JPS6318343A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photosensitive material having improved photosensitivity by providing a layer contg. a specific azulenium salt compd. thereto. CONSTITUTION:At least one layer contg. at least one kind of the compd. expressed by the formula I is provided. In the formula, R1-R7, R10-R13 denote a hydrogen atom, halogen atom or residual monovalent org. group, R8 and R9 denote a hydrogen atom, alkyl group which may be substd., aryl group which may be substd., or aralkyl group which may be substd. Said compd. is used at 5X10<-7>-1X10<-2>mol, more preferably 5X10<-6>-5X10<-3>mol per mol of silver halide in the case of adding the same into the silver halide emulsion layer. The optimum amt. of use varies with the chemical structure of a sensitizing dye and the crystal habit and particle size of the silver halide emulsion. Said compd. may be added in any stage of prepn. of the silver halide emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photosensitive material containing an azulenium salt compound.

(Prior art) Adding various dyes to silver halide light-sensitive materials outside the inherent sensitivity range of silver halide to impart a spectral sensitization range due to the dyes expands the sensitivity range of silver halide. This is an important technology for increasing total sensitivity and sensitivity.

(Problem to be solved by the invention) Various dyes have been developed in the past to provide a range of spectral sensitivity, but it is an important mission of researchers to develop new dyes for photography. be.

In addition, various filter dyes, antihalation dyes, etc. are used in silver halide photosensitive materials for purposes such as improving sharpness and color resolution, but it is necessary to develop new dyes for these purposes. This is also an important mission of researchers.

An object of the present invention is to provide a silver halide photosensitive material with improved photosensitivity.

Another object of the present invention is to provide a spectrally sensitized silver halide photosensitive material.

Another object of the present invention is to provide a highly sensitive direct positive silver halide photosensitive material.

Another object of the present invention is to provide a silver halide photosensitive material containing a coloring dye.

(Means for Solving the Problems) The above aspects of the present invention are such that a silver halide photographic material comprising a support and a silver halide emulsion layer contains at least a compound represented by the following general formula (I). This can be achieved using a silver halide photographic material characterized by having at least one layer containing one type of silver halide.

(I) In the formula, R□, R2, R3, R5, R6, R, RR
R and R13 are 7110\11%12%, a hydrogen atom, a halogen atom, or a monovalent organic residue β-
Expression: Mano R and R2, R3 and R4 and R5・R,
and R6, R6, R7, R10, "11," and
Aromatic mt-shading may be substituted with at least one combination of and 几□3.

几 and B represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. Further, R8 and 几 may form a ring together with the nitrogen atom.

XCI plays with anions.

n is 0.　　　　　　　/or ko.

Each substituent of the compound represented by general formula (I) is preferably the substituent shown below.

R1, 几2, R3, 燠いR5, R6, R7, R1゜, 几□1, R工2 and 几□3 are hydrogen atoms, halogen atoms (
(for example, chlorine atom, bromine atom, iodine atom, etc.) or a monovalent organic residue tl-, the -valent organic residue can be selected from a wide range of options, but in particular an alkyl group (for example, methyl , ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-amyl, n-
hexyl, n-octyl, -1ethylhexyl, t-octyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, br:1boxy, butoxy, etc.), substituted or unsubstituted aryl groups (e.g., phenyl, tolyl,
xylyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, chlorophenyl, di)Cl phenyl, dimethylaminyl, α-naphthyl, β-s7tyl, etc.), substituted or unsubstituted aralkyl groups (e.g. benzyl, Phenylethyl, -1 phenyl/-
methylbenzyl, bromobenzyl, copromophenylethyl, methylbenzyl, methoxybenzyl, nitrobenzyl, etc.), acyl groups (such as acetyl, propionyl, phthyryl, valeryl, benzoyl, trioyl,
naphthoyl, 7-taloyl, furoyl, etc.), substituted or unsubstituted amine groups (e.g., amine, dimethylamino, diethylamine, dipropylamino, acetylamino, benzoylamino, etc.), substituted or unsubstituted styryl groups (e.g., styryl, dimethyl aminostyryl, diethylaminostyryl, dipropylaminostyryl, methoxystyryl, ethoxystyryl, methylsteryl, etc.), nitro group, hydroxy group, carboxyl group,
Cyano group or substituted or unsubstituted arylazo group (
For example, phenylazo, α-naphthylazo, β-naphthylazo, dimethylaminophenylazochlorophenylazo, nitrophenylazo, methoxyphenylazo,
tolylazo, etc.).

Mano, 几l, R2, R3 and 几4, R4 and R5, B and R
几 and R17, Rlo and 几□□ and 5 6S
Even if at least one combination of 6 B and □3 forms a substituted or unsubstituted aromatic @ (for example, benz, naphtho, chlorobenzo, bromobenzo, methylbenzo, ethylbenzo, methoxybenzo, ethoxybenzo, etc.) good.

and R9 are hydrogen atoms, substituted or device-substituted alkyl groups (e.g., methyl, ethyl, n-propyl, isozolobyl, n-butyl, t-butyl, n-7 mil, n
- Hechusyl, n-octyl, coethylhexyl, t-
octyl, co-hydroxyethyl, carboxymethyl,
chloromethyl, cochloroethyl, etc.), substituted or unsubstituted aryl groups (e.g., phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, nitrophenyl, methoxyphenyl, ethoxyphenyl, α-naphthyl, β-naphthyl, etc.), or Represents a substituted or unsubstituted aralkyl group (benzyl, cophenylethyl, cophenyl-i-)thyl ether, methylbenzyl, methoxybenzyl, nitrobenzyl, etc.). Also, R
8 and Ro can form a ring (eg, morpholino, pyrrolidino, zeberidino, indolyl, pyrrolyl, pyrazolyl, etc.) together with the nitrogen atom.

Specifically, Xe may be an inorganic anion or an organic anion, such as halogen ions (e.g., fluorine ions, chloride ions, bromide ions, iodine ions, etc.), substituted arylsulfonate ions, etc. (eg, p-toluenesulfonate ion, p-chlorophenylsulfonate ion, etc.), sulfate ion, thiophane ion, perchlorate ion, hydroborofluoride ion, and the like.

Specific examples of the metal compound represented by the general formula (I) of the present invention are shown below, but the present invention is not limited thereto.

10° //.

13゜α r- /IA lyo/6゜/L ko0゜Compounds represented by general formula (I)K are Journal of
he Chemical 5ociety (Journal of the Chemical Society) I),
/// 0~p , / / / 7 (/ 9 j
,! 'can), p, 4L91A~p, yo0/(/9tO year), p, 3!7ri~p.

3! It can be obtained by mixing an azulene compound and a corresponding aldehyde compound in a suitable solvent in the presence of an acid, as described in 2003.

In particular, synthesis can be achieved with high purity and high yield by carrying out a condensation reaction using para-toluenesulfonic acid as the acid, followed by salt exchange as necessary, as shown below.

Synthesis Example 1 Synthesis of compound 1, /, Hiro-dimethyl-7-itsuprobil azulene u, t
Dissolve f and p-dimethylaminobenzaldehyde in 00 ntl of acetic anhydride, add p-toluenesulfonic acid l hydrate, and stir at room temperature for 30 minutes.

In addition to this reaction bath at water 47, add sodium iodide, rt, and stir at room temperature to precipitate crystals.
After removing these crystals by suction filtration, chloroform! 0
Dissolve in 0ytl. After gravity filtration, when ethyl acetate TL is added to the filtrate, crystals are precipitated. The crystals are removed by suction filtration and dried to obtain purple crystals J-2 (yield 1'7).

mp, /42~/A3 °C Solution absorption spectrum: λmaX=AJ in acetonitrile
Synthesis Example 2 Synthesis of Compound A The reaction was carried out in the same manner as in Synthesis Example 1, and the reaction solution was added to water-4, followed by addition of sodium perchlorate.

When Jff is added and stirred at room temperature, crystals are precipitated.

Purification in the same manner as in Example 1 yields purple crystals! , 3? (yield: r) is obtained.

mp, /l! ~/j7 @C Solution absorption spectrum: λmax=63 in acetonitrile
2nm 2=1.02×lO5 Synthesis Example 3 Synthesis of Compound 3 The reaction was carried out in the same manner as in Synthesis Example 1, and the reaction solution was added to water 21, and then borofluoric acid was added. is added and stirred at room temperature to precipitate crystals.

Purification is carried out in the same manner as in Example 1 to obtain purple crystals II, ff (yield: 1%).

mp, /7 & θ ~ /710C Solution absorption is quetor: λmax in acetonitrile = AI
IONm ε=/, 0! ×105 Synthesis Example 4 Synthesis of Compound Hiro/, 4(-dimethyl-7-itsuprobil azulene, 2.
jf and p-dimethylaminocinnamic arghyde λ,
If was dissolved in 100 trtl of acetic anhydride, p-toluenesulfonic acid l hydrate/co2 was added, and the solution was dissolved at room temperature for 30 trtl.
Stir for a minute.

Add this reaction solution to 2 g of water, and add sodium iodide, r? If f is added and stirred at room temperature, crystals will precipitate. After removing these crystals by suction filtration, the aaform-! o
Dissolve in d @ After natural filtration, add ethyl acetate to the filtrate!
When 00 tdf is added, crystals precipitate. When all of these crystals are taken out by suction filtration and dried, they become purple crystals! 6λf (yield rze
4) is obtained.

mp, /74~/Jr7 °C Solution absorption spectrum: λma) CH2 in acetonitrile
Onnm t=i, 3oxio5 Synthesis Example 5 Synthesis of Compound j The reaction was carried out in the same manner as in Synthesis Example, and after adding to the reaction bath ik water 21, further adding 291 sodium bromide and stirring at room temperature, crystals precipitated. do.

Purification is carried out in the same manner as in Example ≠ to obtain purple crystal μ, 61 (yield 10%).

mp, 11r/~1Ir3°C Solution absorption spectrum: λmaX=70 in acetonitrile
7nm &==/, λ! ×105 When using the compound represented by the general formula (T) as a photographic sensitizer and sensitizing dye (hereinafter referred to as sensitizing dye) or as a desensitizer and desensitizing dye (hereinafter referred to as desensitizing dye), When added to the silver halide emulsion layer, /% a)y' Silver heptaide/
Moni hit)! X10-7~/xIO-2 mol, preferably j×10''-6~zxio-3 mol. In addition, these sensitizing dyes may be added at any stage of silver halide emulsion preparation, such as pre-ripening, pre-ripening, post-ripening, etc., or may be added as a Kmm liquid before coating. It may be used in combination with the addition method.

The azulenium salt compound used in the present invention can be directly dispersed in an emulsion or a hydrophilic colloid solution. They can also be used in suitable solvents, such as methyl alcohol,
Ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A Showat-Tough 11, home special fff3.7jt
, halogenated alcohol described in rJO issue, acetone,
It can also be added to the emulsion in the form of a solution dissolved in water, pyridine, etc. or a mixed solvent thereof.

Another addition method is Tokko Sho≠4−λ≠/r! No. 3,122. /3j issue, same j, J, 40°10/ issue, same, ri/, 2. J4tJ issue, same, 7 ribs, co, r
No. 7, 3,4t Kota, r3! No. 3゜bu! r,! ≠
The method described in No. 6 can be used. Also, the method described in German patent application CO, IOP, CO R3, US patent!
, tlA, No. 216 can also be used.

Furthermore, the azulenium salt compound of the present invention can be used as various filter dyes, anti-irradiation dyes, anti-halation dyes, etc. for purposes such as improving sharpness and color resolution.

This azulenium salt compound can be incorporated into a coating solution for a silver halide photographic emulsion layer, a filter layer and/or an antihalation layer by a conventional method. The amount of dye to be used is sufficient to color the photographic layer, and those skilled in the art can easily select this amount as appropriate depending on the purpose of use.

Generally, it is preferable to use the optical density in the range of o, or to J, <7.

The addition time may be any step before coating.

It is also possible to make a polymer having an opposite charge to the dye ion coexist in the layer as a mordant and localize it in the dye t-% constant layer by interaction with the dye molecules.

As a polymer mordant, for example, US Patent Co.,! Hiro! ,!
6 ≠ issue, same pe, l co ≠, Jrt issue, same 3゜ A co z, t
y≠ issue, same 3. the law of nature! ! , Tata! No., Dohiro, /4. r,?
7j issue, same! , 4A'A! , No. 23/.

The silver halide emulsion that can be used in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. Preferred silver halides are silver bromide, silver chlorobromide, silver iodobromide, or silver iodochlorobromide.

Silver halide grains in photographic emulsions are cubic, octahedral, l
Regular like monohedron, rhombus/J-hedron
It may have a crystalline form, or it may have an irregular crystal shape such as a round spherical shape or a plate shape, or it may have a composite shape of these crystal shapes. It may also consist of a mixture of particles of various crystalline forms.

The silver halide emulsion used in the present invention has a thickness of 0.1 micron or less, preferably 0.1 micron or less. The diameter is preferably O, T micron or more, and the average aspect ratio is J micron or less! The above grains may be tabular grains that occupy 10% or more of the total projected area. In addition, ±4to of the average particle diameter
Particles with a particle size within es are the number of particles! It may be a monodisperse emulsion that accounts for more than 100%.

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

In addition, grains in which latent images are mainly formed on different surfaces (for example, negative emulsions), grains in which latent images are mainly formed inside the grains (for example, internal latent image emulsions), or particles in which latent images are pre-fogged (for example, internal latent image emulsions) may be used. For example, it may be a direct positive emulsion).

Silver halide emulsions having the various halogen compositions, crystal habits, intragrain structures, shapes and distributions described above are used in light-sensitive photographic elements for a variety of applications. Therefore, the compounds of the present invention can be used as sensitizers, sensitizing dyes, desensitizers, desensitizing dyes, filters,
It is used with emulsions for the following uses for the purpose of antihalation or irradiation prevention. These dyes can be added to desired layers such as intermediate layers, protective layers, and pack layers in addition to the emulsion layer.

The dyes of the present invention are used with silver halide photographic emulsions for various color and black and white sensitive materials.

More specifically, color positive emulsions, color paper emulsions, color negative emulsions, color reversal emulsions (which may or may not contain couplers), direct positive silver halide photographic emulsions, and photosensitive materials for plate making. emulsions used in photosensitive materials for cathode ray tube displays; emulsions used in X-ray recording materials (materials for direct and indirect photography using special trap screens); Silver salt diffusion transfer process (Si
lver 5alt diffusion tra
Emulsions used in color diffusion transfer processes, emulsions used in color diffusion transfer processes, dye transfer processes
It is used together with emulsions used in silver dye bleaching methods, emulsions used in photosensitive materials for heat development, etc.

The photographic emulsion used in the present invention is P.
, Glafkides) [Shimmy! l Physique Photography (Chimie et
Physique Photographique)J
(Published by Paul Monte1, 1947), G.F.
, Duffin, “Photographic Emulsion Chemistry”
lsion Chemistry) J (Defocal Bray, published by The Focal Press, 1993), Dai L. Zelikman et al. V, L, Zal
“Making-and-” by Ikman et al.
Coating photographic emulsion:ry(M
making and coating photo -
graphic Emulsion) J (7Ocal Press The Focal Press
It can be prepared using the method described in, for example, 1961, published by J.D.

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (e.g., U.S. Pat. .Au, r No. 3,7014,130
No. 1. λF7.4tJP No. 1. Core J,
37μ, etc.) thione compounds (for example, JP-A-Sho!!-1
Hiroa, 3i number, same number z3-rtaor, same number 7j-
77, 7J7, etc.), amine compounds (listed in JP-A No. 3
4m700717, etc.) can be used.

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

Examples of internal latent image type emulsions used in the present invention include US Pat. Octopus, 2jO, 3,2Qt, JlJ,
Same J, 444L7. ') No. 27, rFfJ3t741
, Core No. 6, and conversion emulsions, core/shell emulsions, emulsions containing strange metals, and the like, which are described in J, PJj, 0/Hiro, etc., can be mentioned.

Next, the prefogged direct positive type emulsion used in the present invention includes a direct positive type silver halide photographic emulsion which has been fogged with a single or chemical fogging agent.

Generally, these emulsions are classified into the following two types.

One of them is a silver halide crystal which has a nucleus t- which can trap free electrons inside the crystal, and whose surface has been chemically fogged in advance. The feature of this type of emulsion is that it directly gives a positive image by itself, and by adding a sensitizing dye, it can not only increase the sensitivity through dispectral sensitization but also sensitize the intrinsic absorption region. can give. This type of emulsion requires a combination of its halogen composition to facilitate the incorporation of chemical sensitizers and Group I metal salts used to provide free electron tozonuclei into the silver halide. Must not be. Furthermore, by adding an organic desensitizer, it is possible to improve shedding, especially to prevent "reinversion", and by adding bromide ions and iodide ions, the maximum concentration can be increased, the sensitivity can be increased, and the shedding can be improved2. can be done.

Another raw emulsion is an emulsion in which free electron trap nuclei are not provided inside the silver halide, and the interface of the silver halide is chemically fogged. This emulsion contains as few crystal defects as possible, and is preferably a silver halide emulsion consisting of pure silver bromide and strong regular crystals with twin planes. This emulsion itself does not give any direct positive image. However, if an organic desensitizer is adsorbed to the silver halide of this emulsion, a direct positive image with high sensitivity can be obtained.

Either emulsion can be used in the present invention. In other words, either emulsion can be effectively sensitized by the compound represented by formula (I).

The silver halide emulsion used in the present invention is fogged by light or chemically, but chemical fogging is caused by reducing organic compounds such as hydrazine derivatives, formalin, thiourea oxidized with lambda, and holamine compounds. , ami/phon, methyldichlorosilane, etc.

Also applicable is a method of providing fog nuclei by using a reducing agent in combination with metal ions other than silver (for example, gold ions, platinum ions, iridium ions, etc.), or by using these in combination with halogen ions.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, e.g. Aite Freezer H, F
Die Grundlagen der Fotografitzien Prosesse Mituto Zilberhalogenieden (DieGrundlagen d
er PhotographischenProze
sse mit 8i1berhalogenide
n (Akadamische Verlagsgesel)
lschaft.

The method described in t7J--73 Hiroshi pages can be used.

That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin or silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts); , amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts, Pt, Ir.

A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as Pd can be used alone or in combination.

The photographic emulsion used in the present invention has the following properties:
Alternatively, various compounds can be included for the purpose of stabilizing photographic performance. That is, thisols such as benzothiazolium salts, nitroindazoles, triazoles, penztriasiques, benzimidazoles (% nitro- or halogen substituted); heterocyclic mercapto compounds such as mercaptothiazoles\
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptotetrazoles (especially l-7enyl!-mercaptotetrazole), mercaptopyrimidines; the above heterocycles having a water-soluble group such as a carboxyl group or a sulfone group; Mercapto compounds; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (especially Hiro-hydroquine substituted (/, j, ja, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; Many compounds known as antifoggants or stabilizers can be added.

The silver halide photographic emulsion of the present invention can contain color pigments such as cyan coupler, magenta coupler, yellow coupler, etc.
It can include a coupler and a compound that disperses the coupler.

That is, it may contain a compound that can develop color by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative, an aminophenol derivative, etc.) in color development treatment.

For example, as a magenta coupler! - There are pyrazolone cutlers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, piparoylacetanilides), etc., and cyan couplers include , naphthol couplers, and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be monoequivalent or monoequivalent with respect to silver ion. Also, the effect of color correction 3!1. It may also be a coupler (so-called DIR coupler) that releases all of the development inhibitor during development.

In addition to t*DIR couplers, the coupling reaction may include colorless DI coupling compounds that are colorless and release development inhibitors.

For the purpose of increasing sensitivity, increasing contrast, or accelerating development, the photographic emulsion of the present invention may contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines.
It may also contain thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, log derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The silver halide photographic emulsion of the present invention may contain known water-soluble dyes other than the dyes shown in the present invention (for example, oxonol dyes, hemioxonol dyes, and merocyanine dyes) as filter dyes or for various purposes such as preventing irradiation. f+) may be used in combination. Further, as a spectral sensitizer, it may be used in combination with known cyanine dyes, merocyanine dyes, and hemicyanine dyes other than the dyes shown in the present invention.

The photographic emulsion of the present invention may contain various surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). But that's fine.

Other additives may be used with photographic emulsions or other hydrocolloids in the practice of this invention. Examples include anti-fading agents, inorganic or organic hardeners, anti-fogging agents, ultraviolet absorbers, mordants, plasticizers, latex polymers, matting agents and the like. in particular,"
Research Disclosure
sclosure)JVol,/yg(/y7r,XI
), D-/7tlt3, etc.

In the photographic emulsion used in the present invention, a water-retentive polymer such as gelatin is used as a protective colloid.

The finished emulsion can be prepared on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film,
Other plastic bases or coated on glass plates.

Exposure to obtain a photographic image may be carried out using a conventional method. i.e. natural light (sunlight), tungsten electric light,
Any of a wide variety of known light sources can be used, such as fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, and cathode ray tube flying spots. Exposure time is typically used in cameras //1ooo seconds to 7
Exposure times shorter than 771,000 seconds, such as xenon flash lamps or cathode ray tubes, can be used.
Exposures of 4 to / / / o' seconds can be used, or exposures longer than 7 seconds can be used.

If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. A laser source can also be used for exposure. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, r-rays, α-rays, or the like.

Photographic processing of light-sensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure).
Disclosure)/No. 7A, pages 30 to 30 (
Any of the known methods and known treatment liquids as described in RD-/7Ag 3) can be applied. This photographic processing may be either a photographic processing for forming a silver image (subject photographic processing) or a photographic processing for forming a dye image (color photographic processing), depending on the purpose. The processing temperature is usually selected between tr c and to 6c, but it may also be below ir'c or above io'c.

(Example) Next, examples according to the present invention are shown below, but the present invention is not limited thereto.

Example 1 (@Contact Emulsion/) First, in order to adjust the emulsion, the 1st to μth liquids were prepared using the following formulation.
A liquid was prepared.

WJl liquid 1st liquid 3rd liquid Hiroshi liquid 1st liquid, 2nd liquid and 3rd liquid and 1 (while keeping it at BOOC, 3
The mixture was added over a period of 0 minutes, and then subjected to physical ripening for another minute. Next, an O,co-normal solution of potassium iodide (total/jcc) was added, and then the pAg was adjusted to t,o using a silver nitrate solution. It was added to hydrazine and gold chloride salt, the pH was adjusted to 10 using sodium hydroxide solution, and the mixture was aged for 70 minutes. It was neutralized using citric acid and then washed with water. Melt it again and add the first liquid to obtain an emulsion. In the obtained emulsion, the average grain size of silver halide grains was about O0-μ (I00
) containing regular tetragonal grains with planes.

To this emulsion was added a molar concentration of dye (compound -
11 or 14/-) methanol solution 1 tcc/
/ 00 f emulsion and each emulsion with an appropriate amount of saponin added to cellulose triacetate film with a dry film thickness of approximately! Next, obtain a sample by coating it so that it becomes μ. Copy each sample! Light wedge exposure was performed using tungsten light at ≠@ as a light source. Separately, exposure was carried out to obtain a spectrogram using a diffraction grating type spectrophotograph with a tungsten light source having a color temperature of -4t6°.

It was developed for 2 minutes at 2o''C using the following developer and fixed with an acidic hardening fixer.The density was measured using a P-type densitometer manufactured by Fuji Photo Film to obtain a characteristic curve.

[Composition of developer]

This is used by diluting it with water.

The condensation compound-7 is! The sensitization maximum obtained by spectrally sensitizing between 70 and 7≠Onm gives an inverted image at 700 nm from ArOnm, fc.

Compound-μ is 13 from &00nm! Spectral sensitization was performed between 7 nm and 7 nm, giving an inverted image with a sensitization maximum between 7 A Onm and 7 r Onm.

Example 2 (direct positive emulsion) First, a raw emulsion was prepared as follows.

1st solution (l of inert gelatin IO'y and sodium chloride)
Add the specified solution JCC and water to 00CCf and heat to ao'c to dissolve).
Add cf and heat to to''c to dissolve) and the third liquid (add 300 CCt of water to sodium chloride Jjf and heat to to''c and dissolve) while maintaining the temperature at 600C and stir for 20 minutes. It was added over a period of time. After addition! Aged for 1 minute, then added 00CCf of water to the first solution (potassium bromide/lit)
In addition t.

"C heating and dissolving) was added over 3 minutes with stirring. Then it was aged for io minutes, the temperature was lowered and washed with water. It was heated again to dissolve and the pH was adjusted to -IO. hydrazine and gold chloride salt were added thereto, ripened for 10 minutes, and then adjusted to pHya,j using citric acid.The average grain size of the silver halide grains in the resulting emulsion was about O6/!μ. Ta.

For this emulsion! ×10 molar concentration of pinacryptol yellow methanol solution 3 cc//002 emulsion was added, rxio-2 molar concentration of dye (compound -co or -yo) methanol solution t-3-cc//0
A sample was prepared by adding a 0 f emulsion and further adding appropriate amounts of mucochloric acid and saponin, and applying the emulsion to a cellulose triacetate film to a dry film thickness of about 0 μm.

Copy each sample! Exposure was performed through a light wedge using a tungsten light source from Hiro@.

Separately, exposure was carried out to obtain a spectrogram using a diffraction grating spectrograph equipped with a tungsten light source with a color temperature of 66°.

It was developed for 3 minutes at 20°C with a developer having the following formulation, and fixed with an acidic hardening fixer.

The density of this was measured using a Fuji Photo Film ■Crack P-o densitometer, and a characteristic curve was obtained.

As a result, Compound-1 was spectrally sensitized between 170 and 74 LO nm, giving an inverted image with a maximum sensitization between AIO nm and 7 OO nm.

Compound-! was spectrally sensitized between toonm and IJrnm, and gave an inverted image with a sensitization maximum of 7&Onm to 7rOnmK.

Example 3 (Negative-working emulsion) 70 mmol silver chloride, 100 mmol silver chloride, 10 mmol silver chloride, 0.0 mmol silver chloride,
A sulfur-sensitized halide emulsion consisting of 2 molar silver iodide was prepared. The average grain size of these silver halogenide grains is 0.3! It was μ.

Weigh out 9 of this emulsion into a pot, dissolve it, add the compound -/or -4t'ji-rXlo mol/kl emulsion, and further add ≠-human axicutmethyl-/, J, Ja, 7- Citrazainde: yfO9J2/halogen (t [1 mol, sodium dodecylbenzenesulfonate t-2F/silver halide 1 mol, mucochlor fllt
-0. rf/silver halide/-T-ru and then coated on a polyethylene terephthalate film base to obtain a negative photographic material.

The color temperature of these film samples is −r! A 5c-to filter manufactured by Fuji Photo Film Co., Ltd. (a red filter that only transmits light with wavelengths longer than 400 nm. In this case, only light in the spectral sensitization region caused by the dye is transmitted) is attached to the light source at μ'. It was exposed to light.

Separately, exposure was carried out to obtain a spectrogram using a diffraction grating type spectrograph having a tungsten light source with a color temperature of 0.

After exposure, develop with O'C for 1 minute using a developer with the following composition and stop.1. A fixing bath was carried out and the strips were washed with water to obtain strips having a desired black and white image. The density and fog of this strip were measured to obtain the sensitivity and fog. Sensitivity and fog are determined, and the reference point for dimensional density is [fog +7. ! ].

Composition of developer Add water to make /l When using, add 2 volumes of water to make a working solution.

As a result, Compound-7 was a silver chlorobromide emulsion 2sr.

Spectral sensitization is performed between nm and 7uOnm, and the maximum sensitization is Ar.
Onm to 700nm.

Compound-4t is laon from silver chlorobromide emulsion fAOOnm
Spectral sensitization is performed between 7A Onm and 710 nm.
It was in nm.

Example 4 (Antihalation layer) Gelatin rott-dissolved in water Il, to which a j% aqueous solution of poly(diethylaminoethyl methacrylate) rOx
! , 30 tttl of a 10% aqueous solution of saponin.

2% aqueous solution of chrome alum! A dye gelatin solution was prepared by adding 1,100 rnl't of flathead aqueous solution of Od and the above-mentioned compound-1 of the present invention.

The above dye gelatin solution was coated on a cellulose acetate photographic support to form an antihalation layer. Anhydro-l/-ethyl-3,3/-bis(sulfopropyl)naphtho(/,,2-d)thiacarbocyanine hydroxide and terethyl-J,J'-bis(sulfobdel)zelenacarbocyanine hydride were added thereto. A silver chlorobromide emulsion (approximately 77 mol of silver bromide) which had been spectrally sensitized panchromatically in combination with lacquer was completely coated, and a protective gelatin layer was provided thereon to produce a photographic material for plate making.

A contact screen (33 lines per finch) was closely attached to the photographic material thus prepared, and a light wedge exposure was applied to the photographic material. After developing for 3 minutes at O'C using a developer having the composition shown below, method (therefore fixed, washed and dried).

Developer composition water j00y
nl Anhydrous sodium sulfite JOf noraformaldehyde 7,12 Sodium bisulfite Boric acid 7. J2 Hydroquinone 22. Jf potassium bromide /, add t2 water
After IP processing, the photographic material shows almost no contamination in the unexposed areas. In addition, the halftone image with excellent edge gradient (f) was changed.

[Brief explanation of drawings]

1 and 1 show spectral sensitivity curves obtained by using Compound / and Compound μ in the silver chlorobromide emulsion of Example 3, respectively. Patent applicant Fuji Photo Film Co., Ltd. Figure 1 Drafting table

Claims (1)

[Scope of Claims] A silver halide photographic material comprising a support and a silver halide emulsion layer, characterized by having at least one layer containing at least one compound represented by the following general formula (I). Silver halide photographic material. (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3, R_4, R_5, R
_6, R_7, R_1_0, R_1_1, R_1_2,
and R_1_3 is a hydrogen atom, a halogen atom, or 1
R_1 and R_2, R_3 and R_4, R_4 and R_5, R_5 and R_6, R_6 and R
_7, R_1_0 and R_1_1, and R_1_2 and R
An aromatic ring may be formed which may be substituted with at least one combination of the combinations _1_3. R_8 and R_9 represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. Also, R_8 and R_9
may form a ring with the nitrogen atom. X^■ represents an anion. n represents 0, 1 or 2. )