JPS5891444A - Photographic sensitive silver halide material - Google Patents

Abstract

PURPOSE:To improve the blue sensitivity of a silver halide emulsion with a high chloride content and the suitability to rapid processing by adding a specified merocyanine dye to the emulsion. CONSTITUTION:To an emulsion of silver halide particles contg. at least 80mol% silver chloride is added a merocyanine dye represented by general formulaI (where each of R<1> and R<2> is alkyl or aryl, at least one of them has sulfo, each of R<3>, R<4>, R<5> and R<6> is H, halogen, lower alkyl, lower alkoxy or phenyl, two of them may bond to each other to form a ring, and X is O or S). When the dye is added to an emulsion aged chemically with a sulfur sensitizer, the gradation is improved. This method is suitably applied to a blue sensitive emulsion layer which is used as the lowest layer of color photographic paper.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material, and more particularly to a blue-sensitized high chloride silver halide color photographic material, particularly a color photographic paper.

It is known that high chloride silver halide emulsions (meaning silver halide containing more than 80 moles of silver chloride) are capable of rapid processing. There may be several reasons for this, and one of the reasons may be that it is highly soluble. In conventional silver halide photographic materials, especially color photographic papers, a blue-sensitive emulsion layer using silver halide grains with a large grain size is located at the bottom layer, which makes it difficult to develop the blue-sensitive emulsion layer. Decline in sexuality was a problem0
However, by using the high chloride silver halide characteristic K,
Not only are these problems solved, but the current processing time is significantly reduced. In addition, since silver chloride hardly absorbs visible light, when used in silver halide color photographic light-sensitive materials, the blue sensitivity of edge-sensitive emulsions and red-sensitive emulsions and the blue sensitivity of blue-sensitive emulsions are higher than conventional emulsions. The difference between the two colors is enlarged, color turbidity is reduced, and good color reproduction is achieved. On the other hand, however, silver chloride emulsions are extremely disadvantageous when used as blue-sensitive emulsions because they have a narrow photosensitive range. Furthermore, according to research conducted by the present inventors, when the high chloride silver halide characteristic is chemically ripened using a sulfur sensitizer such as sodium thiosulfate, significant sensitization is observed only in the low concentration region of the aqueous curve at the initial stage. After that, sensitization was observed from medium to high concentration ranges, and it was found that a process of recovery of the brown tone was observed. In this case, the point at which gradation recovers, the point at which Capri begins to rise, and the point at which maximum sensitivity is reached are very close to each other, and the range in which satisfactory photographic performance can be obtained is limited to a very narrow time range. It has the following drawback. This is even more noticeable with relatively large grains, and the capri may begin to rise before the gradation is restored, making it clear that it is practically impossible to obtain satisfactory photographic performance.

In the chemical ripening of high silver chloride emulsions, the induction period is relatively long, and the subsequent changes are rapid, which together result in poor reproducibility of the photographic performance of chemically ripened emulsions.

Silver halide photographic materials, especially silver chlorobromide, which is mainly composed of silver bromide, used in color photographic paper, have spectral absorption biased toward the ultraviolet region. Does not react with properties. In order to eliminate the drawback of poor color reproducibility of the resulting yellow dye, attempts have been made to color-sensitize the blue-sensitive emulsion layer to impart absorption on the longer wavelength side. In addition, since the energy distribution of the exposure light source is biased toward the long wavelength side, it has been attempted to give the 710 silver germide emulsion a Wk value on the long wavelength side for the purpose of shortening the exposure time. For example, special public service in 1977-
No. 19034, No. 46-30023, No. 46-360
A method of color sensitization using a certain mepcyanine dye described in No. 75, etc., Japanese Patent Publication No. 50-37538, etc.
``It is known that sensitivity can be increased by using certain cyanine dyes that have been used in E-chemistry.

However, these methods do not suggest the same sensitizing effect when used in high-chloride silver halide emulsions as in the present invention, and they also do not suggest the same sensitizing effect when applied to high-speed color photographic materials using silver chloride. No mention is made of how the deficiencies will be improved.

It has been known that silver chloride emulsions have superior developability compared to conventionally used silver chlorobromide emulsions (containing 90 mo/I/% silver bromide). However, in this case, not only did the photosensitive range specific to silver halide become narrow to 400 nm, but it also suffered from the serious drawback that it was susceptible to capriulation, and the photographic performance of the chemically ripened emulsion significantly varied. In other words, in order to fully utilize the characteristics of excellent developability as a silver halide photographic light-sensitive material, it is necessary to keep the capri low, improve the reproducibility of chemical ripening, and further apply sufficient color sensitization. was occurring.

Therefore, the first object of the present invention is to provide a silver halide photographic material with high blue sensitivity that can be rapidly processed. It is an object of the present invention to provide a silver halide color photographic light-sensitive material with a small amount of color and good color reproducibility. The third object of the present invention is to
To provide a high-sensitivity silver halide color photographic material that can be rapidly processed and exhibits small sensitivity fluctuations by using high-chloride silver halide whose stability in photographic performance is significantly improved through chemical ripening. In view of these points, the present inventors have conducted intensive research and have arrived at the present invention.

That is, the present inventors have developed a photographic material having at least one silver tetragenide emulsion layer on a support, in which the silver tetragenide contains at least 480 g of silver chloride. It has been found that the above object can be achieved by using an emulsion comprising silver halide grains containing silver halide grains and color sensitized with at least one type of merocyanine dye represented by the following general formula (I).

General formula (I) 3 In the formula, R+ and V are an alkyl group (preferably 7 to 7 carbon atoms, such as a methyl group, a butyl group, an isopropyl group, a cyclohexyl group, a cyclopentyl group, and these can be used as substituents [e.g. may have a hydroxy group, methoxy group, sulfo group, ethoxycarbonyl group, carbamoyl group, oryl group, etc.), alkenyl group (e.g. allyl group), aryl group (e.g. phenyl group, etc.) as a substituent. For example, it may have a methoxy group, a sulfo group, a methyl group, etc.). However, R1 and R3
is an alkyl or aryl having a sulfo group, preferably R1 is a sulfo-substituted alkyl or a sulfo-substituted aryl.

11% R4, R1 and Ra are hydrogen atoms, halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom), lower alkyl groups (preferably 1 to 4 carbon atoms, e.g. methyl group, ethyl group, etc.), lower alkoxy It represents a group (preferably having 1 to 3 carbon atoms, such as a methoxy group, an ethoxy group, etc.) or a phenyl group. R4 and Ra may be combined with each other to form a ring to complete a naphtho(2,3-+1)azole ring*, or may form a dioxacyclopentane ring. R3 is bonded to a hydrogen atom or R4 to form a ring to form a naphtho(2,1-d)azole ring, and R6 is bonded to R3 to form a naphtho(2,1-d)azole ring.
-(IJ represents a group which may combine with an azole ring or with R1 to form a 5-membered or 6-membered ring. X represents an atom selected from an oxygen atom or a sulfur atom.

In the present invention, in order to realize good developability and good color reproducibility with less color turbidity, the silver halide composition of the silver halide grains is silver iodide of 1 molar or less and silver bromide of less than 20 molar. , furthermore at least 80 mol% silver chloride, preferably <F
It is preferable to use a helekenized chain emulsion having an i of 100 mol %.

When the high chloride silver halide emulsion according to the present invention is used instead of the conventional silver halide emulsion mainly composed of silver bromide, the drawbacks are a decrease in sensitivity, a fluctuation in sensitivity during chemical ripening, and a narrowing of the photosensitive area. Conventional color sensitization techniques did not improve the problem. For example, when the merocyanine dye described in Japanese Patent Publication No. 45-19034 and the cyanine dye disclosed in Japanese Patent Publication No. 50-37538 are used in the high chloride silver halide emulsion according to the present invention, a sensitizing effect is observed in some cases. However, it was unsatisfactory due to a severe increase in capri during chemical ripening. However, the addition of the specific compound represented by the above general formula of the present invention resulted in a good photograph with high blue sensitivity and the above drawbacks improved. It was found that the characteristics can be obtained.

The following compounds can be mentioned as typical examples of the compounds according to the present invention, but the present invention is not limited by these.〇291011
12Sos1m
So, N(0, H,)3
OsK The dyes used in the present invention can be dyed using known methods such as Th@0ynnin@Dy@s and Re.
1ated Oow+ -pounds) (Inter Science Publishers (Entsr 8o
1enas Publishers) 1964)
and U.S. Patent Nos. 2,185,182 and 2.519.
．． It can be easily synthesized by referring to the methods described in No. 001, British Patent No. 450,958, and the like. Next, a specific synthesis method will be shown.

Synthesis Example 3-Ethyl-5-(3-(-4-sulfobutyl)-2(
3a) Synthesis of triethyl acetic acid salt of penzothiazoliden]-2-thousand-1゜3-7-shinasiridine-2,4-dione (exemplary dye 1) 4-(2-methylthio-3-benzothiazolio)-butane -1-sulfoner) 8. ON and 3-ethyl-2-
Thio-1,3-selenazolidine-2,4-dione 5.2
# and T ethanol "200", added 6jl'l of triethylamine [heated on a water bath for 15 minutes] After cooling, the precipitated dye line was removed and washed with ethanol to obtain crude crystals 9.4i. Melting point 198-200℃ , λwax432n Oboro.

Conventionally known methods can be used to add the compound represented by the above general formula according to the present invention (sensitizing dye according to the present invention) to a silver halide emulsion. For example, special public service in 1973
-44895, method of adding by dispersing with a surfactant described in JP-A-50-11419, JP-A-53-1
No. 6624, No. 53-102732, No. 53-102
Examples include the method of adding as a dispersion with a hydrophilic substrate as described in No. 733, and the method of adding as a solid solution as described in East German Patent No. 143.324.

Also, water-soluble solvents such as water, methanol, ethanol,
It may be dissolved in acetone or fluorinated alcohol alone or in a mixed solvent and added to the emulsion. The sensitizing dye according to the present invention may be added to the emulsion at any stage during the emulsion manufacturing process, but preferably during or after chemical ripening. The compound represented by the general formula according to the present invention is generally #i1 is added in an amount of from 5.times.10 to 3.times.10" mol, preferably from #i1 to 7.5.times.10" mol per mole of silver halide.

As mentioned above, the silver halide emulsion used in the present invention contains at least 1t80 moles of silver chloride,
Written by Be Graphkid (P, Glafk1d@s)
himls at Physiqu Photogra
phiqus) (Foul Mo
(1967), Photographic Emulsion Chemistry (G, P, Duffin)
hio Emulsion Oh@m1stry)
(The Focal Pre
ss) published in 1966), V, L, Zsllkmmn *tal) Making and Coating Photographic
Emulsion soda (Making IL!L(l Ooot)
ingPhOtOgraphiOmmulslom)
(The Focal Press
It can be produced by a conventionally known method as described in 1964). That is, any of the acid method, neutral method, and ammonia method may be used. In addition, regarding the method of mixing hetetragenide salt and silver salt aqueous solution, see Sekiku Hirata, Nippon Photographic Instruments "Fundamentals of Photographic Engineering - Silver Salt Photography Edition" (
■The positive mixing method, which is described in Chapter 3 of Corona Publishing Co., Ltd.
Either the back mixing method or the simultaneous mixing method can be preferably used, but the simultaneous mixing method is preferable for ll#.

This silver halide emulsion is described in, for example, Research Disclosure.
The sensitization can be carried out using a chemical sensitizer selected from those published in Japanese Journal 17643.゛Specifically, sulfur sensitizers such as allylthiocarbamide, N,W-diphenylthiourea, sodium thiosulfate, and cystine, selenium sensitizers such as tetramethylselenourea, potassium chlorofluoride),
Palladium compounds such as auric trichloride, potassium auric thiocyanate, 2-aurothiabeammonium chloroparadate, sodium chloropaladite, platinium compounds such as potassium chloroplatinate, noble metal sensitizers such as ruthenium compounds, rhodium compounds, iridium compounds, etc. , or a combination of such sensitizers. In addition to such chemical sensitization, this emulsion can also be subjected to reduction sensitization using hydrogen gas and a reducing agent such as stannous chloride.

Furthermore, if the sensitizing dye according to the present invention is added to the emulsion prior to or immediately after the addition of the sensitizer in the chemical ripening process, there will be no change in tone due to chemical ripening. Addition of a substance such as adenine is also known to have the effect of shortening the induction period of sensitivity change, and is particularly preferred as a technique for improving gradation changes associated with chemical ripening. The present invention solves these drawbacks, which not only reduce the maximum sensitivity but also relatively increase fog.

In the present invention, the yellow dye-forming coupler contained in the silver halide emulsion is a conventionally known open-chain ketomethylene coupler.
α-benzoylacetamide coupler with water solubilizing group described in No. 30, U.S. Pat. No. 2,407,210;
2.87.5,057, 3.409.439,
3.551.155, 3.551.156, 3.649.276, 3.685.995, and α-benzoylacetamide couplers described in British Patent No. 1,286,411; 4, such as α-pivaloylacetamide couplers described in U.S. Pat. No. 3,265,506.
Equivalent couplers, as well as U.S. Pat. No. 3,277.155;
No. 3,447,928, No. 3,408,194, No. 3,415,652, West German Patent Publication No. 2,213.4
A two-equivalent force puller described in No. 61 can be used. Specific examples of preferred yellow-dye forming couplers include the following.

The magenta dye-forming couplers used in the present invention include generally known pyrazolone couplers, etc.
As cyan dye-forming couplers, generally known phenolic and naphthol couplers can be used. Various known techniques can be applied to incorporate these couplers into the silver halide emulsion. For example, after dissolving in a high boiling point organic solvent such as tri'cresylphosphenide or dibutyl phthalate or a low boiling point organic solvent such as ethyl acetate or butyl propionate, alone or in a mixed solvent, it is dispersed in an aqueous gelatin solution containing a surfactant. te/%0
Added to silver oxide/silver oxide emulsion. Furthermore, those having alkali solubility can also be added by the Fischer dispersion method.

The silver halide photographic material according to the present invention may contain various other photographic additives. For example, anti-capri agents, stabilizers, ultraviolet absorbers, color image fading inhibitors, color stain inhibitors, fluorescent whitening agents, antistatic agents, as described in Research Disclosure, No. 17643,
Hardeners, surfactants, lubricants, fMIIi agents, etc. can be used.

In the silver halide photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the photosensitive emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyethyl cellulose. , cellulose S conductors such as carboxymethyl cellulose, Iwako derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

The green-sensitive emulsion and red-sensitive emulsion used together with the silver halide photographic light-sensitive material of the present invention are each optically sensitized using an appropriate sensitizing dye in order to impart a desired sensitivity wavelength range Ks. . Various sensitizing dyes can be used, and 11 types of sensitizing dyes or a combination of two or more types can be used. Examples of sensitizing dyes that can be advantageously used in the present invention include the following.

That is, as sensitizing dyes used in edge-sensitive emulsions, for example, U.S. Pat.
, No. 908, No. 2,739,149, No. 2.94
Cyanine dyes, merocyanine dyes, and Fi
Complex cyanine dyes can be cited as a typical example. Further, as sensitizing dyes used in red-sensitive emulsions, for example, U.S. Pat.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 442.710, No. 2,454,629, No. 2776.280, etc. .

Furthermore, U.S. Patent No. 2,213,995;
．． Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 493,748, German Patent No. 2,519,001, West German Patent No. 929,080, etc. can be advantageously used in green-sensitive emulsions or red-sensitive emulsions. ◇ The silver halide photographic light-sensitive material of the present invention has a blue-sensitive emulsion layer according to the present invention containing various photographic additives as described above, a green-sensitive emulsion layer, a red-sensitive emulsion layer, and a green-sensitive emulsion layer. Advantageously produced on a support which has been treated with a corona discharge treatment, flame treatment or UV irradiation together with the layers and other constituent layers or by coating the support via a subbing layer, an intermediate layer. Supports that can be used include, for example, baryta paper, polyethylene-coated paper, polypyrene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc. These supports are appropriately selected depending on the purpose of use of the silver silveride photographic material. In the present invention, the intended effects of the present invention can be satisfactorily exhibited as described above in any arrangement of the light-sensitive emulsion layers. Preferably, a blue-sensitive emulsion layer, an edge-sensitive emulsion layer, and a red-sensitive emulsion layer are arranged in order from the body side.

In addition, in the silver halide photographic light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and various layers such as a filter layer, an anti-curl layer, an insulating layer, and an anti-halation layer can be provided. The layers can be used in appropriate combination as constituent layers. Hydrophilic colloids that can be used in photosensitive emulsions such as those described above can be similarly used as binders in these constituent layers, and various types of colloids that can be contained in photosensitive emulsions such as those described above can be used in these layers. Photographic additives may be included as well.

The silver halide photographic material of the present invention is used for various purposes and exhibits excellent characteristics depending on the purpose. It can be used in direct positive light-sensitive materials, special purpose (for example, printing, X-ray, high resolution, infrared, and ultraviolet) silver-silveride photographic light-sensitive materials, etc., but especially for color photographic paper. Appropriate.

After exposure, the silver halide color photographic light-sensitive material of the present invention is advantageously color-developed by a color development method used for conventional coupler-containing internal type 710 silver halide color photographic light-sensitive materials. In the reversal method, the film is first developed with a black-and-white negative developer, then exposed to white light or treated with a bath containing a capri agent, and then developed with an alkaline developer containing a color developer. Then, as an oxidizing agent, ferricyanide or aminopolycarboxylic acids (e.g. aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, tonic hydroxyethylethylenediaminediacetic acid, malonic acid, tartaric acid, malic acid, diglycolic acid, The silver image and residual silver halide are removed by processing with a bleaching solution containing a ferric salt of dithioglycolic acid (such as dithioglycolic acid), and then fixing with a fixing solution containing a silver salt solvent rumored to be thiosulfate. Instead of using a bleach and fix solution that leaves a dye image, a one-bath bleach-fix solution containing one part ferric salt of an aminopolycarboxylic acid as an oxidizing agent and one part silver salt solvent as thiosulfate is used to bleach-fix. You can also. Further, in combination with color development, bleaching, fixing, or bleach-fixing, various treatments such as washing with water, stopping, stabilizing, etc. can be performed. In particular, the processing steps in which the silver halide color photographic light-sensitive material of the present invention is advantageously developed include, for example, color development, water washing if necessary, white fixing, washing, and stabilization and drying steps if necessary. - This processing step is carried out at a high temperature of, for example, 30° C. or higher and within a very short time.

Color-forming silver halide color photographic light-sensitive material of the present invention 11t
Particularly useful color developing chemicals used in gIA are primary phenylene diamines and derivatives thereof, such as the following representative examples:

M,N-dimethyl-p-phenylenediamine N,N-
Die-μmp-phenylenediamine, carbamidomethyl-N-methyl-p-phenylenediamine, N-carbamidomethyl-1-tetrahydrofurfuryru-2-methyl-p-phenylenediamine, ethyl-N-carboxymethyl-2- Methyl-p-phenylenediamine, U-rubamidomethyl-ethyl-2-methyl-p
-phenylenediamine, N-ethyl-tetrahydrofurfuryl-2-methyl-p-aminophenol, 3
-acetylamino-4-amino/dimethylaniline, bi-ethyl-N-β-methanesulfonamidoethyl-4-
Aminoaniline, σ-ethyl ruby β-methanesulfonamidoethyl-3-methyl-4-aminoaniline, d-
Sodium salt of methyl-β-sulfoethyl-p-phenylenediamine, etc.

The silver halide photographic material of the present invention may contain these color developing agents in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath. A color developing agent precursor is a compound that can produce a color developing agent under alkaline conditions, and is a Schiff base [2 recasa, polyvalent metal ion complex precursor,
Examples include phthalic acid imide derivative precursor and urethane type breaker. Precursors of these aromatic primary amine color developing agents are, for example, U.S. Pat. No. 3,342,59
No. 9, No. 2,507,114, No. 2,695,2
．． No. 34, No. 3,719,492, British Patent No. 80
No. 3,783, Special No. 53-185628, No. 54-
No. 79035, Research Disclosure Magazine 151
59, 12146, 13924. These aromatic primary amine coloring agents or their precursors need to be added in such amounts that sufficient coloring can be obtained when activated. This amount varies depending on the type of photosensitive material, but it is generally in the range of 0.1 to 5 mol, preferably 0.5 to 3 mol, per 1 mol of photosensitive silver halide. The main drug or its precursor can be used alone or in combination.In the photosensitive material: Built-in f
It can also be added by dissolving it in an appropriate solvent such as water, methanol, ethanol, or acetate, or it can be emulsified using a high-boiling organic solvent such as dibutyl phthalate, dioctyl phthalate, or tricresyl phosphate. It can also be added as a dispersion, Research Disclosure Magazine 1
They can also be added by impregnation into latex polymers as described in US Pat.

The present invention will be illustrated below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A silver chloride emulsion with an average grain size of 0.6 μm prepared by neutral simultaneous mixing was prepared using 2×10 −1 moles of sodium thiosulfate pentahydrate per mole of silver halide. The mixture was aged and divided into 20 pieces. The following was added per mole of silver halide, 0.3 mole of yellow coupler (YO--IF) and 0.15 mole of a color stain inhibitor (color) per mole of silver halide. Dibutyl phthalate (hereinafter DB
P) was added. The above emulsion was coated on a photographic support coated with polyethylene containing anatase-type titanium oxide at an amount of 0.35 N/j (in terms of silver) and an amount of gelatin of 39/d, and gelatin was further applied thereon at a rate of 29/vtl. It was applied to form a protective layer. The coating contained bis(vinylsulfonylmethyl)ether as a hardener and saponin as a spreading agent.

For each of the samples prepared above, a photosensitive needle (
The film was exposed to blue light using a 1s-7m (manufactured by Konishi Roku Photo Industry Co., Ltd.), and then subjected to the following color development treatment.

* (An'flj-1) 4-hydroxy-6-methyl-1,3,3&,7-chitrazaindene → (yo-1)α-(1-benzyl-2,4-leoquine-3-imidazolidini, / I/)-α-Vivaliru 2
-Chloro 5-[γ-1,2,4-di-t-amylphenoxy)butanamide] Acetanilide -, Stirring (color stain prevention agent) 2,5-di-t-octylhehydroquinone treatment step Color development 33°C 3 Minute 30 seconds sake white fixation
Wash with water at 33℃ for 1 minute and 30 seconds 30
Dry for 3 minutes at ~34°C [Color developer composition] Pure water. . .

Ethylene glycol 15 sIj Benzyl alcohol 18-Hydoxylamine sulfate 2.09 Anhydrous potassium carbonate
30, Ov potassium bromide
0.5g sodium chloride
1.5 N anhydrous sulfite/potassium
2.09-ethyl-1-β-methanesulfonate ethyl-3-methyl-4-aminoaniline sulfate
4.5j Add pure water to make 11, and adjust the pH to 10.2 with potassium hydroxide or sulfuric acid.

[Bleach-fix solution composition]

Pure water
750 dEthylenediaminetetraacetic acid (iron) sodium
509 Ammonium thiosulfate 859
Sodium bisulfite 10 IJ Sodium metabisulfite 29 Ethylenediaminetetraacetic acid 11-2-sodium salt 20 g Sodium bromide 3.0j Add pure water to make 11, and adjust to pH == 7.0 with aqueous ammonia or sulfuric acid. adjust.

The reflection density of the dye formed in each sample was measured using a photoelectric density needle (PI A-60 model manufactured by Konishiroku Photo Industry Co., Ltd.).
Measurements were made using the included blue filter, and the characteristic values of capri, sensitivity, and gradation were measured. The results are shown in Table 1.

Table 1 Note) Sensitivity is based on blue light sensitivity vk100 of sample number 9.
'expressed.

As is clear from Table 1, it can be seen that samples Nos. 5 to 9 according to the present invention are significantly superior in capri and sensitivity compared to comparative samples Nos. 1 to 4.

Comparison pigment B'
C0,4)m (Example 2) A silver chloride emulsion with an average grain size of 0.8, vpH 5,8, and PAg 7.6 K prepared by neutral simultaneous mixing was divided into 6 parts and shown in Table 2 below. A sensitizing color chart was added to each of the samples shown in Table 5, and after 5 minutes, sodium thiosulfate pentahydrate containing 2×1 O-mol of silver halide was added, and chemical ripening was performed at 55°C. A coated sample was prepared according to the method of Example 1, and developed. The results are expressed in relative sensitivity and capri for the maximum sensitivity achieved for each sample.

Table 2 (1) Sensitivity: Blue light sensitivity of sample number 16 expressed as 100 As is clear from Table 2, even in systems where dye coexists during chemical ripening, the sample according to the present invention is superior to the comparative sample. It can be seen that it has higher sensitivity and lower Cub IJV compared to .

Example 3 A silver chloride emulsion with an average grain size of 0.7 μm prepared by neutral simultaneous mixing was prepared with a vpH of 5.4 and a pAg of 7.6, and then divided into three parts and subjected to chemical ripening.

Sample No. 17 A comparison dye of 3X10-' mole per mole of silver halide was added, and after 5 minutes, 1X10-' mole per mole of silver halide was added.
'Mole of sodium thiosulfate pentahydrate was added at 55 °C.
Chemical ripening was performed.

Sample No. 18 Chemical ripening was carried out in the same manner as Sample No. 17 except that 3×10''-' moles of exemplified dye A5t- were added per mole of silver halide.

Sample No. 19 1X10-' mol of sodium thiosulfate pentahydrate per 1 mol of silver halide was added, and chemical ripening was performed at 60°C.

For each aging time, except that dye v#i is not added at the end of aging,
A coating sample was prepared according to the method of Example 1. Exposure and development were carried out in accordance with Example 1, but since Sample 19 did not contain a sensitizing dye, the exposure amount was increased. The results are shown in Figure 1 (Sample 17), Figure 2 (Sample 18), and Figure 2. 3 (Sample 19
)k shown.

In the comparative sample that does not contain any dye, the # sea bream changes as chemical ripening progresses, and even though the capri has already started to rise by the time the maximum sensitivity is reached, the gradation has not fully recovered. is well understood. 1. The lag period is long. It is well understood that the changes that followed were rapid. On the other hand, in sample 17 of the comparative example and sample 18 of the present invention, there is almost no change in gradation, but in the comparative example, the increase in S degree due to chemical aging is much greater than that observed in the sample without pigment. It can be seen that Capri has already begun to rise when a small increase in st is shown, and that the tone is softening overall. No such defects were observed in Sample I8 according to the present invention. In Examples 1 and 2, low capri and high sensitivity were achieved by the sensitizing dye according to the present invention when applied to chemically ripened emulsions. 0 And in this Example 3, Mori,
Chemical ripening KfI of high silver chloride using the sensitizing dye according to the present invention
These drawbacks were very serious problems in producing color photographic materials using high chloride p-genide emulsions. It will be easily understood how useful the sensitizing dye according to the present invention is in fully exhibiting the excellent properties of silver shigenide as a one-color photographic material.

Example 4 A photographic paper support covered with a polyethylene film containing anatase lid titanium oxide was subjected to corona discharge machining, and the following six layers were sequentially coated on this support to form a color photosensitive material for printing. Created. The amounts of each substance are expressed per one photosensitive material, and silver halide is expressed in terms of silver.

Layer 1 0.45# blue-sensitive silver chloride emulsion (average grain size 0.7 μm
), 1.47j' gelatin, and 0.89 yellow coupler (YO-1 used in Example 1), and 0.01
5N color stain inhibitor (color stain inhibitor-1 used in Example-1) tl- Blue-sensitive emulsion layer layer 2 containing dissolved 0,41 DBP 1.03F gelatin, 0.0159 color stain inhibitor (
0 in which the color stain inhibitor-1) used in Example-1 was dissolved;
03j' I) First intermediate layer containing BP 113 0.4j' green-sensitive silver chloride emulsion (average grain size 0.45μ
A green-sensitive emulsion layer containing mλ 1.85 g of gelatin and 0.34 g of tricresyl phosphate (hereinafter abbreviated as TCP) V in which 0.63j' of magenta coupler (MO-1*) was dissolved *MO-1' 3-L2-chloro-5-(l-octadecenylsuccinimide)anilino) --1-(2,4,6-)lichlorophenyl)-
5-pyrazolone layer 4 1.451 Zera f7.0.2!9 UV absorber (t
yv-1 town, 0.3F ultraviolet absorber (Uy z record)
and 0.01 color stain inhibitor (color stain inhibitor-1 used in Example-1) v second intermediate layer containing dissolved 0,22F DBP* υV-12-(2-hydroxy-3 ,5-di-t-
(butylphenyl)-benzotriazole UV-22-(2-hy)"o+--t-methylphenyl)-benzotriazole.

Layer 5 0.3 g red-sensitive silver chloride emulsion (average grain size 0.40 μm
), 1,6 N nogelatin, and 0.42 N cyan coupler (oo-1*), 0.05 jl DMOI (
and 0.005 N color stain inhibitor (color stain inhibitor-1 used in Example-1) v dissolved “0.3j” DB
Red-sensitive emulsion layer containing P* 00-1 2-(2-(2,4-di-t-amylphenoxy)butanamide J-4,6-di-chloro-5-methylphenol layer 6 1.8jl The silver halognide emulsion used in protective layer 1 containing gelatin was prepared as follows: 1 x 10 mol of sodium thiosulfate dihydrate was added per mol of silver halide emulsion. 5 minutes after the completion of chemical ripening, a previously prepared sensitizing dye was added as a 0.1% solution. After 5 minutes,
At the end of the chemical ripening, a stabilizer (stabilizer-1 used in Example-1) was added as a 5% aqueous solution. After the addition, a 10% W/Y gelatin aqueous solution was added, stirred, and then cooled to obtain a set.

The silver halide emulsion used in layer 3 was chemically ripened using 1.5 x 10 moles of sodium thiosulfate pentahydrate per mole of silver halide, and 3XIO-' moles of anhydro-5,5'- as a sensitizing dye. diphenyl-9-ethyl-3,
It was prepared in the same manner as the emulsion in Layer 1 except that 3'-di-3-sulfopropyl)oxacarbocyanine hydroxide was used.

The silver tetragnide emulsion used in layer 5 contained 3. Gorge (2-hydro+'y
The emulsion was prepared in the same manner as the emulsion in Layer 3 except that ethyl)selenathiadicarbocyanine bromide was used as the sensitizing dye.

In addition to the above materials, bis-(vinylsulfonylmethyl)ether as a hardening agent and saponin as a fabric aid were contained.

Each emulsion layer of sample 29.30 according to the present invention had an average grain size of 0.
Silver chlorobromide emulsion (blue-sensitive emulsion layer) containing 15 moles of silver chloride at 7 μm, average grain size o, 45 μm, 20 mole % silver chloride.
silver chlorobromide emulsion (CaWA photosensitive emulsion layer), average grain size 0
．． Sample 28 was prepared under the same conditions except that the silver chlorobromide emulsion (red-sensitive emulsion layer) containing 20 mol % of silver chloride (4μ) was changed.

The amount of sensitizing dye added to the blue-sensitive emulsion layer was 3.times.10-' mol 1 mol silver, and the dyes used are shown below.

Sample number N(OtHs)s 21 Exemplary dye 2 22 Exemplary dye 8 The above three samples! When exposed and printed through a color negative and subjected to the same color developing process as described in Example 1, both the photosensitive materials 21 and 22 of the present invention produced color prints showing the same good color reproduction and tone reproduction II as comparative sample 20. Obtained. In particular, the decrease in saturation of red and green was suppressed even in the high-density range, and it was found that color photographic paper using silver chloride had improved color reproduction compared to conventional color photographic paper using silver chlorobromide. 0

[Brief explanation of the drawing]

Comparative dye 1v prior to chemical ripening of gl-1 silver chloride emulsion.
It shows changes in the aqueous curve with the progress of chemical ripening when added. (Aging time was measured immediately after addition of sodium thiosulfate.) 1. Aging time 0 minutes 2. Aging time: 30 minutes3, Aging time: 50 minutes4, Aging time: 70 minutes5, Aging time: 90 minutesFigure-2 Aqueous curve accompanying the progress of chemical ripening when Exemplary Dye 5 is added prior to chemical ripening of a silver chloride emulsion Indicates a change in 1. RIjJO minute during ripening 2, Aging time 30 minutes 3, Aging time 50 minutes 4, Aging time 70 minutes 5, Aging time 90 minutes Figure 3 shows the change in the aqueous curve as the chemical ripening of the silver chloride emulsion progresses. (Il light intensity is different from Figure-11wJ-2 and cannot be compared directly @) 1. Aging time 0 minutes 2, Aging time 60 minutes 3, Heat sensitivity time 75 minutes 4, Aging time 90 minutes 5, Aging time 105 minutes 6, ripening time 120 minutes Agent: Yoshi Kuwahara Mikyu χ; L furnace procedure amendment November 1980 2911 Patent jj Director Kazuo Wakasugi■ Indication of the case 1983 Patent application No. 1903g4 ぢ2, Invention Name of Silver Halide Photographic Light-sensitive Material 3, Relationship to the Amendment Case Applicant Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (+27) Representative Director of Konishiroku Photo Industry Co., Ltd. river
Nobuhiko Moto 4, Agent Address: 191, Address: 6, IWt, Sakura-cho, Hino-shi, Tokyo, Ill. Contents (1) Amend the claims as shown in the attached sheet. Q) The detailed description of the invention is amended as follows. Attachment Claim α) A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer ti on a support, wherein the silver halide labeled # contains at least 80 moles of silver chloride. 1. A silver halide photographic material characterized in that it contains at least one type of merocyanide/dye contained in silver particles and represented by the following general formula CI). General formula CI) (In the formula, R1 and R1 represent an alkyl group, an alnanyl group, and an aryl group, respectively.However, at least one of R1j+5 and V represents a sulfo group, or a 7A/kyl group! or an aryl group. Represents R8%114, R1 and R@
is either a hydrogen atom or a halogen atom! 1
lFi may be combined with each other to form a vote. X represents an oxygen atom or a sulfur atom. ) ■) Claim I characterized in that the silver halide photosensitive material is a silver halide color photosensitive material.
K The halogenated III photographic material described in item (1).

Claims (2)

[Claims] (1) A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide comprises silver halide grains containing at least 80 moles of silver chloride; A silver halide photographic material comprising at least one merocyanine dye represented by the following general formula [1]. General formula CI) 1 (wherein R1 and R1 each represent an alkyl group, an alkenyl group, or an aryl group. However, at least one of R1 and R3 represents an alkyl or aryl group having a sulfo group. na, R4, BS and R@ each represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, or a 7-enyl group. Any one set of R3 and R4, R4 and R1, 11 and R', or R1 and R@ may be bonded to each other to form a ring. X represents an oxygen atom or a sulfur atom.) (2) The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material is a silver halide color photographic light-sensitive material.