JPS6340139A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a high-sensitivity silver halide photographic sensitive material by incorporating a specific spectral sensitizing agent and the silver halide emulsion treated with an ion exchange resin or porous adsorbent in the production process of the silver halide emulsion into the emulsion layer of said material. CONSTITUTION:This photosensitive material contains the spectral sensitizing agent expressed by formula I or II and the silver halide emulsion treated with the ion exchange resin or porous adsorbent in the production process of the silver halide emulsion in the emulsion layer. The dye to be used is preferably the cyanine dye expressed by formula I. In formula I, Z1, Z2 denotes atomic groups for forming 5-, 6-membered nitrogenous heterocycles, Q1 denotes an atomic group for forming 5-, 6-membered nitrogenous ketomethylene rings, R1-R4 denote a hydrogen atom, lower alkyl group, etc., R5, R6 denote an alkyl group or the same alkenyl group, l1 and n1 denote 0 or <=3 positive integer, j1, k1 and m1 denote 1, X1<-> denotes an acid anion, r1 denotes 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention (Technical Field) The present invention relates to a silver halide photographic material, and particularly to a spectrally sensitized silver halide photographic material with improved sensitivity.

(Prior Art) Spectral sensitization technology is an extremely important and essential technology for producing photosensitive materials with high sensitivity and excellent color reproducibility. Providing highly sensitive light-sensitive materials (While the development of spectral sensitizers has been progressing to a great extent, many technical developments have also been made in the use of supersensitizing methods, addition methods, etc.) Spectral sensitizers originally...absorb light in the long wavelength range that is not substantially absorbed by silver rokenide photographic emulsions, and absorb the light-absorbed electrons and/or light.
Or, it has the effect of transmitting light absorption energy to silver locnide. Therefore, increasing the amount of light captured by a spectral sensitizer is advantageous in increasing photographic sensitivity.

For this reason, not only attempts have been made to develop spectral sensitizers with high light absorption coefficients (...) but also attempts have been made to increase the amount of light captured by increasing the amount added to silver gonide emulsions.

However, there is an optimum addition range for the amount of spectral sensitizer added to the silver halide emulsion, which is usually less than the amount that covers the entire surface of the silver halide grains with the spectral sensitizer, and more than that. Addition of @ causes a large desensitization as described above. This is discussed in T. H. James, ed., The Theory of the
Photographic Pro Seventh (The Theory)
of the Photographic Proc
essJ th edition” Macmillan (~facmillan,
New York)/Re 77, Pλ4j-261.

(Problems to be Solved by the Invention) For this reason, attempts have been made to improve the method of adding a spectral sensitizer by increasing the amount of the spectral sensitizer added, and to improve the method of preparing silver halide grain emulsions.

FIt Hatomas El K- (Thomas LP
Enner), B.B. Gilman Jr. (P.

B, Gi 1man, Jr), Photographic Science and Engineering (Photo, Sc
i.

Eng-), 20 (3), 27-10A (/ri76)
As shown in Figure 2, a large amount of two types of spectral sensitizers with an appropriate potential relationship are adsorbed in a layered manner on a silver halide crystal to increase the amount of light captured by the spectral sensitizer and to reduce the desensitization caused by adding a large amount. Attempts are being made to suppress it. However, this method has not been effective against high-performance silver halide emulsions with high sensitivity that are used as photographic materials. In addition, attempts have also been made to suppress the addition rate of halogenated moth particles as a spectral sensitizer to an optimal range where desensitization does not occur, and to increase the total addition fit to increase the amount of light captured and improve the spectral sensitivity. There is.

Here, the addition amount ratio refers to the ratio expressed below.

・- Adsorption agent when a spectral sensitizer is saturated with the dispersed silver halide grains added to the silver halide grains. -7/3. This method is disclosed in Publication No. 26, etc. However, even if tabular copper halide grains with a large specific surface area are used, the addition ratio of the spectral sensitizer is different from other silver halide grains called cubic, octahedral, /≠hedral, twinned, etc. Since the amount tends to be rather low compared to that of the chromophore, the amount added cannot be increased as much as expected, and the effect of increasing the spectral sensitization by 4 degrees as described above is still insufficient.

(2) Purpose of the Invention An object of the present invention is to provide a spectrally sensitized silver halide photographic material with high sensitivity.

■Disclosure of invention These objects have been achieved by the invention described below.

Specifically, the present invention provides a silver halide photographic material having at least one silver halide emulsion layer on a support, in which a spectral sensitizer represented by the following general formula (N or (II)) is added to the emulsion layer. This is a silver halide photographic material characterized by containing a silver halide emulsion treated with an ion exchange resin or a porous adsorbent during the production process of the silver halide emulsion.

■Specific structure of the invention The specific structure of the present invention will be explained in detail below. In the present invention, in the process of producing a silver halide emulsion,
Before coating the silver halide emulsion, the silver halide emulsion is treated with a porous adsorbent or ion exchange resin.
A silver halide emulsion subjected to such treatment is used in the halogenated photosensitive material of the present invention.

When the emulsion is chemically sensitized, the treatment with a porous adsorbent or ion exchange resin is preferably carried out during the chemical sensitization process or after the chemical sensitization process and before coating. .

The porous adsorbent mentioned here is a porous solid adsorbent (also called an adsorbent) with a large surface area, and specifically includes activated carbon, activated alumina, activated carbon, soil, and 7-liquid adsorbents. (Water resistant ones are preferred), inorganic porous adsorbents such as zeolite adsorbents, porous glass, and porous ceramics.

Among these, activated carbon is most preferred.

In addition, ion exchange resins specifically include cation exchange resins (for example, product name Amberly? JR-/20, manufactured by Rohm and Haas Co., Ltd.), anion exchange resins (for example, part name Tire Ion), S.A.
-Color A: Manufactured by Mitsubishi Kasei Co., Ltd., product name: Taiweknu/×r
; manufactured by Dow Chemical Company, etc.), amphoteric resins, and chelate resins (for example, trade name: Diaion CR-, 2o; manufactured by Mitsubishi Chemical Company, etc.).

Many types of these ion exchange resins are commercially available, and one suitable for each purpose can be easily obtained.

Among these, anion exchange resins, amphoteric resins and chelate resins are preferred, and anion exchange resins are most preferred.

For details on how to use these adsorbents and ion exchange resins, please refer to %Gan No. 60-61'727 and No. 40-40.
It is detailed in A/Ko No. 30.

The dye used in the present invention has the following general formula (IJ or (I
Among these are cyanine dyes, merocyanine dyes, and logocyanine dyes represented by IJ, and more preferred are cyanine dyes represented by the general formula (IJ).

General formula (N In the formula, Z1%Z2 may be different or the same r,
Represents a group of atoms forming a 6-membered nitrogen-containing heterocycle.

For example, thiazoline, thiazole, benzothiazole,
naphthothiazole, selenazoline, sennazole, benzoselenazole, naphthoselenasol, oxazole,
Benzoxazole, naphthoxazole, benzimidazole, naphthoibadazole, pyridine, quinoline,
Examples include heterocycles such as indolenine and imidazo(" + '-l)quinoxaline, and these heterocycle nuclei may be substituted. Examples of substituents include lower alkyl groups (preferably those having 6 carbon atoms). The following may be further substituted with a hydroxy group, a halogen atom, a phenyl group, a substituted phenyl group, a carboxy group, an alkoxycarbonyl group, an alkoxy group, etc.), a lower alkoxy group (preferably having 6 or less carbon atoms), an acylamino group (preferably carbon number r
Examples include a monocyclic aryl group, a carboxy group, a lower alkoxycarbonyl group (preferably having 6 or less carbon atoms), a hydroxy group, a cyan group, and a halogen atom.

Ql represents j and an atomic group forming an A-membered nitrogen-containing ketomethene ring, such as thiazolidin-≠-one, selenazolidine-
Examples include ≠-one, oxipzolidine-μ-one, imidazolidine-t-one, and the like.

R1, R2, R3 and R4 represent a hydrogen atom, a lower alkyl group (preferably carbon number of μ or less), an optionally substituted phenyl group, an aral group, and ll is 2 or 3.
and when n is 2 or 3, different R1 and R1s R2 and R2, R3 and R3, or R4 and R4 are connected and contain an oxygen atom, sulfur atom, or nitrogen atom, etc. However, this shows that a six-membered ring can also be formed.

R5 and R6 represent an optionally substituted alkyl group or alkenyl group having io or less carbon atoms and which may contain a VCM elementary atom, a sulfur atom, or a nitrogen atom in the carbon chain. Examples of the substituent include a sulfo group, a carboxy group, a hydroxy group, a halogen atom, an alkoxycarbonyl group, a carbamoyl group, a phenyl group, and a substituted phenyl group.

In addition, when the above-mentioned zl and z2 represent a heterocyclic ring, benzimidazole, naphthoimidazole, ibatazo [Hiroshi].

! -A J When the heterocycle contains another substitutable nitrogen atom such as quinoxaline, the other nitrogen atom of these heterocycles may be, for example, a hydroxy group, alkoxy group, halogen atom, phenyl group, or alkoxy group having 6 or less carbon atoms. an alkyl group which may be further substituted with a pylyl group,
It may be substituted with an alkenyl group or the like.

11 and nl are O or positive integers less than or equal to 1l-1
-nl represents 3 or less, and when lJx is /, 2 or 3, R5 and R may be connected to form an A-membered ring.

jl, kl and ml represent O or l.

xl represents an acid anion 2 and %rl represents O or l.

More preferably, at least one of R5, R6 and R7 is a group containing a sulfo group or a carboxy group.

General formula (IIJ) In the formula, Zll represents a nitrogen-containing group of atoms forming a heterocyclic ring. Benzoxazole, naphthoxazole, penzimitazole, naphthoidazole, pyridine, quinoline, pyrrolidine, indolenine, imidazo [≠, j
-t) Heterocyclic nuclei commonly used for cyanine formation, such as quinoxalinetetrazole, may be mentioned, and these heterocyclic nuclei may be substituted. Examples of substituents include lower alkyl-JI! : (preferably has 10 or less carbon atoms and may be further substituted with a hydroxy group, a halogen atom, a phenyl group, an it+substituted phenyl group, a carboxy group, an alkoxycarbonyl group, an alkoxy group), a lower alkoxy group group (preferably 7 or less carbon atoms), acylamino group (preferably 7 carbon atoms or less), monocyclic aryl group, monocyclic aryloxy group, carboxy group, lower alkoxycarbonyl group (preferably 7 or less carbon atoms), hydroxy group,
Examples include a cyano group and a halogen atom.

Qll represents a nitrogen-containing atomic group forming a 6-membered ketomethylene ring. Examples include atomic groups forming thiazolidine-guones, senna siridine-guones, oxazolidine-q-ones, imidazolidine-guones, and the like.

Q12 represents a nitrogen-containing atomic group forming a six-convex ketomethylene ring. For example, rotanine, corchiohidantoin, -
Monoselenathiohitoin, Nithiooxazolidine-2,≠-dione, 2-Selenaoxazolidine-29μ
mdione, di-thioselenazolidine, hirodione,
λ-Selena thiazolidine-λ, Hiro-dione, λ-Selena selenazolidine-2. Examples include atomic groups that form heterocyclic nuclei that can form melonanine pigments such as Hiro-dione.

In the heterocycle represented by ``111'' and ``Q12'', when one or more nitrogen atoms are included in the heterocycle-forming atoms, such as benzimidazole or thiohitaantoin, R13, R15, The nitrogen atom to which R14 is not connected may be substituted, and the carbon atom in the alkyl chain may be substituted with an oxygen atom, sulfur atom or nitrogen atom, and further substituents may be substituted. An alkyl group with carbon number j or less, which may be an alkenyl group! or a monocyclic aryl group which may be substituted.

all represents a hydrogen atom or an alkyl group having j or less carbon atoms, and R12 is a hydrogen atom, an optionally substituted phenyl group (examples of substituents include alkyl having 7 or less carbon atoms, an alkoxy group, a norogen atom, a carboxy group) , and a doxy group), or an alkyl group which may be substituted with a hydroxy group, a carboxy group, an alkoxy group, or an alkyl group. When m21 represents 2 or 3, different R12 and R12 may be linked to form a j-, A-membered ring which may contain an oxygen atom, sulfur atom or nitrogen atom.

R13 represents an optionally substituted alkyl group or alkenyl group having 70 or less carbon atoms which may contain an oxygen atom, sulfur atom or nitrogen atom in the carbon chain. Examples of the substituent include a sulfo group, a carboxy group, a hydroxy group, a norogen atom, an alkoxycarinyl group, a carbamoyl group, a phenyl group, a substituted phenyl J1, or a monocyclic saturated heterocyclic group.

R14 and R15 have the same meaning as R13, and in addition, a hydrogen atom or a substituted monocyclic aryl group (examples of substituents include a sulfo group, a carboxy group, a hydroxy group, a halogen atom, a carbon number The following alkyl groups, acylamino groups, or alkoxy groups are mentioned)
It also represents.

m21 represents O or a positive integer of 3 or less, j represents 0 or l, and 21 represents o- or /.

m2. is a positive integer less than or equal to 3, all and R13
may be interlocked to form a j, A-membered ring (So It is more preferable that at least one of R13, R14 and R15 is a group containing a sulfo group or a carboxy group.

Next, typical compounds of the spectral sensitizer used in the present invention are shown below.

I)-/ 503Na SO3 SO2 total S(,)3 SO3Na 5O3 D-≠ ])-j' SOaK SO3- ■ (CH2)4 (CH2) 3 l 5O3K 5O3- SO3Na 5O3 D-♂ CH3 C2H5(-2) 4 8O3Na SO3 SO2 total 5O3- 8O3K 303 D-73 1)-/ Hiroichi/ ! (C)42)3 (CH2)3SO3i
Na 5O3- I C2H5(CH2)3 O3- 8U31i-N(C2H5)3 5o5-1)-/,
r 2H5 ■ So 3K So 3-])-/ri2H5 CH2C0OH C2H5 (C11□)3 o3 D-Kohiro (C)i2)3SO3Na (CH2)
3S (J3D-2! D-26 D-λ7 -2g D-λr) Examples of documents describing the sensitizing dye used in the present invention include F
0M, No --7- (Hamer J [The Chemistry of Heterocyclic Compounds]
The Chemistry of Heter
The Cyanine Dyes and Re
ratedCompounds)j (edited by A. Weissberger, published by Interscience, New York, 176μ), D. M. Sturmer, Volume 30: The Cyanine
Soybean and Related Compounds (The
Cyanine Dyes and Rel
atedCompoundsJJ (A, Weissberger+ E, C, Tiller
Edited by Taylor, John Wiley Company-New York-/
Published in 1977), Ripuchi Disclosure (I (E
SEARCHDTSCLO3UIE) Volume 176, /16
776≠3, p, 23-214 (/971), German patent'? 29.01rO, US time R2, -23/, bs
r issue, same, 2, 't9! , No. 714r, 2, 5
03゜776, same 2. ! /ri, ooi issue, 2.21
λ, No. 32, J, l, 36, No. 57, No. 3
゜672,? No. 27, 3.62 Hiroshi, 217, ≠,
Oλj, 3 Hiroshi No. 7, Room Clerk, O 1. ．． ! No. 72.

British Patent/, 2hiro-9jlt, Special Publication Akihirohiro-7hiro03
No. 0, same number j2-λ≠l≠ issue number Mi UK shipping license
No. o, clerk P-991, No. 20, same≠ter//u'A2
No. 0, same! 2-101//! No., U.S. Patent λ1.27≠
, No. 7Jλ, No. 633, No. u72, No. 2. ! P!
ls, 17th issue, same 3゜iur, /♂7, same 3. /
No. 77.071, same! , 21A7. /No.27, same J,
6410, l#7, same J,! 7! ; , 70
No. u, 3, 1. j3, ri05, same J, 7/, 1
', Hiroshi 71, 41.07/, 372, ≠, 07
0, Jj Ko issue, etc.

These spectral sensitizers may be used alone or in combination (in particular, combinations of spectral sensitizers (i)
Often used for the purpose of supersensitization.

Along with the spectral sensitizer, a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits strong spectral sensitization may be placed in the emulsion. For example, abanonuterbene compounds substituted with a nitrogen-containing heterocyclic group (for example, U.S. Pat.
63! , 7 Co/No.), aromatic organic acid formaldehyde condensates (for example, those described in U.S. Pat. No. 3,7≠3,61
0), cadmium salts, azaindene compounds, etc. US Patent 3. T/! .

1.13, 3,6/j, 641/, 3.6/
7. Kotayo issue, same! , 63! , No. 72/ is particularly useful.

In order to incorporate the spectral sensitizers used in the present invention into the I/silver halide emulsion of the present invention, they may be directly dispersed in the emulsion, or they may be dispersed in water, methanol, ethanol, furopanol, methyl selon, etc. Lug, λ, λ, 3.3-
It may be added to the emulsion after being dissolved in a solvent such as tetrafluorobronoξol or in a mixed solvent. Also, Tokuko Akihiro -23,3r, Tokuko Akihiro≠-27,! j! , Tokuko Shoj7-22. A water bath solution is prepared by coexisting a Vc acid or a base as described in Ori et al., US Pat.
3j, U.S. Pat. An aqueous solution or colloidal dispersion may be added to the emulsion.

After dissolving the compound in a substantially water-immiscible solvent such as phenoxyethanol, a dispersion in water or a hydrophilic colloid may be added to the emulsion. Tokukai ShojJ-10u, 7
33, Tokukai Akira! l-10! .

Directly dispersed in a hydrophilic colloid as described in /Hirol,
The dispersion may be added to the emulsion.

Furthermore, when these compounds are added to an emulsion, they may be added as a mixture or may be added separately.

The timing of adding the emulsion to the emulsion depends on the process at which the emulsion is coated on a suitable support (for example, silver halide grain formation process, physical ripening process, chemical ripening process, grain precipitation process, and post-chemical ripening process before coating). etc.) may be used.

In addition, as for the degradation of the spectral sensitizer used in the present invention, ordinary halogenated mvc is applied.
2 mol/silver mol can be used, but is this an advantage of the present invention?
In order to achieve a sufficient effect, it is preferable that the amount corresponds to an addition rate of 50% or more. Even more preferably 60-300%
This amount corresponds to the amount of added powder.

In other words, if no ion exchange resin or porous adsorbent is used, at least 0. /lOgE or more,
More preferably 0. The advantages and effects of the present invention are significant when the amount of the spectral sensitizer added is such that it brings about a reduction in the intrinsic sensitivity of /JlogE~/, 01ogE.

Here, when measuring the decrease in the intrinsic sensitivity, the decrease in the intrinsic sensitivity can be determined by ordinary development using, for example, Irendol (manufactured by Fuji Photo Film 2) and a full-bodied 0C Hirobin.

In the present invention, any of silver bromide, silver iodobromide, iodochlorobromide, silver chlorobromide, silver iodide and lead chloride may be used as silver halide in the photographic emulsion.

The particle size distribution may be narrow or wide.

Silver halide grains in photographic emulsions can be cubic, octahedral, or
Regular (regular) such as prohohedron and rhombic dodecahedron
), or irregular crystal shapes such as spherical or plate-like, or composites of these crystal shapes.

It may also consist of a mixture of particles of various crystalline forms.

The silver halide grains may have different layers inside and on the surface, or they may consist of a uniform phase.

Also, for example, bonded silver halide crystals that combine oxide crystals such as PbO and silver halide crystals such as lead chloride, and epitaxially grown silver halide crystals (for example, silver chloride crystals on bromide tablets, Silver iodobromide, silver iodide, etc. are grown epitaxially.

Further, the grain size distribution of the Rogonkahan grains in the photographic emulsion is arbitrary, but may be monodisperse.

Here, monodisperse means that 75% of the particles are within ± the number average particle size.
The dispersion system has a size within 60%, preferably within 0%. Here, the number average grain size is the number average diameter of the silver halide grains over the projected area.

Photographic emulsions were invented by B. Grafkides (P, G.
Chimie et Physiq Photographic (Chimie et Physiq)
uePhotographique), published by Paul Montel (1967), Photographic Emulsion Chemistry (Ph
otographic Emulsion Che
mistry), The Focal B/S (The
Published by Focal Press (1966), written by Guier Zelikman et al.
n et al) Making and Coating Photographic Emulsion (Makin
g and CoatingPhotographic
Emulsion), The Focal Bush vs.
e Published by Focal Press J (/6μ)
It can be prepared using the method described in et al.

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the polarizable silver salt with the polarizable silver salt may include the one-sided mixing method, the simultaneous mixing method, a combination thereof, etc. Either method may be used, but a method in which particles are formed in an excess of silver ions (so-called back mixing method) may also be used.

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

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

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

・-During the process of silver oxide formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium @ or its complex salts, rhodium salts or its complex salts, iron layers or iron complex salts, etc. are allowed to coexist. It's okay. Further, the amount of these additives may be either a certain amount or a large amount depending on the intended photosensitive material.

In order to remove all soluble salts from the emulsion after precipitation or physical ripening, gelatin may be completely gelled, or the Nudelbo method may be used, and inorganic salts, anionic surfactants, and anionic polymers (e.g. polystyrene sulfonate, or gelatin derivatives (e.g. acylated gelatin).

A sedimentation method (flocculation method) using carbamoylated gelatin (such as carbamoylated gelatin) may also be used.

The silver halide grains of the present invention have been chemically sensitized.

As a chemical M sensitization method, a gold sensitization method using a so-called gold compound (for example, U.S. Pat.
No. 0.06) or sensitization method using metals such as iridium, platinum, rhodium, and radium (f! Al is US patent rate -91S, No. 060, λ, !66.2 Hiroj, λ)
,! 66.26j) or a sulfur sensitization method using sulfur-containing compounds (for example, sulfur-containing sensitizers such as thiosulfates, thioureas, mercapto compounds, rhodanines, etc.). The first ψ0, the same ko, the ψ10, the 61r, the same λ.

No. 271.9147, IU, 7Jlr, 6Ar, No. 3, 6! A. No. 55, U.S. Patent No. KO, KO.
Co2 Jun No. 2, or selenium sensitization method using selenium compounds, or reduction sensitization method using tin salts, polyamines, etc. (for example, U.S. patent rate 22 μm No. 7.1jO, Co.,!/r
, tr-r, same, ssi.

2j), or a combination of two or more of these can also be used.

It is preferable that the silver halide grains of the present invention be gold sensitized, and more preferably gold sensitization and sulfur sensitization are used in combination.

Furthermore, when carrying out a sensitization method using a gold complex salt, it is preferable to use a gold ligand such as thiosulfate, potassium thioheptanoate, or thioether as an auxiliary agent.

The amount of sensitizer added varies depending on the type of silver halide emulsion, but usually sulfur sensitizer is /×/θ
~/X10 mol 1 mol Ag.

The contribution of the short sensitizer is preferably /×10 mol 1 mol Ag or more.

In the present invention, the photographic emulsion can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for improving the photographic performance.

Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or
- Heterosubstituted mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzibadazoles, mercaptothiadiazoles, mercaptotetrazoles (especially /-
phenyl-yo-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a nurphone group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (especially μm hydroxy Substituted (/, 3゜ja, 7) tetraazaindenes); benzenethionurphonic acids; benzenesulfinic acid;
compounds can be added.

For more information, see E.J. Birr,
Stabilization of Photo Photographic Silver Halide Emulsions
graphic3i1ver Halide Em
ulsions), Focal Press (Focal
Please refer to Press J (published in 1997), etc.

The photographic emulsion layer or other hydrophilic colloid of the light-sensitive material of the present invention may contain coating aids, prevention of peeling, improvement of slipperiness, emulsion dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration,
Various surfactants may be included for various purposes such as high contrast, sensitization, etc.

For example, saponins (steroids), alkylene oxide conductors (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers), glycol esters, polyethylene glycol esters, etc. hythane esters, polyalkylene glycol alkyl abanes or amides, polyethylene oxypoid adducts of silicones), grindol derivatives (e.g. alkenyl co-phosphate polyglycerides, alkylphenol polyglycerides), fatty acids of polyhydric alcohols Nonionic surfactants such as Nethers, alkyl esters of sugar; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphate esters, N -acyl-N-alkyltaurines,
Acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Containing anionic surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfones, aminoalkyl sulfates or phosphoric acid esters, alkyl taurines, and abalones; alkylamine salts, aliphatic or aromatic surfactants; Cationic surfactants such as μ class ammonium salts, heterocyclic primary ammonium salts such as vizidinium, imita'zolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

Among these, for the purpose of accelerating development, US Patent No. tAsi022
No. 9, No. 1t332171, Tokukai Sho! 6-257.2
No. 7, No. 60-767 Hiro/No. 60-767, etc., nonionic surfactants having an alkylene oxide group as id& can be preferably used.

As an antistatic agent, US Patent No. V20/! The fluorine-containing surfactants described in JP-A No. 1983-1, JP-A-60-1983-1, and the like can be preferably used.

Various color couplers can be used in the present invention, specific examples of which include the aforementioned Research Dayne Closure (
RD)/1617g≠3, Vu -C-, described in #f described in G.

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic 7-fluacetamide coupler having a ballast group.

For the uninvented VC, it is preferable to use a second generation yellow coupler, representative examples of which include an oxygen atom elimination type yellow coupler or a nitrogen atom elimination type yellow coupler. Particularly preferred are α-pivaloylacetanilide couplers and α-benzoylacetanilide couplers.

Examples of magenta couplers that can be used in the present invention include hydrophobic indasilone-based or cyanacetyl-based couplers having a ballast group, preferably j-hyzolone-based and pyrazoloazole-based couplers. ! The -pyrazolone coupler is preferably a coupler substituted at the 3-position with an arylamino group or an azilabano group.

A nitrogen atom leaving group or an arylthio group is particularly preferred as the leaving group for the two-equivalent pyrazolone coupler. Also European Patent No. 7J, i! The terpyrazolone-based cutler having a ballast group described in No. JA has a high color density.
Ru. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles, preferably pyrazolo(j,/-C
J(/,λ.

&J To IJ Azoles, Ribuch Disclosure Co 4L Co λ0 (/Rhiro June 1996) and JP-A-1979-J
Examples include the pyrazolotetrazoles described in J. J. No. 62 and the pyrazolo pyrazoles described in JP-A No. 2006-230 (June 1999) and JP-A No. 36. It will be done. Ii Dashi (/, 2-b
J pyrazoles are preferred, pyrazolo [/, yo-bJ
(/, 2.≠” triazole is particularly preferred.

Cyan couplers that can be used in the present invention include the naphthol couplers described in U.S. Patent Nos.
,/Hiro 6,326, IA, 221,233 and ? A representative example is the oxygen atom dissociating type two-equivalent naphthol coupler described in ptA, 2Fls, No. 200. A specific example of a phenolic coupler is U.S. Patent No. 2.36? , 92? No., same H4x, to/, /
No. 7, No. 7, 772. /6th issue, same issue, ♂rij.

It is described in No. 126, etc.

Couplers capable of forming cyan dyes that are stable against humidity and temperature are preferably used in the present invention, and include phenolic cyan couplers having an alkyl group of ethyl group or higher at the meta position of the phenol nucleus, and phenylureido groups at the co position. But! These include phenolic couplers having an acylamino group at the - position. ! ,! -Diacylamino-substituted phenolic couplers and cyan couplers in which naphthol is substituted with a sulfonamide group, amide group, etc. at the j-position are also preferred.

Furthermore, colored couplers, couplers in which coloring dyes have proper diffusibility, polymerized color patch-forming couplers, and DIR couplers that release development inhibitors can be used. As a DIR coupler, JP-A-Shoj7-/j
Preferably, the compounds described in /ritA Hiroki No. 7-/j≠23 Hiromu and the like are preferred.

As the photographic material of the present invention, all kinds of color and black and white light-sensitive materials can be mentioned.

gAI includes color negative film for photography (general use, movie use, etc.), color reversal film (for slide use, movie use, etc.)
color photographic paper, color positive film (for movies, etc.), color reversal photographic paper, photothermographic materials (details, fJ5Q!j)
pH-,! 00, 1, 21. No., Japanese Patent Publication No. 1.0-/3
3 Hirohiro No. 3, same Jter 2/I Hirohiro No. 3, special request 1986-7
(described in No. 70), color photosensitive materials using the silver dye bleaching method, photosensitive materials for plate making (lith film, scanner film, etc.), X-ray photosensitive materials (direct/indirect medical use, industrial use, etc.), Black and white negative film for photography, black and white photographic paper,
Microphotosensitive materials (for C0M, microfilm, etc.)
, color diffusion transfer photosensitive material (D T 11), silver salt diffusion transfer photosensitive material, printout photosensitive material, etc.

There are no particular limitations on other additives for the photographic material of the present invention (for example, Research Disclosure Magazine (R)
The entire descriptions in Item/76≠j (RD/74 Ko3) and Volume 17, Item/17/A (RD/17/A) can be referred to.

The description of each fm additive in RD/7A143 and RD/7/A is listed below.

l Chemical sensitizers, page 23, page 6, right column - 2 Sensitivity increasing agents Same as above 3 Spectral sensitizers, pages 23 to λμ, page ggr, right column - supersensitizers, page 6, right column - 2 Sensitizers Brightening agents
-24' page 7 Stain inhibitor Page 25 right column t, SO page left to right column t Dye image stabilizer 2! Teita hardening agent page 26 63/left column 10
Binder, page 26 Same as above //Plasticizer, lubricant, page 27 6jQ Right column Any known method can be used for photographic processing of the light-sensitive material of the present invention, and known processing liquids can be used. can. In addition, the processing temperature is usually between 0C and 5oC.
chosen between 0c but below /r0c or j
The temperature may exceed 0 cy. Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied.

The black and white developer contains dihydroxybenzenes (f! Aj Ehahydroginone), 3-pyrazolidones (for example l-
Phenyl-3-virazolidon, abataphenols (
For example, known developing agents such as N-methyl-p-aminophenol can be used alone or in combination.

Color developers generally consist of an alkaline aqueous bath solution containing a color developing agent.
Amino-N, N-diethylaniline, 3-methyl-Hiro-
Amino-N, N-diethylaniline, Hiro-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-Hiro-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-Hiro-amino-N-ethyl-
N-β-methanesulfamide ethylaniline, Hiro-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) are used. be able to.

In addition, "Photographic Brothecine Chemistry" by F. A. Menn, published by Focal Press (i.
ytt year) 2-6~2? Page, U.S. Patent λ, /ri J,
0/j issue, same 2. Juri λ, 3A Hiro No., Akihiro No. F-44
'? Those described in No. 33 may also be used.

The developer may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic anti-capri agents. can be included. Also, if necessary,
Water softeners, hydroxyl 7<, preservatives, organic solvents such as benzyl alcohol, diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as agons, dye-forming couplers, competitive couplers, sodium Boron I ~ Covered shore like Idride! , auxiliary developers such as /-phenyl-3-pyrazolidone, viscosity imparting agents, polycarboxylic acid chelating agents described in U.S. Pat.
, 22. It may also contain antioxidants as described in No.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually subjected to whitening processing. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. bleaching
For example, iron (Ill), cobalt (lit)
), chromium (■), compounds of polyvalent metals such as copper (II), peracids, quinones, nitrone compounds, etc. are used.

For example, ferricyanide, dichromate, iron (Ill
) or cobalt tetraN) organic complex salts, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 7,3-diamino-
Aminopolycarinic acids such as λ-pro/ξ-nortetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates, and nitronephenols may be used. Among these, potassium ferricyanide, ethylenediamine tetraH1:sodium iron(III) acid, and ethylenediaminetetraI'll:iron(II) acid
I) Ammonium is particularly useful. The ethylene diamine tetramate iron ([1) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, U.S. Patent 3.0≠2.32
No. 0, copper 3. Ko≠/, No. 766, Tokuko Akihiro r-rjot
Bleaching accelerators described in Tokko Sho≠yo-g136, etc.
Tokukai Akira! In addition to the thiol compound described in No. J-Aj7J2, various additives may also be added.

■Specific Effects of the Invention According to the invention, in the process of producing a silver halide emulsion, before coating a silver halide emulsion on a support,
- Since the silver halide emulsion is treated with a porous adsorbent or ion exchange resin, a highly sensitive halogenated photosensitive material can be obtained when a sensitizer for spectral sensitization is included. .

(1) Toxic Example 1 of the Invention The effects of the present invention will be explained in more detail below by showing 7 specific embodiments of the present invention.

Example 1 Add and dissolve odor (1 jl lium, ammonia and gelatin, and add nitric acid solution and potassium bromide bath solution with stirring to a bath solution maintained at 0° C. while keeping pAg at ♂♂♂). After the addition was completed, the temperature was lowered to 3!0C, and after all soluble salts were removed by a sedimentation method, gelatin was added to adjust the pH to 76.3.

The silver bromide particles obtained were octahedral grains with a diameter of 6 μm. This emulsion was separated for 72 minutes to give emulsions A-/ and A-1.

Emulsion A-/ was optimally chemically sensitized by aging with j-benzylidene-3-ethyl o-tanine, potassium chloroaurate and potassium thiocyanate at 6°C for 35 minutes.

Emulsion A-co was chemically sensitized in the same way as emulsion A-/, and silver 1
Activated carbon per mole! Chemical ripening was performed so that the optimum result was obtained by adding g and processing for 20 minutes.

Thereafter, it was filtered through a microfilter to remove activated carbon.

Each of these λ emulsions was divided into two parts, expressed as uo'c, and potassium iodide λoom9 was added per mole of the emulsion. Then, one of the two divided emulsions was treated with a spectral sensitizer 1)-/! is added to λ per mole of silver, and the other is not added,
Furthermore, a stabilizer (≠-hydroxy-6-methyl-/,!,3
a, 7-chitrazaindene) coating aid (sodium dodecylbenzenesulfonate) and hardener (sodium 2,≠-dichloro-6-hydroxy!-triazine)?
It was coated on a polyethylene terephthalate (PET) film support together with a surface protective layer containing polyethylene oxide and having gelatin as a main component, and dried.

The cold cloth sample was exposed to pre-color light for 0.7 seconds using a band pass filter with a peak of 10 nm VC transmitted light.
The film was developed for micro minutes at λO0C, fixed, washed with water, and dried.

The results are shown in Table 1. Here, the relative sensitivity was calculated from the exposure amount necessary to obtain a fog value of 10 and a degree of blackening of λ.

The results shown in Table 1 and Table 7 show that emulsions that do not use activated carbon have a large intrinsic desensitization, whereas the present invention of Sample/-Hiroshi has a small intrinsic desensitization and a high sensitivity.

As a matter of course, the color sensitization sensitivity of the photosensitive material of the present invention when exposed to negative blue light is extremely high.

Similar effects are obtained with sensitizing dyes 1)-/ri, ])-/♂, D-g
, D--6, l)-/, and 2 were also observed.

Example 2 Potassium bromide, ammonia and gelatin were added and dissolved in a bath solution, and a silver nitrate solution and a potassium bromide bath solution were added to the bath solution maintained at 00CVc while stirring, while maintaining the pAg at 7.7 using the triple jet method. Added Eri. After addition,
After the temperature was lowered to 3°C and soluble salts were removed by a sedimentation method, gelatin was added to adjust p)inA and jVc.

The obtained bromide particles were cubic particles with a diameter of 0 rμm. This emulsion was divided into two to give emulsions) 3-/ and B-2.

Emulsion B-/ is! Benzylidene-3-ethylrhodanine, potassium chloroaurate and potassium thiocyanate? The sample was aged at 56°C for 0 minutes to perform optimal chemical sensitization.

Emulsion B-2 was chemically sensitized in the same manner as Emulsion I3-/, which was best achieved by treatment with activated carbon at /i/mole of silver for 20 minutes, and then filtered through a microfilter. Activated carbon was removed.

200 m of potassium iodide per mole of silver in these two emulsions.
9 and a spectral sensitizer])-/j to 7 and a half moles of silver/ornl
? Added. This emulsion was coated in the same manner as in Example 1.

After exposing the coated sample to wavelengths longer than 20 nm for 0.17 seconds using a Tocho sharp cut filter, it was exposed to light at 200C using a developer made by Fuji Photo Film ``Illendor''.
Developed for μ minutes, fixed, washed, and dried.
Shown in the table.

The results shown in Table 2 show that the emulsion using Eri activated carbon exhibits good spectral sensitization sensitivity.

Example 3 After adding ammonia while vigorously stirring a gelatin water bath solution containing potassium bromide that maintained Ao0ctc,
Silver nitrate aqueous solution and a mixed aqueous solution of potassium bromide and potassium iodide were added at the same time.

After the addition, the temperature was lowered to 350C, soluble salts were removed using a sedimentation method, and the gelatin was added to the pH to 6. He abused Hiroshi.

The obtained particles mainly consist of twin grains and have an average particle size of approximately 0.
．． The silver iodobromide grains were 7 μm in size (6 mol %). This emulsion was divided into two to give emulsions C-/ and C-λ.

Milk LiC-/ha! -benzylidene-3-propylrhodanine, chloroauric acid and potassium thiocyanate were used to ripen at 0C for 60 minutes. Emulsion C-2 is Emulsion C-/
Similarly, chemical sensitization was performed to achieve optimum results when treated with activated carbon/Ig (per mole of silver) for 70 minutes. Thereafter, activated carbon was removed by filtering through a microfilter.

A sensitizing dye, a sensitizing dye, a stabilizer, a hardening agent, and a coating aid as described below were added to these λ emulsions, which were then coated on a cellulose acetate film support and dried.

Stabilizer; Hiro-Hydroxy-6-Menalu/, 3゜3a
, 7-chitrazaindene coupler;/-(2, μ, 6-dolichlorophenyl J-
J-(3-(2,4j-G-t-avalphenoxy)-
Acedobado] Benzamide-Yoichi Pyrazolone Gelatin Hardening Agent; 2. Hiro-dichloro-6-hydroxy-
Sodium s-triazine coating aid; dodecylbenzenesulfonic acid; These samples were exposed to light for 17,100 seconds) and then subjected to the following color development process.

Processing step 1, color development λ minutes≠j seconds (Jf'C) 2, bleaching
White 6 minutes 30 seconds 3, washing 3 minutes/second 4, fixing 6 minutes 30 seconds 5, washing 3 minutes/! 6 seconds, stable 3 minutes/j seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate /, 09 Sodium sulfite Hiroshi, 0g Sodium carbonate
30.0g potassium bromide
1. ≠yhydroxylamine & acid salt
r, HiroI Hiro-(N-Ether-N-β-hydroxyethylamino)-2-methyl-aniline sulfate μ, jg Add water ll 1 vote Shiragishi 1 Ammonium bromide 760.0g Aqueous ammonia (21%) λr, ozeethylenediamine-four-drinking sodium trilam iron salt / 30fi glacial acetic acid 1 hiroM add water
/l Fixer Sodium Tetra Polyphosphate 2.0g Sodium Sulfite a, oy Ammonium Thiokylate (70%) /7! , 0rrt1 Bisulfite, sodium acid Hiroshi, B Add water /l Stabilizing liquid formalin t, Add 0ml water /l The results obtained are shown in Table 3.

弗3 table

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer, the following general formula [
A silver halide characterized by containing a spectral sensitizer represented by [I] or [II] and a silver halide emulsion treated with an ion exchange resin or a porous adsorbent during the production process of the silver halide emulsion. Photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z_1 and Z_2 may be different or the same5
, represents a group of atoms forming a 6-membered nitrogen-containing heterocycle. Q_1 represents a 5- or 6-membered nitrogen-containing ketomethylene ring-forming atomic group. R_1, R_2, R_3 and R_4 represent a hydrogen atom, a lower alkyl group, an optionally substituted phenyl group, an aralkyl group, and when l_1 represents 2 or 3 and when n represents 2 or 3, they are different. R_1
and R_1, R_2 and R_2, R_3 and R_3 or R_
4 and R_4 can be linked to form a 5- or 6-membered heterocycle that may contain an oxygen atom, sulfur atom, or nitrogen atom. R_5, R_6 represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms which may contain an oxygen atom, sulfur atom or nitrogen atom in the carbon chain. Further, the heterocycle represented by Z_1 and Z_2 is benzimidazole, naphthoimidazole, imidazo[4,5-
6] When containing another substitutable nitrogen such as quinoxaline, the other nitrogen atom of those heterocycles is a hydroxy group, alkoxy group, halogen atom, phenyl group, or alkoxycarbonyl group having 6 or less carbon atoms. It may be further substituted with an optionally substituted alkyl group or alkenyl group. l_1 and n_1 are 0 or positive integers less than or equal to 3, and l_
1+n_1 represents 3 or less, l_1 is 1,
2 or 3, R_5 and R_1 are connected to form 5
, may form a 6-membered ring. j_1, k_1 and m_1 represent 0 or 0. X_1^- represents an acid anion, r_1 is 0 or 1
represents. General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, Z_1_1 represents a group of atoms forming a nitrogen-containing 5- or 6-membered heterocycle. Q_1_1 represents a nitrogen-containing 5- or 6-membered ketomethylene ring-forming group. Q_1_2 represents a nitrogen-containing 5- or 6-membered ketomethylene ring-forming atomic group. In the heterocycle represented by Z_1_1, Q_1_1 and Q_1_2, when the heterocycle-forming atoms contain two or more nitrogen atoms, such as benzimidazole or thiohydantoin, R_1_3, R_1_5, R_1_, respectively.
Nitrogen atoms to which 4 is not connected may be substituted. R_1_1 represents a hydrogen atom or an alkyl group having 4 or less carbon atoms, and R_1_2 represents a hydrogen atom, an optionally substituted phenyl group, or an optionally substituted alkyl group. When m_2_1 represents 2 or 3, different R
_1_2 and R_1_2 may be linked to form a 5- or 6-membered heterocycle that may contain an oxygen atom, a sulfur atom, or a nitrogen atom. R_1_3 represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms which may contain an oxygen atom, sulfur atom or nitrogen atom in the carbon chain. R_1_4 and R_1_5 have the same meaning as R_1_3, and also represent a hydrogen atom or an optionally substituted monocyclic aryl group. m_2_1 represents 0 or a positive integer less than or equal to 3, and j_
2_1 represents 0 or 1, and n_2_1 represents 0 or 1. When m_2_1 is a positive integer of 3 or less, R_
1_1 and R_1_3 may be connected to form a 5- or 6-membered ring.