JPH03127045A - Production of photographic silver halide emulsion - Google Patents

Abstract

PURPOSE:To obtain the planar silver chlorobromide emulsion having excellent rapid processability and high silver chloride content by adding a spectral sensitizing dyestuff to the emulsion at >=50 deg. before the end of the chemical sensitization. CONSTITUTION:The spectral sensitizing dyestuff is added at >=50 deg.C to the emulsion before the chemical sensitization ends at the time of producing the photographic silver halide emulsion which consists of the silver chlorobromide particles contg. at least 80mol% silver chloride and in which at least 50% of the total projection area of the silver chlorobromide particles is occupied by the planar particles having <0.5mum thickness, >=0.5mum diameter and >=(2:1) average aspect ratio. Adenine or the salt thereof is preferably used in order to obtain the silver chlorobromide particles. The planar chlorobromide emulsion which is extremely fast in the development progression suitable for rapid development processing and has the high silver chloride content is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide emulsion for photography;
In particular, it relates to a tabular silver chlorobromide emulsion with a high silver chloride content and excellent rapid processability.

(Conventional technology) Currently Xi! In the development processing of photosensitive materials, it is required to shorten the processing time and reduce the amount of waste liquid generated during processing. Generally, silver iodobromide emulsions are used in X-ray sensitive materials, but to meet the above requirements, it is advantageous to use silver chlorobromide emulsions, which have a high solubility. It is clear to those skilled in the art that it is desirable to increase image density with a small amount of silver in order to reduce waste liquid, and that tabular grains are suitable in terms of sensitivity, granularity, sharpness, color sensitization efficiency, etc. It is well known. However, when silver chlorobromide tabular emulsions contain a large amount of spectral sensitizing dyes, such as silver iodobromide tabular emulsions, the color sensitization efficiency and sharpness cannot be improved simply by adding the dye.

(Objective of the Invention) The object of the present invention is to provide a tabular silver chlorobromide emulsion having a high silver chloride content and which is suitable for the first rc rapid development process and has a high silver chloride content. Another object of the present invention is to provide a manufacturing method that increases color sensitization efficiency when a large amount of sensitizing dye is used.A third object is to provide a light-sensitive material containing a tabular silver chlorobromide emulsion with high sharpness. The first objective is to provide a photosensitive material with high covering power.

(Disclosure of the Invention) As a result of intensive research by the present inventors, the object of the present invention is to provide a photographic silver halide film comprising silver chloride particles or silver chloride particles each containing at least 80 moles of silver chloride. an emulsion, and at least 80% of the total projected area of the silver chlorobromide grains.
% is dominated by tabular grains having a thickness of less than rμm, a diameter of 0.2μm or more, and an average aspect ratio of 1 or more,
This was achieved by a method for producing a photographic silver emulsion, which is characterized in that a spectral sensitizing dye is added at a temperature of 50'C or higher after chemical sensitization is completed.

It is preferable to use adenine or a salt thereof to obtain the silver chlorobromide grains in the present invention. The amount of adenine or its salt added is 0-4 to 1/ScI silver monoxide/silver monoxide.
It can be used in the range of 80-2 mol, and jXlo
-! X80 mol is particularly favorable.

In the present invention, the addition timing of adenine or its salt is such that it is added at any time from the time of nucleation of silver halide grains in the production process of the silver halide emulsion to the time of grain formation at the end of physical ripening 1. However, it is preferable that at least a portion of the particles be present from the beginning of particle formation! Yes.

Once the tabular high silver chloride grains are formed, adenine is no longer needed, but usually at least a portion of it is adsorbed to the grain surface. Compounds that exhibit a strong affinity for the silver halide grain surfaces, such as spectral sensitizing dyes, can replace adenine and thus substantially wash and remove the adenine from the emulsion.

Encapsulated adenine is well known as an excellent anti-capri agent and its remaining in the emulsion is beneficial.

Adenine or its salts are used to create normal crystals (hedrons ~ 14!
Separating the formation of (hedral) grains and tabular grains can be achieved by adjusting the chloride concentration and pa at the initial stage of one grain formation (so-called nucleation). Specifically, roughly speaking, the chloride concentration during nucleation is approximately 0.0! If the concentration is less than molar, normal crystals are likely to occur, and about 17. /J molar concentration or higher, non-parallel twin plane t-
The number of non-tabular grains increases. Normal crystal grains tend to form at a pH higher than or equal to E), and non-tabular grains tend to form at a pH lower than E)H.

Chloride concentration during particle harvesting ha! A molar concentration or less is preferred, and a 0.07 to 3 molar concentration is particularly preferred.

The temperature during particle formation in the present invention can be used in the range of 10-PjoC, preferably 3j to "c".

The high silver chloride grains of the present invention have a silver chloride content of at least 80
It means more than a mole fight. How about Yoshikazu? θ mole fight is better! Shi < Hari! More than Mor Yu.

The remainder consists of silver bromide, but a phase mainly consisting of silver bromide may be localized near the surface of the particle, and the particle may be a so-called core/shell type particle.

The tabular grains of the present invention have a diameter/thickness ratio (aspect ratio) of 2:1 or more, which is preferable! is from 2:l to 20:l, more preferably from 3:l to 80:/
It is.

The diameter of a tabular grain herein refers to the diameter of a circle having an area equal to the projected area of the grain. In the present invention, the diameter of the tabular grains is preferably 7.7 μm or more, more preferably 0.7 to φμm.

The term ``4'' of a tabular grain that is casing refers to the distance between two opposing parallel main planes of the surfaces constituting the tabular grain. In the present invention, the preferred thickness of the tabular grains is 0.
* less than j, #m, more preferably 0.3 μm
less than

The grain size distribution of the silver halide grains of the present invention may be monodisperse or polydisperse, but monodisperse is more preferable.

A silver halide solvent may be used during production of the silver halide grains of the present invention. Frequently used silver halide solvents include, for example, thiocyanates (e.g., U.S. Pat.
, JJJ, Jbu← issue, same No. 1, aar, zsu issue, same No. 1, 3 J0. 06Y, etc.), thioether compounds (for example, U.S. Pat. No. 3.27/, 717, U.S. Pat. No. 3. Tough!
, j, No. 21, same No. 3.70, No. 730, same No. G, 2
27. No. 132, No. ←, 274, Jφ7, etc.)
, thione compounds, and thiourea compounds (e.g.
-/17413/ri issue, same! 3-r21801r, same! ! -77737, etc.), amine compounds (for example, JP-A No. 4 (-/θ0777, etc.)), and these can be used.

Ammonia can also be used in combination as long as it does not cause sensitizing effects.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be coexisting. Especially iridium salt! or rhodium salts are preferred.

Addition rate of silver salt solution (e.g. AgNO3 aqueous solution) and halide solution (e.g. Naα aqueous solution) added to accelerate grain growth during production of silver halide grains of the present invention,
A method of increasing the amount and concentration of addition according to the total addition time is preferably used.

Regarding these methods, for example, the British special liver No. 1゜33! ,
R-2! No. 3, U.S. Patent No. 3. t72.900, same No. 7
．． 4jf7.7j7, same number ψ, ko←ko, lpi! No., Tokukai Akira! ! -lφ232 No., same j'j-/11/24A
No. 11-//3?27, Mukai 5r-ttiy2r, Same! The descriptions in r-///ri No. 3←, jr-///ri No. 36, etc. can be referred to.

The tabular silver halide grains of the present invention are chemically sensitized.

As a chemical sensitization method, there is a gold sensitization method using a so-called gold compound (for example, US Pat. No. 2, ot).

Sensitization method using metals such as iridium, platinum, rhodium, and palladium (for example, U.S. Patent No. 1, No. J, No. 320.042) and sensitization method using metals such as iridium, platinum, rhodium, palladium, etc. j44..247) or a sulfur sensitization method using a sulfur-containing compound (for example, U.S. Patent No. 2.22,
24 da), a selenium sensitization method using selenium compounds, or a reduction sensitization method using tin salts, thiourea dioxide, polyamines, etc. (for example, U.S. Pat. No. 2,4L17,180,
Same girl.

sty, tyr issue, same 2,! -27, 92j- issue)
, or a combination of two or more of these can be used.

In particular, the silver halide grains of the present invention are preferably sensitized using a gold intensifying tube or sulfur sensitizing tube, or a combination thereof.

The photographic emulsions of the present invention are spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Styryl color R and hemioquinol dyes are included.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a pigment belonging to complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes.

Namely, viroline nucleus, oxazoline nucleus, thia/phosphorus nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenanol nucleus, imidazole nucleus, tetranol nucleus, pyridine nucleus, etc.; A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei. ;
and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, ben/selenazole nucleus. Nuclei, benzimidazole nuclei, quinoline nuclei, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes and composite merocyanine dyes contain pyrazoline-! as a core with a ketomethylene structure. -one nucleus, thiohydantoin nucleus, cochoxazolidine nucleus, ψ-dione nucleus, thiazolidine-a, a-dione nucleus, rhodanine nucleus, thiobarbir rR nucleus, etc.! It is also possible to apply a member heteroartic ring nucleus.

For example, Re5earch Disclosure magazine/7
Volume 4 RD/744LJ, page 23, section ■ (/P7r year 12
It is possible to use the compounds described in 1996 or the cited literature.

Preferably, as a sensitizing dye, the following general formula (s-I), (S
-n), (8-111), <5-tV>, (S-Va)
Alternatively, spectral sensitization is performed by adding at least one kind of spectral sensitizing dye represented by (8-Vb).

General formula (S-1) General formula ( ) In the formula, Z' (i = "/-'? ) and W' (i = /, ,
2) ti represents a group of nonmetallic atoms necessary to form a 3- to 6-membered nitrogen-containing heterocycle, and each may be the same or different. R, 1, R2, R3, R5, R7R8 and Bl
1 may be the same or different, and represents an alkyl group. R4, R6, R9, and RIO represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

ps qs rs J%ks S* 's u, x%"
is 0 or 8 m, n, i, v, w, α, y, O1/
, λ, also represents 3.

Ll (i=/~/s) is a methine group (. represents a substituted methine group.

)(!(i=/~3) represents an anion.

W is a halogen atom, a cyano group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkyl group,
Represents an alkoxy group or an acyl group.

Formed by Zl, Z2, z3, Z5, Z6, z' or tiz'! Examples of 6-membered heterocycles include the following. The above heterocycle may be further substituted as exemplified below.

Thiazole nucleus (e.g., thiazole, q-methylthiazole, gouphenylthiazole, ψ,3-dimethylthiazole, φ,j-diphenylthiazole), benzothiazole nucleus (e.g., benzothiazole, ψ-chlorobenzothiazole, t-chlorobenzo Thiazole, 6-chlorobenzothiazole, j-nitropenzothiazole, ψ
-Methylbenzothiazole, j-methylbenzothiazole, 6-methylbenzothiazole, j-bromobenzothiazole, 6-bromobenzothiazole, j-iodobenzothiazole,! -phenylbenzothiazole, j-
Methoxybenzothiazole, 6-medoxibe/zothiazole, j-ethoxybenzothiazole,! -Ethoxycarbonylbenzothiazole,! -carboxybenzothiazole, 3-7enethylbenzothiazole, j-fluorobenzothiazole, j-chloro-6-methylbenzothiazole,! , 6-dimethylpenzothiazole, j-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, q-phenylbenzothiazole),
Naphthothiazole core (e.g. naph) [:, 2. /-d
) thiazole, naphtho [:/,, 2-d) thiazole,
Nat(y,3-d)thiazole, j-methoxynaphtho(/,,2-d)thiazole, 7-nitoxynaphtho(,
! ,/-d) Thiazole, ♂-methoxynaphtho (,2,
/-d) Thiazole, j-methoxynaphtho (!, 3-d
) Thiazo-A/), thiazoline nucleus (e.g., thiazoline, l-methylthiazoline, ←-nitrothiazoline), oxazole nucleus (e.g., oxazole, ψ-methyloxazole, goonitrooxazole, !-methyloxazole, ψ- phenyloxazole, ←, j-diphenyloxazole, ψ-ethyloxazole), benzoxazole nucleus (benzoxazole, j-chlorobenzoxazole, !-methylbenzoxazole, j-7
0mobenzoxazole,! -fluorobenzoxazole, j-phenylbenzoxazole,! -Methoxybenzoxanol,! - di-abenzoxazole,
j-trifluoromethylbenzoxazole, j-humanmixibenzoxazole, j-carboxybenzoxanol, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitoabenzoxazole,
6-Medoxybenzoxazole% 6-Hydooxybenzoxazole, j,6-dimethylbenzoxazole, φ,6-dimethylbenzoxazole, j-ethoxybenzoxazole), naphthoxazole core (e.g. naphtho(,2 ,/-d) Oxazole, nut (t,
2-d) Oxazole, Na7) (,2,J-d)Oxazole,! - di-naphtho(,2,/-d)oxazole), oxazoline nucleus (e.g., ri, φ-dimethyloxazoline), selenazole nucleus (e.g., g-methylselenazole, danito-selenazole, ψ-phenylselenazole), Benzoselenazole nucleus (fl'lJ Eva,
benzoselenazole, j-chlorobenzoselenazole,
j-dito-Obe/zoselenazole, j-methoxybenzoselenazole, j-hydroxybenzoselenazole, 6-
Nidrobenno serenazole #, j-? )0-6-nitropenzoselenazole), naphthoselenazole core (e.g., naphtho(2,/-d) selenazole, naphtho(/,,
2-d] selenazole), 3,3-dialkylindolenine core (e.g. 3,3-dimethylindolenine, 3.
3-') Ethylindolenine, 3,3-dimethyl-! −
Cyanoindolenine, 3,3-dimethy/L/-1,-ditroindolenine, 3,3-dimethyl-j-ditroindolenine, 3,3-dimethyl-j-methoxyindolenine, 3.3. J-) dimethylindolenine, 3,3
-Dimethyl-! -chloroindolenine), imidazole nucleus (e.g. /-alkylimidazole, l-alkyl-ψ-phenylimidazole, /-alkylbenzimidazole, /-alkyl-!-chloropenzimitasole, l-furkyl-!, 6 -dichlorobenzimidazole, l-alkyl-!-methoxybenzimidazole,
l-Alkyl-! -cyanobenzimidazole, l-alkyl-! -fluorobenzimidazole, /-alkyl-3-trifluoromethylbenzimidazole, l-
Alkyl-6-chloro-! -cyanobenzimidazole, l-alkyl-6-chloro-j-trifluoromethylbenzimidazole, l-alkylnaphtho(/, 2-
d) Imidazole, l-allyl-j.

6-dichlorobenzimidazole, /-allyl-! -chlorobenzimidazole, l-arylimidazole,
/-Arylbenzimidazole, l-aryl-! −
Lopenzimidazole, l-aryl-j, 6-dichlorobenzimidazole, l-aryl-j-methoxybenzimidazole, l-aryl-j-cyanobenzimidazole, l-arylnaphtho(/, 2-d )
imidazole, the aforementioned alkyl groups are those having l-carbon atoms, such as unsubstituted alkyl groups such as methyl, ethyl, butyl, isopropyl, butyl, and hydroxyalkyl groups (e.g., 2-hydroxyethyl, 3-hydroxy propyl) etc. are preferred. Particularly preferred are methyl group and ethyl group. The aforementioned aryl includes phenyl, halogen (lll hachloro) substituted phenyl, alkyl (e.g. methyl) substituted 7-enyl, alkoxy (e.g. methoxy) substituted 7-enyl, etc. ), pyridine nucleus (e.g. 2
-Pyridine, ←-Pyridine,! -methyl-2-pyridine, 3-methyl-ψ-pyridine), quinoline nucleus (e.g.
2-quinoline, 3-methyl-2-quinoline, j-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, g-fluoro-2-quinoline, 6-
Medoxy-2-quinoline, 6-hydroxy-λ-quinoline, g-chloro-2-quinoline, ←-quinoline, 6-nitoxy≠-quinoline, 6-nitro-ψ-quinoline, l
-chloro-ψ-quinoline, za-fluoro-guquinoline, l-methyl-←-quinoline, g-methoxy-←-quinoline, isoquinoline, 6-nitro-7-inquinoline,
3. l-dihydro-7-isoquinoline, 6-nitoO-j
-isoquinoline), imidazo[ψ, j-b) quinoxaline nucleus (e.g. 1,3-diethylimidazo[ψ, 3-b
) quinoxaline, 6-chloro-1,3-diallylimidazo(44,j-b)quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus, tellazole nucleus, penzotelllazole nucleus, etc. can.

Examples of the j tx 6-membered heterocycle formed by z4 or 2 include the following. For example, rhodanine nucleus,
2-Thiohydantoin nucleus, 2-thioxooxazolidine-ψ-one nucleus, 2-pyrazolin-j-one nucleus, barbylic acid group, 2-thiobarbital acid group, thiazolidine-
There are 2,'l-dione nucleus, thiazolidine-φ-one nucleus, inoxacillone nucleus, hydantoin nucleus, and indandione nucleus.

A j- to 6-membered heterocycle formed by Wl or W is formed by Z or Z! to 6-membered heterocycle at an appropriate position. It excludes the oxo group or thioxo group. L1L2,L%L,L,
L,L,L,L9L%L,L%
Among the methine group and substituted methine group represented by L,
Examples of substituents include alkyl groups (e.g. methyl, ethyl, benzyl), aryl groups (e.g. phenyl)
, /) rogene (for example, methoxy, bromo), alkoxy groups (methoxy, ethoxy, etc.), and the substituents of the methine chain may form a 1/2-membered ring.

The alkyl group represented by 1, B2, B3, R5, R7, R8 or Bll is, for example, a carbon atom /~/
1. Preferably / to 7, particularly preferably / to j alkyl group (unsubstituted alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl group, For example, aralkyl groups (e.g. benzyl,
2-phenylethyl), hydroxyalkyl groups (e.g., 2-hydroxyethyl, 3-hydroxypropyl),
Carboxyalkyl groups (e.g., 2-carboxyethyl, 3-carboxypropyl, carboxybutyl, carboxymethyl), alkoxyalkyl groups (e.g., 2-carboxypropyl, carboxybutyl, carboxymethyl),
-methoxyethyl, 2-(comethoxyethoxy)ethyl), sulfoalkyl group C example 1f, x-sulfoethyl,
3-sulfopropyl, 3-sulfobutyl, ←-sulfobutyl, 2-[3-sulfopropoxy]ethyl, l-humanOxy3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl group (e.g. 3-
sulfatopropyl, dasulfatobutyl), heterocyclic-substituted alkyl groups (e.g. 2-(pyrrolidin-2-one-
2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl, allyl group, etc.). The above-mentioned sulfo group, carboxy group, and sulfato group may be their alkali metal salts or amine salts.

Examples of the alkyl group, aryl group, and heterocyclic group represented by R4, R%R, or R include unsubstituted alkyl groups and substituted alkyl groups having a carbon number of l to /g, preferably / to 7, particularly preferably l-φ. groups (specific examples of these are R, R, R, R,
R'R, the same meaning as described for R), unsubstituted aryl group (e.g. phenyl group, 2-naphthyl group), substituted aryl group (e.g. ≠-carboxyphenyl group, kusulfophenyl group, 3-chlorophenyl group) group, 3-methylphenyl group), multiple X ring group (e.g., 2-pyridyl group,
2-thiagril group, etc., and these heterocyclic groups may be further substituted) tL, etc.

ps qs 's J%ks Ss "s"s X
or 2ba0 or /l-represented. m,n%! ,v,w
, α, y are 0. /, , 2.3.

In addition to those shown in the general formula above, styryl dyes, oxonol dyes, etc. may also be used.

Specific compound examples are shown below.

S-/ 503) i1'111(C2H5)3 -r -j S-← (CH2)3SO3Na -5 8-6 -7 (CH2)sSo2NH(C2H5) 3(CH2),
803NH(C2H6)3S-zaS-Turf0 (CH2)3S(J3Nl((C2)-1ρ3(CH2
)3S(J3NH(C2)15)3-tt S-/2 -tJ 8-/ ← -tj 8-/A S-/7 S-7za8-/ri-20 S-,2/-22 S -,! 3 S-uψ S-2! Completed H20 -26 -x7 S-, 2g re S-, 2ri5-30 -37 -32 -33 -317 2H5 ) S-←← S-←j S-4! A S-ψ7 S-ψri5-50 8-j/ S-3,2 -33 S-3pi S-3! A feature of the present invention is that a spectral sensitizing dye is added to the emulsion of ro0c or higher before the end of chemical sensitization.

The specific timing of addition is, for example, after the completion of grain formation and before chemical sensitization, at the start of chemical sensitization, or during chemical sensitization, but in any case, before the end of chemical sensitization to the emulsion at a temperature of J17'C or higher. It is necessary to add

Preferably, use a sensitizing dye at the start of chemical sensitization or during chemical sensitization! θ~70'(:) is added to the emulsion.

It is known that the adsorption of sensitizing dyes is further enhanced when bromide is added to silver chloride or silver chlorobromide emulsions, and this effect is similarly exhibited in the present invention. This is especially preferable as it results in better rice feeding. The addition of bromide i is 0.0% of the total amount of silver in the emulsion. /-80 moles is good, Oo, 2~! More preferably during a quarrel.

The bromide may be water-soluble (for example, potassium bromide) or water-resistant (for example, fine-grained silver bromide).

The amount of dye added is DaX80 per mole of silver halide.
#rX80 mol can be used, but z
xto-coX70 mol is more preferred. More preferably, it is 0.times.80@-/X10@-3 moles.

The emulsion layer of the silver halide photographic material of the present invention may contain ordinary silver halide grains in addition to the silver halide grains of the present invention.

In the photographic emulsion of the present invention containing the high silver chloride tabular grains according to the present invention, the high silver chloride tabular grains have a projected area of !
0% or more, preferably 7Q% or more, especially preferably 0
% or more.

Even when the photographic emulsion of the present invention and other photographic emulsions are mixed and used, the high silver chloride tabular grains according to the present invention are present in the mixed emulsion! It is preferable to use a mixture so that the amount of O or more is present.

The silver halide emulsion prepared according to the present invention can be used in both color photographic materials and black and white photographic materials.

Examples of color photographic materials include color paper, color reversal film, and black and white photographic materials include X-ray film, general photography film, and printing film.
It can be preferably used for Q films.

There are no particular restrictions on other additives for the photographic material to which the emulsion of the present invention is applied; for example, Re5earch
Disclosure magazine/74 volumes RD/7444! Reference may be made to the descriptions in Volume 117 of RD/r7/4.

The descriptions of each compound 27I in RI)/7j #J and RD/r7/4Ktd are listed below.

l Chemical sensitizers 2 Sensitivity enhancers 3 Spectral sensitizers, supersensitizers 4 Brighteners 5 Anti-fogging agents and stabilizers 6 Party absorbers, filter dyes UV absorbers 7 Anti-stinting agents 8 Dye image stabilization Agent 9 Hardener 80 Binder 11 Plasticizer, lubricant 12 Coating aid, Surface active agent 13 Static inhibitor page 23 Buttr page right column Same as above 23 ~ Cog page Tar page right column ~ 61 R page right column 21 page 2 Da~, 2! Page 6φ2 page right column Jj-24 page 6φ2 page right column ~ tsuzo left column 21 page right column 2! Page 26 Page 16 Core page, 26 to Core page 120 Left to right column tri Left column Same as above tS-O Right column Same as above Page 27 Same as above As for the internal force pre-preventing agent and stabilizer of the above additives, azole (for example, benzene) is used. thiazolium salts, nitroimidazoles, nido-abenzimidazoles, chlorobenzimidazole M, 7'lomobenzimidazoles, nitroindazoles, aminotriazoles, benzotriazoles, etc.); heterocyclic mercapto compounds (e.g. mercaptothia mercaptobenzothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially /-phenyl-!-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc.); carboxyl groups, sulfone groups, etc. The above-mentioned heterocyclic mercapto compounds having a water-soluble group 't-; for example, thioketo compounds such as oxazolinthion; azaindenes (for example, triazaindenes, tetraazaindenes ←Special Vcψ-
Hydroxy-substituted -/, 3.3m, 7-titraazaindenes), pentaazaindenes, etc.); benzenethiosulfonic acids, pensenesulfinic acids; benzenesulfonamide, etc. can be preferably used.

The color coupler is preferably a non-diffusible one having a hydrophobic group called a ballast group in its molecule, or a polymerized one. The coupler may be either φ-equivalent or di-equivalent to silver ions. There are also colored couplers that have a color correction effect, or couplers that release a development inhibitor during development (so-called DIR).
coupler). A colorless DI in which the product of the coupling reaction is colorless and releases a development inhibitor.
It may also contain an R coupling compound.

For example, as a macenta coupler! -Pyrazolone coupler, pyrazolobenzimidazole coupler, pyrazolotriazole coupler, pyrazolotetrazole coupler,
Examples include cyanoacetylcoumarone couplers and open-chain acylacetonitrile couplers; examples of yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides and piparoylacetanilides); and examples of cyanide couplers include naphthol couplers and phenol couplers. As a cyan coupler, US Patent No. 777JOOCo, US Patent No. 72162, and US Patent No. 72162 are used. 7-11301, same $/J6J? No. 6, same +L3344
0// issue, $jJ7/77 issue, 3 da φ66 coco issue,
Same 3 j jP No. 72, same 4Iφ! /! 19, 14c Core No. 767, etc., a phenolic coupler having an ethyl group tV at the meta position of the 7 enol nucleus; 2. j-Diacylamino substituted phenolic coupler A phenylureido group at the 2nd position and an acylamino group at the 3rd position! Sulfonamide coupler, sulfonamide at the 3rd position of naphthol,
The coupler handle replaced with amide etc. has excellent image robustness and is a good choice.

In order to satisfy the characteristics required of a photosensitive material, two or more types of the above couplers etc. can be used together in the same layer, or the same compound can be added to two or more different layers.
Of course it doesn't matter.

As anti-fading agents, hydroquinones, 6-hydroxychromans,! - Hydroxycoumarans, spiro/a-man, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives,
Typical examples include methylenedioxybenzenes, aminophenols, hindered amines, and silylated or alkylated ether or ester derivatives of the heptaenolic hydroxyl group of each of these compounds. In addition, metal complexes such as (bis-salicyaldoximatone nickel complex) and (bis-N,N-dialkyldithiocarbamado) nickel complex can also be used.

For photographic processing of the light-sensitive material using the present invention, any known method can be used, and a known processing solution VC can be used. In addition, the processing temperature is usually /r0
The temperature is selected between c and 50°C, but the temperature may be lower than /r0c or higher than /r0c. Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that includes a development process that forms a dye image can be applied.

The black and white developer contains dihydroxybenzenes (e.g., t-hydroquinone), 3-pyrazolidones (e.g., t-ba/-7).
22-3-pyrazolidone) 1, aminophenol M (
For example, known developing agents such as N-methyl-p-aminophenol can be used alone or in combination.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g. l-
Amino-N, N-diethylaniline, 3-methyl-ψ-
Amino-N, N-diethylaniline, Guamino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-←-amino-N-ethyl-N-β-human axyethylaniline, 3-methyl-l-amino-N-ethyl-N
-β-methanesulfoa□doethylaniline, guamino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, "Photographic Professional Chemistry" by F.A. Menn, published by 7Ocal Press (/
PjJ), pp. 6-2.22, U.S. Patent 2. /ri3
,0/! No. 2. Tade No. 2.361, JP-A-Sho←r-+
Those described in φri No. 33 may also be used.

The developer may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors such as bromides, iodides, and anti-capri agents, and antifoggants. can include. Also, if necessary,
Water softeners, preservatives like hydroxylamine, benzyl alcohol, and diethylene glycol! 1! Solvents, development accelerators such as polyethylene glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, head racers such as sodium boron hydride, auxiliary developers such as /-phenyl-3-pyrazolidone, viscosity-imparting agents. , US-Fixed FF←, polycarboxylic acid-based chelating agent described in No. 01?3゜723, West German Publication (OL
S) J, 712, Ri! It may also contain an antioxidant described in No. θ.

The photographic material of the present invention is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (1),
Compounds of polyvalent metals such as cobalt (In), chromium (Vl), and copper (II), peracids, quinones, nitroso compounds, and the like are used. For example, ferricyanide, dichromate, organic complex salts of iron (ill)'' or cobal) (11), such as ethylenediamine tetracomplex, nitrilotriacetic acid, 1,3-diamino-2-propatoltetraacetic acid, etc.
Minopolycarbonate, complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates, and nitrone phenols can be used.

Among these, potassium ferricyanide, sodium iron(III) ethylenediaminetetracomplex, and ammonium iron(In) ethylenediaminetetraacetate are particularly useful. Ethylenediamine tetracomplex iron (Ill) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, US 4IiFFFi, oφ
λ,! No. 20, same! , 2 (1/, No. 946, Special Publication Showa 4c
In addition to the bleaching accelerators described in Japanese Patent Application Publication No. 3-3-4!1732, etc., and the thiol compounds described in Japanese Patent Application Laid-open No. 3-3-4!1732, various additives can also be added. Further, after the bleaching or bleaching/fixing treatment, a water washing treatment or a stabilizing bath treatment may be sufficient.

(Examples) The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 (Preparation of silver chloride emulsion A-H) Silver chloride emulsion A-
H'i was prepared as follows.

Solution (1) Solution (2) A g N Oa /fi LH20 is added to the solution (3)
/, adjusted to 0φ, and then stirred vigorously until the solution (,
2) and solution (3) were added simultaneously at a constant flow rate over a period of 1 minute. Further, add the solution (+Q and solution ← 0 simultaneously at a constant flow rate between the outside of the UO, wash with water using the usual 7o curing method, desalinate, and add 7XJ 440'c' to Zera f7'
t'pH+, J, pAg6.

Adjusted to 2. (Unripened tabular grain emulsion A) Chemical sensitization was carried out under the conditions listed in Table 1.

<Preparation of coating sample> On a biaxially stretched polyethylene terephthalate film with a thickness of 171 μm: 1c! discharge, process,
The coating amount of the first undercoat liquid having the following composition is j, 800
It was applied to a total area of 7 m2 using a wire bar coater and dried for 1 minute at /7j0CVC. Next, a first undercoat layer was provided on the opposite side in the same manner.

On the first undercoat layer on both sides, apply a second undercoat liquid having the following composition to both sides one by one in a coating amount of rr (38/m2) and dry to form the undercoated film. completed the program.

The following chemicals were added to the second undercoat solution per mole of silver halide to prepare a coating solution.

・K, 6-bis(hydroxyamino)-φ-diethylamino-/ = J I J-Triazine Sodium polyacrylate (average molecular weight da, 10,000) 80 kuda, OI O ethyl acrylate/acrylic acid/methacrylic acid- Copolymerized plasticizer Onitron with a composition ratio of 4j/2/3 20°Oθ! Qda2H5! , Q The emulsion layer coating solution thus obtained was coated in the same manner on both sides of the support by co-extrusion with the surface protection layer solution. At this time, the amounts of the emulsion layer and surface protective layer coated on one side were as follows.

<Emulsion layer> O coated silver amount / -P Ji'
/ m20 coated gelatin il/ , j , lil 7
m2〈Surface protective layer〉 Ocera f7 0. Ir/l/m2・
Dextran (average molecular weight J, P 10,000) 0.11177m2・
Matting agent (average particle size 3.! μm) Copolymer of polymethyl methacrylate/methacrylic acid = RI/l, OA 9/rn2 60/m2 Oφ-hydroxy-6-methyl-/.

3, Jan7-Chitrazai/Den l! O
Sodium polyacrylate (average molecular weight 1.1 million)! η/m2 70m97m2 Hard 31 agent/J-bis(sulfonylacetamido)ethane per side! It was applied so that the coating amount was 6μ/m. In this way, a photographic material of the present invention was obtained.

Evaluation of Photographic Performance A photographic material 1 was brought into close contact with both sides of the photographic material using a Fuji Photo Film ■GRENEX Ornscreen HR-Jt cassette, and XS sensitometry was performed. To adjust the exposure amount, adjust the distance st between the X-ray tube and the cassette.
- It was done by changing. After exposure, use Fuji Photo Film's FPM-Pθ00 automatic processor to process 3! roc
Automatic processing was carried out using RD-■ developer manufactured by Fuji Photo Film ■ under the processing conditions of ``WO''.The sensitivity was photographic material/l.
The specific sensitivity was -800.

H Nucleic Acid As can be seen from Table 2, the samples of the present invention have high sensitivity, especially in areas where there is a large amount of sensitizing dye.

Claims (1)

[Scope of Claims] 1) A photographic silver halide emulsion consisting of silver chlorobromide grains or silver chloride grains, each grain containing at least 80 mol% of silver chloride, At least 50% of the total projected area has a thickness of less than 0.5 μm and a diameter of 0.5 μm
In the method for producing a photographic silver halide emulsion that is dominated by tabular grains having a grain size of 2:1 or more and an average aspect ratio of 2:1 or more, a spectral sensitizing dye is added at a temperature of 50°C or more before the end of chemical sensitization. A method for producing a photographic silver halide emulsion, characterized by: 2) The method for producing a photographic silver halide emulsion according to claim 1, wherein the tabular grains are nucleated in the presence of adenine or a salt thereof.