JPH03109547A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material used for infrared exposure, small in change of sensitivity and fog due to storage and enhanceable in processing speed by incorporating a specified compound having a >=95mol% silver chloride content in a silver halide emulsion and regulating the water content of the photosensitive material in the range of 3 - 10wt.%. CONSTITUTION:The silver halide color photographic sensitive material has 3 kinds of silver halide photosensitive layers different from each other in spectrally sensitizing wavelength region on a support, and at least one of the photosensitive layers contains in the silver halide emulsion the >=95mol% silver chloride and one of the compounds represented by formula I in which Z<11> is a nonmetallic atomic group necessary to form a 5- or 6-membered N-containing hetero ring; R<11> is H, alkyl, or alkenyl; R<12> is H or lower alkyl; and X<11> is an acid anion. The photosensitive material is regulated to the water content range of 3 - 10wt.%, thus permitting the obtained photosensitive material to be sensitized in the infrared region and superior in storage stability and easily and rapidly processable.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a silver halide color printing system for the purpose of obtaining a color print image by scanning exposure using high-density light such as a laser or a light emitting diode. It relates to photographic materials.

[Conventional technology]

In recent years, image information has been transmitted and stored by converting it into electrical signals,
The technology for reproducing images on a CRT has been greatly developed.

Along with this, the demand for hard copies from this image information has increased, and various hard copy means have been proposed. However, many of these have low image quality and cannot be compared to prints using current color paper. The methods that provide high-quality hard copies include silver halide heat-developable dye diffusion methods;
There are products such as Pictrography (trade name) manufactured by Fuji Photo Film ■ that use the D-scanning exposure method, but the cost of the photosensitive material,
Further improvements are desired in terms of processing stability and the like.

On the other hand, with advances in silver halide window optical materials and compact, simple, rapid development methods (eg, minilab systems), high-quality printed photographs can be provided relatively easily, in a short time, and at relatively low cost.

Therefore, as a hard copy of image information, there is a very high demand for a hard copy material that is less expensive, can be processed simply and quickly, has stable performance, and has high image quality.

As a method of obtaining a hard copy from an electrical signal, a scanning exposure method is generally used in which image information is sequentially extracted and exposed, and a photosensitive material suitable for this method is required.

As a method of forming an image by scanning exposure, there is a so-called image forming method using a scanner. There are various types of recording apparatuses that have put a scanner type into practical use, and glow lamps, xenon lamps, mercury lamps, tungsten lamps, light emitting diodes, and the like have conventionally been used as recording light sources for these scanner type recording apparatuses. However, all of these light sources have practical drawbacks of low output and short lifespan.

To compensate for these drawbacks, there are scanners that use a coherent laser light source such as a gas laser such as a He--Ne laser, an argon laser, a He--Cd laser, or a semiconductor laser as a one-side light source.

Although gas lasers can provide high output, they have disadvantages such as large size, high cost, and the need for a modulator.

On the other hand, semiconductor lasers have advantages such as being small, inexpensive, easy to modulate, and have a longer lifespan than gas lasers. The emission wavelength of these semiconductor lasers is mainly in the infrared region, and therefore a sensitive material having high photosensitivity in the infrared region is required.

However, conventional infrared-sensitive photosensitive materials have poor storage stability due to the instability of infrared sensitizing dyes, and require refrigerated or frozen storage, making them extremely difficult to handle. Ta.

For these reasons, a method has been considered that retains the advantages of semiconductor lasers and forms images by exposing a silver halide photosensitive material that has been spectrally sensitized with a visible range sensitizing dye that has good storage stability. There is.

For example, as shown in Japanese Patent Application Laid-Open No. 63-18343, a semiconductor laser and a nonlinear optical material are combined to extract the second harmonic of the semiconductor laser and use it as visible light. However, considering the manufacturing stability, cost, conversion efficiency to second harmonics, life span, etc. of this nonlinear optical material, there are still considerable problems in practical use.

[Problem to be solved by the invention]

Therefore, it is thought that the shortest way is to solve the storage problem of infrared sensitized materials and use them as scanning exposure materials in combination with semiconductor lasers, and research is being carried out to this end.

Furthermore, when considering color printing as output by scanning exposure of images, it is very important to simplify and speed up the processing. Therefore, it is advantageous to use a method of rapidly processing a high silver chloride silver halide color photographic light-sensitive material with a color developer substantially free of sulfite ions and Hensyl alcohol, as described in WO 37-04534. Therefore, it is important to incorporate these techniques into scanning exposure photosensitive materials to make them suitable for simpler and faster processing.

Based on the above, we have developed a high-silver chloride color photosensitive material that has spectral sensitivity in the infrared region suitable for scanning exposure using a semiconductor laser, is easy to process, and has excellent storage stability. is very much awaited.

On the other hand, as a method for solving the storage problems of light-sensitive materials, US Pat. No. 4,596,767 proposes the use of a tetracyclic compound containing quaternary nitrogen together with an infrared sensitizing dye. However, even when this compound is used in a silver halide emulsion containing a coupler and having a high silver chloride content (95 mol% or more) intended for rapid processing, satisfactory storage performance of the sensitive material cannot be obtained. It turned out that I couldn't do it.

Therefore, an object of the present invention is to provide a silver halide color photosensitive material suitable for simple and rapid processing and further suitable for scanning exposure using a semiconductor laser light source. More specifically, the object of the present invention is to provide a high silver chloride color light-sensitive material that is infrared sensitized, has excellent storage stability, and is suitable for simple and rapid processing.

[Means for Solving the Problems] The above object is to provide a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler, which are mutually connected to each other. In a silver halide color photographic light-sensitive material having at least three types of silver halide photosensitive layers having different spectral sensitization wavelength ranges on a support, at least one of the photosensitive layers has a maximum spectral sensitivity at 750 nm or more,
The silver halide emulsion contained in at least one photosensitive layer of the photosensitive material has a silver chloride content of 95 mol% or more, and has the following general formulas (Ia), (Ib), (Ic) and (Id). ) A silver halide color photographic light-sensitive material, which contains at least one compound selected from the group of compounds represented by: We found that this can be achieved by

General formula Ha) R General formula (■b) 0=C R+4 General formula (I c) General formula (Id) In the formula, 2. represents a group of nonmetallic atoms necessary to complete a 5-membered or 6-membered nitrogen-containing heterocycle. ZI2 and I13
represents the atoms necessary to complete the aromatic ring. R8 represents a hydrogen atom, an alkyl group, or an alkenyl group. Il+
z represents a hydrogen atom or a lower alkyl group. RI2 represents an alkyl group or an alkenyl group. RI5 represents a substituted alkyl group or a substituted alkenyl group. R14 and R1& represent a hydrogen atom, an alkyl group, an aryl group, R
1, and R11 may be the same or different (respectively a hydrogen atom, an alkyl group, an aryl group, a cyano group, a halogen atom, an alkoxycarbonyl group, a carboxy group, an optionally substituted aminocarbonyl group, a formyl group,
Represents an alkylcarbonyl group, an arylcarbonyl group or an aryloxycarbonyl group.

X and XI2 represent acid anions, G is an oxygen atom,
Represents a sulfur atom, selenium atom or tellurium atom. K.Re represents a cation of valence n selected from the group consisting of onium ions, ions of Group IA or Group IIA elements, and metal ions of Group 1B, Group 2B, Group IVA or Group VA. r represents 1 or 2, and r is 1 when the compound forms an inner salt. q represents 1 or 2, H+
2/Q represents a 2/q-valent cation.

More specifically, Z represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. This ring may be fused with a benzene ring or a naphthalene ring.

For example, thiazoliums (e.g. thiazolium, 4-methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium, 5-
Methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho(1
, 2-d) thiazolium, naphtho[2,1-d) thiazolium), oxacilliums (e.g. oxacillium,
4-methyloxacillium, benzoxacillium, 5
-chlorobenzoxacilium, 5-phenylbenzoxacilium, 5-methylbenzoxacilium, naphtho[1°2-d]oxacillium), imidazolium M
(e.g. 1-methylbenzimidazolium, 1-propyl-5-chloropenzimidazolium, 1-ethyl-5,
6-cyclopenzimidazolium, 1-allyl-5-
trifluoromethyl-6-chloropenzimidazolium)
, selenazolium M (e.g. benzoselenazolium, 5
-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, and (1,2-d) selenazolium).

R11 represents a hydrogen atom, an alkyl group (preferably having 8 or less carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl), or an alkenyl group (such as allyl). R
1 represents a hydrogen atom, a lower alkyl group (e.g. methyl, ethyl) * Xll represents an acid anion (e.g. CI-,
Br-do, ClO4-), and Z++, thiazoliums are preferred, and substituted or unsubstituted benzothiazolium or naphthothiazolium is more preferred.

R11 represents an alkyl group or an alkenyl group.

+1+s represents a substituted alkyl group or a substituted alkenyl group.

RI4 and R1& represent a hydrogen atom, an alkyl group, or an aryl group.

G represents an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom.

zl! and ZI! represent the atoms necessary to complete the aromatic ring.

K4111 is an onium ion, an ion of a group IA or group IIA element, and a group IIB, ■B, IVA or V
Represents a cation of valence n selected from the group consisting of Group A metal ions.

X11 has the same meaning as X in general formula (!a).

"represents 1 or 2, and r is 1 when the compound forms an inner salt.

The alkyl group of R13 includes a substituted alkyl group. The unsubstituted alkyl group preferably has 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, heptyl, and octyl.

Examples of the substituted alkyl group include a carboxyl group, a sulfo group, a cyan group, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom), a hydroxyl group, an alkoxycarbonyl group (preferably a carbon atom number of 8 or less, e.g., methoxycarbonyl, ethoxycarbonyl, hensyloxycarbonyl), alkoxy group (preferably 7 carbon atoms)
The following examples include methoxy, ethoxy, propoxy, butoxy, hensyloxy), aryloxy groups (e.g. phenoxy, P-)lyloxy), acyloxy groups (preferably having up to 3 carbon atoms, e.g. acetyloxy, propionyloxy), acyl groups (preferably has up to 8 carbon atoms, e.g. acetyl, propionyl, benzoyl, mesyl), carbamoyl5 (e.g. carbamoyl, N, N-
dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl groups (e.g. sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl), aryl groups (e.g. phenyl, p-
an alkyl group (preferably the number of carbon atoms in the alkyl moiety is 6 or less) substituted with hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl), etc.
can be mentioned. However, two or more of these substituents may be substituted with an alkyl group in combination.

The alkenyl group of R1ff includes substituted alkenyl groups.

The unsubstituted alkenyl group preferably has 3 to 3 carbon atoms.
8, for example allyl, 3-butenyl, 2-butenyl,
Examples include 4-pentenyl, 3-pentenyl, and 5-hexenyl. Examples of the substituents for the substituted alkenyl group include those described as substituents for the alkyl group of Ls.

Examples of the substituents of the substituted alkyl group or substituted alkenyl group for R+5 include the substituents explained in R13, and the number of carbon atoms in the alkyl group substituted with these substituents is preferably 1 to 8, and the alkenyl The number of carbon atoms in the base is preferably 3 to 8. Examples include methoxyethyl, phenylethyl, ethoxypropyl, carboxypropyl, chloropropyl, benzylallyl, chloroethyl, phenylpropyl, fluoroethyl, and methylsulfonamidoethyl.

RI4 and R are hydrogen atoms, alkyl groups (including substituted alkyl groups. Unsubstituted alkyl groups preferably have 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, heptyl, and octyl. , as the substituent, the substituents explained in R13 can be mentioned. The unsubstituted aryl group is preferably one having 6 to 12 carbon atoms, such as phenyl or naphthyl, and its substituents include the substituents described in RI3. The number of carbon atoms in the substituted aryl moiety is preferably 6 to 12.

The aromatic ring completed by Z1□ and Z13 is 6 to 1
Preferably, it contains 0 ring carbon atoms. (For example, phenyl, naphthyl.) Useful substituents for Z, t and Z13 include those mentioned in RI3.

Cations include inorganic and organic cations, such as onium ions (e.g. ammonium, sulfonium, alkylammonium, arylammonium, alkylsulfonium or arylsulfonium), those of the periodic table I
Ions of group A elements (e.g. alkali metals, e.g. lithium, sodium, potassium), ions of alkaline earth metals of group IIA of the periodic table (e.g. magnesium, calcium, strontium) and IIB, ■B of the periodic table.

IVA or VA metal ions (eg manganese, cadmium, lead or bismuth). (The periodic table described in this specification is manufactured by G & G Morrlam Company, Springfield, Massachusetts, USA.
y Published in 1969 1 Webater s 5even
th New Collegiate Dictionary
ry page 628. ) As the acid anion of Xll and X, □, for example, Cl-
1Br\l-1C! 04-.

R1? The alkyl group, alkoxycarbonyl group, and alkyl moiety of the alkylcarbonyl group represented by Il+s each more preferably have 10 or less carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, an octyl group, (2-ethylhexyl group, decyl group, etc.), unsubstituted and substituted groups. Useful substituents include halogen atoms, cyano groups, aryl groups, carboxyl groups, alkylcarbonyl groups, arylcarbonyl groups, and alkylamino groups having 6 or less carbon atoms.

R1? The aryl group, arylcarbonyl group, and aryloxycarbonyl group represented by R11+ each more preferably has 16 or less carbon atoms, and includes unsubstituted and substituted groups. Preferred substituents include a halogen atom, a cyano group, a sulfo group, a carboxyl group, an alkyl group having 6 or less carbon atoms, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, a perfluoroalkyl group, an alkylaminocarbonyl group, and an alkylcarbonyl group. Examples include an amino group, an aryl group having 10 or less carbon atoms, an arylcarbonyl group, and an aryloxy group.

The cations represented by N.2/4 include organic and inorganic ions, and more preferable examples include protons, ammonium (e.g., ammonium, benzylammonium, triethylammonium, hensylmethylammonium, etc.) , pyridinium, alkali metal ions (e.g. N
a”, K゛), alkaline earth metal ions (e.g. Ca”)
), Zn'', A'', etc.

Next, general formulas (Ia), (I b), (I c) and (
Specific examples of the compound represented by Id) are shown below. However, the present invention is not limited to these.

(Ia 1) CH2 (Ia 2) CI3 (Ia-3) CI2-C1, CH2 (Ia-4) (Ia-5) CsII.

(Ia-6) CIl□-CI=CHz (Ia-7) CHz-CI=CHz (Ia-8) zHs (Ia-9) (Ia-10) CH.

(Ia 11) C21(S (la 12) C, 11° (Ia 13) C,)I.

tHs (r　a　-15) zHs 5Hq (Ia-16) C,H.

(Ia 17) CH2 Cll=CH2 (Ia-18) (Ib-1) ■ (Ib-2) 0=C (Ib-3) ■ (Ib 4) 0=C CH3 (Ib 5) 0=C lh (Ib 6) (Ib-7) 0=C CH3 (Ib-8) 0=C CH.

(Ib-9) (Ib-10) 0=C (Ib-11) 0=C C11゜(Ib-12) (,zH3 (Ib 13) (Ib-14) 0=C C11゜(Ib- 15) 0=C 113 (Ic-1) ■ (:H2CH20CH3 (Ic-2) (Ic-3) CHgCHzCHzOCHzCHi (Ic-4) CH2CH2CI12COOI+ (Ic 5) C) IzCHzCIIzCZ (lc 6) ( Ic 7) CHzCHzCl (Ic 8) (Id-1) Hs (I d-2) General formula (Ia), (I b), (I d-2) used in the present invention
The compounds of c) or (1d) are advantageously used in amounts of about 0.01 to 5 grams per mole of silver halide in the emulsion.

The light-sensitive material of the present invention has on a support at least three types of silver halide photographic light-sensitive layers each having a different spectral sensitization wavelength range, consisting of a yellow coupler-containing emulsion layer, a magenta coupler-containing emulsion layer, and a cyan coupler-containing emulsion layer. However, among them, at least one of the layers has a maximum spectral sensitivity at 0 nm or more, preferably at least one of the layers has a maximum spectral sensitivity at 0 nm or more, and more preferably at least one layer has a maximum spectral sensitivity at 0 nm or more. It is preferable that six photosensitive layers have maximum spectral sensitivity at 0 nm or more.

General formulas (Ia), (I b), (I
The compound represented by c) or (I d) is contained in at least one silver halide emulsion layer having a silver chloride content of 95 mol% or more, and the emulsion layer has a spectral sensitivity of 0 nm or more. Preferably, the emulsion layer has a maximum.

The ratio (weight ratio) between the infrared sensitizing dye used in the present invention and the compound represented by the general formula % is dye/-general formula Ia), (I b), (I b) or (Id ) is preferably used in the range of 1/1 to 1/300, particularly preferably 1/2 to 1/100.

General formulas (Ia), (I b), (I
The compound represented by c) or (ld) can be directly dispersed in the emulsion or dispersed in a suitable solvent (for example, water, methyl alcohol, ethyl alcohol, propatool, methyl cellosolve, acetone, etc.) or these solvents. It is also possible to dissolve it in a mixed solvent using two or more of them and add it to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes.

General formula (Ia), (I b), (I c) or (Id
The compound represented by ) may be added to the emulsion before or after the addition of the sensitizing dye used in the present invention. Also, general formula (Ia), (T b),
The compound (Ic) or (Id) and the sensitizing dye may be dissolved separately and added to the emulsion separately and simultaneously, or they may be mixed and then added to the emulsion. Alternatively, it may be added to another layer and transferred to the emulsion layer by diffusion after coating.

The halogen composition of the silver halide grains in at least one photosensitive layer (preferably three types of photosensitive layers) of the photosensitive material of the present invention is 95 mol % or more (more preferably 98 mol % or more) of the total silver halide constituting the silver halide grains. The silver halide is silver chloride (mol% or more), and is preferably silver chlorobromide that does not substantially contain silver iodide. Here, "substantially free of silver iodide" means This means that the silver content is 1.0 mol% or less.

Further, the above-mentioned silver chloride content means the average proportion of silver chloride in each grain with respect to silver halide in one silver halide emulsion.

Further, the silver halide grains according to the present invention preferably have a silver bromide content of at least 10 mol % and 70 mol %.
It is preferred to have less than mol % silver bromide localized phase. Further, the localized phase may have a layered structure surrounding the silver halide grains or may have a discontinuously isolated structure inside or on the surface of the grains. One preferred example of the arrangement of the silver bromide localized phase is epitaxial growth of a localized phase with a silver bromide content of at least 10 mol %, more preferably more than 20 mol %, on the surface of the silver halide grains. This is what I did.

It is preferable that the silver bromide content of the localized phase exceeds 20 mol%; however, if the silver bromide content is too high, it may cause desensitization when pressure is applied to the photosensitive material, or the composition of the processing solution may be affected. Fluctuations may impart unfavorable characteristics to the photographic material, such as large changes in sensitivity and gradation.

Taking these points into consideration, the silver bromide content of the localized phase is determined by
The range is preferably 20 to 60 mol%, and 30 to 50 mol%
The most preferred range is . The other silver halide constituting the localized phase is preferably silver chloride. The silver bromide content of the localized phase can be determined by the X-ray diffraction method (for example, described in "Nippon Kagaku Yoshin, New Experimental Chemistry Course 6, Structural Analysis") or the xPS method (for example, "Surface Analysis, 1MA, Application of Auger Electron/Photoelectron Spectroscopy'' (published by Kodansha), etc. can be used for analysis. The localized phase accounts for 0.1 to 20% of the amount of gold and silver constituting the silver halide grains of the present invention.
% of silver, and more preferably 0.5 to 7% of silver. The interface between such localized silver bromide phase and other phases forms a clear phase boundary. It may have a short transition region in which the halogen composition gradually changes.

Various methods can be used to form such a localized silver bromide phase. For example, a localized phase can be formed by reacting a soluble silver salt and a soluble halide salt by one-sided mixing method or simultaneous mixing method. can be formed. Furthermore, the localized phase can also be formed using a so-called conversion method, which involves converting already formed silver halide into silver halide having a smaller solubility product. Alternatively, a localized phase can also be formed by adding silver bromide fine particles and recrystallizing them on the surface of silver chloride particles (EPo, 273, 430).

The substrate or localized phase of the silver halide grains of the present invention preferably contains metal ions different from silver ions or complex ions thereof. Metal ions or complex ions thereof mainly selected from iridium ions, rhodium ions, iron ions, osmium, platinum, ruthenium, palladium, cobalt, nickel, etc. can be used in combination.

Furthermore, the type and concentration of metal ions can be adjusted between the localized phase and the substrate. A plurality of these metals may be used.

Furthermore, metal ions such as cadmium, zinc, lead, mercury, and thallium can also be used.

These metal ions will be explained in more detail. The iridium ion-containing compound is a trivalent or tetravalent salt or a complex salt, and a complex salt is particularly preferred. For example, iridium chloride (■), iridium bromide (■), iridium chloride (■), sodium hexachloroiridate (III), potassium hexachloroiridate (IV),
Hexaammineiridium (IV) salt, trioxalatoiridium (III) salt, trioxalatoiridium (
IV) Halogen, amine, and oxalate complex salts such as salts are preferred. The amount used is 5 x 10 per mole of silver.
-9 moles -lXl0-' moles, preferably 5X10-8
˜5XIQ”6 moles.

The platinum ion-containing compound is a divalent or tetravalent salt or a complex salt, preferably a complex salt. For example, platinum chloride (■), potassium hexachloropalladate (TV), tetrachloropalladium (n) acid, tetrabromoplatinum (II)
Acid, sodium tetrakis(thiocyanato)platinum(IV), hexaammineplatinum(IV) chloride, etc. are used. The dosage thereof is about 1X10-11 mol to IX10-' mol per 1 mole.

The palladium ion-containing compound is usually a divalent or tetravalent salt or a complex salt, and complex salts are particularly preferred.

For example, sodium tetrachloropalladate (n), sodium tetrachloropalladate (IV), potassium hexachloropalladate (TV), tetraamminepalladium (It) chloride, potassium tetracyanopalladate (II), etc. are used.

As the nickel ion-containing compound, for example, nickel chloride, nickel bromide, potassium tetrachloronickel (It), hexaamminenickel (II) chloride, sodium tetracyanonickel (n), etc. are used.

The rhodium ion-containing compound is usually preferably a trivalent salt or a complex salt. For example, potassium hexachlororhodate, sodium hexachlororhodate, ammonium hexachlororhodate, etc. are used. The amount used is about to-'' to 10-4 mol per mol of silver.

The iron ion-containing compound is a divalent or trivalent iron ion-containing compound, preferably an iron salt or an iron complex salt that is water-soluble within the concentration range used. Particularly preferred are iron complex salts that are easy to incorporate into silver halide grains. Specifically, there are hexacyanoferrate(n) salts, hexacyanoferrate(II[) complex salts, ferrous thiocyanate salts, ferric thiocyanate salts, and the like. The amount used is 5 x 10-' mol to 1 x 10'' 3 mol, preferably 1 x 10-8 mol - 1X10-' mol, per 1 mol of silver halide.

The above-mentioned metal ion-providing compound may be used in an aqueous gelatin solution, a halide aqueous solution, a silver salt aqueous solution, or other aqueous solution, which becomes a dispersion medium during the formation of silver halide grains, or in silver halide grains containing metal ions in advance. It is incorporated into the localized phase and/or other grain parts (substrate) of the silver halide grains of the present invention by adding in the form of and dissolving the fine grains.

The metal ions used in the present invention can be incorporated into emulsion grains either before grain formation, during grain formation, or immediately after grain formation. This can be changed depending on where in the particles the metal ions are contained.

Furthermore, it is more preferable that the localized phase in the silver halide emulsion of the present invention be deposited together with at least 50% of the total iridium added during the preparation of the silver halide grains.

Here, depositing the localized phase together with iridium ions means supplying an iridium compound simultaneously with, immediately before, or immediately after supplying silver and/or halogen to form the localized phase. say.

The silver halide grains according to the present invention have (100
) surface, (111) surface, or both surfaces, and even those containing higher-order surfaces are preferably used. It will be done.

The shape of the silver halide grains used in the present invention is cubic,
Those with regular crystal shapes such as tetradecahedrons and octahedrons, those with irregular crystal shapes such as spherical and plate shapes, or composites of these crystal shapes. There are things that have a shape. It is also possible to use a mixture of particles with various crystal forms, but in particular, particles with the above-mentioned regular crystal forms account for 50% or more, preferably 70% or more, and more preferably 90% or more. It is better to include % or more.

The silver halide emulsion used in the present invention is such that tabular grains having an average aspect ratio (length/thickness ratio) of 5 or more, particularly preferably 8 or more, occupy 50% or more of the total projected area of the grains. It may also be an emulsion.

The size of the silver halide grains used in the present invention may be within the commonly used range, but the average grain size is 0.1t! m-
1,5- is preferred. The particle size distribution may be polydisperse or monodisperse, but monodisperse is preferable. The particle size distribution, which indicates the degree of monodispersity, is determined by the statistical coefficient of variation (standard deviation S when the projected area is rounded).
The value S/d divided by the diameter d) is preferably 20% or less, more preferably 15% or less.

Further, two or more of such tabular grain emulsions and monodispersed emulsions may be mixed. When emulsions are mixed, it is preferred that at least one emulsion has the above-mentioned coefficient of variation.

The so-called matrix portion other than the localized phase of the silver halide grains used in the present invention may have different phases inside and on the surface, or may consist of a uniform phase.

The photographic emulsion used in the present invention is P. gelafchides (
Chimie er Ph.
Photographic Emulsion Chemistry (r'ho t.

graphic emulsion chemist
y (Focal Press, 1966), Bouy El Zelikman (V, L.

Making and Coating Photographic Emulsions (Making and Coating Photographic Emulsions) by Zelikman et al.
Kingand Coating Photograp
hic Emulsion) (published by Focal Press,
(1964) and others.

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Pat. No. 3,271,157,
Same No. 3,574,628, Same No. 3,704, 130, Same No. 4.297,439, Same No. 4,276.374
), thione compounds (for example, JP-A-53-144
No. 319, No. 53-82408, No. 55-77737
), amine compounds (e.g. JP-A-1007-1987), amine compounds (e.g.
No. 17, etc.) can be used.

The silver halide grains used in the present invention are essentially of the surface latent image type, and the surface must be chemically sensitized to some extent.

Chemical sensitization includes active gelatin and sulfur-containing compounds that can react with silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., Reduction sensitization method using stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); metal compounds (for example, total complex salts, as well as pt, b, Pb, Rh, Fe, etc. in the periodic table) ■ Noble metal aggravation method using complex salts of group metals, etc. alone,
Alternatively, it is preferable to use them in combination.

For details on these methods, see Japanese Patent Application Laid-Open No. 62-21527.
It is described in the lower left column, line 18, on page 12 of Specification No. 2 to line 16, lower right column, of the same page.

By adding at least one compound represented by any of the following general formulas (II) to IV) to the high silver chloride emulsion used in the present invention, the capri can be increased, especially when a gold sensitizer is used. It is extremely effective in preventing growth. It can be added at the time of particle formation, desalination, chemical ripening, or just before coating.
It is preferably added during the desalting and chemical ripening steps, especially before the addition of the gold sensitizer.

Compounds having a thiosulfonyl group represented by the general formula (■), (I[l) or (rV)] will be explained.

General formula (n) Q-5OzS-M In the formula, Q represents an alkyl group, an aryl group, or a heterocyclic group, which may be further substituted. W represents an atomic group necessary to form an aromatic ring or a heterocycle, and these rings may be further substituted. M represents a metal atom or an organic cation; m represents an integer of 2 to 10;

Examples of substituents that can be substituted on the alkyl group, aryl group, aromatic ring or heterocycle include lower alkyl groups such as methyl and ethyl groups, aryl groups such as phenyl, alkoxyl groups having 1 to 8 carbon atoms, Examples include halogen atoms such as chlorine, nitro groups, amino groups, and carboxyl groups.

The alkyl group represented by Q has 1 to 18 carbon atoms,
The number of carbon atoms in the aryl group and aromatic ring represented by Q and W is 6.
~18.

The heterocycle represented by Q and W includes thiazole,
Examples include henzthiazole, imidazole, benzimidazole, and oxazole ring.

The metal cation represented by M is preferably an alkali metal cation such as sodium ion or potassium ion, and the organic cation is preferably ammonium ion or guanidinium ion.

General formula (n), (I) or (rV) represented by Specific examples of compounds that Listed below.

(A5) H3C-Sow ・5Na (A9) (A-10) (A-11) L-cystine-disulfoxide (
A 12) HsCt・So, -S -K(A
13) l117CIl ・SOx ・5Na Compounds represented by the general formula (II), (I can do.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole and those in which the m-position of the phenyl group is substituted with an N-methylureido group), mercaptopyrimidines, mercapto Triazines, etc.;
thioketo compounds, such as oxadorinthione; azaindenes, such as triazaindenes, tetraazaindenes, especially 4-hydroxy substituted (1,3,3a
, 7) tetraazaindene), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. .

Among them, the following general formula (V
), (Vl) or (■) are preferably added. The amount to be added is preferably IXl0-' to 5XIO-'' moles per mole of silver halide, and particularly preferably lXl0-' to lx10) moles.

General formula (V) In the formula, Rst is an alkyl group, an alkenyl group, or an alkyl group.
represents a group. XSI is a hydrogen atom, an alkali metal atom,
Represents an ammonium group or precursor. The alkali metal atom is, for example, a sodium atom, a potassium atom, etc., and the ammonium group is, for example, a tetramethylammonium group, a trimethylbenzylammonium group, etc. Further, the precursor refers to a group that can become X, =H, or an alkali metal under alkaline conditions, and represents, for example, an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, and the like.

Among the above R51, the alkyl group and alkenyl group include unsubstituted and substituted groups, and also include alicyclic groups. Substituents for substituted alkyl groups include halogen atoms, nitro groups, cyano groups, hydroxyl groups, alkoxy groups, aryl groups,
Acylamino groups, alkoxycarbonylamino groups, ureido groups, amido groups, heterocyclic groups, acyl groups, sulfamoyl groups, sulfonamide groups, thioureido groups, carbamoyl groups, alkylthio groups, arylthio groups, peterocyclic thio groups, and even carboxylic acid groups , sulfonic acid groups, or salts thereof.

The above ureido group, thioureido group, sulfamoyl group, carbamoyl group, and amino group are each unsubstituted,
Including those substituted with N-alkyl and those substituted with N-aryl. Examples of the aryl group include a phenyl group and a substituted phenyl group, and examples of the substituent include an alkyl group and the substituents of the alkyl group listed above.

General formula (Vl) In the formula, Y61 represents an oxygen atom or a sulfur atom.

L represents a divalent linking group, and R6+ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

The alkyl group, alkenyl group and XSI of R61 have the same meanings as RSI+ X s+ in general formula (V).

Specific examples of the divalent linking group represented by the above can be mentioned.

! represents O or l, and Ro, R1, and RZ each represent a hydrogen atom, an alkyl group, or an aralkyl group.

General formula (■) In the formula, R? I and X? I is R61°X of general formula (V)
SI and each have the same meaning, L and l are the general formula (Vl
) is synonymous with that of Rtt is synonymous with R and I, and may be the same or different.

The following general formula (■), general formula (V[) and general formula (■)
Specific examples of the compounds are listed below, but the invention is not limited thereto.

(B-2) N=N 5-CCHs) a CH3 NHCOClll Hi The silver halide photographic material of the present invention contains 3% by weight or more 1
It is necessary to have a water content of 0% by weight or less.

The term "moisture content" used herein refers to a value measured by the following method.

After leaving the sample to be measured at 25° C. for 12 hours under the condition of 55% R)l, its weight is measured and designated as W. Next, this sample was dried at 100°C for 12 hours, and then the weight was measured again and designated as h. At this time, the water content is expressed by the following formula.

Moisture content [%] = (en, −-g) / ICxio.

If the water content measured by the above method is less than 3% by weight or greater than 10% by weight, the storage performance of the resulting silver halide photographic material will be poor. The moisture content is
From the viewpoint of storage performance, the content is more preferably 3.5% by weight or more and 8.0% by weight or less.

Methods for controlling the moisture content include selecting drying conditions after coating the photographic layer on the support, and incorporating a moisture absorbent into the photographic layer. This method is a method of controlling the water content of the support. That is, it is preferable to use a support that is made of a paper base material coated with resin on both sides and has an appropriate moisture content.

The moisture content of the support is preferably controlled before the photographic layer is coated onto the support.

More preferably, this is carried out before coating the paper base material with the synthetic resin.

In the silver halide photographic light-sensitive material of the present invention, a paper base material whose surface is coated with a synthetic resin is preferably used as a support. As the resin used for coating the paper base material, polyolefin resins are preferably used, such as homopolymers of α-olefins such as ethylene and propylene (or copolymers consisting of two or more α-olefins such as ethylene and propylene). or copolymers containing α-olefin as a main component and other monomers copolymerizable therewith, and mixtures thereof are preferably used.To obtain the support used in the present invention using the above-mentioned polyolefin resin, Usually, a so-called extrusion coating method is used in which the above-mentioned resin is heated and melted and then cast onto a moving paper base material, whereby both sides of the paper base material are coated with the resin.

In addition, preferable methods other than the above-mentioned methods include JP-A-57-27257, JP-A-57-30830, and JP-A-60.
-249145 etc., that is, on a paper base material,
A method may be mentioned in which a coating layer that can be cured by electron beam irradiation is applied, and then the coating layer is cured by irradiating the electron beam to form the coating layer.

The resin coating layer of the paper base contains white pigments such as titanium oxide and aluminum oxide, colored pigments, stabilizers that are usually mixed with resins, antioxidants, dispersants, slip agents, etc. as necessary. can be done.

The silver halide photographic light-sensitive material of the present invention can be prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, and then directly or (adhesiveness, antistatic property,
It may be applied via one or more subbing layers (to improve dimensional stability, abrasion resistance, hardness, antihalation properties, and/or other properties).

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is most typically calculated by dividing the observed area into 6-×6- adjacent unit areas and projecting them onto that unit area. It can be determined by measuring the occupied area ratio (%) (Ri) of the fine particles. The coefficient of variation of the occupied area ratio (%) can be determined by the ratio s/R of the standard deviation S of R4 to the average value (R) of R4. The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation s
/R can be found by

In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, particularly 0.12 or less.

A thin metal film such as aluminum or a light alloy on a light-reflecting substance, JP-A-63-118154, JP-A-6324
No. 247, No. 63-24251 or No. 63-242
It is also possible to use a metal having a specular reflective surface or a type 2 diffuse reflective surface as described in Japanese Patent No. 53, No. 63-24255, and the like.

The support used in the present invention is preferably lightweight, thin, and strong. Also, it is better to use something that is inexpensive.

The reflective support may be polyethylene-coated paper or synthetic paper having a thickness of 10 to 250 ts, preferably 30 to 180 ts.

In the present invention, the use of spectral sensitizing dyes is important. As the spectral sensitizing dye used in the present invention, cyanine dyes, merocyanine dyes, composite merocyanine dyes, etc. are used.

In addition, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used. As cyanine dyes, simple cyanine dyes, carbocyanine dyes, and dicarboxyanine dyes are used. In particular, for red or infrared sensitization, it is possible to select and use aggravating dyes represented by the following general formulas (■), (IX) and (X). These aggravating dyes are chemically relatively stable, relatively strongly adsorbed onto the silver halide grain surface, and are resistant to desorption by coexisting dispersions such as couplers.

In the silver halide photosensitive layer of the present invention, preferably at least two photosensitive layers out of at least three photosensitive layers, more preferably three photosensitive layers are represented by general formulas (■), (IX) and (X). 660 to 690 nm using at least one sensitizing dye selected from the group of compounds shown above.
It is preferable that it is selectively spectrally sensitized in accordance with the wavelength of the semiconductor laser beam in any one of the wavelength ranges of 740 to 790 nm, 800 to 850 nm, and 850 to 900 nm.

In the present invention, '660~690nm, 740~
790n Mai, 800-850n+s and 850-9
"Selectively spectral sensitization according to the wavelength of a semiconductor laser beam in any wavelength range of 00 nm" means that the dominant wavelength of one laser beam is in any one of the wavelength ranges mentioned above, and Compared to the sensitivity at the main wavelength of the laser beam of the main photosensitive layer that has been spectrally sensitized to match the main wavelength of the laser beam, the sensitivity of other photosensitive layers at the main wavelength is practically small (both 0. 8 (logarithmic expression) refers to spectral sensitization with low
It is preferable to set them apart by nm. The sensitizing dye used is
Use one that provides high sensitivity at the main wavelength and a sharp spectral sensitivity distribution. Furthermore, the term "dominant wavelength" is used here because although laser light is originally coherent light, it actually has some blurring, so it must be considered with a certain degree of latitude.

The sensitizing dyes represented by the general formulas (■), (IX) and (X) are detailed below.

General formula (■) (Xs+)ns+ In the formula, ZIII and Z each represent an atomic group necessary to form a heterocyclic nucleus.

The heterocyclic nucleus includes a 5- to 6-membered ring nucleus containing a nitrogen atom and optionally a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom as a heteroatom (a fused ring is further bonded to these rings). (or a substituent may be further bonded) is preferred.

Specific examples of the above-mentioned heterocyclic nucleus include thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, imidazole nucleus, benz Imidazole nucleus, naphthoimidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenine nucleus, indole nucleus, tellurazole nucleus, penzotelllazole nucleus, naphthotellazole nucleus, etc. I can do it.

Ro and R,z are each an alkyl group, an alkenyl group,
Represents an alkynyl group or an aralkyl group.

These groups and the groups described below are used to include their respective substituted forms. For example, taking an alkyl group as an example, it includes unsubstituted and substituted alkyl groups, and these groups may be linear, branched, or cyclic. The alkyl group preferably has 1 to 8 carbon atoms.

Specific examples of substituents for substituted alkyl groups include halogen atoms (chlorine, bromine, fluorine, etc.), cyano groups, alkoxy groups, substituted or unsubstituted amino groups, carboxylic acid groups, sulfonic acid groups, hydroxyl groups, etc. One or more of these may be substituted in combination.

A specific example of the alkenyl group is a vinylmethyl group.

Specific examples of the aralkyl group include benzyl group and phenethyl group.

i□ represents a positive number of 1.2 or 3.

Ro represents a hydrogen atom, and RB4 represents a hydrogen atom, a lower alkyl group, or an aralkyl group, and can also be linked to Rez to form a 5- to 6-membered ring.

In addition, when RM4 represents a hydrogen atom, R113 is another R
It may be linked with o to form a hydrocarbon ring or a heterocycle. These rings are preferably 5- to 6-membered rings. jo, k□ is 0
or l, Xal represents an acid anion, n□
represents 0 or 1.

General formula (IX) In the formula, Zl1 and Zl11 have the same meanings as the above Z or Zll. R1% Rqz has the same meaning as R□ or R112, and R93 represents an alkyl, alkenyl, alkynyl, or aryl group (for example, a substituted or unsubstituted phenyl group). iq+ represents 2 or 3.

R94 represents a hydrogen atom, a lower alkyl group, or an aryl group, and R9J and another R94 may be linked to form a hydrocarbon ring or a heterocycle. These rings are preferably 5- or 6-membered rings.

Q□ is a sulfur atom, an oxygen atom, a selenium atom or; N R
1, and R9S is synonymous with R93.

, 985, 91, to X9. 9. My husband is j81, kl
Synonymous with ll, X9 and nll+.

General formula (X) In the formula, Zl. 1 represents an atomic group necessary to form a heterocycle. Examples of the heterocycle include those mentioned regarding Z and Z8□, and other specific examples thereof include thiazolidine, thiazoline, benzothiazoline, naphthothiapurine, selenazolidine, selenazoline, benzoselenazoline, naphthoselenazoline, benzoxazoline, and naphthoxazoline. , dihydropyridine, dihydroquinoline, benzimidacillin, naphthymidacillin, etc.

Q. 1 is synonymous with Qqr. R1゜1 is R□ or R11! and Rloz are synonymous with R9, respectively.

j io+ represents 2 or 3; R1° has the same meaning as R94, and R1° and another R103 may be linked to form a hydrocarbon ring or a heterocycle. jl. , is synonymous with j.

In the general formula (■), the heterocyclic nucleus of Z and/or zmt is particularly a naphthothiazole nucleus, a naphthoselenazole nucleus, a naphthoxazole nucleus, a naphthoimidazole nucleus, 4
- enhancing dyes with a quinoline core are preferred, general formula (IX
) in 291 and/or z9+ also general formula (X)
The same applies to

Furthermore, aggravating dyes in which the methine chain forms a hydrocarbon ring or a heterocycle are preferred.

Since infrared sensitization uses sensitization using the M band of an enhancing dye, the spectral sensitivity distribution is generally broader than that using sensitization using the J band. For this reason, it is preferable to correct the spectral sensitivity distribution by providing a colored layer containing a dye in the colloid layer closer to the photosensitive surface than a predetermined photosensitive layer. This colored layer is effective in preventing color mixing due to its filter effect.

As the sensitizing dye for red sensitivity or infrared sensitization, compounds having a reduction potential of -1.00 (VvsSCE) or less than that are particularly preferred, and in particular compounds with a reduction potential of -1.
, 10 or less are preferred. Aggravating dyes having this property are advantageous in increasing sensitivity, particularly in stabilizing sensitivity and stabilizing latent images.

The reduction potential can be measured using phase-discriminative second-harmonic AC polarography. A mercury dropping electrode is used as the working electrode, a saturated calomel electrode is used as the reference electrode, and platinum is used as the counter electrode.

In addition, reduction potential can be measured by phase-discriminating second-harmonic AC portammetry using platinum as a working electrode.
of Imaging Science” (Journal
of Imaging 5science), Vol. 30, pp. 27-35 (1986).

Specific examples of sensitizing dyes of general formulas [■], (IXI and [X]) are shown below.

(D 3) (D-4) (D-5) (D-6) (D 7) (D-8) ut, +13 (D 9) (D-10) (D-11) (D-12) (D-13) (D-14) Shisut'I5 (D-15) (D 16) (D-17) (D-28) (D-29) (D-30) (D 31) (D-32) (D-44) (D-45) C, H5 (D-46) (D-47) C, H5 zns C1 (zcOJ (D-55) (D-56) (D-57) (CHHz)tOH lh (D-58) (D-59) (D-60) CHtCOzll (D 68) (D-69) C11゜ (D-78) (D-79) (D 80) (D-81) C2I+.

(D-87) (D-88) e le (D-95) (D 96) Engineering θ CH□C1+ CI□ (D-97) 5HII C,H.

e (D-98) Iθ (D-99) Iθ (D 100) zHs (L; Lit), su, c' (D-101) t (D-102) t C, H5 (D-107) (D-108) (D-109) (D-110) (D-111) (D-112) (D 113) CM.

(D 115) (D-116) (D-118) (D-119) zHs C! (CHz)20COCH3 2■5 t Iθ t The aggravating dye used in the present invention is 5 per mole of halogenated vA.
X10-' mol to 5XlO-' mol, preferably I
It is contained in the silver halide photographic emulsion in a ratio of X 10-' mol to 1X10-3 mol, particularly preferably 2X10-' mol to 5X10-' mol.

The enhancing dye used in the present invention can be directly dispersed into the emulsion. Also, are these appropriate? Dissolved in a vehicle, such as evaporative methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent of these, ? It can also be added to the emulsion in the form of a liquid. Ultrasonic waves can also be used for dissolution. In addition, the method of adding this infrared sensitizing dye is as described in U.S. Pat. A method of adding this dispersion to an emulsion is as described in Japanese Patent Publication No. 46-24185, etc., in which the water-insoluble dye is dispersed in a water-soluble solvent without dissolving it, and this dispersion is added to the emulsion. Method, U.S. Pat. No. 3,822
, a method of dissolving a dye in a surfactant and adding the solution to an emulsion, as described in JP-A-51-135.
A method of dissolving a red-shifting compound using a red-shifting compound and adding the solution into an emulsion as described in Japanese Patent Publication No. 74624, and a method of dissolving a dye in substantially water-free acid as described in JP-A-50-80826. A method is used in which the solution is added to the emulsion. In addition, U.S. Patent No. 2,912,343, U.S. Pat. No. 3,342,605,
Methods described in Japanese Patent No. 2,996°287 and Japanese Patent No. 3,429,835 can also be used. The infrared sensitizing dyes described above may also be uniformly dispersed in the silver halide emulsion before being coated on a suitable support. It is also preferable to add it before chemical sensitization or in the latter half of silver halide grain formation.

In the red to infrared sensitization in the present invention, the general formula [χ■] (Xlla
), (XIIb), (Xllc) is useful.

The supersensitizer represented by the general formula (XI) is a compound represented by the general formula (Ia), Bb), (re), or a heterogeneous compound represented by the general formula (V), (Vl), [■]. It can be used in combination with a ring mercapto compound to specifically increase its supersensitizing effect.

General formula (XI) In the formula, A and I represent divalent aromatic residues.

R111% Rr+z, RII3 and R114 are each a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group,
It represents an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an arylthio group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an aryl group, or a mercapto group, and these groups may be substituted.

However, at least one of A111, RIII, R1,2, R113 and R114 has a sulfo group. Xl□ and Y, 1 are respectively -CH= -N
=, and even if X Ill and Ylll are not used, one of them represents -N=.

More specifically, in general formula (XI), -A and 1- represent divalent aromatic residues, and these are -501M groups [however, M
represents a hydrogen atom or a cation (eg, sodium, potassium, etc.) that confers water solubility.

-A, 1- is, for example, the following -A I + ! -or-
Those selected from A, , - are useful. However, R11l
, R112R113 or R04 does not contain a -305M+++ group, -A, , - is selected from the group -A, t.

−A1+t　　　’ Such.

Here, M represents a hydrogen atom or a cation that provides water solubility.

A I+ z R811, R1+! , RI I 3 and R814 are each a hydrogen atom, a hydroxyl group, an alkyl group (the number of carbon atoms is preferably 1 to 8. For example, a methyl group, an ethyl group,
n-propyl group, n-butyl group, etc.), alkoxy group (
The number of carbon atoms is preferably 1 to 8. For example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), aryloxy group (for example, phenoxy group, naphthoxy group, 0
-tolyloxy group, p-sulfophenoxy group, etc.), halogen atoms (e.g., chlorine atom, bromine atom, etc.), heterocyclic nuclei (e.g., morpholinyl group, piperidyl group, etc.),
Alkylthio groups (e.g. methylthio group, ethylthio group, etc.), heterocyclylthio groups (e.g. benzothiazolylthio group, benzimidazolylthio group, phenyltetrazolylthio group, etc.), arylthio groups (e.g. phenylthio group, tolylthio group), amino group, alkyl Amino group or substituted alkylamino group (e.g. methylamino group,
ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, di(β
-hydroxyethyl) amino group, β-sulfoethylamino group), arylamino group, or substituted arylamino group (e.g. anilino group, 〇-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, 0-toluidino group, m- Toluidino group, P-toluidino group, 0-carboxyanilino group, m-carboxyanilino group, p-carboxyanilino group, 0-chloroanilino group, mchloroanilino group, P-chloroanilino group, p-aminoanilino group, 0- Anisidino group, m-anisidino group, p-anisidino group, O-acetaminoanilino group, hydroxyanilino group, disulfophenylamino group, naphthylamino group,
sulfonaphthylamino group, etc.), heterocyclylamino group (e.g., 2-benzothiazolylamino group, 2-pyridyl-amino group, etc.), substituted or unsubstituted aralkylamino group (e.g., benzylamino group, 0-anisylamino group, m -anisyl amino group, p-anisyl amino group, etc.)
, an aryl group (such as a phenyl group), or a mercapto group.

R111, R111% R113 and RI+4 may be the same or different from each other. -A I I +- is selected from the group of -A1°, R111, RII□
, R1,1, and R114, one of which is a sulfo group (which may be a free acid group or may form a salt)
It is necessary to have the following. X1ll and Yll+
represents -CH- or -N=, preferably X111
10H=, Yll+ is -N=, and the later ones are used.

Next, specific examples of compounds included in general formula (XI) used in the present invention will be given. However, the present invention is not limited only to these compounds.

(XI-1) 4.4'-bis[2,6-di(2-naphthoxy)pyrimidin-4-ylaminocostilbene-2,21-disulfonic acid disodium salt 4.4'-bis[2,6 -di(2-naphthotylamino)pyrimidin-4-ylaminocostilhen-2,2'-disulfonic acid disodium salt 4,4'-bis(2,6-dianilinopyrimidin-4-ylamino)stilbene- 2,2'-disulfonic acid disodium salt 4.4'-bis(2-(2-naphthylamino)-6-anilinobyrimidin-4-ylamino]stilbene-2,2'-disulfonic acid disodium salt 4. 4'-bis(2,6-diphenoxypyrimidin-4-ylamino)stilbene-2,2'-disulfonic acid triethylammonium salt 3) 5) (XI-2) (XI-4) (XI-6) 4. 4'-bia, (2,6-di(benzimidazolyl-2-thio)pyrimidin-4-ylaminocostilbene-2゜2'-disulfonic acid disodium salt 4,4'-bis[4,6-di( Benzothiazolyl-2-thio)pyrimidine 2-ylaminocostilben-2,2'-disulfonic acid disodium salt 4.4'-bis[4,6-di(benzothiazolyl-2-amino)pyrimidin-2-ylaminoco Stilbene-2゜2'-disulfonic acid disodium salt 4,4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt (χl-10) 4,4'-bis(4,6-diphenoxypyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (XI-7) (XI-8) (Xr-9 ) (XI-11) (ni-12) 13) (XI-14) (xl-15) 4.4'-bis(4,6-cyphenylthiopyrimidin-2-ylamino)stilbene-2,2 '-Disulfonic acid disodium salt 4.4'-bis(4,6-dimethylcabutovirimidin-2-ylamino)biphenyl-2,2'-disulfonic acid disodium salt 4.4'-bis(4,6 -dianilino-triazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt 4.4'-bis(4-anilino-6-hydroxy-triazin-2-ylamino)stilbene-2,2'-disulfonic acid Disodium salt 4.4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino]bibenzyl-2,2'-disulfonic acid disodium salt (XI-16) (Ni-17 ) (XI-18) (XI-19) (XI-20) 4.4'-bis(4,6-dianilinopyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt 4.4 '-Bis[4-chloro-6-(2-naphthyloxy)pyrimidin-2-ylamino)biphenyl-2,2'-disulfonic acid disodium salt 4.4'-Bis[4,6-di(1-phenyltetra) Zolyl-5thio)pyrimidin-2-ylaminocostilbene 2.2'-disulfonic acid disodium salt 4.4'-bis[4,6-di(benzimidazolyl-2-thio)pyrimidin-2-ylaminocostilbene Stilbene-2゜2'-disulfonic acid disodium salt 4.4'-bis(4-naphthylamino-6-anisotutriazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt Specific examples thereof Among (XI -1) to (χI-6)
are preferable, especially (XI-1), (XI-2), (XI
-4), (XI-5), (XI-9), (XI-15'
), (χl-20) are preferred.

The compound represented by the general formula [x1] is used in an amount of 0.01 to 5 g per mole of silver halide, and the weight ratio to the sensitizing dye is 1/1 to 1/100, preferably 1/1.
There are advantageous usage amounts in the range 2-1150.

Furthermore, for red sensitization or infrared sensitization according to the present invention, the following general formulas (XIIa) and (Xllb) are used as supersensitizers.
.

A condensate of 2 to 10 condensed units of substituted or unsubstituted polyhydroxybenzene and formaldehyde, represented by (XIIc), is useful. It also has the effect of preventing the latent image from deteriorating over time and also preventing the gradation from decreasing.

General formula (Xlla) OR General formula (Xllb) SOzR■4 General formula (XIIc) During the ceremony, l1ls R11t2 are each OH.

0M OR,,,, N.H.

HR (R+z4)t -NHNH.

or -NHNHR represents.

However, R114 represents an alkyl group (having 1 to 8 carbon atoms), an allyl group, or an aralkyl group.

M1□ represents an alkali metal or an alkaline earth metal.

R1□3 represents OH or a halogen atom.

n l! l, n1□2 represent l, 2 or 3, respectively.

Next, specific examples of substituted or unsubstituted polyhydroxybenzene as a condensation component of the aldehyde condensate used in the present invention will be shown, but the invention is not limited thereto.

□NI-1) β-resorcinic acid (Xll-2)
T-resorcinic acid (XII-3) 4-
Hydroxybenzoic acid hydrazide 3.5-Hydroxybenzoic acid hydrazide P-chlorophenol Sodium hydroxybenzenesulfonate p-hydroxybenzoic acid (XII-5) (XII-6) (Xll7) (Xrl-4) (X11-8 > ( Xll-9) (XII-10) (XII-11) (x+■-t2) (X11-13) (XII-14) 0-hydroxybenzoic acid m-hydroxybenzoic acid p-dioxyhensengallic acid p-hydroxybenzoic acid Methyl acid 0-hydroxybenzenesulfonic acid amide N-ethyl-〇-hydroxybenzoic acid amide C0NH (C, R5) (X11-15 ) N-diethyl-〇-hydroxybenzoic acid amide CON (CzHs)z (Xll- 16) 0-Hydroxybenzoic acid-2-methyl hydrazide More specifically, general formulas (I[a), (I[b) and (
Ilc).

When the present invention is applied to a color photosensitive material, the color photosensitive material includes a yellow coupler, a magenta coupler, and a cyan coupler that form yellow, magenta, and cyan colors respectively by coupling with an oxidized product of an aromatic amine color developer. is usually used.

Cyan couplers, magenta couplers and yellow couplers preferably used in the present invention are represented by the following general formulas (C-I), (c-n), (M-1), (M-11) and (Y). It is something.

General formula (c-B H 1 General formula (C-If) 0I ( Z General formula (M-1) 19 General formula (M-11) General formula (Y) General formula (C-1) and (C-■ ), R18,
R12 and R14 represent substituted or unsubstituted aliphatic, aromatic or heterocyclic groups, Hll, P', and R1
6 represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, or an acylamino group, R1, may represent a nonmetallic atomic group forming a nitrogen-containing 5- or 6-membered ring together with R12, Y3 , v2 represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized product of a developing agent. 2 represents O or l.

R+ in general formula (C-n) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert 7'
thyl group, cyclohexyl group, cyclohexylmethyl group,
Examples include phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by the general formula (C-I) or (C-■) are as follows.

-a In formula (C-1), R11 is preferably an aryl group or a heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, In general formula (C-1), which is more preferably an aryl group substituted with a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group, when R13 and R°2 do not form a ring, R12 is preferably substituted or They are unsubstituted alkyl groups and aryl groups, particularly preferably substituted aryloxy-directly substituted alkyl groups, and R13 is preferably a hydrogen atom.

In the general formula ((, II), preferred Ro is a substituted or unsubstituted alkyl group or an alkyl group, particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-■), preferable R' has 2 to 2 carbon atoms.
It is a methyl group having 15 alkyl groups and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In general formula (C-n), R+ is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In general formula (C-n), preferable R1 is a hydrogen atom,
A halogen atom, with chlorine and fluorine atoms being particularly preferred. Preferred Y and yz in general formulas (C-1) and (C-It) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In general formula (M-1), R17 and R1 represent an aryl group, Ro represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y3 represents a hydrogen atom or Represents a leaving group. The substituents allowed for the aryl group (preferably the phenyl group) of R't and R1 are the same as the substituents allowed for the substituent R, and when there are two or more substituents, they are the same. But they can be different. R1 is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, particularly preferably a hydrogen atom. Preferred Y3 is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, such as those described in US Pat. No. 4,351,897 and International Publication W088.
Particularly preferred are the sulfur atom-eliminating types as described in No. 10479'5.

In general formula (Mn), R1,. represents a hydrogen atom or a substituent. Y represents a hydrogen atom or a leaving group, particularly a halogen atom or an arylthio group, Za,
Zb and Zc are methine, substituted methine, -N- or -
It represents NH-, and one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond.

The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. R1,. Or Y.

When forming a dimer or more multimer, Za, zb
Alternatively, when Zc is a substituted methine, this includes the case where the substituted methine forms a dimer or more multimer.

Among the pyrazoloazole couplers represented by the general formula (M-11), imidazo (1,2 -b) pyrazoles are preferred;
Pyrazolo (1
,5-b)(1,2,4)l-riazole is particularly preferred.

In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent Publication No. 226. It is preferred to use pyrazolotriazole couplers having an alkoxy or aryloxy group at the 6-position, such as those described in No. 849 and No. 294,785.

-a In formula (Y), R' and 1 represent a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, and R11□ represents a hydrogen atom, a halogen atom, or an alkoxy group. T is -NHCOR' + 3, -NH5O
t-R'+3, -So□NHR'+z, -COOR'+
3, -5O, NR'R'+4. However, Ro1. and Ro and 4 each represent an alkyl group, an aryl group or an acyl group. Y represents a leaving group, R' and Roll, the substituents for Ro14 are the same as those allowed for R1, and the leaving group Y is preferably either an oxygen atom or a nitrogen atom. The nitrogen atom-eliminating type is particularly preferable.

General formula (C-1), (C-11), (M-1), (M-
Specific examples of couplers represented by n) and (Y) are listed below.

(C-1) 1 (C 2) death! (C-3) 2 (C-4) 0) (C, -5) death! (C-6) C! I! .

death! (C-7) (C 8) C,)l.

(C-9) (C-10) (C 12) H (C-13) (C 14) (C-15) (C-16) C,)! .

(C-17) (C-18) (C-19) 1 death! (C-20) (C-21) (C-22) OCR.

(M-1) 7 death! (M-2) I (M-3) (M-4) (M-6) Shil HI (M-7) (M-8) Shil CH.

(Y-1) (Y-2) (Y-3) υ■ (Y-4) (Y, -5) (Y-6) (Y-7) (Y 8) (Y 9) The above general formula ( Couplers represented by C-1) to (Y) are
The silver halide emulsion layer constituting the photosensitive layer usually contains 0.1 to 1.0 mol per mol of silver halide, preferably 0.
．． It is contained in an amount of 1 to 0.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low-boiling organic solvent may be removed by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

As a dispersion medium for such couplers, the dielectric constant (25°C
) 2 to 20 and a high boiling point organic solvent and/or a water-insoluble polymer compound having a refractive index (25° C.) of 1.5 to 1.7.

As a high boiling point organic solvent, Preferably the following general formula %formula%() A high boiling point organic solvent represented by It will be done.

General formula (A) 1 2 P;0 General formula (B) W, -Coo-111゜ General formula (E) W, -0-W.

(In the formula, 1, 2 and W are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group,
represents an aryl group or a heterocyclic group, W4 is Wls O
represents W+ or S-L, n is an integer from 1 to 5, and when n is 2 or more, the characters may be the same or different, and in the general formula (E), 1 and W2 are condensed. may form a ring).

The high boiling point organic solvent that can be used in the present invention also has a melting point of 100°C or less and a boiling point of 140°C or less, even if it is not the general formula (A) or E).
It can be used as long as it is a compound that is immiscible with water at temperatures above °C and is a good solvent for the coupler. The melting point of the high boiling point organic solvent is preferably 80°C or lower. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C.
C or higher.

For details on these high boiling point organic solvents, please refer to JP-A-62
-Page 137 of the published specification No. 215272, lower right column - 1
It is written in the upper right column of page 44.

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a water-insoluble but organic solvent-soluble polymer (for example, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W088100723 are used, and acrylamide-based polymers are particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Also, (bissalicylaldoximado)nickel complex and (bis-N,N dialkyldithiocarbamado)
Metal complexes such as nickel complexes can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are disclosed in U.S. Patent No. 2,360,290;
No. 2,418,613, No. 2,700.453, No. 2,701.197, No. 2,728.659
No. 2,732,300, No. 2,735,76
No. 5, No. 3,982.944, No. 4.430.4
25, British Patent No. 1,363,921, U.S. Patent No. 2,710.801, U.S. Patent No. 2,816,028, etc. U.S. Patent No. 3,432,30
No. 0, No. 3,573,050, No. 3,574,6
No. 27, No. 3.698゜909, No. 3,764,
No. 337, JP-A-52-152225, etc., and spiroindanes are described in U.S. Pat. No. 4,360,589, p-
Alkoxyphenols are U.S. Patent No. 2,735,76
No. 5, British Patent No. 2,066.975, Japanese Unexamined Patent Publication No. 1983-
No. 10539, Japanese Patent Publication No. 57-1.9765, etc., and hindered phenols are disclosed in U.S. Patent No. 3.700,455.
No., JP-A-52-72224, U.S. Patent No. 4,228,
No. 235 and Japanese Patent Publication No. 52-6623, gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Pat. No. 3,457.079 and U.S. Pat. No. 4, respectively.
', No. 332.886, Japanese Patent Publication No. 56-21144, etc., and hindered amines are disclosed in U.S. Pat.
No. 35, No. 4,268,593, British Patent No. 1.3
No. 26,889, No. 1,354,313, No. 1.
No. 410.846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 1973
No. 8-114036, No. 59-53846, No. 5
No. 9-78344, etc., metal complexes are disclosed in U.S. Patent No. 4,0
50,938, British Patent No. 4.241°155, and British Patent No. 2,027,73H^). The purpose of these compounds can be achieved by co-emulsifying the corresponding color coupler with a coupler that usually has a weight of 5 to 100 and adding it to the photosensitive layer. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314,794, U.S. Pat. No. 3,352.
681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,705,805,
No. 3,707,395), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxidole compounds (e.g., U.S. Pat. No. 3,406,070). , No. 677.672 and No. 4.271,307) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

In addition to the above-mentioned couplers, it is particularly preferable to use the following compounds. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferred compound (F) has a second-order reaction rate constant with P-anisidine (in trioctyl phosphate at 80°C) of 1. Ql/mol ・see ~I
It is a compound that reacts in the range of X10-'42/mol·sec.

Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

When R2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if R2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented.

A more preferable compound (F) can be represented by the following general formula (FM) or (FII).

General formula (Fl) R+ (A)llX General formula (FII) Z-C-Y In the formula, Rls Rt each represents an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or O.

A represents a group that reacts with an aromatic amine developer to form a chemical bond, X represents a group that reacts with an aromatic amine developer and leaves, B represents a hydrogen atom, an aliphatic group, an aromatic group group, heterocyclic group, acyl group, or sulfonyl group,
Y represents a group that promotes addition of an aromatic amine developing agent to the compound of general formula (Fn). Here, R1 and X, Y and R2, or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (Fl) and (FII), see JP-A-63-158545 and JP-A-622.
83338, European Patent Publication No. 298321, European Patent Publication No. 277
Those described in specifications such as No. 589 are preferred.

On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound is the following general formula (CI ).

General formula (Gl) -Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. In the compound represented by the general formula (CI), Z has Pearson's nucleophilicity 'C11ff value (R, G, Pearson, et al., J.
Am.

Chem, Sac, 90.319 (1968)
) is preferably 5 or more, or a group derived therefrom.

For specific examples of compounds represented by the general formula (Gl), see European Patent Publication No. 255722, Japanese Patent Application Laid-Open No. 1430-1980
No. 48, No. 62-229145, patent application No. 63-136
No. 724, Japanese Patent Application Publication No. 1-57259, European Patent Publication No. 29
Those described in No. 8321, No. 277589, etc. are preferred.

Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 277589.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with an oryl group (such as those described in US Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in US Pat. No. 3,314,794, US Pat. 352.681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat.
Nos. 705,805 and 3,707,375), butadiene compounds (e.g., U.S. Pat. No. 4,045)
, 229) or benzoxidole compounds (eg, those described in US Pat. No. 3,700,455). An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used.

These ultraviolet absorbers may be mordanted in specific layers.

In the full-color recording material of the present invention, colloidal silver and dyes are used to prevent irradiation and haley silane, particularly to separate the spectral sensitivity distribution of each photosensitive layer and to ensure safety against safelight in the visible wavelength range. Such dyes include oxonol dyes, hemioxonol dyes,
Included are styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

Especially for red rice or infrared dyes, for example, JP-A-62-32
No. 50, No. 62-181381, No. 62-12345
4, No. 63-197947, etc., as well as dyes for back layers and JP-A-62-39682, JP-A-62-123192, JP-A-62-158779, JP-A-62-174741, etc. The described dyes or the same dyes can be used by introducing water-soluble groups which can be washed off during processing. The infrared dye of the present invention may be a colorless dye that does not substantially absorb light in the visible wavelength range.

When the infrared dye of the present invention is mixed into a silver halide emulsion that has been spectrally sensitized in the red rice or infrared wavelength range, it causes desensitization, fogging, and in some cases, the dye itself is adsorbed to the silver halide grains and becomes weak. There are problems such as broad spectral sensitization. Preferably, the dye is substantially contained only in colloid layers other than the photosensitive layer. For this purpose, the dye is preferably contained in a predetermined colored layer in a diffusion-resistant state. The first step is to add a ballast group to the dye to make it resistant to diffusion. However, it tends to cause residual color and processing stains.

Second, the anionic dye of the present invention is mordanted with a polymer or polymer latex that provides cationic sites. The third method is to use a dye that is insoluble in water with a pH of 7 or less and is decolored and eluted during the treatment process in fine particle dispersion.

For this purpose, it is used by dissolving it in a low boiling point organic solvent or solubilizing it in a surfactant and dispersing it in an aqueous solution of a hydrophilic protective colloid such as gelatin. Preferably, the solid dye is kneaded with an aqueous surfactant solution and mechanically made into fine particles using a mill, which is then dispersed in an aqueous solution of a hydrophilic colloid such as gelatin.

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

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in "The Macromolecular Chemistry of Gelatin" by Arthur Vuis (Academic Press, published in 1964).

The color photosensitive material of the present invention includes, on a support, photosensitive layer 1 (YL) containing a yellow coupler, photosensitive layer (ML) containing a magenta coupler, photosensitive layer (CL) containing a cyan coupler, and a protective layer. (PL), intermediate ji (I
I.) If necessary, a colored layer, especially an antihalation layer (AH), which can be decolorized during development processing, is provided. YL, M.L.
and CL have spectral sensitivities suitable for at least three types of light beams each having a different dominant wavelength. YL, ML and CL
The main sensitivity wavelength of each is 30nm or more, preferably 50nm.
m to 120 nm, and the main sensitivity wavelength of one photosensitive layer is at least 0.0 nm to 120 nm apart from the other photosensitive layers. 8
Log, E (light amount), preferably 1. There is a sensitivity difference of 0 or more. At least two of each photosensitive layer is 670 nm
It is preferable that the layer be sensitive to wavelengths longer than 750 nm, and more preferably, that at least one layer be sensitive to wavelengths longer than 750 nm.

For example, an arbitrary structure of the photosensitive layer can be adopted as shown in the following table. In the table, R means red sensitized, and IR-
1 and IR-2 indicate that they are spectrally sensitized to different infrared wavelength regions.

In the present invention, a photosensitive layer having spectral sensitivity in a wavelength region longer than 670 nm is imagewise exposed to a laser beam. Therefore, the spectral sensitivity distribution should be in the wavelength range of 25 nm, preferably ±15 nm of the main sensitivity wavelength. the other 67
The spectral sensitivity of the present invention tends to be relatively broad in wavelengths longer than 0 nm, particularly in the infrared wavelength region. Therefore, the spectral sensitivity distribution of the photosensitive layer may be modified using a dye, preferably by fixing and containing the dye in a specific layer. For this purpose, the dye is contained in the colloid layer in a diffusion-resistant state and is used so that it can be decolored during the development process.

The first is to use a solid fine particle dispersion of a dye that is substantially insoluble in water at pH 7 and soluble in water at pH 9 or higher. The second is to use acid dyes with polymers or polymer latexes that provide cation sites. In the first and second methods, JP-A-63-
No. 197,947, dyes represented by the general formulas (Vl) and (■) are useful. In particular, dyes with carboxyl groups are useful for the first method.

The luminous flux output mechanism used in the present invention will be explained.

Specific examples of lasers that can be used in the present invention include In+-x Ga, P (~700 nm
), GaAs+-, Px (610-900 nm)
, Ga+-xAZxAs (690-900 nm)
, rnGaAsP (1100-1670 nm), MG
Examples include semiconductor lasers using materials such as aAsSb (1250 to 1400 nm). In addition to the irradiation of light to the color photosensitive material in the present invention with the above-mentioned semiconductor laser, Nb:YAG crystal is irradiated with GaAs, P (1-0
YAG laser (106
4 nm), preferably 670.680
．． 750.780.810.830.8 B On'm
It is preferable to select and use one of the following semiconductor laser beams.

Further, in the present invention, a second harmonic generating element (SHG element) and the above laser can be used in combination.

(SHC, element) is a device that converts the wavelength of laser light into half by applying a nonlinear optical effect. For example, it uses CD "A and KD" P as a nonlinear optical crystal. (Laser Handbook, Laser Science Kinkan, published December 15, 1981, pp. 122-1
(See page 39). In addition, we added Li” to H in the LiNbO3 crystal.
A LiNb0* optical waveguide element in which an ion-exchanged optical waveguide is formed can be used (JJ[KEI EL
ECTRONIC31986, 7, 14 (no, 399
), pp. 89-90).

The output device described in Japanese Patent Application No. 63-226552 can be used in the present invention.

The color photographic material of the present invention is preferably subjected to color development, bleach-fixing, and water washing treatment (or stabilization treatment). Bleaching and fixing may be carried out separately instead of in one bath as described above.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-I N,N-diethyl-p-phenylenediamine-2 -9 -10 2-amino-5-diethylaminotriene 2-amino-5-(N-ethyl-N-laurylamino)
Toluene 4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline 2-methyl-4-[N-ethyl-N (β-hydroxyethyl)aminocoaniline 4-amino-3-methyl-N- Ethyl-N-(β-(methanesulfonamido)ethyl)-aniline N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide N,N-dimethyl-p-phenylenediamine 4-amino-3-methyl- N-ethyl N-methoxyethylaniline 4-amino-3-methyl-N-ethyl N-β-ethoxyethylaniline D-114-amino-3-methyl-N-ethyl N-β-
Butoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl N-[β-(methanesulfonamido)ethyltoaniline (exemplified compound D-6) is particularly preferred.

Further, salts of these p-phenylenediamine derivatives such as sulfates, hydrochlorides, sulfites, and p-)luenesulfonates may be used. The amount of the aromatic primary amine developing agent used is 1! Preferably about 0.1g to about 20g
, more preferably at a concentration of about 0.5 g to about Log.

In carrying out the present invention, it is preferable to use a developing solution that does not substantially contain benzyl alcohol, where "substantially free" means preferably 2ttdl/I
t or less, more preferably 0.5ad! /f or less, and most preferably no benzyl alcohol at all.

It is more preferable that the developer used in the present invention does not substantially contain sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency.

Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" preferably means a sulfite ion concentration of 3.0 x 10 -' mol/2 or less, and most preferably no sulfite ion at all.

However, in the present invention, a very small amount of sulfite ion used for oxidation prevention in a processing agent kit in which the developing agent is concentrated before being mixed into a solution for use is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is believed that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.

Here, "not containing substantially hydroxylamine" preferably means 5. A hydroxylamine concentration of OX 10-3 mole/2 or less, and most preferably no hydroxylamine at all.

It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or sulfite ion.

The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. That is, organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, Especially α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused cyclic amines, etc. It is an effective organic preservative. These are JP-A-63
-4235, 63-30845, 63-216
No. 47, No. 63-44655, No. 63-53551, No. 63-43140, No. 63-56654, No. 6
No. 3-58346, No. 63-43138, No. 63-1
No. 46041, No. 63-44657, No. 63-446
No. 56, U.S. Patent No. 3,615.503, U.S. Patent No. 2.49
No. 4,903, Japanese Patent Publication No. 52-143020, Special Publication No. 4
No. 8-30496 and the like.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, 3.
If necessary, aromatic polyhydroxy compounds described in No. 746.544 and the like may be contained. In particular, alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine,
Preferably, a hydrazine derivative or an aromatic polyhydroxy compound is added.

Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred.
No. 5270, No. 63-9713, No. 639714,
It is described in No. 63-11300.

Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developer and further improving the stability during continuous processing.

Examples of the above-mentioned amines include cyclic amines as described in JP-A-63-239447 and JP-A-63-128.
Amines such as those described in No. 340 and other patent applications filed in 1983
Examples include amines such as those described in No. 3-9713 and No. 63-11300.

In the present invention, 3.5% of chloride ions are added to the color developer.
Xl0-"~1.5 XIO"'mol/I! , is preferably contained. Particularly preferably, 4X10-'' to lX
10-'mol/i. Chlorine ion concentration is 1.5X1
If the amount is more than 0-' to 10-1 mol/l, it has the disadvantage of delaying development, which is not preferable in achieving the object of the present invention of rapid development and high maximum density. Also, 3.5xi
If the amount is less than 72 o-'' moles, it is not preferable in terms of preventing capri.

In the present invention, 3.0% bromine ion is added to the color developer.
X10-'mol/l-1,0X10-''
'mol/l. If the bromide ion concentration is more than 1X10-' mol/l, the development will be delayed and the maximum density and sensitivity will be reduced, and if it is less than 3.0X10-' mol/1, capri cannot be sufficiently prevented.

Here, the chlorine ions and bromine ions may be added directly to the developer, or may be eluted from the photosensitive material into the developer during the development process.

When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. are sodium chloride and potassium chloride.

Alternatively, it may be supplied from an optical brightener added to the developer.

As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among these, preferred are potassium bromide and sodium bromide.

When extracted from a light-sensitive material during development processing, both chloride ions and bromine ions may be supplied from the emulsion or from a source other than the emulsion.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3゜4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-
Methyl-1°3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. Especially carbonates, phosphates, tetraborates, hydroxybenzoates are soluble, pl+ 9
．． These buffers have the advantage of having excellent buffering ability in the high pH range of 0 or higher, having no adverse effects on photographic performance (fogging, etc.) even when added to color developers, and being inexpensive. is particularly preferred.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium O-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
etc. can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/!
It is preferable that it is more than 0.1 mol/2 to 0.1 mol/2.
Particularly preferred is 4 mol/2.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediaminetetraacetic acid, N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N',N'-
Tetramethylene sulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2
, 4-tricarboxylic acid, 1-hydroxyethylidene-1
, 1-diphosphonic acid, N.

Examples include N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.

Two or more of these chelating agents may be used in combination, if necessary.

The amount of these chelating agents added may be sufficient as long as the amount is sufficient to sequester metal ions in the color developer. For example, 11
It is about 0.1g-1og per serving.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 3B-7826, No. 44-12
No. 380, No. 45-9019 and U.S. Patent No. 3,81
3,247, p-phinidine diamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-Sho 50
-137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 56-156826 and Japanese Patent Publication No. 52-43429, etc., U.S. Patent No. 2゜494
．． No. 903, No. 3.128.182, No. 4,230,
No. 796, No. 3.253.919, Special Publication No. 41-11
431, U.S. Patent No. 2.482.546, U.S. Pat.
96,926 and 3,582,346, etc.; Japanese Patent Publication No. 37-16088, 42-
25201, U.S. Patent No. 3.128.183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3,532゜501, etc., and other l-phenyl-3-pyrazolidones. etc., imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5methylbenzotriazole, 5-nitrohencitriazole, 5-chloro-benzotriazole, 2=thiazolyl-benzimidazole, 2 -Thiazolylmethyl-
Representative examples include nitrogen-containing heterocyclic compounds such as benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains an optical brightener. As an optical brightener, 4.4'
-Diamino-2,2'-disulfostylhene compounds are preferred. The amount added is 0 to 5g/2, preferably O, 1g to
It is 4/l.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color phenomenon liquid that can be applied to the present invention is 20~
50°C, preferably 30 to 40''C. Processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The replenishment amount is preferably small, but it is 20 to 20 seconds per rrr of photosensitive material.
600 mf is appropriate, preferably 50 to 300 mf
It is l. More preferably 60 m2 to 200 mβ, most preferably 60 m1 to 150 mβ.

Next, a desilvering process that can be applied to the present invention will be explained.

The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step.

The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below.

As the bleaching agent used in the bleach or bleach-fix solution, any bleaching agent can be used, but especially iron (
I[I] organic complex salts (e.g. ethylenediaminetetraacetic acid,
Preferred are aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, etc. .

Among these, organic complex salts of iron(1) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (I[[) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1.3- Examples include diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, and the like. These compounds may be sodium, potassium, thium or ammonium salts. Among these compounds, iron (I [[) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1.3=diaminopropanetetraacetic acid, and methyliminodiacetic acid] are preferred because they have a high bleaching edge.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid.
It may be used in excess to form an iron ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/2, preferably 0.05 to 0.50 mol/2.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, US Pat. No. 3,893,858, German Pat.
Publication No. 630, Research Disclosure No. 1712
No. 9 (July 1978 issue), compounds having a mercapto group or disulfide bond, and Japanese Patent Publication No. 45-85
No. 06, JP-A-52-20832, JP-A No. 53-3273
Thiourea compounds described in No. 5 and US Pat. No. 3,706,561, or halides such as iodine and bromide ions are preferred because they have excellent bleaching properties.

In addition, the bleaching solution or bleach-fixing solution that can be applied to the present invention contains bromides (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg, potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. If necessary, one or more inorganic acids having a pH 1l binding capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Organic acids and their alkali metal or ammonium salts or corrosion inhibitors such as 77monium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution is a known fixing agent, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid. , 3,6-sithia-1,8-octanediol, and other water-soluble silver halide solubilizers such as thioureas, and these can be used alone or in combination of two or more.

It is also possible to use a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per 11 is
Preferably 0.3 to 2 mol, more preferably 0.5 to 1 mol
．． It is in the range of 0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9.

Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives.
, metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.).

These compounds are approximately 0.02 to 0.02 in terms of sulfite ion.
The content is preferably 0.05 mol/l, more preferably 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. may be added as necessary.

After desilvering treatment such as fixing or bleach-fixing, washing with water and/or stabilization treatment is generally performed.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and other conditions of the species. Can be set to . Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers.
nalof the 5ociety of Moti
on Picture and Television
Engineers) Volume 64, p. 248-253
(May 1955 issue).

Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, to 0.51 to 11 or less per 1 nf of photosensitive material, and the effect of the present invention is remarkable, but the amount of water stagnation in the tank can be reduced. As the time increases, problems arise such as bacteria propagating and resulting floating matter adhering to the photosensitive material. As a solution to such problems, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Also, JP-A-57-8
Isothiazolone compounds and thiabendazoles described in No. 542, chlorine-based disinfectants such as chlorinated sodium isotheaterate described in No. 61-120145, JP-A No. 61-1201-
Benzotriazole, copper ion, etc. described in No. 267761, Hiroshi Horiguchi, “Chemistry of antibacterial and antifungal J (1986)
Sankyo Publishing, Hygiene Technology Kinkan "Sterilization of Microorganisms, Disinfection, Anti-Mold Technology J (1982) Japan Society of Industrial Engineers, Japan Antibacterial and Anti-Mold Research Kinkan"
The fungicides described in Dictionary of Antibacterial and Antifungal Agents J (1986) can also be used.

Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound such as formalin, or a film suitable for stabilizing the dye.
Buffers for preparing l+ and ammonium compounds can be mentioned. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the light-sensitive material of the present invention, stabilization is performed without going through a water washing step (if it is carried out directly, it is
No. 8543, No. 58-14834, No. 60-2203
All known methods described in No. 45 and the like can be used.

In addition, it is also a preferred embodiment to use chelating agents such as 1-hydroxyethylidene-1,1 diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

A so-called rinsing solution is also used as a washing solution or stabilizing solution used after desilvering treatment.

The preferred pH of the water washing step or stabilization step is 4 to 10, more preferably 5 to 8. The temperature can be set in various ways depending on the use and characteristics of the photosensitive material, but generally it is between 15 and 45 degrees.
C is preferably 20 to 40°C. Although the time can be set arbitrarily, a shorter time is preferable from the viewpoint of reducing processing time. Preferably it is 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute 30 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.

A specific preferable replenishment amount is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. Or 12 or less, preferably 500 mj per 1M of photosensitive material! It is as follows. Further, replenishment may be performed continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to reduce the amount of waste liquid by using a multi-stage counter-current system to allow the overflow of the wash water to flow into the bleach-fix bath, which is a pre-bath, and to replenish the bleach-fix bath with concentrated liquid.

(Examples) The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

Example 1 32g of lime-treated gelatin was added to 1000m2 of distilled water and after dissolving at 40°C, 3.3g of sodium chloride was added and the temperature was raised to 52°C.

3.2 ml of N,N'-dimethylimidapurine-2-thione (1% aqueous solution) was added to this solution.

Subsequently, a solution in which 32.0 g of silver nitrate was dissolved in 200 mj2 of distilled water and a solution in which 11.0 g of sodium chloride was dissolved in 200 m1 of distilled water were added to and mixed with the above solution over 14 minutes while maintaining the temperature at 52°C. Furthermore, a solution of 128.0 g of silver nitrate dissolved in 560 mff1 of distilled water and 4 ml of sodium chloride were added.
4.0 g, potassium hexachloroiridate (IV) O, 1 mg dissolved in 560 mj2 of distilled water,
The mixture was added and mixed for 20 minutes while maintaining the temperature at 2°C. 52
After being kept at °C for 15 minutes, the temperature was lowered to 40 °C and desalted and washed with water. Furthermore, lime-treated gelatin is added to emulsion (
A) was obtained. The resulting emulsion had an average grain size of 0°45μ.
, containing cubic silver chloride grains with a coefficient of variation of grain size distribution of 0.08.

After adjusting the pH and PAg of this emulsion, triethylthiourea was added to optimally chemically sensitize each emulsion.
-1) Emulsion was obtained.

Separately, a fine grain silver bromide emulsion (a-1) having an average grain size of 0.05 .mu.m was prepared.

After adding emulsion (a-1) in an amount equivalent to 2 mol% of silver halide to emulsion (A), triethylthiourea is added to prepare an optimally chemically sensitized emulsion. -2).

These two types of silver halide emulsions each contained the following compound as a stabilizer at a rate of 5.0×1 per mole of silver halide.
0-'mol was added.

The halogen composition and its distribution of the two types of silver halide emulsions obtained were investigated by X-ray diffraction.

As a result, emulsion (A-1) exhibited a single diffraction peak of 100% silver chloride. On the other hand, for emulsion (A-2), in addition to the main peak of 100% silver chloride, 70% silver chloride (
silver bromide (30%), silver chloride 60% (silver bromide 4
A broad diffraction pattern with a tail around 0%) could be observed.

Next, an emulsified dispersion of color couplers and the like was prepared, combined with each silver halide emulsion, and coated on a paper support laminated on both sides with polyethylene to produce a multilayer color light-sensitive material having the layer structure shown below.

(Layer structure) The composition of each layer is shown below. The numbers represent the coating IJk (g/i; ml/rtf for solvents). The silver halide emulsion represents the coated amount in terms of silver.

Printed polyethylene laminate paper [1-yellow silver halide emulsion (A-2) containing white pigment (TiOz) and bluish dye (ulmarine) in the polyethylene of the emulsion layer 0.30 spectral sensitizing dye (Dye-1) Yellow coupler (Y-1) 0.82 Color image stabilizer (Cpd-7) 0.09 Solvent (
Solv5) 0.28 Gelatin 1.752
゛Gelatin filter dye (Dye-10) Color mixing prevention agent
(Cpd-4) Solvent (Solv2) (Solv5) 3 Magenta silver halide emulsion (A-2) Spectral enhancing dye (Dye-2) 0° magenta coupler (M-1) Magenta coupler (M-2) Color image stability Agent (Cpd-1) (Cpd-2) (Cpd-8) (Cpd-9) Solvent (Solvl) (Solv2) Gelatin Rose gelatin Filter dye Ultraviolet absorber Color mixing inhibitor Solvent (Dye-11) (UV- 1) (Cpd-4) (Solv3) Cyanide silver halide emulsion (A-2) Spectral enhancing dye (Dye-3) Cyan coupler color image stabilizer solvent (C-1) (Cpd-5) (Cpd-6) (Cpd-7) (Solv4) Gelatin plate gelatin UV absorber (UV-1) Color mixing inhibitor (Cpd-4) Solvent (Solv3) Seventh, acrylic modified copolymer of C-11 and gelatin polyvinyl alcohol (modified As the gelatin hardening agent for each layer of liquid paraffin, 14.0 mg of 1oxy-3.5-dichloro-5-)riazine sodium salt was used per 1 g of gelatin.

Yellow coupler (Y l) Cyan coupler (C-1) R = Ct Hs, C4H9 and '2:4:4 mixture (weight ratio) Magenta coupler (M ■) c, o + t (t) Magenta coupler (M-2) Color image stabilizer (Cpd-1) Color image stabilizer (Cpd-2) Color mixture inhibitor (Cpd-4) Color image stabilizer (Cpd 5) 2:4:4 mixture (weight ratio) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-7) →CH, -CH)-t-CONHC,HqQ) (molecular weight 80,000) Color image stabilizer (Cpd-8) Color image stabilizer ( Cpd-9) Solvent (Solv-1) aHs 0 = P +oCHt CHCa H9)! (Solv-2) )8 medium (Solv 3) COOC,H (CHt)g COOCIIHI7? 8 medium (Solv-4) Solvent (Solv-5) ) 8 medium (Solv 6) Ultraviolet absorber (UV-1) 4:'2:4 mixture (weight ratio) (Dye-10) Coating Il! 10mg per pot (for filter and irradiation prevention) (Dye-11) (C11□)nsOt.

(CHz) 0 mg per coating film M on asO3 (Dye-1) t 1.1 x 10' mol per mol of silver halide/ 9.3 x IO mo 1 (Dye-2) CJs e 1 per mol of silver halide i .4X10 101 (Dye-3) 0.7X10-'mol (Dye-3) per mol of silver halide
When using Dye-2) and (Dye-3), the following compound (Xl-1) was added at 2.6x per mole of silver halide.
10-3 mol was added.

(xr-1) Regarding this sample, the 5th layer (cyan coloring N), the 1st layer
As shown in the table, various compounds corresponding to general formulas (Ia), (Ib), and Ic) were optionally added to prepare samples 1 to 16 in which the moisture content of the materials was changed.

These samples were incubated cold (5 °C) and at 35 °C for 2
The sample was stored for a week, and the sensitivity and fog change of the cyan coloring layer were measured to evaluate the storage stability. Changes in sensitivity and yellowing are respectively 35℃ 5℃ 35℃ 5℃ 31.0-3
1.0) and (fog − fog ) were used.

35°C 5°C Here, S , , S are 1.0 and 1.0 at 35°C and 5'C, respectively.When the stored product was subjected to gradation exposure, the cyan density was 1.0. O
It means the inverse logarithm of the amount of exposure required to give a high density.

Exposure and processing of these samples is described below.

The results obtained are shown in Table 2.

Exposure device-1) As a laser, a semiconductor laser AZGalnP (oscillation length, approximately 67 (l n+*)), a semiconductor laser GaA
fAs (oscillation length, approximately 780 nm), GaAlAs
(oscillation wavelength, approximately 830 nm) was used. An apparatus was constructed in which the laser beams were sequentially scanned and exposed onto color photographic paper, which was moved in a direction perpendicular to the scanning direction using a rotating polyhedron. The exposure amount was electrically controlled by the exposure time of the semiconductor laser.

The development process is as shown below.

Processing process: 1-degree single-plate color development
Bleach and fix at 35°C for 45 seconds Rinse at 30-35°C for 45 seconds ■ Rinse at 30-35°C for 20 seconds ■ Rinse at 30-35°C for 20 seconds ■ Rinse at 30-35°C for 20 seconds ■ Dry at 30-35°C for 30 seconds Dry at 70-80° C60 seconds (rinse -
■It was a 4-tank countercurrent force type. ) The composition of each treatment liquid is as follows.

Tomori Futou Image Tatsumizu 800
mff ethylenediamine-N,N,N.

N-Tetramethylphosphonic acid 1.5g Triethylenediamine (1,4 diazabicyclo(2,2,2) octane) Sodium chloride Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3 Methyl-4-aminoaniline Sulfate N,N-diethylhydroxylamine fluorescent brightener (UVITEX CK Add water to 1000mff1pH
(25°c)! 0.10 1 water sprinkling 400
mj2 ammonium thiosulfate (70%) 100r
r+j! Sodium sulfite 18
g Ethylenediaminetetraacetic acid iron (I[[) Ammonium Ethylenediaminetetraacetic acid disodium ammonium bromide Add glacial acetic acid water and pH (25°C) Yulmuk ion exchange water (calcium, less than appm) g 0 g g 1000m1 5.5 Magnesium is as shown in each table 35℃ 5℃ *Δ5=S1.0 ”'1.0 Δfog 35℃ 5℃ = fog −fog From the above results, the structure of the present invention reduces the sensitivity change and fog change due to storage. It can be seen that a small sensitive material can be obtained.

Example 2 In the light-sensitive material of Example 1, the sensitizing dye in the magenta color-forming layer was changed to the following (Dye-4), and the general formulas (Ia) and (Ib) were added to this magenta color-forming layer in the same manner as in Example 1. ) or (Ic) were used, and the water content was further varied. When this sample was evaluated in the same manner as in Example 1, it was found that a magenta layer with excellent preservability can be obtained by the structure of the present invention. The exposure device used here used GaMAs (oscillation wavelength 750 nn+) instead of the 780 nm semiconductor laser of exposure device (1).

Example 3 In the light-sensitive material of Example 1, the sensitizing dyes in the magenta and cyan coloring layers were (Dye-4) and (Dye-4), respectively.
5), and other than that, a sample similar to that of Example 1 was made and evaluated in the same manner. The obtained results were similar to those of Example 1, and it was found that a sensitive material with excellent preservability could be obtained by the structure of the present invention.

The exposure device used here was the 780 nm exposure device (1).
Semiconductor laser: 830 nm semiconductor laser, GaA/As (oscillation wavelength 750 nm) laser,
A Ga+VAs (oscillation wavelength: 810 nm) laser was used instead.

Dye-4 3.5X10-' mo+ was added per mole of silver halide, and (Xl-1) was further used in combination with 2.6X10-3 mo+1 mole Ag.

Dye-5 was added in an amount of 1.7×10 −Smol per 111 moles of halogenide, and (XI=1) was added in an amount of 2.6×10 −′mol 1 mol^g.

Example 4 A similar sample was prepared in Example 1 except that the emulsion in the cyan coloring layer was changed to emulsion A1. Similar results were obtained with these samples.

(Effects of the Invention) According to the present invention, a silver halide color light-sensitive material for infrared exposure and capable of rapid processing with small sensitivity changes and capri changes due to storage can be obtained.

Claims (2)

[Claims] (1) At least three types of halogens having different spectral sensitization wavelength ranges, consisting of a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler. In a silver halide color photographic light-sensitive material having a silver halide light-sensitive layer on a support, at least one of which has a maximum spectral sensitivity at 750 nm or more, a halogenated material contained in at least one light-sensitive layer of the light-sensitive material; The silver emulsion has a silver chloride content of 95 mol% or more and contains at least one compound selected from the group of compounds represented by the following general formulas (Ia), (Ib), (Ic) and (Id). 1. A silver halide color photographic light-sensitive material, which contains a compound, and further has a water content of 3% by weight or more and 10% by weight or less. (2) The silver halide color photographic light-sensitive material according to claim 1, wherein the water content of the light-sensitive material is 8% by weight or less. General formula ( I a) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula ( I b) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula ( I c) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (I d) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z_1_1 represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. Z_1_2 and Z_1_3 represent atoms necessary to complete the aromatic ring. R_1_1 represents a hydrogen atom, an alkyl group, or an alkenyl group. R_1_2 represents a hydrogen atom or a lower alkyl group. R_1_3 represents an alkyl group or an alkenyl group. R_1_5 represents a substituted alkyl group or a substituted alkenyl group. R_1_4 and R_1_6 represent a hydrogen atom, an alkyl group or an aryl group. R_1_7
and R_1_8 may be the same or different, and each represents a hydrogen atom, an alkyl group, an aryl group, a cyano group, a halogen atom, an alkoxycarbonyl group, a carboxy group, an optionally substituted aminocarbonyl group, a formyl group,
Represents an alkylcarbonyl group, an arylcarbonyl group or an aryloxycarbonyl group. X_1_1 and X
_1_2 represents an acid anion. G represents an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom. K^n is an onium ion, an ion of a group IA or group IIA element, and
Represents a cation of valence n selected from the group consisting of metal ions of group IIB, group VIIB, group IVA or group VA. r
represents 1 or 2, and is 1 when the compound forms an inner salt. q represents 1 or 2, M^+^2^
/^q represents a cation with a valence of 2/q.