide photographic light-sensitive material of the present invention having the above-mentioned structure can be, for example, color print paper such as Nep and Bott film, color photographic paper, etc., but in particular, color print paper used for direct viewing can be used. When used, the effects of the method of the present invention are effectively exhibited.

The silver halide photographic light-sensitive materials of the present invention, including this color photographic paper, may be monochromatic or multicolor, and in the case of multicolor silver halide photographic materials, subtractive color For reproduction, usually as a photographic coupler,
It has a structure in which silver halide holes containing magenta, yellow, and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers. may be changed as appropriate depending on the important performance and purpose of use.

When the present invention is applied to a multicolor light-sensitive material, the specific M configuration includes a yellow dye image-forming layer, an intermediate layer, a magenta dye image-forming layer,
Particularly preferred is an arrangement consisting of an intermediate layer, a cyan image-forming layer, an intermediate layer, and a protective layer.

The dye image-forming coupler used in the silver halide photosensitive material of the present invention is not particularly limited. Various couplers can be used, but the compounds described in the following patent specifications are included as representative ones. be done.

Yellow dye image-forming couplers include 4-equivalent or 2-equivalent couplers of the acylacetamide type and benzoylmethane type; these are described, for example, in U.S. Pat.
．． No. 658, Pt No. 52,875,057, No. 2.
No. 908,573, No. 2,908,513, No. 3
．． No. 227,155, No. 3,227,550, No. t
JS3,253,924, t53゜285, 50
No. 6, No. 3,277.155, No. 3,341,3
No. 31, No. 3,369,895, in No. 3,38
No. 4,657, No. 3,408゜194, No. 3,4
No. 15,652, No. 3.447,928, in3
, No. 551,155, No. 3,582,322, P
t53,725,072, German Patent No. 1,547,
No. 868, No. 2.057,941, No. 2,182
, No. 899, No. 2,183,812, No. 2゜21
3.461, 2,219.917, 2.2
61,361, Pt 52,263.875, JP 49-13576, JP 48-29432, JP 48-66834, JP 49-10736, JP 49-
No. 122335, No. 50-28834, No. 50-13
No. 2926, No. 55-144240, No. 56-87
It is described in each light*M of No. 041.

The magenta dye image-forming couplers include 4-equivalent or 2-equivalent magenta dye image-forming couplers such as 5-pyrazolone type, pyrazolotriazole type, birazolizobenzimiguzole type, ingzolone type, and cyanoacetyl type. For example, US Pat. No. 2.60 (1,788, US Pat. No. 3.061.432, US Pat.
No. 3,127,289, No. 3,311,47
No. 6, No. 3,152,896, ffE 3,41
No. 9,391, No. 3゜519.429, No. 3,5
No. 55.318, No. 3,684.514, No. 3,
No. 705,896, No. 3,888.680, tt.
S3,907゜571, f53,928,044, f3,930,861, f3,930,810
No. 3,933,500, JP-A-49-2963
No. 9, No. 49-111831, No. 49-129538
No. 51-112341, No. 52-58922,
No. 55-62454, No. 55-118034, No. 5
No. 6-38643, No. 56-135841, Special Publication No. 4
No. 6-60479, No. 52-34937, No. 55-2
No. 9421, No. 55-35696, British Patent Nos. 1 and 2
47,493, Specifications of Belgian Patent No. 769.116, West German Patent No. 2,156,111, Japanese Patent Publication No. 1973
-60479, JP-A-59-125732, JP-A No. 59
-228252, 59-162548, 59-
No. 171956, No. 60-33552, No. 60-43
No. 659, West German Patent No. 1,070.030 and U.S. Patent No. 3. ) No. 25,067.

As the cyan dye image forming coupler, 7 er/-leum,
Naphthol type 4-equivalent or 2-equivalent type cyan dye image-forming couplers are typical, and U.S. Patent Pt52,306
, No. 410, No. 2, No. 356, No. 475, No. 2,
No. 362.598, No. 2,367.531, No. 2
．． 369,929, 2,423.730, 2,474, 293, 2.476°008,
Pt No. 52,498,466, Pt No. 2,545,68
No. 7, No. 2,728,660, No. 2,772.1
No. 82, No. 2.895.826, No. 2,976.
No. 146, No. 3,002,836, No. 3゜419
．． No. 390, No. 13,446.622, No. 3,47
No. 6.563, No. 3,737,316, No. 3,
758, No. 308, tI43,839°044,
British Patent No. 478,991, British Patent No. 945,542,
1,084,480, 1,377.233, 1,388.

024 and m 1,543.040 each.
book, as well as JP-A-47-37425 and JP-A No. 50-101.
No. 35, No. 50-25228, No. 50-112038
No. 50-117422, No. 50-130441, No. 51-6551, No. 51-37647, No. 51
-52828, 51-108841, 53-1
No. 09630, No. 54-48237, No. 54-861
No. 29, No. 54-131931, No. 55-32071
No. 59-146050, No. 59-31953, and No. 60-117249.

It is desirable that these dye-forming couplers have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Either the 4-equivalence type, in which 1 silver ion needs to be reduced, or the 2-equivalence type, in which only 2 silver ions need to be reduced, may be used.

It is advantageous to use gelatin as the pineapple (or protective colloid) used in the silver halide photographic light-sensitive material of the present invention, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugars, etc. Hydrophilic colloids such as derivatives, cellulose derivatives, synthetic hydrophilic polymeric materials such as single or copolymers can also be used.

The silver halide photographic material of the present invention further includes a hardening agent, a color clouding inhibitor, an image stabilizer, an ultraviolet absorber, a plasticizer, a latex, a surfactant, a matting agent, a lubricant, and a lubricant. Additives such as rl antistatic agents can optionally be used.

Images can be formed using the halogenated nail photographic material of the present invention by subjecting it to a color development treatment known in the art.

The color developing agent used in the color developer in the development process of the silver halide photographic light-sensitive material of the present invention may be any of the 7 types that are widely used in various color photographic processes.
It includes 27-yl and 9-7x nylennoamine derivatives.

In addition to the above-mentioned primary aromatic amine color developing agent, known developer component compounds may be added to the color developing solution applied to the development of the silver halide photographic light-sensitive material of the present invention. .

The pH value of the color developer is usually above 7, most commonly about 10-13.

Color development temperature is usually 15°C or higher, generally 20°C.
~50°C. For rapid development, it is preferable to carry out the process at 30°C or higher. In addition, conventional processing takes 3 minutes or more.
4 minutes, but the color development time of the silver halide photographic material of the present invention aimed at rapid processing is generally 20 seconds to
It is preferable that the heating time is within a range of 60 seconds, and more preferably within a range of 30 seconds to 50 seconds.

The silver halide photosensitive material of the present invention is subjected to a bleaching treatment and a fixing treatment after color development. Bleaching treatment may be performed simultaneously with fixing treatment.

After the joseki treatment, a water washing treatment is usually performed.

Furthermore, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination.

[Specific effects of the invention]

As explained above, the silver halide photographic light-sensitive material of the present invention has excellent rapid processing properties, high sensitivity, and little variation in sensitivity and gradation with respect to temperature changes during exposure.

[Specific embodiments of the invention]

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments are not limited thereto.

Example-1 In the presence of inert gelatin, at 60°C and ρ = 7.0, silver nitrate aqueous solution, potassium bromide and sodium chloride were prepared according to the method described in JP-A-59-45437. The silver chloride content was 50.
A monodispersed silver chlorobromide emulsion (EM-1) of mol % was prepared. As a result of electron microscopy observation of E-1, the silver herodenide grains had an average particle diameter (in terms of spheres) of 0.71 .mu.- and a cubic shape.

Dogs were given a pAg of 7.3 with a silver chloride content of 95 mol% (
Silver chlorobromide emulsions and silver chloride emulsions of EM-2), 99.5 moles/% (EN-3), and 100 moles (EM-4) were prepared.

The silver halide grains of each emulsion have a cubic shape, and the average grain size is EM-2: 0, 70μI%EM-3: 0.6
It was an 8μ jacket.

Next, EM-1, E14-2, EN-3 and EM-4
■ Adding only sodium thiosulfate, ■ Adding sodium thiosulfate and chloroauric acid, ■ Adding the organic compound of the present invention (Example No. 5B-5, solubility product with silver ion 1 × 10-th ) was added just before chemical sensitization, and Thio I
Adding sodium It acid, ■ Adding the organic compound of the present invention (Example No. 5B-5) immediately after chemical sensitization,
further adding sodium thiosulfate and chloroauric acid;
All emulsions were added using the above four methods of addition, and all emulsions were spectral sensitized using a blue-sensitive sensitizing dye (Example No. A12), and at the end of chemical ripening, 1 mol of silver halide was added as a stabilizer. 1) I Xl0-2 mol of the organic compound of the present invention (Example No.

5O-2, solubility product with ffi ion 1×10-”・5
) and emulsion No. shown in Table 1, EM Row 1 to EI
4[1-16] was prepared.

The amounts of sodium thiosulfate, chloroauric acid, and the organic compound of the present invention (Example No. 5B-5) are also shown in Table 1.

Margin table below -1 Next, using EMB-1 to EMB-16 as blue-sensitive emulsions, silver lodenide photographic 1 light-sensitive materials having the following configuration were prepared, and designated as Samples-1 to Sample-16, respectively.

(H-1> Na Sensitometric evaluation was performed.

[Sensitometric evaluation] Each sample was tested with a sensitometer (Konishi Roku Photo Industry Co., Ltd.).
-7 type) through the optical wedge,
When exposing to white light (the temperature at the time of exposure is 10℃,
The temperature was changed from 20°C to 130°C, and the following treatments were applied.
.

[Processing step 1 Temperature Time color development 34.7±0.3°C 45 seconds Bleach fixing 34.7±0.5°C 45 seconds Stabilization 30-3
Dry at 4℃ for 90 seconds 60-80'C for 60 seconds (color developer) Pure water 8
00 company ethylene glycol 10-! N,
N-noethylhydroxylamine 10.

Potassium chloride 2gN-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4
-Aminoaniline nitrate 5g Sodium tetrapolyphosphate 2g Potassium carbonate
30.

Fluorescent brightener (4,4-noaminostyrpentsulfonic acid! conductor) Add 1 g of water to bring the total amount to 11, and adjust to 7I4 to 01110.08.

(Bleach-fixing-a) Ethylene di7minetetra vinegar l! ! Ferric ammonium 2
Water salt 60.

Ethylenenoamine thitraacetic acid 3g ammonium thiosulfate (70% solution) 100ml 7 ammonium sulfite (
(40% solution) Adjust the volume to 17.1 with 27.5 ml of potassium carbonate or glacial acetic acid, and add water to bring the total volume to 11.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothi7zolin-3-one 1g 1-hydroxyethylidene-1,1-nophosphone a 2g Add water to 1
1 and set pi to 7.0 with sulfuric acid or potassium hydroxide.
11 Set up.

The reflection density of the obtained sample was measured using a densitometer PD^-65 (manufactured by Konishiroku Photo Industry Co., Ltd., 9J). Sensitivity is expressed as the reciprocal of the exposure amount required to obtain a density of 0.8, and the sensitivity at a temperature of 10°C during exposure of sample 1 is 100
The 0 gradation indicated by the relative sensitivity when The results are shown in Table-2.

Furthermore, DIlla in the table indicates the maximum reflection density of each sample.

As is clear from the results in Margin Table 2 below, samples No. 1 to 4 using comparative emulsions E14B-1 to E14B-4, which have high silver bromide, have high sensitivity and stable temperature dependence, but the maximum density is low and rapid Lack of processability. In addition, samples using high silver chloride grains according to the present invention had satisfactory rapid processing properties, but samples No. 5.9 and 13, which were sensitized with sulfuric acid by adding only sodium thiosulfate, had low sensitivity and In addition, samples No. 3, '10 and 14 to which sodium thiosulfate and gold compounds were added had some improvement in sensitivity compared to samples No. 5.9 and 13, but the exposure temperature was also large. Furthermore, sample No. 7.1 to which the organic compound according to the present invention and sodium thiosulfate were added had extremely large sensitivity and gradation variation.
Samples Nos. 1 and 15 have improved variability with respect to exposure temperature but have low sensitivity.On the other hand, only sample Nos. 8, 12 and 16, which constitute the present invention, have large maximum densities and are excellent in rapid processability. The sensitivity is excellent overall, with small fluctuations in sensitivity and gradation due to temperature changes during exposure.

Looking more closely, it can be seen that among the high silver chloride grains according to the present invention, sample No. 12, which uses silver halide grains containing 0.5 mol% silver bromide, has the greatest effect of the present invention. Recognize.

Example 2 Cubic silver halide grains with a grain size of 0.35 μm were prepared using silver chlorobromide with a silver chloride content of 99.3 mol % in the same manner as in Example fN-1. Two minutes after addition of sodium thiosulfate, chloroauric acid and these sensitizers, the organic compound of the present invention (Example No.

5B-5) was chemically ripened to an optimum value, and color sensitization was performed using green-sensitive sensitizing color X (B-4). The organic compound of the invention (Example No. 5O-5) was added at 1× per mole of halogenated kite.
Added 10-2 mol of chloroplast EM (knees 1 to E).
14G-10 was prepared. This ENG-1~EMG
-10 emulsion of Example-1 [l-1 to EM13-
In place of 16, C, which will be described later as a magenta coupler,
Sample No. 1 was prepared in the same manner as in Example-1 except that M-1 was used.
, 17-26 were created. These samples were evaluated in the same manner as in Example 1 by varying the temperature during exposure. The results are shown in Table 4.

As is clear from Margin Table 4 below, even in the green-sensitive emulsion layer,
It can be seen that samples Nos. 18 to 26 having the configuration of the present invention have small sensitivity to temperature change during exposure and small variations in gradation. Looking more closely, it can be seen that among the samples of the present invention, samples Nos. 19, 22, 25, and 26 have particularly high sensitivity, and are excellent in sensitivity to temperature changes during exposure and variation in gradation is extremely small.

Sample No. 17, in which the organic compound of the present invention (Example No., SB-5) was added only at the end of chemical sensitization, showed sensitivity to temperature changes and t! of gradation. It was found that the effects of the present invention cannot be obtained when alJ is large and the organic compound is not present during chemical sensitization.

Example-3 For the unchemically ripened emulsion used in Example-2, the following table-
As shown in 5, exemplary compounds S^ are used as organic compounds of the present invention.
-7, SB-1,5C-30% 5C-39, Slow 5 and the following comparative compound book were added prior to chemical ripening, and then gold/sulfur sensitized and used as a sensitizing dye with red sensitivity. Samples were prepared in the same manner as in Example 2, except that CC-1 described later was used as the sensitizing dye (C-6) and the cyan coupler, and the evaluation results are shown in Table 6 below.

Table 5 Comparative Compounds From these results, it can be seen that in the organic compounds of the present invention having various Ksp values within the Ksp value of the present invention,
It can be seen that the silver denride photographic material has little variation in sensitivity and gradation due to temperature changes during exposure, and the effect of the organic compound of the present invention on comparative compounds having Ksp values outside the range of the Ksp value of the present invention.

Example 4 The silver halide emulsions used in Examples 1, 2, and 3 were combined, and samples No. 27.
28 was created.

Table 7 Margin Table 8 CJs (t) Using this sample, the same tests as in Examples 1, 2, and 3 were conducted. 1 result! -9.

As can be seen from the results in Table 9, even in the multilayer sample,
The effects of the present invention were confirmed. That is, the MIJ sample of the present invention has higher sensitivity than the comparative sample, has smaller sensitivity fluctuations with respect to exposure temperature, and is superior in that the imbalance in sensitivity between the blue, green and red sensitive layers is clearly reduced. It can be seen that

Applicant: Konishiroku Photo Industry Co., Ltd. Procedural amendment January 1986! 9th day

Claims (1)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is chemically sensitized in the presence of an unstable sulfur compound and a gold compound. Silver chloride content 90
The solubility product (Ksp) between high chloride silver halide grains of mole % or more and silver ions is 1×10^-^1^1^. ＾0
At least one compound selected from organic compounds having the following physical property values is contained, and the organic compound is added between the formation of the silver halide grains and the end of chemical sensitization of the silver halide grains. A silver halide photographic material characterized by: