JPH0743517B2 - Silver halide photographic emulsion - Google Patents

Description

TECHNICAL FIELD The present invention relates to a spectrally sensitized silver halide photographic emulsion, and more particularly to a spectrally sensitized silver halide photographic emulsion. is there.

(Prior Art) It is well known in the art of producing silver halide photographic emulsions that the addition of a sensitizing dye to a silver halide emulsion extends the photosensitive wavelength range, that is, spectral sensitization. Spectral sensitization in the red wavelength region is a photosensitive material for photographing, a positive photosensitive material for adhesion or stretching, as a technique for imparting the red sensitivity required for a photosensitive material for printing, or a diode, a laser emitting in the red wavelength region, It is important as a manufacturing technology of a photosensitive material for printing or recording using a CRT as a light source. Certain benzimidazolodicarbocyanine dyes are known as means for increasing the red sensitivity of silver halide emulsions. For example, Japanese Patent Publication No. 43-22,883 and 48-42,4
No. 95, No. 52-25,331, JP-A-48-24,726, No. 52-4,822, No. 52-151,026,
U.S. Pat.No. 3,264,110, 3,431,110,
Etc. However, none of the benzimidazolodicarbocyanine dyes disclosed in the above specification have a low sensitivity and can be put to practical use. In addition, there is a problem in that the sensitivity decreases with time. Further, in recent years, in terms of printing, a Scanner type electronic color separation meshing machine using a laser light source has been widely used. Of these, a neon helium laser with an output wavelength of 632,8 nm is often used. As a spectral sensitization technique for a silver halide light-sensitive material which forms a halftone image by performing high-intensity short-time exposure by such a Scanner method, there is disclosed in Japanese Patent Laid-Open No. 50-62,425.
Nos. 54-18,726, 56-151,933 and the like are known. However, there is a demand for a spectral sensitization method having higher sensitivity to neon / helium laser light and less residual coloring due to a dye after development / fixing treatment.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a silver halide photographic emulsion having high sensitivity in the red wavelength region, particularly 600 nm to 690 nm. Secondly, lasers with emission energy in the above wavelength range, CRTs (Cathode ray tube), LEDs (Ligh
To provide a photographic light-sensitive material for printing or recording using a light emitting diode (t emitting diode) as a light source. Thirdly, to provide a silver halide photographic emulsion having good stability over time after the production of a light-sensitive material.

(Means for Solving Problems) The above-mentioned various objects of the present invention are to provide at least one sensitizing dye represented by the following general formula (I) and at least one compound represented by the general formula (II). Was incorporated into a silver halide emulsion.

Where R₁, R₂, R₃, R_FourAre the same or different
Also represents an alkyl group or a substituted alkyl group, R₁, R₂
At least one of which is a sulfoalkyl group, and
Tsu R₁~ R_FourAt least one of them is a fluorine-substituted alkyl group
Is. V₁, V₂, V₃, V_FourAre the same but different
May be attached, hydrogen atom, halogen atom, alkyl
Group, alkoxy group, acyl group, acyloxy group, alcohol
Xycarbonyl group, carboxyl group, alkyl sulfonyl group
Group, cyano group or trifluoromethyl group.
Q represents a hydrogen atom, an alkyl group, or an aralkyl group
You X Represents an anion. m represents 1 or 2
However, it is 1 when the dye forms an inner salt.

Here, A represents a divalent aromatic residue. R ₅ , R ₆ , R ₇ , and R ₈ are each a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an arylthio group, an amino group, a substituted or unsubstituted group. Represents an alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aralkylamino group, an aryl group, or a mercapto group.

However, at least one of A, R ₅ , R ₆ , R ₇ and R ₈ has a sulfo group. W represents -CH = or -N =.

The sensitizing dye used in the present invention preferably has the following substituents in formula (I). That is, R ₁ , R ₂ ,
R ₃ and R ₄ may be the same or different, and an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a vinylmethyl group and the like, preferably an alkyl group having a carbon number of 6 or less). ) Or a substituted alkyl group [as a substituent, for example, a sulfo group, a carboxy group, a hydroxy group, a cyano group, an alkoxy group having 6 or less carbon atoms (eg, a methoxy group, an ethoxy group, etc.), an alkoxycarbonyl having 6 or less carbon atoms. Group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), acyloxy group having 3 or less carbon atoms (eg acetoxy group, propionyloxy group etc.), acyl group having 8 or less carbon atoms (eg acetyl group, propionyl group, benzoyl group etc.) A carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarba group Moyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfamoyl group, etc.), aryl group having 10 or less carbon atoms (eg, phenyl group, p- Hydroxyphenyl group, p-
Carboxyphenyl group, p-sulfophenyl group, etc.),
A C6 or less alkyl group substituted with a fluorine atom or the like is preferable.

V ₁ , V ₂ , V ₃ , and V ₄ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.),
Alkoxy group having 6 or less carbon atoms (eg, methoxy group, ethoxy group, etc.), acyl group having 8 or less carbon atoms (eg, acetyl group, propionyl group, etc.), acyloxy group having 3 or less carbon atoms (eg, acetoxy group, propionyloxy group, etc.) ), An alkoxycarbonyl group having 8 or less carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonyl group, etc.),
A carboxyl group, an alkylsulfonyl group, a cyano group, or a trifluoromethyl group is preferable.

Q is preferably a hydrogen atom, an alkyl group having 4 or less carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), an aralkyl group, and particularly a phenylalkyl group (eg, benzyl group, phenethyl group, phenylpropyl group, etc.).

In the sensitizing dye used in the present invention, the following substituents are particularly preferably used in the general formula (I). That is, R ₁ ,
R ₂ , R ₃ and R ₄ may be the same or different,
An alkyl group having 5 or less carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), sulfo group, carboxy group, alkyl group having 4 or less carbon atoms substituted with a hydroxy group, p-
Particularly preferred are an alkyl group having 3 or less carbon atoms substituted with a sulfophenyl group, a p-carboxyphenyl group, a p-hydroxyphenyl group, and an alkyl group having 6 or less carbon atoms substituted with a fluorine atom.

V ₁ , V ₂ , V ₃ , and V ₄ may be the same or different and each is a hydrogen atom, a halogen atom, an acyloxy group having 3 or less carbon atoms (eg, acetoxy group, propionyloxy group, etc.), 4 or less carbon atoms. Particularly preferred are alkoxycarbonyl groups (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), cyano group, and trifluoromethyl group. Q is particularly preferably a hydrogen atom.

Next, the general formula (II) will be described in detail.

In the formula, -A- represents a divalent aromatic residue, and these are -S
O ₃ M group (wherein M represents a hydrogen atom or a cation imparting water solubility (for example, sodium, potassium, etc.). ] May be included.

As -A-, those selected from the following -A ₁ -or -A _2- are useful. However R _5, R _6, when the R ₇ or R ₈ contains no -SO ₃ M is, -A- is -A ₁ - is selected from the group consisting of.

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

R ₅ , R ₆ , R ₇ and R ₈ are each a hydrogen atom, a hydroxy group, a lower alkyl group (the number of carbon atoms is preferably 1 to 8, for example, methyl group, ethyl group, n-propyl group, n-butyl group). Etc.), an alkoxy group (preferably having 1 to 8 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), an aryloxy group (for example, a phenoxy group, a naphthoxy group, an o-tolyloxy group, a p-sulfophenoxy group). Group, etc.), halogen atom (eg chlorine atom, bromine atom etc.), heterocyclic nucleus (eg morpholinyl group, piperidyl group etc.), alkylthio group (eg methylthio group, ethylthio group etc.), heterocyclylthio group (eg benzothiazolylthio group) Group, benzimidazolylthio group, phenyltetrazolylthio group, etc.), arylthio group (eg, phenyl group) Ruthio group, tolylthio group), amino group, alkylamino group or substituted alkylamino group (eg, methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxy group) Ethylamino group),-(β-hydroxyethyl) amino group, β-sulfoethylamino group), arylamino group,
Or a substituted arylamino group (eg, anilino group, o-
Sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, o-toluidino group, m-toluidino group, p
-Toluidino group, o-carboxyanilino group, m-carboxyanilino group, p-carboxyanilino group, o-chloroanilino group, m-chloroanilino group, p-chloroanilino group, p-aminoanilino group, o-anisino group,
m-anisidino group, p-anisidino group, o-acetaminoanilino group, hydroxyanilino group, disulfophenylamino group, naphthylamino group, sulfonaphthylamino group, etc., heterocyclylamino group (eg 2-benzo) Thiazolylamino group, 2-pyridyl-amino group, etc.), substituted or unsubstituted aralkylamino group (eg, benzylamino group, o-anisylamino group, m-anisylamino group, p-anisylamino group, etc.), aryl group (eg, Phenyl group) and mercapto group. R ₅ , R ₆ ,
R ₇ and R ₈ may be the same or different from each other. -A-
Is selected from the group of —A ₂ —, at least one sulfo group of R ₅ , R ₆ , R ₇ , and R ₈ (which may be a free acid group,
May form a salt).
W represents -CH = or -N =, preferably -CH = is used.

Next, specific examples of the sensitizing dye of the general formula (I) and the compound of the general formula (II) used in the present invention are shown below. However, it is not limited to this.

Specific examples of sensitizing dyes represented by formula (I) Specific examples of compounds represented by general formula (II) (II-1) 4,4'-bis [4,6-di (benzothiazolyl-
2-Thio) pyrimidin-2-ylamino] stilbene-
2,2'-Disulfonic acid disodium salt (II-2) 4,4'-bis [4,6-di (benzothiazolyl-
2-Amino) pyrimidin-2-ylamino)] stilbene-2,2′-disulfonic acid disodium salt (II-3) 4,4′-bis [4,6-di (naphthyl-2-oxy) pyrimidine-2 -Ylamino] stilbene-2,2 '
-Disulfonic acid disodium salt (II-4) 4,4'-bis [4,6-di (naphthyl-2-oxy) pyrimidin-2-ylamino] bibenzyl-2,2 '
-Disulfonic acid sodium salt (II-5) 4,4'-bis (4,6-dianilinopyrimidine-
2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (II-6) 4,4'-bis [4-chloro-6- (naphthyloxy) pyrimidin-2-ylamino] biphenyl-2,
2'-Disulfonic acid disodium salt (II-7) 4,4'-bis [4,6-di (1-phenyltetrazolyl-5thio) pyrimidin-2-ylamino] stilbene-2,2'- Disulfonic acid disodium salt (II-8) 4,4'-bis [4,6-di (benzimidazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (II- 9) 4,4'-bis (4,6-diphenoxypyrimidin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (II-10) 4,4'-bis (4,6- Diphenylthiopyrimidin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (II-11) 4,4'-bis (4,6-dimercaptopyrimidin-2-ylamino) biphenyl-2,2 ′ -Disulfonic acid disodium salt (II-12) 4,4′-bis (4,6-dianilino- Triazin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (II-13) 4,4'-bis (4-anilino-6-hydrokira-triazin-2-ylamino) stilbene-2,2 '
-Disulfonic acid disodium salt (II-14) 4,4'-bis (4-naphthylamino-6-anilino-triazin-2-ylamino) stilbene-2,
2'-Disulfonic acid disodium salt In these specific examples, (II-1) to (II-12) are preferable, and particularly (II-1), (II-2), (II-3), (II-
4), (II-5), (II-7) and (II-12) are preferred.

The dye of the general formula (I) used in the present invention is 5 × 10 ^-7 mol to 5 × 10 ^-3 mol, preferably 5
It is contained in the silver halide photographic emulsion in a proportion of from ^{10.times.10@-6} mol to 2.times.10.sup.- ³ mol, particularly preferably from 1.times.10.sup.- ⁵ mol to 1.times.10.sup.- ³ mol.

The sensitizing dye used in the present invention is “Heterocyclic Compounds-Cyanine dyes and rel” written by FM Hamer, “Heterocyclic Compounds-Cyanine dyes and rel”.
ated compounds-) ", Chapter 5, pp. 116-147 (John Wiley & Sons-New York, London-, published 1964), DMSturmer," Heterocyclic. Compounds-Specified Topicals in Heterocyclic Chemistry
ial topics in heterocyclic chemistry−) ”, Chapter 8,
It can be synthesized based on the method described in Section 4, pages 482 to 515 (John Wiley & Sons, Inc.-New York, London-, 1977).

The compound represented by the general formula (II) is a generally known compound.

The sensitizing dye represented by formula (I) used in the present invention can be directly dispersed in the emulsion. In addition, these are suitable solvents, for example, methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A-48-9715, halogenated alcohols described in U.S. Pat. It can also be added to the emulsion in the form of a solution which is dissolved in a mixed solvent such as. As another addition method, Japanese Patent Publication No. 46-2
4185, U.S. Pat.Nos. 3,822,135, 3,660,101, 2,91
2,343, 2,996,287, 3,429,835, 3,469,987
Nos. 3,658,546 and 3,822,135 can be used. Further, the method described in German Patent Application 2,104,283 and the method described in US Pat. No. 3,649,286 can also be used.

The compound represented by formula (II) used in the present invention is advantageously used in an amount of about 0.01 to 5 grams per mol of silver halide in the emulsion.

The ratio (weight ratio) of the dye represented by the general formula (I) to the compound represented by the general formula (II) is such that the dye represented by the general formula (I) / the compound represented by the general formula (II) = 1 / 1
The range from 1/100 to 1/100 is preferably used, and the range from 1/2 to 1/50 is particularly preferably used.

The compound represented by the general formula (II) used in the present invention can be directly dispersed in an emulsion, or in a suitable solvent (eg methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. It is also possible to add it to the emulsion by dissolving it in. Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of addition. In addition, JP-A-50-801
It can also be dispersed and added to the emulsion by the method described in JP-A-19.

The above sensitizing dye may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but it may be dispersed at any stage of preparation of the silver halide emulsion.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide in the photographic emulsion of the present invention. Preferred silver halides are silver bromide, silver chlorobromide, silver iodochloride, or silver iodochlorobromide.

Spectral sensitization is carried out regardless of the crystal phase of silver halide grains. However, in order to give higher spectral sensitization,
A silver halide grain having a (100) face is preferable, and more specifically, the area ratio of the [1,0,0] face to the total surface area of all grains is preferably 50%, more preferably 80% or more. . Also, the higher the area ratio of the [1,0,0] plane is, the harder the image becomes.

To determine the crystal phase of silver halide grains, that is, the area ratio of the [1,0,0] plane to the total surface area of all grains, see Tadaaki Tani, "Silver Halide in Photographic Emulsion Utilizing Dye Adsorption Phenomenon. Identification of Crystalline Phase of Fine Particles ”Journal of Chemical Society of Japan, 1984, (6) p-942
To 947.

The silver halide emulsion used in the present invention has a thickness of 0.5 micron or less, preferably 0.3 micron or less, and a diameter of
It may be a tabular grain having a grain size of 0.6 micron or more and an average aspect ratio of 5 or more occupying 50% or more of the entire projected area. Further, it may be a monodisperse emulsion in which grains having a grain size within ± 40% of the average grain size account for 95% or more of the number of grains.

The silver halide grains may have different phases in the inside and the surface layer, or may be composed of a uniform phase. Also, grains in which a latent image is mainly formed on the surface (eg negative emulsion).
Alternatively, it may be a grain that is mainly formed inside the grain (for example, an internal latent image type emulsion, a direct inversion type emulsion which has been fogged in advance).

The photographic emulsion used in the present invention is described in "Chimie et Physique Photographiqu" by P. Glafkides.
e)] (Published by Paul Montel, 1967),
GF Duffin, "Photographic Emulsion Chemistry" (Photographic E
mulsion Chemistry) "(Focal Press The Focal
Press, 1966), VLZelikman et al., "Making and Coating Ottografique Emargyon (Making and
Coating Photographic Emulsion) "(Focal Press, published by The Focal Press, 1964) and the like.

That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. .

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
It is also possible to use a method of keeping constant, that is, a so-called control double jet method.

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

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

Further, in order to control the growth of grains during the formation of the silver halide grains, as a silver halide solvent, for example, ammonia, rodancali, rodanammon, and a thioether compound (for example, U.S. Pat.Nos. 3,271,157 and 3,574,628).
No., No. 3,704,130, No. 4,297,439, No. 4,276,374
, Etc.) thione compounds (for example, JP-A-53-144,319,
Nos. 53-82408 and 55-77,737), amine compounds (for example, JP-A-54-100717, etc.) and the like can be used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, thallium salt, iridium salt or complex salt thereof, rhodium salt or complex salt thereof, iron salt or iron complex salt may be allowed to coexist.

Further, as the internal latent image type emulsion used in the present invention, for example, U.S. Patent Nos. 2,592,250, 3,206,313, and 3,447,92.
No. 7, No. 3,761,276, No. 3,935,014, etc., can be cited, for example, a convergence type emulsion, a core / shell type emulsion, an emulsion containing a different kind of metal, and the like.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, H. Freezer (H.Friese
r) ed. "Day Grand Ruggedder Photographischen Prozesse miz Die Grundlagender Photographischen Prozesse mi
t Silber-halogeniden) "(Akademische Verlagsgesellschaft, 1968)
The method described on pages 675 to 734 can be used.

That is, a sulfur sensitization method using a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate, thioureas, mercapto compounds, rhodanines); a reducing substance (for example, first tin salt, Reduction sensitization method using amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds; precious metal compounds (for example, gold complex salts, and complex salts of metals of Group VIII of the periodic table such as Pt, Ph, Ir, Pd) Noble metal sensitization method and the like can be used alone or in combination.

These examples are described in US Pat.
No. 574,944, No. 2,410,689, No. 2,278,947, No.
No. 2,728,668, No. 3,656,955, etc., for reduction sensitization methods, U.S. Patent Nos. 2,983,609, 2,419,974, 4,05
US Patent No. 2,399,083 for Noble Metal Sensitization Method such as 4,458
No. 2,448,060, British Patent No. 618,061 and the like.

More specific chemical sensitizers include sulfur sensitizers such as allylthiocarbamide, thiourea, sodium thiosulfate and cystine; precious metal sensitizers such as botadium chloroaurate, olas thiosulfate and botadium chloroparadate. Agents; reduction sensitizers such as tin chloride, phenylhydrazine and reductones may be included. Sensitizers such as polyoxyene compounds, polyoxypropylene compounds, and compounds having a quaternary ammonium group may also be included.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, and mercaptobenz. Imidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazoline Thione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); benzenethiosulfonic acids Benzenesulfonic Huynh acid; many compounds known to the antifoggants or stabilizers, such as can be added.

The silver halide emulsions of this invention are described in U.S. Pat.
, 3,411,912, 3,142,568, 3,325,286,
No. 3,547,650, Japanese Patent Publication No. 45-5331, etc., polymer latex made of homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc. is used to improve dimensional stability of photographic materials, film. It can be contained for the purpose of improving physical properties.

When the silver halide emulsion of the present invention is used as a lithographic printing light-sensitive material, a polyalkyleneoside compound which enhances the infectious development effect can be used. For example, U.S. Patents 2,400,532, 3,294,537 and 3,294,540
Japanese Patent No. 1,491,805, Japanese Patent No. 1,596,673, Japanese Patent Publication No. 40-23466, Japanese Patent Laid-Open No. 50-156423, No. 5
Compounds as described in 4-18726 and 56-151,993 can be used. Preferred example has 2 carbon atoms
~ 4 alkylene oxides, such as ethylene oxide,
Propylene-1,2-oxide, butylene-1,2-oxide and the like, preferably a polyalkyne oxide consisting of at least 10 units of ethylene oxide and water, an aliphatic alcohol,
It includes a condensate with a compound having at least one active hydrogen atom such as an aromatic alcohol, a fatty acid, an organic amine and a hexitol derivative, or a broth copolymer of two or more polyalkylene oxides. That is, as the polyalkylene oxide compound, specifically, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol alkylaryls, polyalkylene glycol esters, polyalkylene glycol fatty acid amides, polyalkylene glycol amines. Examples thereof include polyalkylene glycol block copolymers and polyalkylene glycol graft polymers. The polyalkylene oxide compound which can be used has a molecular weight of 300 to 15,000, preferably 600 to 8,000. The addition amount of these polyalkylene oxide compounds is 1 mol of silver halide
10 mg to 3 g is preferred. The addition time can be selected at any time during the manufacturing process.

The silver halide photographic emulsion of the present invention can contain color couplers such as cyan couplers, magenta couplers and yellow couplers and compounds that disperse the couplers.

That is, it may contain a compound capable of forming a color by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in the color development processing. For example, as a magenta coupler, a 5-pyrazolone coupler, a pyrazolobenzimidazole coupler, a cyanoacetylcoumarone coupler,
There are open-chain acylacetonitrile couplers and the like, yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, bivaloylacetanilides), and the like, and cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion. Further, a colored coupler having a color correction effect, or a coupler releasing a development inhibitor upon development (so-called DI
R coupler).

In addition to the DIR coupler, a non-colored DIR coupling compound which is colorless in the coupling reaction product and releases a development inhibitor may be contained.

The silver halide photographic emulsion of the present invention may contain a water-soluble dye (for example, oxonol dye; hemioxonol dye and merocyanine dye) as a filter dye or for various purposes such as prevention of irradiation.

The photographic emulsion of the present invention contains various surfactants for various purposes such as coating aid, antistatic property, sliding property improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization). But it's okay.

Nonionic surfactants such as saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol alkyl ethers, glycidol derivatives, fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates , Alkylsulfonates, alkylbenzene sulphonates, alkylsulfates, etc. amphoteric surfactants; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium and other heterocyclic fourth groups Cationic surfactants such as secondary ammonium salts can be used.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more kinds. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and bisphenols.

The photographic emulsion of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (homulaldehyde, glyoxal, kurtalaldehyde, etc.), active vinyl compounds (1,3,5-triacryloyl-hexohydro-s-triazine, 1,3 -Vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), and the like can be used alone or in combination.

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

In the silver halide photographic emulsion used in the present invention, in addition to gelatin as a protective colloid, acylated gelatin such as phthalated gelatin and malonated gelatin, cellulose compound such as hydroxyethyl cellulose and carboxymethyl cellulose; dextrin such as dextrin. Soluble starch; polyvinyl alcohol, polyvinylpyrrolidone, hydrophilic polymers such as polyacrylamide and polystyrene sulfonic acid, plasticizers for dimension stabilization, latex polymers and matting agents may be added. Finished
The emulsion is coated on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates.

The exposure for obtaining a photographic image may be performed using a usual method. That is, natural light (sunlight), tungsten light,
Any of various known light sources such as a fluorescent lamp, a mercury lamp, a sequinone arc lamp, a carbon arc lamp, a sequinon flash lamp, a laser, an LED, and a CRT can be used. The exposure time is not limited to 1/1000 seconds to 1 second which is usually used in cameras, but it is also necessary to use an exposure shorter than 1/1000 seconds, for example 1/10 ⁴ to 1/10 ⁶ seconds using a xenon flashlight. Exposures longer than 1 second can be used. If necessary, the spectral composition of the light used for exposure can be adjusted with a color filter. Laser light can also be used for the exposure. It may also be exposed by light emitted from the phosphor excited by electron beams, X-rays, γ-rays, α-rays and the like.

The spectral sensitizing dye of the present invention is used for sensitizing silver halide photographic emulsions for various color and black and white photographic materials. Emulsions used include, for example, color positive emulsions, color paper emulsions, color negative emulsions, color reversal emulsions (which may or may not contain couplers), photographic light-sensitive materials for plate making (for example, lith film). Emulsions, emulsions used in cathode ray tube display photosensitive materials, colloids
Transfer process (Colloid transfer proces
s) emulsions used in (for example, US Pat. No. 2,716,059), emulsions used in silver salt diffusion transfer process, emulsions used in color diffusion transfer process, die
Transfer process (imbibitio transfer proce
ss) Emulsion used in US Pat. No. 2,882,156 etc., emulsion used in silver dye bleaching method, and material for recording printout image (described in US Pat. No. 2,369,449 etc.) Emulsion, photo-developing printout (Direct Print image) photosensitive material (eg US patent
No. 3,033,682), an emulsion used in a light-sensitive material for heat development, an emulsion used in a light-sensitive material for physical development (for example, described in British Patent No. 920,277), and the like.

Photographic processing of a light-sensitive material produced by using the present invention includes, for example, Research Disclosur (Research Disclosur).
s) Any known method and known processing solution as described in No. 176, pages 28 to 30 (RD-17643) can be applied. This photographic processing may be either photographic processing for forming a recorded image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. The treatment temperature is usually selected between 18 ° C and 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C.

Next, specific examples used in the present invention will be shown. However, the present invention is not limited to these specific examples.

Example-1 70 mol% silver chloride, 29.5 mol% silver bromide and 0.5 mol%
A sulfur-sensitized silver halide emulsion containing silver iodide was prepared. The area ratio of the [1,0,0] plane to the total surface area of the silver halide grains contained in this emulsion was 94%. The average diameter of the silver halide grains was 0.35μ. 1kg of this emulsion
It contained 1.03 mol of silver halide.

This emulsion was weighed in pots of 1 kg each, and as shown in Tables 1 to 5, the sensitizing dye of the general formula (I) and the compound of the general formula (II) according to the present invention were sequentially added. The mixture was mixed and stirred at ℃. Furthermore, 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene 0.2g / emulsion 1Kg, 1-hydroxy-
0.1 g of 3,5-dichlorotriazine soda / emulsion 1 kg, and further 0.1 g of sodium dodecylbenzenesulfonate / emulsion 1 kg were sequentially added, and then coated on a polyethylene terephthalate film base to obtain a photographic light-sensitive material.

A red filter manufactured by Fuji Photo Film Co., Ltd.
It was exposed to tungsten light (2854 ° K) for 5 seconds through SC-60 (a filter that transmits light having a wavelength longer than 600 nm).

After exposure, development was carried out for 2 minutes at 20 ° C. using a developer having the following composition. The density was measured using a densitometer manufactured by Fuji Photo Film Co., Ltd. to obtain red filter sensitivity (SR) and fog. The optical density reference point that determines the sensitivity is [fog + 1.
5].

When using, add 2 volumes of water to make a working solution.

The obtained results are shown in Tables 1 and 2 as relative values. From these results, it can be seen that the sample using the combination of the sensitizing dye of the general formula (I) of the present invention and the compound of the general formula (II) has extremely high sensitivity.

Example-2 Consisting of pure silver bromide and having a cubic crystal form {area ratio of [1,0,0] face to total grain surface area was 92%}
A silver halide emulsion and a silver halide emulsion having an octahedral crystal form (area ratio of [1,1,1] face to total grain surface area was 85%) were prepared. The silver halide emulsion was subjected to sulfur sensitization treatment. The average diameter of the silver halide grains contained in these emulsions was 0.9μ, and 0.6 kg in 1 kg of emulsion.
Molar silver halide was contained.

The above two kinds of emulsions are weighed in pots of 1 kg each and
As shown in Table 4 and Table 4, the sensitizing dye of the general formula (I) and the compound of the general formula (II) were sequentially added, and mixed and stirred at 40 ° C. Furthermore, 0.1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene / 1 kg of emulsion, 1-hydroxy-3,5
-Sodium dichlorotriazine (0.1 g / emulsion 1 kg) and sodium dodecylbenzenesulfonate (0.1 g / kg) emulsion were sequentially added, and then coated on a polyethylene terephthalate film base to obtain a photographic light-sensitive material.

Each of these samples was replaced with the red filter (SC-6
0) and a blue filter manufactured by Eastman Kodak Company (Rutten-47B ... Filter for transmitting blue light having a maximum transmittance at 433 nm) and exposed to tungsten light (5400 ° K) for 15 seconds.

After exposure, development was carried out at 20 ° C. for 10 minutes using a developer having the following composition. The density of the developed film was measured to obtain red filter sensitivity (SR), blue filter sensitivity (SB) and fog. The optical density reference point that determines the sensitivity is [fog +
0.2].

The results obtained with the silver halide emulsion having the cubic crystal form are shown in Table 3, and the results obtained with the silver halide emulsion having the octahedral crystal form are shown in Table 4. In the table, the term "spectral sensitization" means that the sensitivity SR obtained by the above-mentioned method is represented by a relative value with SB as a reference at each addition amount.

As is apparent from Tables 3 and 4, the silver halide emulsions used in the sensitizing dye of the general formula (I) and the compound of the general formula (II) have halogen grains of [1,0,0] plane. It can be seen that it consists of a significant advantage.

Example-3 The same silver halide emulsion as that used in Example-1 was weighed in pots of 1 kg each, and as shown in Table 5, the sensitizing dye of the general formula (I) of the present invention and the general formula (I) were used. Add the compound of II) 40
The mixture was mixed and stirred at ℃. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.3 g / emulsion 1 kg, the following polyalkylene oxide compound 0.7 g / emulsion 1 kg, sodium dodecylbenzene sulfonate 2 g / emulsion 1 kg , 0.7 g of mucochloric acid / emulsion 1 kg, and 38 g / emulsion 1 kg of the polymer latex described in JP-B-45-5331, page 5, Formulation Example-3, and then sequentially coated on a polyethylene terephthalate film base. Got

Polyalkylene oxide compound used HO (CH ₂ CH ₂ O) _a (CH ₂
CH ₂ O) ₈ (CH ₂ CH ₂ O) ₆ H a + b = 50 These samples were exposed and developed in the same manner as in Example 1 to measure the density and obtain sensitivity and fog. After applying this film sample, the relative humidity is 60% and the temperature is 20 ° C for 5 months.
After being left under the conditions of (1), exposure and development were performed in the same manner as above, and changes in sensitivity and fog with time were measured. The results obtained are shown in Table 5 as relative values.

As is clear from Table 8, the general formula (I) according to the present invention is shown.
It can be seen that the combined use of the sensitizing dye of (1) and the compound of the general formula (II) significantly improves the sensitivity decrease after 5 months, as compared with the single use of the sensitizing dye of the general formula (I).

Example-4 A photographic light-sensitive material was obtained in the same manner as in Example-3. However, the sensitizing dye of the general formula (I) and the compound of the general formula (II) were those shown in Table 6. These samples were exposed by the following method.

A negative gray contact screen (Dainippon Screen, 150 L / inch) was attached to the sample, and there was a step on it.
Neon helium laser oscillator (GAS LASER GLG2 manufactured by NEC Corporation)
034) and exposed for 10 ^-5 seconds. After exposure, it was developed for 100 seconds at 27 ° C. with an automatic processor using a developer having the following composition. The relative sensitivities were compared by the reciprocal of the exposure dose at which the blackened area was 50%.

Chemical structure of dyes used for comparison Dyes (A) and (B) used for comparison are useful sensitizing dyes for a lith-type light-sensitive material for forming a halftone image by scanning with a scanning method using a neon helium laser. , JP-A-56-151933. In particular, the dyes having a chemical structure similar to that of the dyes (A) and (B) (for example, the dyes represented by the general formulas (I) and (II) in the above-mentioned JP-A-56-151933) are the above-mentioned photosensitive materials. As the most suitable compound for producing the material
54-18726. These dyes are excellent dyes having practically sufficient sensitivity, but the combined use of the sensitizing dye of the general formula (I) and the compound of the general formula (II) of the present invention is more sensitive and more excellent. It is possible to provide a silver halide photographic light-sensitive material. The halftone dot quality of the light-sensitive material according to the present invention is such that the blackened area at a developing time of 100 seconds is 10, 50, 9
When 0% halftone dots were observed with a 100-fold loupe, they were equivalent to those of the comparative dye.

Preferred embodiments of the present invention are listed below.

1. The case where V _{1 to} V ₄ of the general formula (I) are at least two or more chlorine atoms in the claims. And when at least one of V _{1 to} V ₄ is a cyano group or a trifluoromethyl group.

2. When Q in the general formula (I) is a hydrogen atom in the claims.

3. When the silver halide photographic light-sensitive material prepared according to the claims is used in combination with a light source having maximum energy in the wavelength range of 620 to 670 nm.

4. In Embodiment 3, the light source is a neon helium laser.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 59-192242 (JP, A) JP 48-42495 (JP, B1) JP 47-51905 (JP, B1) JP Hei 3- 42453 (JP, B2) Japanese Patent Publication 4-46419 (JP, B2)

Claims (1)

[Claims] 1. A silver halide emulsion having the following general formula (I)
Therefore, at least one of the sensitizing dyes represented by the general formula
At least one of the compounds represented by (II)
A silver halide photographic emulsion characterized by being contained.Where R₁, R₂, R₃, R_FourAre the same or different
Also represents an alkyl group or a substituted alkyl group, R₁, R₂
At least one of which is a sulfoalkyl group, and
Tsu R₁~ R_FourAt least one of them is a fluorine-substituted alkyl group
Is. V₁, V₂, V₃, V_FourAre the same or different
Also, hydrogen atom, halogen atom, alkyl group, alcohol
Xy, acyl, acyloxy, alkoxycarbo
Nyl group, carboxyl group, alkylsulfonyl group, sia
No group or trifluoromethyl group. Q represents a hydrogen atom, an alkyl group, or an aralkyl group
You X Represents an anion. m represents 1 or 2
It is 1 when the dye forms an inner salt.(Here, A represents a divalent aromatic residue. R_Five, R₆, R₇,
And R₈Are hydrogen atom, hydroxy group, alkyl group, and
Lucoxy group, aryloxy group, halogen atom, heterocycle
Nucleus, heterocyclylthio group, arylthio group, amino
Group, substituted or unsubstituted alkylamino group, substituted or unsubstituted
Substituted arylamino group, substituted or unsubstituted aralkyl group
It represents a mino group, an aryl group or a mercapto group. However, A, R_Five, R₆, R₇And R₈At least one of them is
It has an e-group. W represents -CH = or -N =
You )