JPH02248945A - Full color high silver chloride photographic sensitive material and color image forming method using the same - Google Patents

Abstract

PURPOSE:To enhance spectral sensitivity and to enable rapid processing by incorporating color couplers capable of forming dyestuffs different from each other in each emulsion layer and specified dyestuffs in at least 2 of emulsion layer units. CONSTITUTION:Each emulsion layer contains silver halide having an average silver chloride content of >=85 molar % and color couplers capable of forming dyestuffs different from each other by coupling reaction with the oxidation product of a color developing agent, and at least 2 of the emulsion layer units are spectrally sensitized to lights in the infrared regions of electromagnetic spectrum different from each other by the dyestuffs represented by formula I and the like in which Z<12> is S, O, or the like; each of R<11> - R<14> is H, an electron attractor, halogen, or the like; each of G<11> and G<12> is optionally substituted alkyl; G<13> is H; each of G<14> and G<15> is H, lower alkyl, or the like; each of n<11> and n<12> or 0 or 1; n<13> is 2, 3, or 4; Y<11> is a cationic group; and m<11> is 0 or 1. Thus, high spectral sensitivity is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to silver halide color photography, and in particular to infrared color photography, which is suitable for short-time exposure with laser light emitting in the infrared region and capable of rapid development. This invention relates to a silver halide color photographic recording material having at least two silver halide emulsion layers spectrally sensitized in the optical range, the silver halide emulsion layers having different spectral sensitivity distributions. .

(Prior Art) In recent years, information storage and processing technology has been rapidly progressing. Along with this, a wide variety of systems for making hard copies have been developed. For example, by using communication circuits, techniques for making hard copies from software information even in remote locations have become widely used.

Conventionally, methods for obtaining bar data from soft information sources include methods using electric or magnetic signals, methods using non-photosensitive recording materials such as inkjet methods, and methods using photosensitive recording materials such as silver halide photosensitive materials and electrophotographic materials. There are means using materials.

The latter method is a means of recording using an optical system that emits light controlled by image information, and is advantageous in obtaining high image quality because the optical system itself has excellent resolution, and is capable of not only complementary value recording but also multi-gradation recording. It is. In particular, compared to systems using electrophotographic materials, silver halide photosensitive materials form images chemically, so higher image quality can be obtained and a larger amount of information can be recorded. On the other hand, since this method involves wet development processing, it is inferior to methods using electrophotographic recording materials in terms of processing time, and has not been widely used in fields where high image quality is not required. However, in recent years, with the advancement of compact, quick and easy developing methods, extremely high-quality printed photographs can now be supplied relatively easily and inexpensively. From software information sources, there has been a growing demand for inexpensive and easy hard copying of printed photographs with high image quality.

An optical system that controls light emission based on image information with a large amount of information needs to be of a high-speed scanning type, resulting in ultra-short exposure using laser light.

5.11. The 4th Non-Impact by Ba5k and others
On pages 245 to 247 of the Proceedings of the Printing (NIP) International Conference 11 (SPSE), there is a report on the main body conditions of a semiconductor laser output control mechanism for a continuous scanning printer.

In order to quickly obtain a full-color image using a silver halide photographic light-sensitive material, it is advantageous to expose it to three types of laser light with different wavelengths. There are no restrictions. However, in the past, it was not easy to incorporate a gas laser light source with three different wavelengths at a low cost and compactly, and it was not necessarily possible to spread it as a popular product. . In recent years, the development of SHO elements has progressed, and it has also been possible to combine this second harmonic generation (S HG ) element with a gas laser beam to modulate the wavelength of the laser beam to produce three types of wavelengths. However, in order to handle photosensitive materials in an environment as bright as possible, it is preferable to be able to use a wide range of visible light as safelight light. Therefore, it is preferable to use sea light in the infrared region.
Due to significant technological advances in the electronics field, infrared LEDs and semiconductor lasers can now be manufactured at low cost, and an environment has emerged in which continuous scanning printers using these can be manufactured relatively inexpensively and compactly. However, more than ever before, there is a growing desire to obtain full-color hard copies inexpensively and quickly using silver halide print materials that have a significantly larger amount of information and high image quality.

Under these circumstances, JP-A-61-137,149 discloses a method in which three types of silver halide emulsion layers each containing a conventional color coupler that develops cyan, magenta, or yellow are provided on a support. , discloses a color photographic material in which at least 2N is not sensitive to visible light but is sensitive to laser light in the infrared region, and its basic conditions. Also, JP-A-6:3-197,947
No. 3 contains three types of color couplers capable of developing cyan, magenta, and yellow colors on a support.
A seed photosensitive layer is provided, at least one of which is spectrally sensitized to a wavelength with a maximum spectral sensitivity longer than about 670 nrn, and is provided to be sensitive to LED or semiconductor laser light, and is provided with a light scanning exposure and a subsequent photosensitive layer. A method of spectral sensitization and a method of using dyes are disclosed, which allow a full-color recording material that obtains a color image through color development processing to be particularly sensitive and stable. Furthermore, Japanese Patent Application Laid-Open No. 55-13505 discloses that by controlling the color development of yellow, magenta, and cyan using three types of light beams with different wavelengths, for example, green, red, and infrared light beams, full-color A method for recording a color image of a color photographic material is disclosed.

JP-A-61-137,149 and JP-A-6, as mentioned above.
No. 3-197,947 discloses the basic structure of the color photosensitive material, but there is no specific record of particularly preferable means for achieving the purpose of the present invention.

Non-photosensitive recording materials used to make hard copies from soft information sources are useful for low-quality images, but they are usually used to print photographs at the commonly used B-4 to B-5 size or smaller. It is almost impossible to achieve average image quality. The price per sheet is cheap at first glance, but when compared to the image quality (for example, per recording capacity), it cannot be said to be cheap.
On the other hand, the method of using halogenated iI light-sensitive materials makes it easy to stably obtain high image quality, but it cannot be put to practical use unless various technological developments are made. Semiconductor lasers suitable for use in the present invention have compact generators and can be obtained at low cost compared to gas lasers, but the emission intensity and emission wave range are still unstable, and the emission intensity In many cases, the modulation range of the dependence is actually narrow, and if you try to use an inexpensive ordering device, it will be difficult to achieve the excellent image quality of silver halide photosensitive materials unless special improvements are made to the silver halide photosensitive materials. Furthermore, in order to obtain hard copies more quickly, it is necessary to perform scanning exposure at a higher speed and to perform color development processing extremely quickly. ---It is first necessary that high sensitivity and stable latent images can be obtained even at 101 seconds in silver halide emulsions that can be developed ultra-rapidly. Ultra-rapidly. For development processing, it is more advantageous to use silver halide grains with a high silver chloride content, but when such silver halide grains are used, the sensitivity at short exposure times is not very high;
Adsorption of spectral sensitizing dyes is also weak and high sensitivity can be obtained. In particular, this tendency becomes even more remarkable when a color coupler necessary for obtaining a full-color image is used together. In order to manufacture and provide color light-sensitive materials in large quantities at low cost, spectrally sensitized silver halide emulsions are made by adding spectrally sensitizing dyes and are kept in a solution state, sometimes for several hours, in the coexistence of color couplers. Therefore, the loss of sensitivity under such conditions is a very serious manufacturing problem. Further, a decrease in sensitivity and an increase in fog during the period from manufacture to use are also serious problems. Even with commercially available silver halide photosensitive materials for black and white infrared light that do not coexist with color couplers, most of them do not maintain their performance unless they are stored in the refrigerator or freezer until use. In general, when color couplers coexist, spectral sensitizing dyes become difficult to adsorb to silver halide grains, and storage becomes difficult. It is known that there is a strong tendency for the product to attach and detach during use. Dyes with long conjugated methine chains, such as infrared spectral-enhancing dyes that are sensitive to infrared light, have poor thermal stability (the longer the conjugated methine chain, the longer the absorption wavelength). Therefore, in situations where color couplers coexist,
Keeping infrared spectral sensitizing dyes stable and stably maintaining high sensitivity is a difficult problem, and a solution has been desired.

The present inventor has proposed a method for spectral sensitization in the infrared region that can improve the above-mentioned problems in emulsions containing high silver chloride grains that can be rapidly developed, especially in the coexistence of color couplers from 750 nm to 110 nm.
We have discovered a method for spectral sensitization in the near-infrared and infrared regions of 00n.

(Problems to be Solved by the Invention) The first object of the present invention is to
An object of the present invention is to provide a full-color photographic material containing an improved high-silver chloride color photographic emulsion that has a maximum wavelength of spectral sensitivity at 11,000 nm, has high spectral sensitivity, and can be rapidly processed.

The second purpose is to develop high silver chloride colors that suppress the decline in photographic sensitivity in the infrared region and the increase in fogging density of the emulsion stored in solution state before coating and during storage after coating. An object of the present invention is to provide a full-color photographic material containing a photographic emulsion.

The third objective is 104 seconds or less, especially 10'8 seconds to 101 seconds.
It is an object of the present invention to provide a full-color photographic material containing a high-silver chloride color photographic emulsion that has high spectral sensitivity in the infrared wavelength region even in short-time exposure of seconds.

The fourth objective is the infrared light range, especially from 750nrn to 1000nrn.
Semiconductor lasers and L
Scanning exposure is performed using an improved high chloride astringent color photographic material with high spectral sensitivity, even for short-time exposure to high-intensity light emitted from ED, etc., and stable J1
1. To provide a method for quickly forming high-quality full-color images.

(Means for Solving the Problems) The above objects of the present invention are achieved by the following photosensitive materials and image forming methods.

(1) In a silver halide photographic light-sensitive material having at least three silver halide emulsion layer units with different electromagnetic and spectrally sensitive layers on a support, each of the emulsion layers has an average content of silver chloride. contains color couplers that form mutually different dyes through a coupling reaction between silver halide and an oxidized product of a color developer in an amount of 85 mol % or more, and at least two layers of the emulsion layer unit each contain the following general dyes. It is characterized by being spectrally sensitized to light in different infrared regions of the electromagnetic spectrum by dyes represented by formulas (1) and/or (II).
color high silver chloride photographic material.

2) A color image forming method, characterized in that the photographic light-sensitive material according to item 11 is scanned and exposed to light in the infrared region, and then subjected to color development processing.

In the formula, Zll and Z1! may be the same or different and each represents a sulfur atom, an oxygen atom, a -CH-CH-selenium atom or >N-R'', and RIS each represents an optionally substituted lower alkyl group, aryl group or allyl group. represents.

R eye and RIIZ when Zll represents 〉N-RIS
RIS and R14 when ">N-R" may be the same or different (representing a hydrogen atom or an electron-withdrawing group, R11 and R14 when Zll represents something other than >N-R+i) R11, zlm > N −
R11 and RI4 when representing something other than RIs may each be the same or different, and include a hydrogen atom, a halogen atom, a hydroxy group, an optionally substituted lower alkyl group, an optionally substituted aryl group, represents an optionally substituted lower alkoxy group, lower alkylthio group, arylthio group, acylamino group, carboxy group, or lower alkoxycarbonyl group, R1 and R11 and/or RIM and RI4 are connected at adjacent positions, and 1. 2
It also represents the ability to form 3.4-tetradehydrotetramethylene, tetramethylene, trimethylene, or methylenedioxy.

G" and G" represent a substituted alkyl group having a sulfonic acid group or a carboxylic acid group, and G1- each represents an optionally substituted alkyl group or alkenyl group,
It also indicates that it can be linked with G'' to form a 5- or 6-membered ring. Furthermore, when G'' is a substituted alkyl group having a carboxylic acid group, G'' has a sulfonic acid group or a carboxylic acid group. Represents a substituted alkyl group.

G13 represents a hydrogen atom.

GI4 and GIs may be the same or different, and each represents a hydrogen atom, an optionally substituted lower alkyl group, a lower alkoxy group, or an aryl group, and G
14 and other G'4 and/or G" and other Gl can be linked to form a 5- or 6-membered ring which may contain an oxygen atom, sulfur atom or nitrogen atom as a ring constituent atom. represents.

n11 and n11 each represent 0 or l, n +
3 represents 2.3 or 4.

Y l represents a cationic group, ml is 0 or l
and 0 if it becomes an inner salt.

G:10 In the formula, Zll represents the same meaning as Zl in general formula (1).

zlm is a sulfur atom, an oxygen atom, a selenium atom or; N-
R'', and R1 has the same meaning as RIS in general formula (1).

zlm represents a sulfur atom or a selenium atom.

RIS and R1 represent the same meanings as R11 and/or Htt in general formula (1).

G1 is G1 in general formula (1), and G1 is - general formula (1
) in G14 and G'' in general formula (1).
and each expresses the same meaning.

G'' has the same meaning as G1 in general formula (1), and each represents an optionally substituted aryl group or heterocyclic group, and at least one of G'' and Glz is a sulfonic acid group or A group having a carboxylic acid group (these groups are neutralized in terms of cationic charge), and when one is a group having a carboxylic acid group, the other is a sulfonic acid group, hydroxy group, or sulfamoyl group. , a carboxylic acid group, or a carbamoyl group.

nII represents O or 1, n8t is 2.3 or 4
represents.

The dye of general formula (1) will be explained in more detail.

2++ and ZI! may be the same or different, and each represents a sulfur atom, an oxygen atom, a -CH-CH-selenium atom, or >N-RIS (RIB is an optionally substituted lower alkyl group [more preferably 8 or less carbon atoms]), Representing an allyl group or an aryl group (preferably a substituted phenyl group), R11 when Zll represents CN-R" and Rlm and Rlm when HtxZ+! represents >N-R", It can be the same or different (
, each representing a hydrogen atom or an electron-withdrawing group. Preferred electron-withdrawing groups include halogen atoms (e.g., fan, chlorine), acyl groups (more preferably carbon atoms of 7 or less, such as acetyl, propionyl, methylsulfonyl, benzoylsulfonyl), cyano group, carboxy group,
Alkoxycarbonyl group (more preferably 6 or less carbon atoms, such as methoxycarbonyl, ethoxycarbonyl,
butoxycarbonyl), perfluoroalkyl group (more preferably has 4 or less carbon atoms, for example trifluoromethyl, 1.l.

2,2-tetrafluoroethyl) and the like.

R11 when Zll represents a sulfur atom, oxygen atom, -CH-CH- or selenium atom and R11 and R14 when Rllzlg represents a sulfur atom, oxygen atom, -CH=CH- or selenium atom may be the same or different. (, hydrogen atoms, halogen atoms (e.g. chlorine,
bromine), hydroxy group, lower alkyl group (preferably carbon number 10 or less), substituted alkyl group (preferably carbon number 12 or less, preferred substituents include hydroxy group,
Alkoxy group, halogen atom, acyl group, acylamino group, aryl group, aryloxy group, alkoxycarbonyl group, carboxy group, etc.), aryl group (preferably a monocyclic aryl group such as phenyl, furyl, pyridyl, thienyl) ), a substituted aryl group (preferably a total carbon number of 10 or less; preferred substituents include the substituents listed as examples of the preferable substituents for the substituted alkyl group), a lower alkoxy group (preferably a carbon number of 8 or less) , lower substituted alkoxy group (preferably carbon number l
θ, examples of preferable substituents include the substituents listed as preferable examples of substituents for the substituted alkyl group), lower alkylthio groups (preferably having 8 or less carbon atoms), arylthio groups (preferably phenylthio groups), ), an acylamino group (preferably having 8 or less carbon atoms), a carboxy group, a lower alkoxycarbonyl group (preferably having 8 or less carbon atoms in total), and the like.

R11, Rlm, Rls and Rlm represent the above-mentioned substituents, and R's and R11 and/or Rls, :R14 are connected at adjacent positions, and 1,2,3,4-tetradehydrotetramethylene, tetramethylene, It also indicates that trimethylene and methylenedioxy can be formed.

G and G" are substituted alkyl groups having a sulfonic acid group or a carboxylic acid group [preferably having 8 or less carbon atoms, such as p-sulfo-2-phenethyl, 2-sulfoethyl,
Examples include 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-(3-sulfopropoxy)ethyl, 2-hydroxy-3-sulfopropyl, carboxymethyl, carboxyethyl, and 3-carboxypropyl. ], G1 represents an alkyl group or an alkenyl group, which may be unsubstituted or substituted, and these alkyl and alkenyl groups preferably have 18 or less carbon atoms, and more preferably have 10 carbon atoms.
For example, in addition to those listed as examples of the substituted alkyl group having a sulfonic acid group or a carboxylic acid group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, dodecyl group, etc. group, octadecyl group, benzyl group, phenethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 2-(2-methoxyethoxy)ethyl group, 3-sulfatopropyl group, 2-( Pyrrolidine-2-
on-1-yl)ethyl group, tetrafurfuryl group, 2-
Acetoxyethyl group, ethoxycarbonylmethyl group, 3
Examples include -cyanopropyl group, 2-methanesulfonylaminoethyl group, 2-phenoxyethyl group, allyl group, 2-butenyl group, and 2-chloro-2-butenyl group.

Furthermore, G1 also represents that it can be linked with G'' to form a 5- or 6-membered ring, and when G'' is a substituted alkyl group having a carboxylic acid group, G'' is a sulfonic acid group or a carboxylic acid group. is a substituted alkyl group having

Gl represents a hydrogen atom.

GIs and GIs may be the same or different, and each contains a hydrogen atom, an optionally substituted lower alkyl group (preferably having 8 or less carbon atoms), and an optionally substituted lower alkoxy group (preferably having 6 carbon atoms). (the following) or an optionally substituted group (preferably less than 10 carbon atoms)
In addition to representing a 5- or 6-membered ring in which G" and another GI' and/or Gl' and another GIS may be linked to each other, the ring constituent atoms may include an oxygen atom, a sulfur atom, or a nitrogen atom. More preferable examples of the lower alkyl group, lower alkoxy group, and aryl group represented by G'' and 01% include methyl group, ethyl group, butyl group, methoxy group, ethoxy group, and phenoxy group. group, benzyl group, phenethyl group, phenyl group or tolyl group.

nII and nl each represent 0 or l, nl
represents 2.3 or 4, more preferably 2 or 3
It is.

Y” represents a cationic group that serves as a counter ion to the acid group, m
” is 0 or l, and is 0 when forming an inner salt.

Examples of cationic counterions include alkali metal cations (e.g., K'', Na''), Ca'', and 4
class ammonium salts (e.g. trimethylammonium,
Examples include triethylammonium, benzyldiethylammonium, pyridinium, morpholinium, and l,8-diazabicyclo(5,4,0)-7-unzocenium).

Next, the dye of general formula (Il) will be explained in detail.

zXl represents a sulfur atom, an oxygen atom, a selenium atom, 〉N-R 3 or -CH-CH-, and R 3 represents the same meaning as R+s in the general formula (R).

Z■ is a sulfur atom, an oxygen atom, a selenium atom or; N-R
” (R” in R”4*-71 formula (1)!: represents the same meaning).

zz3 represents a sulfur atom or a selenium atom.

R rich 1 and R'' are R1 and R11 in general formula (1)
expresses the same meaning as

G″′ has the same meaning as G″ in general formula (1).

G wealth is G'' in general formula (1), and G'' is - general formula (
It has the same meaning as "G" in 1).

Qlm has the same meaning as (, l), and also represents an optionally substituted ring group or heterocyclic group.

Preferred optionally substituted aryl groups and heterocyclic groups include double or two-membered rings having 18 or less carbon atoms, more preferably 12 or less carbon atoms, such as phenyl, tolyl, phenyl, sulfophenyl, carboxyphenyl, p
-Ethoxycarbonylphenyl, naphthyl, sulfonaphthyl, carboxynaphthyl, m-sulfotril, acetylaminophenyl, p-hydroxyphenyl, 2-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-
They are chloro-2-pyridyl and 2-quinolyl.

nl represents 0 or 1, nts represents 2.3 or 4, more preferably 3 when nl is 0,
When n l r is 1, it is 2 or 3.

In the formula, at least one of G1 and G" is a group having a sulfonic acid group or a carboxylic acid group, and neither is a group having a sulfonic acid group, and - is a group having a carboxylic acid group. When , the other is a group having a sulfone Ml, a hydroxyl group, a sulfamoyl group, a carboxylic acid group, or a carbamoyl group.

The above acid groups are used to include those neutralized with cations.

The spectral sensitizing dyes represented by the general formula (1) or (II) that can be used in the present invention include the patents and patents described above, as examples in which the spectral sensitizing dyes for infrared rays are described. Documents cited in the book, or Japanese Patent Application Laid-Open No. 1986-
It can be easily synthesized by referring to No. 262853, and specific compounds are shown below, but the present invention is not limited to these specific examples.

CI officer coon CHtCFItCOOIl! -8 CsH
The spectral sensitizer used in the present invention may be added to OH3O3 in the silver halide photographic plate of the present invention at any time before the silver halide emulsion is coated on the support.
Furthermore, if added before the completion of chemical ripening,
As with other infrared sensitizing dyes, there are many cases where the fog increases compared to when added after chemical ripening is completed.In such cases, a nitrogen-containing heterocyclic compound represented by the following general formula (III) is used. It is more preferable to use these compounds in combination, and even when the sensitizing dye is added after chemical ripening, there is no problem in using these compounds in combination.Addition of such compounds in combination often results in a supersensitizing effect. is more preferable in terms of further increasing sensitivity, and the addition ratio is more preferably 5 to 40 equivalents to the sensitizing dye used in the present invention.

General formula (III) Z"+V")-s+ where ZSl specifically represents an azole ring (e.g. imidazole, triazole, tetrazole, thiazole, oxazole, selenazole, benzimidazole, benzindazole, benztriazole, benzoxazole, benzoxazole, thiazole, thiadiazole, oxadiazole, benzselenazole, pyrazole, naphthothiazole, naphthoimidazole, naphthoxazole, azabenzimidazole, purine, etc.) pyrimidine ring, triazine ring, pyridine ring, azaindene ring (e.g. triazaindene, tetrazaine) den, pentazainden, etc.).

y31 represents a hydrogen atom or a substituent, and specific examples of the substituent include substituted or unsubstituted alkyl groups (e.g., methyl, ethyl, hydroxyethyl, trifluoromethyl,
Sulfopropyl, di-propylaminoethyl, adamantyl, benzyl, p-chlorophenethyl, ethoxyethyl, ethylmercaptoethyl, cyanopropyl, phenoxyethyl, carbamoylethyl, carboxyethyl,
ethoxycarbonylpropyl, acetylaminoethyl, etc.), unsubstituted or substituted alkenyl groups (e.g. allyl, etc.), unsubstituted or substituted aryl groups (e.g.
Phenyl, naphthyl, p-carboxy-phenyl, 3.
5-dicarboxyphenyl, m-sulfophenyl, p-
acetamidophenyl, 3-caprylamidophenyl,
p-sulfamoylphenyl, m-hydroxy-phenyl, p-nitrophenyl, 3,5-dichlorophenyl,
p-phenyl, O-phenyl, p-cyanophenyl, p
-N'-methylureidophenyl, m-fluorophenyl, p-)lyl, m-)lyl, etc.), optionally substituted heterocyclic residues (e.g. pyridyl, 5-methyl-2
-pyridyl, thienyl, etc.), halogen atoms (e.g.
chlorine, bromine), mercapto group, cyano group, carboxy group, sulfo group, hydroxy group, carbamoyl group, sulfamoyl group, amino group, nitro group, optionally substituted alkoxy group (e.g. methoxy, ethoxy, 2-methoxy ethoxy, 2-phenylethoxy, etc.), optionally substituted aryloxy groups (e.g., phenoxy,
p-methylphenoxy, etc.), acyl groups (e.g., acetyl, benzoyl, methanesulfonyl, etc.), acylamino groups (e.g., acetylamino, caproylamino,
methylsulfonylamino), substituted amino groups (e.g. diethylamino, hydroxyamino), alkyl or arylthio groups (e.g. methylthio, carboxyethylthio, sulfobutylthio), alkoxycarbonyl groups (e.g. methoxycarbonyl), aryloxycarbonyl groups (e.g. For example, phenoxycarbonyl) and the like.

m'' represents a positive integer of 5 or less, and represents that a plurality of the substituents represented by s+ may be included in the same or/and in different combinations.

Among the compounds of general formula (Ill), even more preferred compounds are tetrazaindene compounds or mercapto-substituted azole ring compounds.

Furthermore, when the sensitizing dye used in the present invention is added to the silver halide emulsion of the present invention, it is more preferable to add it in combination with a water-soluble bromide disclosed in Japanese Patent Publication No. 49-46゜932, etc., and the order of addition is as follows: , first add water-soluble bromide,
These compounds can be added at the same time, either by converging the surface of high-silver chloride silver halide grains and then adding a sensitizing dye, or conversely by adding a sensitizing dye and then adding water-soluble bromide. The amount of water-soluble bromide used in combination is preferably 5 mol% or less, particularly 0.1 mol% to 2.0 mol%, based on silver halide in order to maintain rapid processability. The higher the silver chloride content of the high silver chloride grains of the invention, the more effective they are.

Furthermore, when the sensitizing dye used in the present invention is added to the silver halide emulsion of the present invention, a compound represented by the following general formula (IV) may be used alone, or a compound represented by the above general formula (III) or/and By coexisting in combination with a water-soluble bromide, the spectral sensitivity can be dramatically increased and the storage stability can be improved, which is more preferable.

General formula (mV) In the formula, Y41, Y, 8, Yas and Y44 may be the same or different <-CH- or -N-, and Y4
1 and Yas, and Y48
and Y44, at least one of which represents -N-.

R4g, R4m and R44 may be the same or different, and each represents a hydrogen atom, a hydroxy group, a lower alkoxy group (preferably having IO or less carbon atoms), an aryloxy group (e.g. phenoxy, tolyloxy group, sulfophenoxy group, β-naphthoxy group, α-naphthoxy group, 2,
4-dimethylphenoxy group, etc.), halogen atoms (e.g., chlorine atom, bromine atom, etc.), heterocyclic rings (e.g., morpholinyl group, piperidine group, etc.), alkylthio groups (e.g., methylthio group, ethylthio group), heterocyclylthio groups (e.g. benzothiazylthio), ruthio (e.g. phenylthio, tolylthio), amino, alkylamino or substituted alkylamino groups (e.g. methylamino, ethylamino, propylamino) , dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, di-β-hydroxyethylamino group, β-sulfoethylamino group), arylamino group or substituted -rulamino group (For example, anilino group, O-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, O-anisylamino group, m-anisylamino group, p-anisylamino group, 0-methylanilino group,
-methylanilino group, pt-amylanilino L O-
Carboxyanilino! , m-carboxyanilino group, p
-carboxyanilino group, hydroxyanilino group, naphthylamino group, sulfonaphthylamino group), heterocyclylamino group (e.g. 2-benzothiazole amino group,
2-pyridylamino group), an aryl group (for example, a phenyl group), and a mercapto group.

A41 represents a group consisting of at least one arylene group, and includes the following groups.

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

Furthermore, in the compound represented by general formula (IV), R
41, R4X, R41, R44 and A41 represents a group having a sulfo group.

Furthermore, among the compounds represented by the general formula (■), the most preferred compound is a stilbene derivative.

Specific examples of the compound represented by the general formula (mV) are listed below, but the invention is not limited thereto.

and≧≧ and≧ and and≧ In addition to these compounds, examples of supersensitizers that can be used in the present invention include JP-A-59-142.54.
Bispyridinium salt described in No. 1, etc., U.S. Patent No. 3,74
Examples include condensates of formaldehyde and aromatic compounds having hydroxyl groups as described in No. 3.510.

The sensitizing dyes used in the present invention may be used alone or in combination. 41 When used in combination, the ratio of the amounts added is preferably 1:10 to 10:1 when two types are used. varies depending on the shape and size of the silver halide grains, but it is lXl0-' to lXl per all halide grains.
0-” mole is preferred, more preferably 2.5X10-
-~4X10-' moles. *The amount added is preferably 25% or less of the amount required for Japanese coating, more preferably 2 to 15%, in the silver halide photographic emulsion.

When supersensitizers are used in combination as described above, the preferable addition ratio of supersensitizers is 0.1 to 100 equivalents based on the total amount of sensitizing dyes used in the present invention.

In order to add the sensitizing dyes used in the present invention to the silver halide emulsion of the present invention, they may be directly dispersed in the emulsion, or they may be added to water, acetone, methanol, ethanol, propatool, tetrahydrofuran, methyl Cellosolve, 2.2,3°3-tetrafluoropropanol,
It may be added to the emulsion after being dissolved in a solvent such as N,N-dimethylformamide alone or in a mixture thereof, and ultrasonic waves may be used during dissolution.

Moreover, as a method of adding this sensitizing dye, US Patent Nos. 3 and 4
69.987, etc., a method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion, Japanese Patent Publication No. 46 A method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 44-23
No. 389, No. 44-27555, No. 57-22091
As described in US Pat.
A method of adding a water-soluble or colloidal dispersion in the presence of a surfactant to an emulsion as described in JP-A-53-102733 and JP-A No. 5B-10.
A method of directly dispersing in a hydrophilic colloid and adding the dispersion to an emulsion as described in No. 5141; JP-A-51-7
It is also possible to use a method such as that described in No. 4624, in which a red-shifting compound is used to dissolve the compound and the solution is added to the emulsion.

The color photographic light-sensitive material of the present invention has a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer (one layer and at least two layers) on a support.
It can be constructed by coating one infrared-sensitive silver halide emulsion layer, or it can also be constructed by coating at least three infrared-sensitive silver halide emulsion layers.

Each of these bill layers contains at least one type of coupler that produces yellow, magenta, and cyan colors, respectively.

The silver halide emulsion used in the present invention is one made of silver chlorobromide or silver chloride and having a silver chloride content of 85 moles or more, which does not substantially contain silver iodide.

Silver halide emulsions preferred in the present invention will be described in detail below.

The silver halide emulsion according to the present invention can be spectrally sensitized in the infrared wavelength range by providing the structure of the silver halide grains, particularly by providing a localized phase on the surface thereof, and has high sensitivity and stability, as well as excellent latent properties. Image stability can be obtained. In addition, by using supersensitization technology, the stability of the latent image can be increased to an acceptable level even in high silver chloride emulsions. This can be said to be a surprising feature.

The halogen composition of the silver halide grains according to the present invention is such that 95 mol % or more of the total silver halide constituting the silver halide grains is silver chloride, and is composed of silver chlorobromide containing substantially no silver iodide. Preferably, the expression "substantially free of silver iodide" here means that the silver iodide content is 1.0 mol % or less.

A preferred halogen composition of the silver halide grains is silver chlorobromide containing substantially no silver iodide, in which 95 mol% to 99.9 mol% of the total silver halide constituting the silver halide grains is silver chloride. be.

Further, it is preferable that the silver halide grains of the present invention have a localized phase in which the silver bromide content is different from that of the substrate in at least one of the interior and the surface. It is preferable to have a localized phase having a silver bromide content of at least 15 mol % or more.The localized phase having a silver bromide content higher than that of its surroundings can be freely arranged depending on the purpose. Even in
The local phase may be present on the surface or subsurface, or may be divided into the interior and the surface or subsurface, and the localized phase may form a layered structure surrounding the silver halide grains inside or on the surface. One preferred example of the arrangement of localized phases having a higher silver bromide content than the surroundings, which may have a discontinuous or isolated structure, is a silver halide grain containing silver bromide on the surface. A localized phase with a ratio exceeding at least 15 mol % is locally grown during epitaxy.

It is preferable that the silver bromide content of the localized phase exceeds 15 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 preferably in the range of 20 to 60 mol%, most preferably in the range of 30 to 50 mol%, with the remainder being silver chloride. The silver bromide content of the localized phase can be determined by the X-ray diffraction method (for example, described in "New Experimental Chemistry Course 6. Structural Analysis," edited by the Chemical Society of Japan, published by Maruzen) or the XPS method (for example, described in "Surface Analysis, 1MA, Application of Auger Electron/Photoelectron Spectroscopy'' (published by Kodansha), etc. can be used for analysis. The localized phase has an amount of 0.0% of the amount of gold and silver constituting the silver halide grains of the present invention. It is preferably comprised of 1-20% silver, more preferably 0.5-7% silver.

The interface between such a localized phase with a high silver bromide content and other phases may have a clear phase boundary or a short transition region where the halogen composition gradually changes. Also good.

Various methods can be used to form such a localized phase with a high silver bromide content.

For example, a localized phase can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-sided mixing method or a simultaneous mixing method. Furthermore, it includes a process of converting already formed silver halide to silver halide with a smaller solubility product,
A localized phase can also be formed using a so-called conversion method. Alternatively, a localized phase can also be formed by recrystallizing the surface of silver chloride particles by adding silver bromide fine particles.

In the case of silver halide grains with a discontinuous, isolated localized phase on the surface, the grain matrix and the localized phase are essentially on the same surface of the grain, so they function simultaneously in the exposure and development processes. , the present invention is advantageous for high sensitivity, latent image formation, rapid processing, especially gradation balance, efficient use of silver halide, etc. In the present invention, problems with infrared sensitized high silver chloride emulsions By providing a localized phase, the important points such as high sensitivity, stabilization of sensitivity, and stability of latent image are significantly improved overall, and the characteristics of silver chloride emulsion regarding rapid processing can be secured. .

Further, it is possible to adsorb an anti-capri agent, a sensitizing dye, etc. so as to functionally separate the particle matrix and the local phase, and also to chemically sensitize the particles to suppress the occurrence of fog and facilitate rapid development.

The silver halide grains according to the present invention have 6
Discontinuously isolated particles on the surface of silver halide grains that are preferably hexahedral, tetradecahedral, etc., and the localized phase is preferably located at or near one corner of the hexahedron, or at the surface region of the (111) plane. The localized phase can be formed by halogen convergence by supplying bromide ions to an emulsion containing substrate particles while controlling PAg, pH 1 temperature and time. It is particularly preferable to supply the halogen ions at a low concentration, and for example, an organic halogen compound or a halogen compound whose capsule membrane is covered with a semi-permeable film can be used. In addition, by supplying line ions and halide ions while controlling PAg etc. to an emulsion containing substrate grains, silver halide can be grown in localized areas, or silver halide with a grain size smaller than that of the substrate grains, such as iodobromide, can be grown in localized areas. It is also possible to form a "localized phase" by recrystallizing fine grains of silver, silver bromide, silver chlorobromide, or silver iodochlorobromide by mixing them into an emulsion containing substrate grains. In this case, a small amount of a halogenated m-solvent can also be used in combination, if necessary. Also, European Patent No. 273430, European Patent No. 273429, Japanese Patent Application No. 1986-8
No. 6163, No. 62-86165, Kaikai No. 62-86
The end point of the formation of the zero localized phase that can be used in combination with the CR-compounds described in the specifications of No. 252 and Kokai No. 62-152330 is determined by comparing the morphology of the silver halide grains of the substrate,
This can be easily determined by observing the morphology of silver halide during the ripening process. The composition of silver halide in such a localized phase is XPS (X-ray Pbotoalecti
oaSpectroscopy method, for example, ESCA 750 manufactured by Shimadzu-Du Pont.
It can be measured using a type spectrometer. More specifically, it is described in "Surface Analysis" by Hadano and Yasumoi, published by Kodansha (1977). Of course, the halide m composition of the localized phase on the surface of the silver halide according to the present invention, for example, the silver bromide content, which can be determined by calculation from the manufacturing recipe, is E D
X (Energy Dispersiva X-ra
It can be measured with an accuracy of about 5 mol % at an aperture of about 0.1 to 0.2 μm in diameter using an EDX spectrometer equipped with a transmission electron microscope. More specifically, it is described in "Electron Beam Microanalysis" by Hiroyoshi Soejima, published by Nikkan Kogyo Shimbunsha (1987).

Average grain size of the silver halide emulsion used in the present invention (
The average diameter of the equivalent sphere in terms of volume) is less than 20. IJ/ or more is preferable, particularly preferably 0°4# or less 0.15
It is more than a.

The narrower the particle size distribution, the better, and monodisperse emulsions are preferred. In particular, monodisperse emulsions with regular shapes are preferred for the present invention.0 Particle number or weight is ±20% of the average particle size.
An emulsion in which 85% or more of the total grains are contained within the range, and particularly an emulsion in which 90% or more is contained within the range, is preferred.

The silver chlorobromide emulsion used in the present invention is P, C1afkid@
Written by srchis+ia at Physique Ph
"otographique" (Paul Mantel)
Publishing, 1967), by G. F. Duffin.
Photographic Es+ulsion Ch
emistry J (published by Focal Press, 1
966), V.L., Zeliksan at a
Author:Making and Coating Pho
tographic I! Mulliion” (Foca
1 Press, 1964). B. Any of the acidic method, neutral method, ammonia method, etc. may be used, but the acidic method is particularly preferred. Also, the methods for reacting soluble silver salt and soluble silver halide include one-sided mixing method, simultaneous mixing method, and the like. Any combination may be used.In order to obtain monodisperse particles which are preferable in the present invention, a simultaneous mixing method is preferable.A method in which particles are formed under conditions of excess silver ions (so-called back mixing method) may also be used. can. As one type of simultaneous mixing method, a method of keeping the silver ion concentration in the liquid phase in which silver halide is produced constant, ie, the so-called Chondrald double jet method, can be used. According to this method, it is possible to obtain a monodisperse silver halide emulsion suitable for the present invention, which has a regular crystal shape and a narrow grain size distribution.

The above-mentioned particles preferably used in the present invention are preferably prepared based on a simultaneous mixing method.

Known silver halide solvents (e.g., ammonia, potassium thiocyanate, or U.S. Pat. No. 3,271,157)
No., JP-A-51-12360, JP-A-53-8240
No. 8, JP-A-53-144319, JP-A-54-10
When physical ripening is performed in the presence of thioethers and thione compounds described in No. 0717 or JP-A-54-155828, a monodisperse silver halide emulsion with a regular crystal shape and a narrow grain size distribution is produced. is obtained, which is preferable.

In order to remove soluble silver salts from the emulsion after physical ripening, a Nudel water washing method, a flochieresin sedimentation method, an ultrafiltration method, or the like can be used.

The silver halide emulsion used in the present invention can be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. That is, active gelatin and compounds containing sulfur that can react with silver ions (for example, J
f) Sulfur sensitization using thiosulfate, thiourea compounds, mercapto compounds, rhodanine compounds, etc.) or reducing substances (e.g. stannous salts, amine salts, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc.) The reduction sensitization method used, and the metal compound (e.g. total complex salt, Pt,
A noble metal sensitization method using complex salts of metals of group (I) of the periodic table such as Ir, Pd, RhvFe, etc.) can be used alone or in combination. In addition, it is preferable to use complex salts of metals in group (1) of the periodic table, such as Ir, Rh, and Fa, by distinguishing or distributing them into the substrate and the localized phase. In silver emulsions, sulfur sensitization or selenium sensitization is particularly preferably used, and it is also preferable to have a hydroxyazaindene compound present during this sensitization.

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

Semiconductor lasers are preferable as lasers that can be used in the present invention, and specific examples thereof include In,
,G,,P (~700ne), GaAs1-*Px(
610-900 nm), Gap-mAs (69
0-900 nm), InGaAsP (1100-167
0 nm), AlGaAsSb (1250-1400
Semiconductor lasers using materials such as
In the present invention, the color photosensitive material is irradiated with light in addition to the above-mentioned semiconductor laser.
aAs++Pu-+g+ May be a YAG laser (1064 nm) excited by a light emitting diode, preferably 670.680.750.780.81O1
It is preferable to select and use the light beam of a semiconductor laser of 830 and 880 nm.

In addition, in the present invention, the second harmonic generation element (SHG element) converts the wavelength of laser light into half by applying a nonlinear optical effect, and for example, a CD'' as a nonlinear optical crystal. Examples include those using A and KD"P (see Laser Handbook, edited by the Laser Society, published December 15, 1980, pages 122 to 139),
Furthermore, it is possible to use a LiNbO5 guiding waveguide element in which a guiding waveguide is formed by ion-exchanging Li with H in the Limb's crystal (Nl■EI ELECTRONIC
31986, 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.

(Processing method) For photographic processing of the light-sensitive material produced using the present invention, for example, Research Disclosure (Research Disclosure)
Disclosure) No. 176, pages 28-30 (
Known photographic processing methods (color photographic processing) and processing solutions for forming dye images, such as those described in RD-17643), can be applied.

Preferred examples of the color development process and processing solution applied to the light-sensitive material of the present invention will be described below.

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 performed 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-IN, N-diethyl-P-7 enylenediamine D-22-amino-5-diethylaminotriene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N- Ethyl-N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-(N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl −N−(β
-(meth,nsulfonamido)ethyl)-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-ON, N-dimethyl-p-phenyl diamine D-94-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-Ajuno-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-7 nylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-(β-(
methanesulfonamido)ethyl]-aniline (exemplified compound D-6).

In addition, the amount of the II aromatic primary amine developing agent, which may be a salt such as sulfate, hydrochloride, sulfite, p-)luenesulfonate, etc., of these P-phenylenediamine derivatives is determined by the developer solution. IJ! Preferably about 0.1 g to about 2
0 g, more preferably from about 0.5 g to about 10 g.

In carrying out the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, "substantially free" means preferably 2d/1 or less,
More preferably 0.5at/j! The benzyl alcohol concentration is below, 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.Sulfite ions act as a preservative for the developing agent, and at the same time, have a dissolving action on halogenated compounds and react with the oxidized developing agent. It also has the effect of reducing pigment 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" means that the sulfite ion i11 degree is preferably 3.0 x 10"3 mol/j! or less, and the amount of sulfite ion is preferably not at all.

However, in the present invention, a very small amount of sulfite ion used to prevent oxidation 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 in the developer. At the same time, it itself has silver development activity, and fluctuations in the concentration of hydroxylamine are thought to greatly affect photographic properties.

The term "substantially not containing hydroxylamine" as used herein means preferably a hydroxylamine concentration of 5.0 x 1 G-" mol/j! or less, and most preferably not containing any hydroxylamine.

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

Here, the term "organic preservative" refers to any compound that is added to the processing solution for color photosensitive materials to reduce the rate of deterioration of aromatic primary color developing agents. Organic compounds that have the function of preventing the oxidation of the main drug by air etc. Among them, hydroxylamine derivatives (excluding hydroxylamine, the same shall apply hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones α-aminoketones, 1
Class 1, monoamines, cyakamens, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, tui-type amines, etc. are particularly effective organic preservatives. . These are JP-A-63-4235, JP-A-63-30845, JP-A-63-2.
No. 1647, No. 63-44655, No. 63-5355
No. 1, No. 63-43140, No. 63-56654,
Oka No. 63-58346, No. 63-43138, No. 63
-146041, 63-44657, 63-4
No. 4656, U.S. Patent No. 3.615.503, U.S. Patent No. 2.
494.903, JP-A-52-143020, JP-B-48-30496, etc.

Other preservatives include various gold xi 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-J4
No. 349, the polyethyleneimines described in U.S. Patent No. 3.
In particular, alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, etc. may optionally contain aromatic polyhydroxy compounds described in No. 746.544, etc.
Preferably, a hydrazine derivative or an aromatic polyhydroxy compound is added.

Among the organic preservatives mentioned above, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides)
is particularly preferable, and its details can be found in Japanese Patent Application No. 62-2
No. 55270, No. 63-9713, No. 63-9714
No. 63-11300, etc.

In addition, the above-mentioned hydroxylamine derivative or hydrazi 7
The combined use of amines and amines improves the stability of color developing solutions, and also improves the stability of color developing solutions, as well as the use of cyclic amines and ←I! 1l-II soup-Kanosho 63-9713
Examples include amines such as those described in No. 63-11300.

In the present invention, 3.5% of chloride ions are added to the color developer.
It is preferable to contain
0-'mol/1. Chlorine ion concentration is 1.5X10
-'~1O-1 mol/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;
If it is less than 0.04 mol/1, it is not preferable in terms of preventing fog.

In the present invention, 3.0% bromine ion is added to the color developer.
It is preferable to contain X10-' mol/12 to 1.0
-% to 5X10-'mol/1. If the bromide ion concentration is more than 1 x 10''3 mol/1, it will retard development and reduce the maximum density and sensitivity, and if it is less than 3.0XIO-' mol/1, capri cannot be sufficiently prevented. Not white.

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

The color developer used in the present invention is preferably 211
9 to 12, more preferably 9 to 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 buffering agents. Examples of buffering agents 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. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are soluble at pH 9,
These buffers have excellent buffering ability in the high pH ftl range of 0 or higher, have no adverse effect on photographic performance (such as capri) even when added to color developers, and are inexpensive. This is particularly preferred.

Specific examples of these 1111i agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium O-hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate,
Sodium 5-sulfo-2-hydroxybenzoate (5-
Examples include sodium sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/1
It is preferably at least 0.1 mol/l-0, particularly 0.1 mol/l-0,
Particularly preferred is 4 mol/l.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

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 diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane- 1, 2, 4
-) Ricarboxylic acid, l-hydroxyethylidene-1,1
-', Phosphonic acid, N, N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid Two or more of these chelating agents may be used in combination as 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
G-1g per serving is about 10g.

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 etc., P-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-5O
-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. J42゜4
No. 94.903, No. 3.128.182, No. 4,23
No. 0.796, No. 3,253.919, Special Publication No. 1979-
No. 11431, U.S. Patent No. 2,482,546, U.S. Pat.
, 596.926 and 3,582.346, etc., Japanese Patent Publication No. 37-16088, 4
No. 2-25201, U.S. Patent No. 3.128.183,
Polyalkylene oxides shown in Japanese Patent Publications No. 41-11431, No. 42-23883, U.S. Pat. be able to.

In the present invention, any anti-gabbing agent can be added as necessary. As anti-capri agents, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic anti-capri agents can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer that can be used in the present invention preferably contains a fluorescent brightener, and the fluorescent brightener is preferably a 4,4'-diamino-2,2'-disulfostilbene compound. Addition amount is 0 to 5 g/l, preferably 0.1 g to
4/j! It is.

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~
The temperature is 50°C, preferably 30 or 40°C. Processing time is 20
The time is from seconds to 5 minutes, preferably from 30 seconds to 2 minutes. It is preferable that the amount of replenishment is small, but it is 20 to 60 per nr of light material.
0m is appropriate, preferably 50 to 300-
3! It is preferably 60d to 200affi, most preferably 60ad to 150m.

Next, a derailment 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 (
mtt salts of III) (for example, complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolyphosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid. Acids; persulfates; hydrogen peroxide and the like are preferred.

Among these, salts with iron(III) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution.Aminopolycarboxylic acids and aminopolybosphonic acids useful for forming organic complex salts of iron(m) or organic phosphonic acids or their salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, Glycol ether diamine tetraacetic acid, etc. can be mentioned. These compounds include sodium,
Among these compounds, which may be potassium, thium or ammonium salts, ethylenediaminetetraacetic acid,
Iron(ll)t of diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodiacetic acid! Salt is preferred because of its high bleaching properties.

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.
Aminopolycarboxylic acid iron complexes are preferred among the iron complexes, which may be used in excess to form iron ion salts, and the amount added is 6.01 to 1.0 mol/2, preferably 0. 05-0.50 mol/j! It is.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. Specification No. 812, JP-A-53-95
Publication No. 630, Research Disclosure No. 1712
No. 9 (July 1978 issue), compounds that grow mercapto groups or disulfide bonds, and Japanese Patent Publication No. 45-85
No. 06, JP-A-52-20832, JP-A No. 53-3273
5, U.S. Pat. No. 3,706.561, etc., 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,
ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodide'
111+1 (eg, ammonium iodide) or an iodide (eg, ammonium iodide).

If necessary, one or more inorganic acids having a ρ11 function 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 ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution is a known fixing agent, i.e., periosulfate such as sodium thiosulfate or ammonium thiosulfate; thiocyanate such as sodium thiocyanate or ammonium thiocyanate; ethylene bisthioglycol. Water-soluble silver halide solubilizers such as acids, thioether compounds such as 3,6-cythio-1,8-octanediol, and thiourea, and these can be used alone or in combination of two or more. .

In addition, a special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used. Preference is given to using salts, especially ammonium thiosulfate salts, 1! The amount of fixative per
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 fluorescent brighteners, antifoaming agents, surfactants, and growth solvents such as polyvinylpyrrolidone and methanol.

Bleach-fix solutions and fixing solutions contain preservatives such as gnitrite (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), ii. , etc.), metabisulfites (e.g., potassium metabisulfite,
It is preferred to contain a sulfite ion releasing compound such as sodium metabisulfite, sodium metabisulfite, etc.).

These compounds are V substanoid, approximately 0102 in terms of acid ion.
The content is preferably from 0.05 mol/l, more preferably from 0.04 to 0.40 mol/l.

As a preservative, TT salt is commonly added, but
In addition, ascorbic acid, carbonyl bisulfite adducts, carbonyl compounds, etc. may be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, and the like may be added as necessary.

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

The amount of water used in the washing process depends 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 (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. 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 Picture and Television Engineers (Journal of the Society of Picture and Television Engineers).
nalor tl+a 5oci@ty of
Motion Picture and Te
It can be obtained by the method described in 1evi-sion EyigLneers) No. 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, from 0.52 to 1 per port of photosensitive material, and the effect of the present invention is remarkable. The increase in residence time causes problems such as bacteria propagation and the 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-57-85
Inchiazolone compounds and thiabendazoles described in No. 42, chlorine-based disinfectants such as chlorinated sodium isocyanurate described in No. 61-120145, JP-A-61-2
Benzotriazole, copper ion, etc. described in No. 67761, Hiroshi Horiguchi, "Chemistry of antibacterial and anti-mildew J" (1986), Sankyo Publishing, Hygiene Technology Golden Wire "Sterilization of microorganisms, sterilization, anti-mildew technology" (1982) Industrial technology It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents J (1986)," compiled by the Japan Antibacterial and Antifungal Society.

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.
Examples include buffering agents and ammonium compounds for preparing a. 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, a surfactant, a fluorescent brightening agent, and a hardening agent may be added. In the processing of the photosensitive material of the present invention, if stabilization is performed directly without going through a water washing process, the method disclosed in JP-A-57
-8543, 5B-14834, 60-220
All known methods described in No. 345 and the like can be used.

In addition, it is also a preferable 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 pH in the water washing step or the stabilization step is preferably 4 to 0, more preferably 5 to B. The temperature can be set in various ways depending on the use and characteristics of the photosensitive material, but generally it is 15 to 45°C.
0 time, which is preferably 20 to 40°C, can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing processing time.
Preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to
It is 1 minute and 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 lj per 1rrf of photosensitive material! Below, t is preferably 500- or less. 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 reducing the amount of waste liquid by using a multi-stage countercurrent system to reduce the overflow of washing water into the bleach-fixing bath, which is the previous bath, and replenishing the bleach-fixing bath with condensate. .

Cyan couplers, magenta couplers, and yellow couplers preferably used in the present invention have the following general formulas (C-1), (C-11), (M-1), and (M-11).
and (Y).

General formula (C-13 n General formula (C-11) General formula (Y) (ill General formula (M-1) ,1,R
8 and R1 represent substituted or unsubstituted aliphatic, aromatic or heterocyclic groups, R1, US and are hydrogen atoms,
represents a halogen atom, an aliphatic group, an aromatic group, or an acylamino group, and Rs together with R represents a nitrogen-containing 5-membered ring or a 6-membered ring.
May represent a group of nonmetallic atoms forming a membered ring e Y1%
Ym represents a hydrogen atom or a group capable of being eliminated during a coupling reaction with an oxidized product of a developing agent; n represents O or 1;

R1 in general formula (C-1) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tart-butyl group, cyclohexyl group, cyclohexylmethyl group, phenyl group. Examples include thiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by the general formula (C-1) or (C-11) are as follows.

In the -In formula (C-1), R1 is preferably an aryl group or a heterocyclic group, and halogen atoms 1. More preferably, it is an aryl group substituted with an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group. .

In general formula (C-1), when Rs and R3 do not form a ring, R8 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxyrIt-substituted alkyl group, and 6 is preferably a hydrogen atom.

In general formula (C-11), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In general formula (C-11), preferably Rs 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-1), Rs is carbon 1ik 2-15
More preferably, it is an alkyl group having 2 to 2 carbon atoms.
Particularly preferred is an alkyl group of No. 4.

In general formula (C-11), preferred are a hydrogen atom and a halogen atom, with chlorine and fluorine atoms being particularly preferred. In general formulas (C-1) and (C-11), preferred Y and Y3 are, respectively, These are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfamide group.

In the general formula CM-1), R1 and R9 represent an aryl group, R8 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
! , represents a hydrogen atom or a leaving group.

Aryl group (preferably phenyl group) of R1 and R1
The substituents allowed for are the same as the substituents allowed for substituent R8, and when there are two or more substituents, they may be the same or different, R is preferably a hydrogen atom, It is an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom.

preferable! , is of the type that undergoes #iII elimination with either sulfur, oxygen or nitrogen atoms; for example, US Pat. No. 4,351,897 and International Publication W 08B10479
The sulfur atom detachment type as described in No. 5 is particularly preferred.

In the general formula (Mu), l1to represents a hydrogen atom or a substituent,! , represents a hydrogen atom or a leaving group, and a halogen atom or an arylthio group is particularly preferred, Z
a, Zb and Zc represent methine, substituted methine, diht or -Nt, one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond.

When the Zb - Zc bond is a carbon-carbon double bond, including when it is part of an aromatic ring *Rlm or! .

When forming a dimer or more multimer, Za, zb
Alternatively, when Zc is a substituted methine, it 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)) riazoles are 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 in the 6-position, such as those described in No. 849 and No. 294.785.

In the general formula (Y), R11 represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, Rlm represents a hydrogen atom, a halogen atom, or an alkoxy group, A represents -NIICORts, (C-1) , However, Rlm and the back, 4 each represent an alkyl group, an aryl group, or an acyl group, Ys represents a leaving group, R18 and R13% As a substituent for R14, it is the same as the substituent allowed for R8. The leaving group Y is preferably a type that leaves at either an oxygen atom or a nitrogen atom J), and a nitrogen atom leaving type is particularly preferred.

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

1 (C-4) H C,H? (C-5) (C-6) (C-7) (C-8) (C-13) (C-14) (C-15) (C-16) 1 C11(s tHs (C-9 ) (C-10) (C-12) (C-17) (C-18) (C-19) H (C-20) (C-21) (C-22) (M-4) (M- 6) Shil (M-1) (M-2) (M-3) (M-7) (M-8) I Shil I Shil (l (Y-1) (Y-2) (Y- 3) S1 (Y-4) (Y-7) (Y-8) (Y-5) (Y-6) (Y-9') Represented by the above general formulas (C-1) to (Y) The coupler is
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, in order to add the coupler to the photosensitive layer, various known techniques can be applied.Usually, the coupler can be added by an oil-in-water dispersion method known as an oil protection method. After dissolving, 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 meat puller solution containing a surfactant to form an oil-in-water 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
)2-20. It is preferable to use a high boiling point Il solvent and/or a water-insoluble polymer compound having a refractive index (25"C) of 1.5 to 1.7.

As the high boiling point 81 solvent, preferably the following general formula (A)
A high boiling point organic solvent represented by ~(E) is used.

General formula (A) W+ w, -o-p 0 +14s General formula (B) Ka+-Coo L General formula (E) w, -o-11° (in the formula, H+%W and - are respectively GL represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group;
represents Wl or S-111, n is an integer from 0 to 5, and when n is 2 or more, -4 may be the same or different from each other, and in general formula (E), 1 and - are may form a fused 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).
Compounds that are immiscible with water at temperatures above ℃ can be used as long as they are good solvents for the coupler. The melting point of the high-boiling 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 or higher.

For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, lower right column ~ 14
It is written in the upper right column of page 4.

Additionally, these couplers can be synthesized with rhodapulu latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a 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 y:conductor, a gallic M derivative, an ascorbic acid derivative, etc. as a color anti-capri agent.

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. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

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

Hydroquinones are U.S. Patent No. 2.360.290,
2,418.613, 2.700.453, 2.701.197, 2,728.659
No. 2,732.300, No. 2,735,76
No. 5, No. 3.982.944, No. 4.430.4
25, British Patent Box No. 1.363.921, U.S. Patent Box No. 2.710.801, U.S. Patent No. 2.816.028, etc., 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are US Patent Tube 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. Patent No. 4,360,589, P-
Alkoxyphenols are US Patent No. 2.735.76
No. 5, British Patent Box 2.066, No. 975, Japanese Unexamined Patent Publication No. 1983-
Hindered phenols are disclosed in U.S. Pat.
, No. 235, and Japanese Patent Publication No. 52-6623, gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Pat. -21144 etc., the hinder door jaws are U.S. Patent No. 3.336.13.
No. 5, No. 4,268.593, British Patent Box 1.32
No. 6.889, No. 1.354,313, No. 1.4
No. 10,846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 1983
-114036, 59-53846, 59
-78344 etc., metal complexes are disclosed in US Patent No. 4.05.
No. 0.938, No. 4.241°155, British Patent Box No. 2.027,731(A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with the respective color couplers, usually in an amount of 5 to 100% by weight, and adding them to the layer. In order to prevent cyan dye images from aging and especially from being degraded by light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (for example, U.S. Pat. No. 3,314,794, U.S. Pat. No. 3,352.
681), benzophenone compounds (e.g., those described in JP-A No. 46-2784), cinnamic acid ester compounds (e.g., those described in U.S. Pat. (as described in U.S. Pat. No. 4,045,229), butadiene compounds (as described in U.S. Pat. No. 3,045,229), or benzoxidol compounds (eg, as described in U.S. Pat. No. 3,700,45S). 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, it is particularly preferable to use the following compounds together with the couplers described above, particularly in combination with pyrazoloazole couplers.

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, after treatment, a stone compound (G) that chemically combines with the oxidized form of a color developing agent to form a chemically inert and substantially colorless compound may be used simultaneously or alone. This is preferable in order to prevent the occurrence of staining and other side effects due to the formation of coloring dyes due to the reaction between the color developing agent remaining in the film or its oxidized product and the coupler during storage.

A preferred compound (F) has a second-order reaction rate constant kg (in trioctyl phosphate at 80°C) with p-anisidine of 1. OJ! /mol-sec ~IX
10-'j! /mol-sec.

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

When 8 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if km is smaller than this range, there will be a lot of reaction force with the remaining aromatic amine developing agent, and as a result, it may not be possible to prevent side effects of the remaining aromatic amine developing agent.

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

General formula (FX) R1-(A), -X General formula (FII) 11t-C In the formula, Rls R* each represents an aliphatic group, an aromatic group, or a heterocyclic group, n is 1 Or represents 0.

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 the addition of an aromatic amine developing agent to the compound of general formula (Fn), where R1 and X, Y and R8 or B are bonded to each other to form a cyclic structure. It's okay.

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

-a For specific examples of compounds represented by formulas (Fl) and (F II), see JP-A-63-158545 and JP-A-63-158545;
Delicious.

On the other hand, more preferable compounds of the compound Th (G) that chemically bond with the oxidized form of the aromatic amine developing agent remaining after the color development process to produce a chemically inert and colorless compound are as follows: (CI).

General formula (GE) -Z In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and 2 is a nucleophilic group or a nucleophilic group that is decomposed in the photosensitive material to release the nucleophilic group. The compound represented by the general formula (CI), which represents a group, has a nucleophilic "C11sl" in which Z is P@arsor+
(if! (R,G, I'earson+ at a
l,, J, ^l.

Chew, Soc, 3j1.319 (1968)
) is preferably 5 or more, or a group derived therefrom.

Specific examples of compounds represented by formula -a (CHI) are disclosed in European Patent Publication No. 255722 and Japanese Patent Application Laid-open No. 1983-143.
No. 048, No. 62-229145, Patent Application No. 63-13
No. 6724, and details of the combination of compound (G) and compound (F) are described in European Patent Publication No. 277589.

The photosensitive material made using the present invention has a hydrophilic colloid layer with ultraviolet &! It may also contain an absorbent. For example, aryl-substituted benzotriazole compounds (e.g., those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314,794)
No. 3,352.681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., those described in U.S. Pat. No. 3,352,681),
, 705.805 and 3.707.375), butadiene compounds (e.g., U.S. Pat. No. 4.04);
5.229) or benzoxidol compounds (such as 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.

Colloidal silver and dyes are used in the full-color recording material of the present invention to prevent irradiation and halation, 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 dye described above or the same dye can be used by introducing a water-soluble group that can flow out during processing.The infrared dye of the present invention is colorless and has no substantial light absorption in the visible wavelength range. It's okay.

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 the colloid layer other than the photosensitive layer. For this purpose, the dye is preferably contained in a predetermined colored layer in a diffusion-resistant state. First, the dye is contained in a ballast group. This is to make it diffusion resistant. 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 gelatin manufacturing method can be found in "The Macromolecular Chemistry of Gelatin" by Arthur Vuis. ” (Academic Press, published in 1964).

The color photosensitive material of the present invention includes a photosensitive layer (YL) containing a yellow coupler, a photosensitive layer (ML) containing a magenta coupler, a photosensitive layer (CL) containing a cyan coupler, and a protective layer on a support. (PL), middle layer (IL)
), and if necessary, a colored layer, especially a haleysilane prevention layer (AH), which can be decolorized during development processing, is provided. YL, ML, and CL have spectral sensitivities that are compatible with at least three types of light beams having different dominant wavelengths. The main sensitivity wavelengths of YL, ML, and CL are each separated by 30 nm or more, preferably 50 nm to 100n100n, and the main sensitivity wavelength of one photosensitive layer is at least 0.8Lo different from that of the other photosensitive layer.
g, E (light amount), preferably there is a sensitivity difference of 1.0 or more. At least one of each photosensitive layer is sensitive to wavelengths longer than 670 nm, more preferably at least one layer is sensitive to wavelengths longer than 670 nm.
Preferably, the layer is sensitive to wavelengths longer than 750 nm.

For example, as shown in the following table, in Table 6, R indicates red sensitization, 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, and 67 nm.
The spectral sensitivity of the present invention in the wavelength region longer than 0 nm and in the infrared wavelength region tends to be relatively broad. 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 a pH of 7 and insoluble in water at a pH of 7 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. 197947, dyes represented by the general formulas (Vl) and (■) are used. In the first method, dyes having a carboxyl group are useful.

As the support used in the present invention, transparent films such as cellulose nitrate films and polyethylene terephthalate used in photographic light-sensitive materials and reflective supports can be used. More preferred.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Hydrophobic resins coated with a hydrophobic resin containing dispersed light-reflecting substances such as titanium oxide, zinc oxide, calcium carbonate, fLM calcium, etc. to increase reflectance in the visible light wavelength range, and hydrophobic resins containing dispersed light-reflecting substances. Examples include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyethylene terephthalate, Examples include polyester films such as cellulose triacetate or cellulose nitrate, polyamide films, polycarbonate films, polystyrene films, and vinyl chloride resins, and these supports can be appropriately selected depending on the purpose of use.

As the 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 inclined 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 calculated by dividing the observed area into adjoining unit areas of 6 μm x 6 μm, and dividing the area of fine particles projected onto that unit area. It can be determined by measuring the occupied area ratio (%) (R4). The coefficient of variation of the occupied area ratio (%) can be determined by the ratio S/R of the standard deviation S of the R direct to the average value (R) of R1. The number of target unit areas (n) is preferably 6 or more, and therefore the coefficient of variation s/R can be determined.

In the present invention, the coefficient of variation of the occupied area ratio (%) of fine pigment particles is 0.15 or less, particularly 0.15 or less. 12 or less is preferable.

Metal THII, such as aluminum or a light alloy, as a light-reflecting substance, JP-A-63-11815'4, JP-A-63-11815'4;
No. 3-24247, No. 63-24251 to No. 63
It is also possible to use metals having a specular reflective surface or a type 2 diffuse reflective surface as described in Japanese Patent No. 24253 and Japanese Patent No. 63-24255.

Since the support used in the present invention is used as a hard copy after image formation, it is preferable to use one that is lightweight, flexible, and has good elasticity, and is also inexpensive.

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

The color photographic material of the present invention includes, for example, color negative film for photography (general use, movie use, etc.), color reversal film (for slide use, movie use, etc.), color photographic paper, color positive film (for movie use, etc.), color reversal printing Paper, color photosensitive materials for heat development, color photosensitive materials for plate making (lith film, scanner film, etc.), color X-ray photosensitive materials (direct/indirect medical use, industrial use, etc.), color diffusion transfer photosensitive materials (DTR) ), etc.

(Example 1) Silver halide emulsion (11) used in the examples of the present invention was prepared as follows.

(Liquid 1) (Liquid 2) Sulfuric acid (IN) (Liquid 3) The following silver halide solvents (1%) 4cc cc (Liquid 4) (Liquid 5) (Liquid 6) The following agents were obtained. This emulsion contains 1.0×10-'mol 1 mol Ag.
of chloroauric acid and sodium thiosulfate were added to perform optimal chemical sensitization.

Next, silver halide emulsions with different silver chloride contents (21°(
3), (4) and (5), above 4 liquid and 6 liquid KB
r.

Similar preparations were made by changing the amount of NaC1 and the addition times of liquids 4 and 5 as shown in Table 1.

(Liquid 7) (Liquid 1) was heated to 56°C, and (Liquid 2) and (Liquid 3) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 30 minutes. After a further 10 minutes, (Liquid 6) and (Liquid 7) were added simultaneously over a period of 20 minutes. After 5 minutes of addition, the temperature was lowered and desalted. Add water and dispersed gelatin and reduce p)l to 6.
2, average particle size 0.45 μm, coefficient of variation (standard deviation divided by average particle size: s/d) o
Table 2 shows the average grain size, coefficient of variation, and halogen composition of the monodisperse cubic silver chlorobromide hole silver halide emulsion ill (5) containing 70 mol % of silver bromide.

Table 2 Emulsions 111 to 111 to (5) previously prepared were added and combined with the emulsified dispersions of aggravating dyes and color couplers shown in Tables 3, 4, 5, and below, and the compounds related to the present invention. In Tables 6 and 7, the samples shown in Table 5 were prepared, and the sample height was A series. For the B series sample magnet in 4, the above-mentioned additives were added to both the third and fifth layer emulsions, and the emulsions were stored in a solution state at 40°C for 8 hours before coating. The first
Layer (S-1) Sensitizing dye (a-1) Color image stabilizer SO3- (Solv-1) Solvent material, and the B series samples in Table 5 are similar to the emulsion for the fifth layer only. This is a sample that was applied after being stored in a solution state for 8 hours at 40'eg.

In addition, in the sample of multilayer color photographic paper coated on a paper support laminated on both sides with polyethylene, emulsion (3) was used as the emulsion for the first layer, and sensitizing dye (
S-1) per 1 silver halide 4. 5 x 1
G-'mol was added. In addition, samples-1-14 to 1-2
Emulsion (3) is used for all emulsions for the third layer in No. 5, and l-12 is halogenated as an infrared sensitizing dye! i1 mol
1.2×1 G-'mol was added per sample.

Furthermore, in all samples, 2.4-dichloro-6-hydroxy-1,3,5-) riazine sodium salt was used as the curing agent for each layer.

(b-1) Dye 50, K SO3 for the second layer (d-1) Color mixture prevention agent 0 ■ For the third layer (a-2) Color image stabilizer R L; H3L; lis (Solv-2) Solvent (2:1 mixture (weight ratio) with 0*HltO±, P-to 0) (b-2) For dye 4th and 6th layers (e-1) For ultraviolet absorbing dye 5th layer (a-3) Color 1:3:3 mixture of image stabilizer (mole ratio) (Solv-4) 1:5:3 mixture of solvent (mole ratio) (d-2) Color mixing inhibitor H H (Solv-3) Solvent (i30cwHtso÷ 3P-0 Electric (C1m)*SOJ (CHm)eSOs- Comparison compound and other compounds added to the billing layer (S-2
) Comparative compound Cs1l++ C10#- C Goose Hs (S-3) Comparative compound C Snowh C,H.

C10,- (S-4) comparative compound C3H fu C,H.

(f-1) Anti-capri agent (f-2) Anti-foggant (f-3) Anti-capri agent Samples A and B of samples 1-1 to 1-13 and 1-20 to 125 have interference at 77Qnm. filter and 820n
Samples 1-14 to 1-19 were exposed to gradation light for sensitometry for 1/10" second through a 5 kW interference filter using a condensing exposure device using a 5 kW tungsten lamp.
Samples A and B were similarly tone-exposed through a 7'ronm interference filter and an 840 nm interference filter.

The exposed sample was subjected to color development in the next processing step using a paper processing machine.

Toro Uni■ Mubi Tomo Roinuki 1 Throw 111 Color development 35℃ 45 seconds 161d 171 Bleach fixing 30~35℃ 45 seconds 215+d 17 Z rinse■ 30~35℃ 20 seconds -ill rinse■ 3
0~35℃ 20 seconds -10Il rinse 030~35
℃ 20 seconds 350d 10 j drying 70
~80 DEG C. for 60 seconds

Meng J:”■1 night water Ethylenediamine-N.

N, N, N-tetramethylenephosphonic acid triethanolamine sodium chloride potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate N,N-bis(carboxymethyl ) Hydrazine optical brightener (WRITEX 4B, manufactured by Sumitomo Chemical) Add water to pH (25℃)! 2! i1. Filter crism 800d 800m 1.5g 2.0g 8.0g 12.0g 1.4 g 5g 5g 5.0g 7.0g 5.5g 7.0g 1.0 g 2.0g 1000m 1000ml lOllo 0O,45 Hoshiwata Mainly produced water (tank fluid and refill fluid are the same)
400d Ammonium thiosulfate (70%) 10 (ld Sodium sulfite 17g Iron(III) ammonium ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Add water 1000adpH (25°C) 6.
0 1-Gosan (tank fluid and refill fluid are the same) Ion-exchanged water (calcium and magnesium are each 3pp
m or less) Photographic properties were evaluated for magenta color density for those exposed through a 770 nm interference filter, and 84
Those exposed through a 0nm interference filter or an 82Qnm interference filter are measured for cyan coloring density, and the overlap density (Dain) and overlap density are 0.
The relative sensitivity was determined by taking the reciprocal of the exposure amount required to give a density of 5.5% as the sensitivity.

Tables 6 and 7 show the results obtained at 40°C for 8 hours.
Relative values of overlap density sensitization and relative sensitivity of B series samples whose emulsions were stored in a solution state with respect to the corresponding A series samples which were not preserved (when the relative sensitivity of each of the A series is set to 100) The relative values of the relative sensitivities of the corresponding B series samples were shown.

Table 7 Table 7 (Continued) From Table 6, sample 1 using a sensitizing dye other than the present invention in two layers
1-B to 1-5-B, as the silver chloride content in silver halide increases, the sensitivity decreases when the emulsion is stored in a solution state for a long time after adding compounds such as sensitizing dyes and coupler emulsions. The decrease in the density and the increase in the overlap density were remarkable, and even in emulsions with a silver bromide content of 70 mol% other than those of the present invention, they were still slightly larger.
It can be seen that when the silver chloride content exceeds 85 mol %, it increases rapidly. On the other hand, samples 1-6-B to 1-11-B, in which the sensitizing dye of the present invention was used in two layers, showed a decrease in sensitivity and an increase in overlap even when the silver chloride content was 85 mol% or more. In sample 1-12-B, which uses a very small amount of compound r-1 or f-3, which also causes a supersensitizing effect, the supersensitizing effect is almost lost as the emulsion solution ages. However, the relative sensitivity of the magenta coloring layer of sample 1-13-A was 363, when that of the corresponding sample 1-9-A, which did not use compound f-1, was taken as 100.
The relative sensitivity of the cyan coloring layer was not only as high as 417, but also as high as 417, when that of the corresponding sample 1-10-A, which did not use compound f-3, was taken as 100.
Although sample -B loses some of the high sensitivity of sample 1-13-A, it maintains it compared to sample 1-12-B, which is not a sample of the present invention, and the superiority of the present invention can be understood. Good morning.

In addition, from the results of the cyan coloring part of Samples 1-14-B to 1-25-B in Table 7, it was found that compound f-3, which uses a merocyanine infrared sensitizing dye and also has a supersensitizing effect, Even when the supersensitizer mV-1 is used in combination, as shown in the results shown in Table 6, even when a high silver chloride emulsion with a silver chloride content of 85% or more is used, the combination of the present invention does not produce an emulsion. It will be understood that when the magenta of sample 1-14-B-1-25-B is left in solution for a long time, the large decrease in sensitivity and increase in overlap brought about by combinations other than those of the present invention are not so significant. From the results of the coloring part, even if an infrared sensitizing dye within the present invention is used in one layer of the infrared sensitive color layer, when an infrared sensitizing dye other than the present invention is used in the other infrared sensitive layer, chloride Silver content is 85 mol%
It will be understood that in the above-mentioned high silver chloride emulsion, the reduction in sensitivity is further increased due to the influence of other layers, and it is not possible to suppress fog even if an anti-fog agent is used.

Samples l-20-A-1-21-A and 1-22-A were f
-3 and IV-1 provide higher cyan sensitivity, but also samples 1-23-A, 1-24-A and 1-
The relative sensitivity of the cyan coloring layer of 25-A is as a relative value, assuming that the relative sensitivity of the cyan coloring layer of the corresponding samples 1-6-A, 1-7-A and 1-9-A is 100. Not only did 331.525 and 479 provide high sensitivity (as mentioned above, they are also an excellent technology that maintains these high sensitivities even when the emulsion is left in solution for a long time). Ta.

In order to provide silver halide color light-sensitive materials in large quantities and at low cost, it is often necessary to store the emulsion with various additives in a solution state for a long time before coating, and the sensitivity Deterioration and increase in overlap are very serious problems in the stable production of high quality photosensitive materials.The combination of the present invention is an excellent solution to these problems.

From the results in Tables 6 and 7, it can be seen that when using halogenated 1 (1) with a silver bromide content of 70 mol%, the above problems are met considerably, and there is no big difference from the combination of the present invention. However, the ratio of the color density obtained by developing for 45 seconds with the sensitivity point at which a color density of 2.5 was obtained with the developing solution, which is twice the development time of 90 seconds, is the cyan color-forming layer and the magenta color-forming layer. In both cases, the high silver chloride emulsions with a silver chloride content of 85 mol% or more were 95% or more, whereas the emulsion (11
However, the percentage is as low as 80 to 85%, which is unfavorable for rapid processing, and cannot meet the demand for rapid processing, which has become increasingly popular in recent years.

Example 2 A semiconductor laser GaAjAa ( (oscillation wavelength approximately 760 nm) and semiconductor laser GaA! Using As (oscillation wavelength of about 830 nm), scanning gradation exposure was performed using an apparatus in which a sample centered on a rotating polyhedron can be moved in the vertical direction with respect to the scanning direction of the laser beam.

The exposure amount was controlled electrically.

The exposed sample was subjected to color development using the same color developer as in Example 1.

In the case of exposure with an oscillation wavelength of about 760 nm, the color density of magenta is 3.5% at 75% RH and 45°C for the density of cyan in the case of exposure with an oscillation wavelength of about 830 nm.
Table 8 shows the relative values of the relative sensitivities of the samples stored under the above conditions for 3 days, when the relative sensitivities of the samples that were not stored for 3 days were each set to 100. In addition, the sensitivity is 1.
It is expressed as the reciprocal of the exposure amount required to give the density plus 0.

Table 8 From Table 8, as in Example 1, samples 11m1-1-A and 1-6 had little desensitization even when stored at 75% RH and 45°C. -A has less desensitization after storage, and 1-6-A in particular seems more preferable than the present invention at first glance, but as described in Example 1, rapid processing with a color development time of 45 seconds In time, the color development rate is 1-
1-A is about 86%, 1-6-A is about 84%, and the other ones have a color development rate of 95% or more (those using silver halide with a silver chloride content of 95 mol% or more are 97% or more) ), which is not desirable in terms of processing speed.

Example 3 Samples 3-1 to 3-1 shown in Tables 9 and 10 were prepared by combining the silver halide emulsions (3) and (5) used in Example 1, an emulsified dispersion of a color coupler, a compound related to the present invention, etc. 3
-7 was created.

At this time, the aggravating dye (S-5) was added to the emulsion for the first layer at 4.0% per 111 mol of halogen. 5 X l O-'+io
l and KBr per mol of silver halide 8 x 10
2.0 x 10'' of anti-fogging agent (f-3) was added per 1 mol of silver halide.

In addition, as anti-eradication dyes, dye (b-1) was added to the emulsion for the first layer, and dye (b-2) was added to the emulsion for the third layer.
), and dye (b-3) was added to the emulsion for the fifth layer. Furthermore, all stations use 2,4-dichloro- as a gelatin hardening agent.
A mixture of 6-hydroxytriazine sodium salt and 2-hydroxy-1,3-bis(vinylsulfonyl)propane in a molar ratio of 3:1 was added.

(S-5) Sensitizing dye SO, Na 5O, - (S-6) Sensitizing dye [comparative compound] l C Hs (S-7) Sensitizing dye [comparative compound] (g-1) Superchromic sensitization Sensitizer CHtCH-CHx Cj- Divide each sample into two and divide only one half into 80% RH14
These samples were stored at 5° C. for 3 days and then exposed using the scanning laser exposure device used in Example 2, and color development was performed in the same manner as in Examples 1 and 2.

The oscillation wavelength of the laser light is approximately 680 nm and approximately 7 nm, respectively.
GaA j As semiconductor lasers of 60 nm and about 830 nm were used and scanned at 84 m/sec.

Table 11 shows the composition sensitivity and coverage results obtained. Sensitivity is expressed as the reciprocal of the exposure amount required to give a density equal to the overlap density plus 0.5. The relative sensitivity in Table 11 is relative to the yellow color density when exposed at an oscillation wavelength of approximately 680 nm. That of approximately 75Qnm is for magenta color density, and that of approximately 830nm is for magenta color density.
m is for the cyan coloring density, and in the case of samples 3-1 to 3-3 with the same silver halide bill division combination, 80% of sample 3-1 (RH, 3 days at 45°C) In the case of samples 3-4 to 3-7, the relative sensitivity for each color development of samples similar to sample 3-4 was calculated as 100. It is shown as a relative value.

From the results in Table 11, even in ultra-short exposure with laser light, the structure of the present invention is effective for heterocyclic quaternary salt compounds such as compound (g-1) and compound (f-3). Heterocyclic compounds and compounds having a mercapto group (IV-7)
It is an excellent technology that not only provides a large sensitizing effect using bisaminostilbene compounds, but also shows very little decrease in sensitivity and increase in fog even when exposed to high humidity of 80 RH. , - You can understand the layers.

Example 4 A multilayer color photographic paper shown in Table 12 having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. '! ! ! The cloth solution was prepared as follows.

1st layer coating solution preparation Yellow coupler (equimolar mixture of Y-1 and Y-4)
19.1 g, 4.4 g of color image stabilizer (a-1), and 0.7 g of color image stabilizer (a-7), and 27.2 cc of ethyl acetate.
Add and dissolve 8.2 g of solvent (3o1v3),
This solution was emulsified and dispersed in 18.5 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.

On the other hand, the coefficient of variation of the grain size distribution of silver chlorobromide emulsion (cubic, 3-near mixture (II molar ratio) of grain sizes 0.88 μm and 0.70 μm is 0.08 and 0.10.
, each emulsion contains 0.2 mol % of silver bromide locally on the grain surface) and a visible light-sensitive dye (S-5) per mol of silver for large-sized emulsions. lX1G-'
molar addition, and for small size emulsions, 2.
A sulfur sensitized product was prepared after adding 6 x 10-' moles. Mixing and dissolving the emulsified dispersion and this emulsion,
A first layer coating solution was prepared to have the composition shown below.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 2.4
-dichloro-6-hydroxy-1°3.5-) riazine sodium salt was used.

(Layer composition) The composition of each layer is shown below, and the numbers indicate coating! (g/cd)
The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO□) and a bluish dye (ulmarine)] -th layer (visible light sensitive layer) The above-mentioned silver chlorobromide emulsion 0.30 gelatin
1.86 yellow coupler (Y
-1 and Y-4 equimolar mixture)
0.82 Color image stabilizer (a-1) 0.19 Solvent (Solv-3) 0.35 Color image stabilizer (a-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention Agent (d-3) 0.08 solvent (So 1v-
1) 0. 16 solvent (Solv-4)
0.08 Fifth layer (infrared light sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture of one with an average grain size of 0.55 μm and one with an average grain size of 0.39 μm (Ag molar ratio) 0 grain size The coefficient of variation of the distribution is 0.10 and 0.0
8. Each emulsion contained 0.8 mol% of AgBr locally on the grain surface) 0.12 Gelatin 1.24 Magenta coupler (Equimolar mixture of M-10 and M-15)
0.20 Color image stabilizer (a-2) 0.15 Color image stabilizer (a-4) 0.02 Color image stabilizer (a-5) 0.03 Solvent (Solv-
2) 0.40 fourth layer (ultraviolet absorption layer) Gelatin 1.58 ultraviolet absorber (13-2) 0.47 color mixture prevention agent (d
-2) 0.05 solvent (Solv-5)
0.24 Fifth layer (infrared light sensitive layer) Silver chlorobromide emulsion (cubic, 1:4 mixture of one with an average grain size of 0.58 μm and one with an average grain size of 0.45 μm (Ag molar ratio) 0 grain size The coefficient of variation of the distribution is 0.'09 and 0.09.
0.23 gelatin 1.34 cyan coupler (C
-2, C-3 and C-4 in a weight ratio of 1:2:2) 0.32 Color image stabilizer (a-6) 0.
17 Color image stabilizer (a-8) 0.04 Color image stabilizer (a-7) 0.40 Solvent (S
olv-6) 0.15 6th layer (ultraviolet absorption layer) Gelatin 0.53 ultraviolet absorber (@-2) 0.16 color mixture prevention agent (d-
2) 0.02 solvent (Solv-5)
0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Also, for the first visible light-sensitive emulsion layer is an anti-irradiation dye (b
-4) and further compound (f-3) with halogenated 11
8.5 x 10-' moles were added per mole. For the third infrared-sensitive emulsion layer, an anti-irradiation dye (
b-3) and compounds related to the present invention such as sensitizing dyes shown in Table 12 were added. To the infrared-sensitive emulsion layer of the fifth layer, eradication prevention dye (b-2) was added,
Further, sensitizing dye (1-11) was added per mole of halogenated wi, 1.2 x 10-' mol for large-sized emulsions and 1.5 x 1 G-' mol for small-sized emulsions, and an anti-fogging agent ( f-3) and supersensitizer (g-2) and (IV-
7), respectively, at 2.0% per 111 moles of halogenation.
X1G-'mol, 1.2X1G-'mol and 1.5X1
G-bow mole was added.

(b-4) Dye (a-6) Color image stabilizer I colt) H (a-5) Color image stabilizer Ca1b(t) H COOC1IIs CJ*(t) 2:4+4 mixture (weight ratio) of (a-7) Color image stabilizer 1000H Yuki-CH-).

C0NHC*H*(n) Average molecular weight 60.000 (a-8) Color image stabilizer (e-2) Ultraviolet absorber C%N□ (1) 4:4 mixture (weight ratio) Table 12 (Solv- 5) Solvent COOCsHlt Direct (CHi)m COOCsH1t (Solv-6) Solvent (g-2) Supersensitizer CH rich CH=CH1 (S-8) Sensitizing dye [comparative compound] The prepared sample was used in Example 3 In exactly the same way as 2
After dividing and storing one portion at 80% RH and 45° C. for 3 days, all the samples were subjected to laser scanning exposure using the exposure device used in Example 3, and color development was performed in the same manner. Table 13 shows the relative sensitivity and overlap obtained. Sensitivity is expressed as the reciprocal of the exposure amount required to give a density of 0.5 plus the overlap density, and the yellow coloring density for exposure with a laser oscillation wavelength of approximately 680 nm is the same as that for exposure with a laser oscillation wavelength of approximately 780 nm. The relative sensitivity in Table 13 was measured for cyan color density, and for magenta color density for exposure of approximately 83 Qnm. It is shown as a relative value when the relative sensitivity of magenta color development and cyan color development is set to 100.

From the results in Table 13, the structure of the present invention shows that when the sensitizing dye of the present invention is used in combination with a color coupler, the sensitizing effect due to the heterocyclic compound having a mercapto group and the supersensitizing side is better. It is large in size, and there is little decrease in sensitivity or increase in capri even when stored at high temperatures. It can also be understood that the sensitivity of the outer emulsion layer also increases, albeit slightly, under high humidity conditions.

The structure of the present invention is an excellent technique that can provide a color photosensitive material with high sensitivity and excellent storage stability.

Claims (1)

[Claims] (1) In a silver halide photographic light-sensitive material having at least three silver halide emulsion layer units with different electromagnetic and spectrally sensitive layers on a support, each of the emulsion layers has an average content of silver chloride. contains color couplers that form mutually different dyes through a coupling reaction between silver halide and an oxidized product of a color developer in an amount of 85 mol % or more, and at least two layers of the emulsion layer unit each contain the following general dyes. Full color high silver chloride characterized by being spectrally sensitized to light in different infrared regions of the electromagnetic spectrum by betaine or anionic dyes represented by formulas (I) and/or (II) Photographic material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z^1^1 and Z^1^2 may be the same or different, and are respectively sulfur atom, oxygen atom -CH=CH-, It represents a selenium atom or ▲There are numerical formulas, chemical formulas, tables, etc.▼, and R^1^5 each represents an optionally substituted lower alkyl group, aryl group, or allyl group. When Z^1^1 represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R^1^1 and R^1^2, Z^1^2 represent ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R^1^ of case
3 and R^1^4 may be the same or different and each represents a hydrogen atom or an electron-withdrawing group. When Z^1^1 represents something other than ▲ there are mathematical formulas, chemical formulas, tables, etc. R^1^1 and R^1^2, Z^1^2 are ▲ mathematical formulas, chemical formulas, tables, etc. When representing something other than ▼, R^1^3 and R^1^4 may each be the same or different and include a hydrogen atom, a halogen atom, a hydroxy group, an optionally substituted lower alkyl group, a substituted R^1^1 and R^1^2 represent an optionally substituted aryl group, optionally substituted lower alkoxy group, lower alkylthio group, arylthio group, acylamino group, carboxy group, or lower alkoxycarbonyl group; and/or R^1
^3 and R^1^4 are connected at adjacent positions, 1, 2, 3
, 4-tetradehydrotetramethylene, tetramethylene, trimethylene, or methylenedioxy. G^1^1 and G^1^2 represent a substituted alkyl group having a sulfonic acid group or a carboxylic acid group, and G^1^
1 represents an optionally substituted alkyl group or alkenyl group, and also represents that it can be linked to G^1^3 to form a 5- or 6-membered ring. Furthermore, when G^1^2 is a substituted alkyl group having a carboxylic acid group, G
^1^1 represents a substituted alkyl group having a sulfonic acid group or a carboxylic acid group. G^1^3 represents a hydrogen atom. G^1^4 and G^1^5 may be the same or different, and each represents a hydrogen atom, an optionally substituted lower alkyl group, a lower alkoxy group, or an aryl group, and G^1^ 4 and other G^1^4 and/or G^
1^5 and other G^1^5 may be connected to each other and the ring constituent atoms may contain an oxygen atom, a sulfur atom, or a nitrogen atom 5
It means that it can also form a 6-membered ring or a 6-membered ring. n^1^1 and n^1^2 each represent 0 or 1,
n^1^3 represents 2, 3 or 4. Y^1^1 represents a cationic group, m^1^1 is 0 or 1, and is 0 when forming an inner salt. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z^2^1 is Z^1^1 in general formula (I)
expresses the same meaning as Z^2^2 is a sulfur atom, oxygen atom, selenium atom or ▲
There are mathematical formulas, chemical formulas, tables, etc. Represents ▼, R^2^3
represents the same meaning as R^1^5 in general formula (I). Z^2^3 represents a sulfur atom or a selenium atom. R^2^1 and R^2^2 are R in general formula (I)
Represents the same meaning as ^1^1 and/or R^1^2. G^2^1 is G^1^1 in general formula (I) and G
^2^3 is G^1^4 in general formula (I) and G^
2^4 represents the same meaning as G^1^5 in general formula (I). G^2^2 has the same meaning as G^1^1 in general formula (I), and also represents an optionally substituted aryl group or heterocyclic group, and G^2^1 and G^ At least one of 2^2 is a group having a sulfonic acid group or a carboxylic acid group, and when one is a group having a carboxylic acid group, the other is a sulfonic acid group, a hydroxy group, a sulfamoyl group, It represents a group having at least one of a carboxylic acid group or a carbamoyl group. n^2^1 represents 0 or 1, n^2^2 represents 2, 3
or 4. 2) A method for forming a color image, which comprises scanningly exposing the photographic material according to claim 1 to light in the infrared region, and then subjecting the material to color development. 3) The method for forming a color image according to claim 2, wherein the exposure is carried out using laser light emitted in an infrared region.