JPS6114637A - Silver halide multilayer photosensitive material - Google Patents

Abstract

PURPOSE:To improve dye stain resistance, etc., by forming an emulsion layer incorporating flat silver halide grains having an average aspect ratio of a specified value or more and consisting essentially of faces (111), and forming a layer contg. polymer latex to increase the spectral sensitivity with the specific dye. CONSTITUTION:The photosensitive material contains in one or more emulsion layers flat silver halide grains having an aspect ratio of >=3/1 (the diameter of a circle equal in area to the projected image of the grain/the thickness of the grain) and consisting essentially of the faces (111), and an AgI concn. distribution increasing from the central part of each grain toward the outer part, having 0- 5mol% AgI in the central part, an AgI content higher by >=1mol% in the outer part than the central part, and the total AgI content of 4-20mol%. Further, one or more layers contain a polymer coupler having monomer units each represented by the formula shown here, and these layers are emulsion layers contg. silver iodobromide spectrally sensitized with a trimethine dye, thus permitting a photosensitive material high in sensitivity and improved in dye stain resistance and desilverability, etc. to be obtained.

Description

Detailed Description of the Invention (1) Object of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic material, and more specifically, to a multilayer color photographic material having tabular silver halide grains. Related to improvement of dye staining and desilvering properties.

(Prior art) Silver halide emulsions having tabular silver halide grains are known as a technology for achieving high sensitivity and high image quality of silver halide photographic materials. It is also known that one color image is used for color photography.

For example, JP-A-I (58-) 1393 (to 1υ:,
A multilayer color photographic material having a color-grading unit having a two-layer structure including an emulsion layer having tabular grains with an aspect ratio of 8:1 or more in the layer is characterized by JP-A-58-113934 discloses a multilayer color photographic light-sensitive material using silver iodobromide or silver bromide emulsions with tabular grains having an aspect ratio of 8:1 in the green-sensitive layer and the red-sensitive layer, and JP-A-58-113934. No. 58-113927 discloses a multilayer color photographic material having plate-like grains in which the central region has a lower silver iodide content than the annular region and an aspect ratio of 8:1 or more. discloses a silver halide photographic material containing tabular silver halide grains having an aspect ratio of 3:1 or more and a specific sensitizing dye and which can be applied to color applications.

However, these techniques suffer from dye contamination and failure.
Another drawback is that the milky white liquor causes poor desilvering, resulting in a brown color.

(Objective of the Invention) The first object of the present invention is to provide a color photographic material for each layer that has high sensitivity, high image quality, and has little brown spot staining.
Sen's objective is to provide a color photographic material with high sensitivity, high image quality, and improved desilvering defects.

(2) N-formation of the invention The object of the present invention is to have an aspect ratio of 3:1 or more,
A silver halide emulsion layer containing all tabular grains mainly consisting of (111) planes and a polymer coupler latex.
This is achieved by a silver halide multilayer photographic material having at least one layer each comprising a silver iodide emulsion spectrally sensitized with a trimethine dye.

The light-sensitive material of the present invention has an aspect ratio of 3:1 or more, and the tabular grains contained in the silver halide emulsion layer containing tabular grains mainly composed of (111) planes have an aspect ratio (diameter/thickness The aspect ratio is preferably 3 or more, preferably L<k, the aspect ratio is 5 or more, particularly preferably l-, < is 8 to 2o.Here, the mountain diameter is the diameter of the circumscribed circle of the particle, and is 111 ), tL< is preferable from 05 to 104 m1,
<+t 1.0 to 60 μm.

The thickness is the distance between two parallel half-cut crystals with 41 planes.

Halogenation of tabular grains & IJ l! + ni ni + 0.
From 5 to 10 mol% silver iodide gold and 1% silver iodide
The composition is 1-t-, and the content of silver 1-t-
It is desirable that it be less than 1%. It is preferable that the composition of silver iodide be uniform (4 white 4) or that the composition be different between the outer part of the grain and the inner part thereof. An example of such an emulsion is a tabular emulsion in which the outer part has a high silver iodide content, as disclosed in JP-A-158-113927; Also preferably used are emulsions containing a certain amount. However, emulsions with low iodine in the outer regions are more preferred.

If the outer part has high iodide content, the silver iodide content in the center part is 0.
~5 mol% silver iodobromide, the silver iodide content in the outer part is at least 1 mol% higher than in the center, and the silver iodide content is at least 1i iodide
Silver oxide in iodine having a tltl content of 4 to 20 mol % is preferably used.

J-Improving silver halide emulsion is disclosed in JP-A-58-1, 1
obtained by the method of Publication No. 3927, and particles WII'
fi:i J, T, Goldstein and B.
Williams J'l'lJM/X- in ATFNI
It can be analyzed by the method described in "Line Analysis", Scanning Electron Microscope (19'77), Vol. 1, p. 651.

In addition, tabular grains having a low iodide content in the outer part have a silver iodide content of O-5 mol% in the outer part and an iodine content of 4 to 20 mol% in the central region. It is preferable that it be captured silver. Such an emulsion can be produced by changing the composition of the halide solution added as described in JP-A-58-113927, but it is preferable to keep the silver iodide content at 2 mol % or less in the nucleation area. . The halogen composition of such an emulsion can also be analyzed by the method described above. Tabular twin grains consisting of (111) planes have external planes that are parallel to each other and one or more twin planes parallel to the external planes. Classified in detail I in ``Basics of Characters # Silver Salt Shasei Edition 1 Fronasha (1979)''.

Further, tabular silver iod9ide grains f)<first and second opposing flat grains? ? trJ made 2+ +f+i and the central area extending 1k between the two main I biplanes is 4+' l-, and further the two 1st yoke Flh K spreads out by at least one horizontal J
Outer territory displaced in the j direction (L to -V direction)/k
It is preferable that the grain has an internal structure in which the iodide content in the central region and the iodide content in the outer region are different. Among these, more preferable grains have an internal structure in which the iodide content in the outer region is lower than the iodide content in the central region. Preferably, the composition distribution is such that the outer region surrounds the central region so as to form a ring in the lateral direction. Incidentally, the change in the legal content in the boundary layer between the central region and the outer region may have a sharp boundary surface, or may have a continuous change in which the boundary is not necessarily obvious.

In the layer containing the tabular silver halide grains of the present invention, the tabular grains should be present in an amount of 40% or more, particularly 60% or more, based on the total silver halide grains in the layer. [,stomach.

The tabular silver halide grains according to the present invention may be polydispersed and may also be lli dispersed, but it is more preferable that they be monodispersed.

Tri-dispersibility number -1 Particle size distribution (this particle size is the diameter of the circumscribed circle of the particle as above)] Variable number of threads or 2
It is below 5% 1゛ξ.

As a method for preparing emulsions from tabular grains with excellent adhesion properties, Japanese Patent Application Laid-open No. 111 (b 1-39027, 54-11882)
3 kj and 1irl 55-211143 can be used.

In addition, as a preferred method for obtaining an emulsion consisting of monodisperse tabular grains, a seed population consisting of monodisperse spherical grains is obtained by physically ripening core grains consisting of multiple twins in the presence of a silver halide solvent. This method is used to create and then grow vines. As a more preferred method, a tetrazaindene compound may be present during the growth of tabular grains to increase the proportion of tabular grains and to improve monodispersity.

When mixed with other silver halide grains (7), tabular grains are preferably used as a high-sensitivity silver halide emulsion. In a silver halide multilayer light-sensitive material having an emulsion layer (1), it is preferable to use it in a silver halide emulsion layer that requires higher sensitivity than J.

The emulsion containing tabular silver halide grains according to the present invention is disclosed in Japanese Patent No. 52-153428 and No. 5B-55426.
No. 58-113928, No. 58-113927, etc., or by referring to the methods described therein.

The tabular grains of the present invention may be doped with various metal salts or metal complex salts during silver halide precipitation, during grain growth, or after grain growth. For example, metal salts or complex salts such as gold, platinum, palladium, iridium, rhodium, bismuth, cadmium, fM, and combinations thereof can be used. In addition, in the method for producing an emulsion containing the above-mentioned particles, the Tardel water washing method, dialysis method, or coagulation precipitation method, which is commonly used in general emulsions, can be appropriately used as a means for desalting.

Furthermore, the above-mentioned silver halide emulsion may contain sulfur sensitizers such as ruthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers.
For example, stannous salts, polyamines, etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-oresulfobenzthiol methyl chloride, etc., or e.g. ruthenium , rhodium, iridium, and other water-soluble salt sensitizers, specifically ammonium chlorovaladate, potassium chloroaurate, and sodium chlorovaladite, which can be chemically sensitized alone or in combination as appropriate. can.

The silver halide emulsion layer containing the tabular grains of the present invention is spectrally sensitized with a trimethine dye.

Useful sensitizing dyes include compounds represented by the following general formula [I].

General formula [I] = 9-" fX, -) I R'++"
In formula m, zl and Z'G: f each 5 to 611
I can't find the atomic group necessary to make f￥the dawn to 1.

R1 and R'+1 aliphatic hydrocarbon groups (which may be replaced by heteroatoms as part of the carbon chain) or Ryl groups;
R1 represents a hydrogen atom, a lower alkyl group having 1 to 3 carbon atoms, an aralkyl group or a monocyclic aryl group, and X■ represents an acid anion. ff 11 years old Hail 1 or 2 each. When forming an inner salt of the dye, m is 1.

The heterocycle formed by zt or Z is a 5- to 6-membered heterocycle usually used in cyanine dyes, or a condensed ring of these with a benzene ring or a naphthalene ring. That is, for example, a cyanine heterocyclic nucleus consisting of a thiazole ring, a zelenazole ring, an oxazole ring, a pyridine ring, a pyrroline ring, or an imidazole ring, such as a thiazole thread (e.g. 4-phenylthiazole; 5-methylthiazole; 5-phenylthiazole; 1,5-dimethylthiazole; benzothiazole;
4-chlorobenzothiazole; 5-chlorobenzothiazole: 6-chlorobenzothiazole; 5-methylbenzothiazole; 6-methylbenzothiazole; 5-bromopendithiazole, 5-carpoxybenzothiazole,
5-ethoxybenzothiazole, 5-hydroxybenzothiazole, 5-phenylbenzothiazole; 4-methoxybenzothiazole; 5-medoxybenzothiazole; 6-medoxybenzothiazole; 5-iodobenzothiazole; 5-nitoxybenzothiazole;
Tetrahydrobenzothiazole; 5,6-cymethoxybenzothiazole; 5,6-cyoxymethylenebenzothiazole; 6-nitoxy5-methylbenzothiazole;
5-Tennethylbenzothiazole; 5-acetylbenzothiazole: Naphtho[1,2-d]thiazole; 7)
[2,1-a] thiazole; naphtho[33-a,]]thiazole; 5-methoxynaphtho1,2-(11 thiazole; 8-methoxynaphtho[2,1-all thiazole 7
-methoxynaphtho[2,1-dlthiazole;5-methoxythionaphtheno[a,7-allthiazole819-
Dihydrona7) 11,2-d] Thiryozole; +, 5-Dihydronaphtho[2,1-dl Thiryozole, etc., Oxazole thread (Example sentences are 4-methyl A casole; 5-methyloxazole; 4- 7J-Nyloxazole; 4,5-
Dimethyloxazole: 5-phenyl oxazole; Benzoxazole: 5-chlorobenzoxazole °5
-Methylbenzoxazole; 5-phenylbenzoxazole; 6-methylbenzoxazole; 5,6-dimethylbenzoxazole; 5-methoxybenzoxazole; 5-ethoxybenzoxazole; 5-7enethylbenzoxazole; 5-carboxybenz Oxazole, 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole, 5-bromobenzoxazole °5-Methyl-6-chlorobenzoxazole'su7to[1,2-a]oxazole; naphtho[2
11-d-1 oxazole; naphtho[2,3-(1]oxazole, etc.), selenazole series (e.g., 4-methylselenazole; 4-phenylselenazole; benzoselenazole; 5-chlorobenzoselenacynobi 5- Methoxybenzoselenazole ° 5-Methylbenzoselenazole; Tetrahydrobenzoselenazole: Naphtho[1,2-
a] selenazole; naphtho r, 2, ], -a
] selenazole], pyridine thread (e.g. 2-pyridine; 5-methyl-2-pyridine 4-pyridine 3-methyl-4-pyridine, etc.), quinoline thread (e.g. 2-quinoline; 3-methyl-2 -Gynoline'5-ethyl-2-quinoline;6-chloro-2-quinoline;8-ri p-2-
Quinoline; 6-medoxy-2-quinoline; 8-ethoxy-2-quinoline; 6-methyl-2-quinoline; 8-fluoro-2-quinoline; 6-dimethyl-2-quinoline; 4-quinoline; 6-medoxy 4 -quinoline; 7-
Methyl-4-quinoline; 8-chloro-4-quinoline, etc., 3,3-dialkylindo-1/nin system (example sentence is 3,
3-dimethylindolenine; 3,3.5-trimethylindolenine; 3,3-dimethyl-3-(dimethylamino)indolenine; 3,3-dimethylindolenine, etc.),
Imidazole series (e.g. imitazole; ]-furkylimidazole; 1-alkyl-4-phenylimidazole; ]-]alkyl-45-dimethylimidazole; benzimitazole"1-alkylbenzimidazole;
]--yeniA/-5,6-cyclobenzimidazole: 1-alkyl-5-cyanobenzimidazole:
1-alkyl-5-chlorobenzimidazole; 1-alkyl-5,6-cyclobenzimidazole l-alkyl-5-trifluoromethylbenzimidazole;
1-alkyl-5-methylsulfonylbenzimidazole; 1-alkyl-5-methylsulfonylbenzimidazole; 1-alkyl-5-methylbenzimidazole; 1-alkylnaphtho[1,2-a]imidazole;
1-alkylnaphtho[2,ld]imidazole; l-
[2,3-a] imidazole, etc. Fusugi. The 1-alkyl group is an alkyl group having 1 to 10 carbon atoms, not only an unsubstituted alkoxy group but also an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 4 carbon atoms, and a carbonyl group having 4 carbon atoms. , carboxy group, carbamoyl group, cyano group, halogen group, sulfo group, phenyl group, substituted phenyl group, vinyl group, etc. (for example, methyl group, ethyl group, cyclohexyl group, butyl group, decyl group) , 2-methoxyethyl group, 3-butoxypropyl group, ethoxycarbonylmethyl group, carboxymethyl group, 2-carboxyethyl group, 2-cyanoethyl group, 2-
Carbamoylethyl group, 2-fluoroethyl 2i, 2,
2.2-) Lifluoroethyl group, 3-sulfopropyl group, 7enethyl group, pencil group, sulfophenethyl group, carboxybenzyl group, allyl group, etc.

The core formed by 2' and
Thiazoline thread (e.g. thiazoline, 4-methylthiazoline), inoxazole type (e.g. inoxazole, benzisoxazole, 5-benzisoxazole, 6-methylbenzisoxazole, 7-methylbenzisoxazole, 6-methylbenzisoxazole) medoxybenziisoxazole, 7-medoxybenziisoAxazole)
It may be a nucleus such as

When R1 and R'' each represent an aliphatic group, a portion of the carbon chain may be replaced or substituted with a different atom such as oxygen, nitrogen, or sulfur.

For example, it may be substituted with sulfo, ryol, carboxy, ryomino (-, secondary, tertiary), alkoxy, aryloxy, sulfonyl, alkoxycarbonyl, acyloxy, halogen, ryol, ryominocarbonyl, or cyano. . It may also be an alkenyl group. Specific examples of aliphatic groups are methyl group, ethyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, benzyl group, phenethyl group, carboxyethyl group, carboxymethyl group, dimethylaminopropyl group, methoxyethyl group, fenogycyprovir group. group, methylsulfonylethyl group, p-t-butylphenoxyethyl group, cyclohexyl group, offthyl group, decyl group, octadecyl group, p-sulfophenethyl group, p
-Sulfobenzyl group, 8-hydroxy-3-sulfopropyl group, a, 3-di(3-sulfopropoxy)propyl group, 2-(2-(3-sulboproboxinoethoxy)ethyl group, 2-carbamoylethyl group) group, 2,2.2-trifluoroethyl group, p-carboxyphenethyl group, ethoxycarbonylmethyl group, pivaloylpropyl group, propionylethyl group, 7disyl group, acetoxyethyl group,
These include benzoyloxypropyl group, chloroethyl group, morpholinoethyl group, acetylaminoethyl group, N-ethylminocarbonylpropyl group, allyl group, 2-butenyl group, and cyanoethyl group. Examples of the Ryl group represented by R1 and R1 include a phenyl group, a tolyl group, a sulfophenyl group, a carboxyphenyl group, a chlorophenyl group,
These include methoxyphenyl group, N,N-dimethylaminophenyl group, pyridyl group, furyl group, chenyl group, and naphthyl group. R3 is a hydrogen atom or a lower aliphatic hydrocarbon group,
Preferably, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a butyl group, a 7-aralkyl group having 7 to 9 carbon atoms (phenethyl group, tolylethyl group, etc.)) or an aryl group (preferably a phenyl group or a substituted xO represents any acid residue such as ethyl sulfate, methyl sulfate, p-tosylate, benzenesulfonate, chloride, bromide, iodide, thiocyanate, verchlorate, etc.

Preferred compounds of the general formula [I] are zl
or a benzothiazole nucleus (e.g. pendithiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole,
-chlorobenzothiazole, 6-chlorobenzothiazole, 5- or 6-methylpendithiazole, 5-bromobenzothiazole, 5-phenylbenzothiazole, 5
-i'1J6-Medoxybenzothiazole, 5-carboxybenzothiazole, 5-hydroxybenzothiazole, 5-ethoxyluponylbenzothiazole 1,5
゜6-Simethoxybenzothiazole, 5,6-cyoxymethylenebenzothiazole, 6-nitoxy5-methylbenzothiazole, 5-phenoxybenzothiazole,
5-phenethylbenzothiazole, 5-cyanobenzothiazole, natu[1°2-d]thiazole, naphtho[
2,1-d cothiazole, na7) [2,3-(L] thiazole, 5-methoxynaphtho[1,2-(l)thiazole, 8-methoxynaphtho Ig, xa] thiazole, 7
-Methoxynaphtho[2,x-d,]thithiazole b-Methoxythionaphtheno(,6,y-a)thithiazole, 8.
9-Dihydronaphtho[1,2-(l-cotyryozole, 4.
5-dihydronaphtho [E,
Chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6'-methylbenzoxazole, 5,6-dimethylbenzoxazole, 5-methoxybenguoxazole, 5-y-1
-xybenzoxazole, 5-7enethylbenz"ki→nozole, 5-benzoxazole, 5-methyl-6-chloroI]benzogisazole, 17[].

2-dldimasole, naphtho(2,+-d1oxazole, naphtho[2,3-dlJxazole, etc.), benzoselenazole nucleus (e.g. λi:r, benzoselenazole, 5-chlorobenzoselenazole, 5 -methoxybenzoselenazole, 5-methylbenzoselenazole, tetrahydrobenzoselenazole; naphtho[l,2-alselenazole, naphtho[2,1-a]selenazole, etc.

Specific examples of trimethine sensitizing dyes preferably used in the present invention are listed below, but the present invention is not limited to these compounds.

(OHtJ4SOqH(OHM)4So.

(T-27 (T-6) (■-7) (■-3) (I-9) Oh.

()-10,) OlHs ((-11J (OH1)ssOs (oH,), so, u
(r-12) (T -14) (■-16) (1-1,87 CI-21) (J-22) (OH*)ssOsH(OH,), Btl.

((-3O) (■-34) (l-3R) Cl-39) (l-40) CI-41) (i42) (T-46) (T-50) (r-51) (T-52 ) (l-53) (T-54) These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used especially for the purpose of supersensitization. It will be done. A typical example is US Patent 2
, No. 688,545, No. 2,977, No. 229, No. 3.
No. 597.060, No. 3,522,052, No. 3.5
No. 27.641, No. 3.617.293, No. 3. fi
No. 28,964, No. 3,666,480, No. 3. fl
No. 72,898, No. 3.6'i'9,428, No. 3
゜'1103.37'i' No. 3,814,609, No. 3,837, 862, No. 4,026,707,
British Patent No. 1,344,281, 1.50 'i',
No. 803, Special Publication No. 43-4936, No. 53-12.
3'i'5, JP-A No. 52-110,618, No. 52
-109,925.

The method for synthesizing the sensitizing dye F is described in Japanese Patent Publication No. 43-4936,
Reference may be made to the descriptions in Japanese Patent Application Publication No. 56-38936, Japanese Patent Application Laid-Open No. 59-77443, and US Patent No. 3,506,443.

Further, the above-mentioned silver halide emulsion can contain various known photographic additives. For example, R55earo
h Diaoroaure 19f December 8 Item 17
643.

Furthermore, this silver halide can be optically sensitized to a desired wavelength range using a sensitizing dye other than trimethine sensitizing dye. For example, optical sensitizers such as xeromethine dyes, monomethine dyes, dimethine dyes, etc. or merocyanine dyes may be used alone or in combination with trimethine dyes (e.g., hyperchromatic j1g) f to chemically sensitize. I can do it. These techniques are described in U.S. Patent No. 2.688.
,')45↓;, Same No. 2,912,329, Same No. 3.
39 'i', Ofl No. 0, Same No. 3,615,63
No. 5, No. 3.628.964, British Patent No. 1,19
No. 5,302, No. 1,242.5F18, No. 1,
No. 293,862, West German Patent (OLs) 2.030,3
No. 26, No. 2, 121. '780, Special Publication No. 43-4
It is also described in No. 936, No. 44-1.4030, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

The above emulsion may contain various commonly used additives depending on the purpose. These additives include, for example, Zaindenes, triazoles, tetrazoles,
Stabilizers and antifoggants such as imidazolium salts, tetrazolium salts, and polyhydroxy compounds; aldehyde-based, silidine threads, inoxazole threads, vinyl sulfone threads, kryloyl threads, albodiimide-based, maleimide-based, methanesulfonic acid ester threads, Hardening agents such as Toryozin thread; Development accelerators such as benzyl alcohol and polyoxyethylene compounds; Image stabilizers such as Chroman, Claman, bisphenol, and phosphite esters; Wax, glycerides of higher fatty acids, Lubricants such as higher alcohol esters of higher fatty acids are available. In addition, as surfactants, coating aids, permeability improvers for processing liquids, antifoaming agents, and wood for controlling various physical properties of photosensitive materials are used. Various ionic or amphoteric types can be used.

M %i As an anti-Iz agent, diacetyl cellulose,
Styrene perfluoroalkyl sodium maleate copolymers, alkali salts of reaction products of styrene-maleic anhydride copolymers and p-aminobenzhine sulfonic acid, and the like are effective. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Also, latex snow added to improve the property of counterfeiting 1. Examples include co-Jl (combination) of acrylic esters, vinyl esters, etc. and monomers with other ethylene groups. Examples of gelatin river plasticizers include 11 chrycerin and glycol thread compounds, and thickeners. Then, examples include styrene-sodium maleate (combination) and alkyl vinyl ether-maleic acid co-combination.

Hydrophilic colloids used in the above emulsion include gelatin, for example, U.S. Pat. '766, same number 3.186゜84
No. 6, No. 3,312,553, British Patent No. 1゜03
3, No. 189, Special Publication No. 39-5514, No. 42-26
Gelatin derivatives, gelatin polymer grafts, synthetic hydrophilic polymer substances, natural hydrophilic polymer substances other than gelatin, etc. described in No. 845 etc. can also be used alone or in combination in the present invention. Polymer macabra is obtained by polymerizing coupler monomers, yellow coupler monomer GJ, represented by the general formula [preferably 12<, cyan coupler monomer iff, represented by the general formula [IVl mF G, v[V] The 71 pinta coupler monomer is preferably one represented by the general formula [vr].

Furthermore, the polymer coupler according to the present invention is not limited to those obtained by polymerizing coupler monomers alone, but also those obtained by polymerizing them together with other copolymerizable monomers other than couplers can be preferably used.

General formula 1: Yellow coupler monomer In the formula, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and X is separated by a coupling reaction with a hydrogen atom or an oxidized product of a color developing agent. represents a possible group.

R4 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen atom, a sulfo group, a carboxy group, a sulfonyl group, a carbamoyl group, a sulfuryl group, or a cyano group. Rs represents an alkyl group or a substituted or unsubstituted aryl group.

Specifically, Q is the general formula [1]
OH; group, ethyl group, t-butyl group, etc.], and this alkyl group may have a substituent.

L is 100NH-, -NHOONH- or -NH-
represents a divalent group, P is 100NH-, -8('l,
It represents a divalent group of - or -ono-, preferably a divalent group of 10ONH-1 or -aOO-. human represents an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms) or a divalent group such as a phenylene group,
The alkylene group may be linear or branched, such as a methylene group, methylmethylene group, dimethylene group, decamethylene group, etc., and the alkylene group and phenylene group may have a substituent. m and n each represent 0 or 1.

The general formula [1] is preferably L or 100NH
- or -NH-, where n is 1, A is m-phenylene, m is 1 and P is 0nNH-, and H6 is a lower alkyl group.

Even more preferably, L is 100NH-, m and n are 0, and R. is a lower alkyl group, especially a methyl group.

Substituents for alkylene or phenylene groups represented by human include aryl group (e.g. 7-enyl group), nitro group, hydroxyl group, cyano group, sulfo group, alkoxy group (e.g. ethoxy group), ryosyloxy group (e.g. acetoxy group], acylamino group (e.g. acetylamino group), sulfone gamma group (e.g. methanesulfonyl group), sulfuryl group 1+1 or methylsulfamoyl group, halogen atom (e.g. fluorine atom, chlorine atom) , deep atoms, carboxyl group, carbamoyl group (e.g. methylcarbamoyl group), alkoxycarbamoyl group (e.g. λi:
These substituents may have two or more groups, and in that case, These IW substituents may be the same or different.

In detail, the group represented by
mc].

General formula [ma] □〇□R General formula [ITIb] 1□ S -R'' In the formula, R', R'LJ represents an alkyl group, a Ryl group, a Ryosil group, etc., and Rt is a 5-membered or 6-membered 4I elemental rings of shellfish (e.g. ζ: f imidazole tomb, pyrazole ring, piperidine ring,
Morpholine ring, succinimide ring, triryozole ring, etc.)
Represents a group of nonmetallic atoms necessary to form .

Next, preferred specific examples of X represented by the general formulas [ma], [Ir1b] and LmO] are shown below, but the present invention is not limited thereto.

(]) Specific example corresponding to -n-B of general formula [rtIa] (2) -8 formula [117bl (7') -9-R
” 4., Applicable specific example 1f2 Formula [rV] General formula [Vl H General formula [1■ In 1, R16 and R11 are each Be
, is the same as R4. Furthermore, Q and X have the same meanings as Q and X in general formula [I].

In the general formula [Vl, R12 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, an alkoxycarbonyl group, an aliphatic mido group, an alkylsulfuryl group, an alkylsulfonamide group, an alkylureido group , represents an arylcarbamoyl group, an arylamido group, an aryl-rusul-moyl group, an arylsulfone-mido group, or an aryl-ureido group.

α represents an integer from 0 to 3. X is a general formula [synonymous with old. Q is the same as the general formula [TI].

General formula [V]′]; magenta coupler monomer formula, Y
represents an electron-withdrawing group, g represents an integer from O to 3, and when l is 2 or more, Y may be the same or different.

The electron-withdrawing group Y represented by the general formula [I] may be substituted at any position of the phenyl group, but is particularly preferably substituted at a position selected from the 3-position, 4-position, 5-position and 6-position. This is the case.

l represents an integer from 0 to 3 as described above, preferably from 0 to 2.

Further, when l is 2 or more, Y may have the same or different electron-withdrawing properties. Here, the electron-withdrawing group is ”
Ph)rsioal Organio Ohemi
stry MoGraw-HllllBook Oo,
As described in New York (1940), the σ value defined by Hamm et al. or J, Amer, Ohem, soc,
Swain (3wθin) and Lupt (Lupt) as described in , 90.4328 (196B).
on) et al. is defined as a substituent whose F value is greater than zero. Specific electron-withdrawing groups include halogen atoms, halogenoalkyl groups, carboxyl groups, sulfo groups, nitro groups, cyano groups, alkylsulfonyl groups, alkylcarbonyl groups, alkoxycarbonyl groups,
Examples include an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonamide group, an arylsulfonamide group, and further J, Med, Ohem
16.111!07 (1973), 20.3
Substituent groups such as those described in Q 4 (1,977) can also be used. Among the electron-withdrawing groups used in the present invention, preferred are alkylsulfamoyl groups in which the alkyl moiety has 1 to 4 carbon atoms, such as dimethylsulfamoyl groups and ethylsulfamoyl groups. halogen atom, an alkoxycarbonyl group, such as a halogen alkyl group, in which the alkyl portion has 1 to 2 carbon atoms, such as trifluoromethyl or trichloromethyl; an alkoxycarbonyl group, in which the alkyl portion has 1 to 4 carbon atoms; such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group,
These include a butoxycarbonyl group, and a particularly preferred one is a halogen atom. A particularly preferred halogen atom is a chlorine atom.

In the general formula [Vrl, Q and X have the same meanings as in the general formula [11].

Specific examples of coupler monomers and coupler polymers are shown below, but the compounds used in the present invention are not limited to these.

Coupler monomer LJ, example 013 −41j − (MO-2) (MO-3) I (MO-4) (MO-5) (MO-6) r (MO-'l) (MO-8J (MO-9) (MO-1,0) e (Mrl-11) (Mf) -1,1! J H (MO-13) OH10 (MO-14) H80 (MO-1,15) 1’llJ (MO-16) (MO-17) (MO-1, 11) OH (MM-1) l (MM-3) ■3r (MM-5J (〕I) (MM-7) (MM-13J (MM-16) 0 (MM-1’j) 0 (MY-3) (MY-4) (MY-57 0-0-OH.

0=O-00Hs n=o-OH.

Subsequently, specific examples of polymer couplers related to the present invention obtained from the above-mentioned various monomers will be shown, but the present invention is not limited thereto.

(PO-IJ x=60wt% y=40f[11%(PO-2) e x=70wt% y-20wt% z=-1oi
k1% (PO-3) x-80weight'IIi% y=201 and company% (
PC-4) OH.

x = 90 weight 11t% y = 5 weight it% m = 5
Weight % (po-fi) x-601 (11% y-40 weight ii
L% (PO-6) OH.

■ +OH, -0 nae (PO-7) OH.

X 100% Ii% (PO-8) 3r x=65% Y=35% (PO-9) OH.

exposure (po-xo) Oh.

x=55 weight it% y=45 ji
it % (plJl) (PM-2) OH.

+OH,-0su〇-0 (PM-3) (PM-4) (-OH,-('IH-chi, 0=C (PM-5) 08% x-70 heavy welfare% y-30 heavy rice %(
PM-6) (PM-7) OH.

x = 80% by weight y - 20% by weight
(PM-8) 0g x-70% by weight y=30% by weight (PM
-9) 0■1゜x=501id% y=25wt% 5a-2
5% by weight (PM-10) OH.

■ o-00(+00.H.

(PY-IJ x += so 17td%
y = ::01(k1%(PY-2) !-35t)1% y-45 width M
%(PY-3) 0=O-OH x=90% y=10%-70-(py-4) 0)I.

0=0-OH.

x = 95% heavy stitching y = 5% by weight (PY-5
) x=50% by weight y=50% by weight (PY −
6) (-OH, -OH nae ■ 0, =O-00H.

x = 100 overlay% (PY-7) OI(.

(PY-8) Oh.

+OH, -0S ? x = 100% by weight (PY-9) Oh.

x-'FO weight 111% y-25 weight 1% 15
cm 5% polymer coupler latex can be obtained by replacing part or all of the commonly used non-polymer type couplers with polymer coupler latex] 11 il
Yes, yes.

photosensitive halogenated tl, including couplers ii f;1, polymeric couplers latex and other couplers;
i! 2× for 1 mole of silver halide in the emulsion layer
The amount is suitably in the range of 10 to 5 x 10 moles (one coupler structural unit is 1 mole in the polymer cabra latex), preferably in the range of L<K1 x 10 to 5 x 10 moles. When it is contained in an intermediate layer, it is advisable to use the above-mentioned range as a guideline based on the mold of photosensitive silver halide 'FL~;)-/- silver halide adjacent to the layer.

A known method may be used to incorporate the coupler into the photosensitive silver halide emulsion layer.

In addition to the coupler, the light-sensitive material of the present invention may contain additives commonly used in silver halide multilayer color-sensitive materials, such as a development inhibitor-releasing substance (DIR substance) and a hydroquinone conductor.

The layer structure of the light-sensitive material of the present invention can be applied to the layer structure of known silver halide multilayer color photographic light-sensitive materials (including color negative films and color reversal films). That is, a blue-sensitive yellow color book is formed on a support. 1-1 Green-sensitive magenta color formation layer and red-sensitive silver color formation layer G1, each of these layers G1 21 parts m 1.;t
-1- Glue includes a layer structure that may be composed of layers with different electric shock characteristics.

In the present invention σ) containing tabular grains [2. The silver iodobromide emulsion layer electrically sensitized with a trimethine dye (hereinafter referred to as the "ablation layer" in the present invention) is a green-sensitive magenta dye-forming layer and a green-sensitive magenta dye-forming layer. )
i Red-sensitive cyan dye applied to the cedar layer. 1. Can remarker latex be applied to each of the above layers? <lj, this is an embodiment in which the emulsion layer of the present invention is applied to the emulsion layer and/or a photosensitive layer or intermediate layer that is farther from the support than the emulsion layer.

In the light-sensitive material of the present invention, at least a portion of the coupler used therein may be polymer coupler latex, but it is desirable that the ratio of the polymer coupler latex to the coupler is high.

Polymer Cabra latex is a commonly used non-polymer
type couplers can be used together. As such a non-polymer type coupler, a known open-chain ketomethylene thread coupler can be used as a yellow coupler. Among these, benzoyl acetate yarn and pivaloylacetanilide compounds are useful. Magenta couplers include pyrazolone compounds, pyrazolotrizole compounds, indacylon compounds, and cyanoacetyl compounds; as cyan couplers, phenolic compounds, naphthol compounds, etc. can be used.

Examples of the support used in the light-sensitive material of the present invention include baryta paper, polyethylene resistant paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, and polyesters such as λ polyethylene terephthalate. There are films, polystyrene, etc., and these supports are appropriately selected depending on the purpose of use of each silver halide photographic material.

These supports are subjected to undercoat processing if necessary.

The layer structure of the photosensitive material of the present invention is as described in 1171 of the present invention.
b! 2. There is no particular restriction as long as the requirements are met, and a commonly used layer structure can be applied. Preferred examples of the layer structure of the photosensitive materials of the present invention are listed below.

In the description of the layer structure below, B is a blue-sensitive yellow dye-forming layer, G is a green-sensitive magenta dye-forming layer, and Ri:
is the red-sensitive cyan dye-forming layer, H is the high-sensitivity layer, and M (
medium sensitivity layer, L stands for low sensitivity layer, S stands for support layer, protective layer, filter layer, intermediate layer, anti-halation layer,
The description & of non-photosensitive layers such as undercoat layers is omitted.

(1) Ox/Dan/R/5 (11) Tomo/Yuzu/Hako/Normal/RH/RL/SΦD Embryo/Animal/-next/Dan/Animal/RL (ψ.../Hexagram/Tomoshibi/Animal ShiRL ” M Skin/Hexagram/Encircle striking symbol RH RM RX above (+)
In ~M, ('' represents the emulsion layer of the present invention, and the underline represents the layer containing the polymer Cabra latex.

The color developing solution used for processing the light-sensitive material of the present invention contains a developing agent and has a pH of 8 or more, preferably a pH of 9 to 12.
It is an alkaline aqueous solution of This aromatic primary amine developing agent as a developing agent is a compound having all primary amine groups on the aromatic ring and capable of developing exposed silver halide, or a precursor for forming such a compound. means the body.

The above-mentioned developing agent is typically p-phenylenediamine type, and the following are preferred examples.

4-Ryominnow N, N-diethylaniline, 3-methyl-
4-Ryominnow N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-minnow N-ethyl N-/-hydroxyethyl-niline, 3-methyl-4-minnow N-ethyl-N-/-methanesulfone, midethyl-niline, 3-
Methyl-4-diminnow N-ethyl-N-β-methoxyethyl-4-diminnow N, N-diethyl diline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3- Methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-minnow N, N-diethyl uniline 4-minnow N, N-dimethyl niline, N-ethyl-N −β
-[/-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β
-(/l-methoxyethoxynoethyl-3-methyl-4
-aminoaniline and their salts such as sulfate, hydrochloride, sulfite, p-)luenesulfonate, etc. Moreover, various additives can be added to these color developing solutions as necessary.

After the light-sensitive material of the present invention is exposed to light in a self-directed manner and subjected to color development processing, it can be subjected to bleaching processing in a conventional manner.

This process may be done simultaneously with the theorem or separately. This processing solution can also be used as a bleach-fixing bath by adding a fixing agent if necessary. Various compounds can be used as bleaching agents, and various additives including bleaching accelerators can also be added.

The light-sensitive material of the present invention is particularly preferably applied to color light-sensitive materials that require relatively high sensitivity, such as color negative films and color reversal films.

EXAMPLES Next, the present invention will be specifically explained using examples, but the embodiments of the present invention are not limited thereby.

Example 1 Samples 1 to 7 as shown in Table 1 were prepared by sequentially coating the following layers on a transparent support made of subbed cellulose triacetate film. (Hereinafter, in all Examples, the amount added to the silver halide photographic light-sensitive material is shown per 1 liter, and the silver halide emulsion and colloidal silver are shown as the value converted to silver.Layer-1 : Black 6. Colloidal silver 0.39 and gelatin 2
Antihalation layer 4-2 containing 9:1. Intermediate layer containing Og gelatin-3
Low-sensitivity red-sensitive emulsion layer layer-4= containing 1.5 g of silver iodobromide with an average grain size of 06 μm and an aspect ratio of 1.5:1, containing near mole % of silver iodide, and the coupler dispersion of Table 1. 1.5 g of the silver halide emulsion shown in Table 1 [(0-3)It-containing high-sensitivity red-sensitive emulsion layer -5 layer -6 same as layer -2 -6 nmol % silver iodide, average grain size 0.6 μm
1.3 g of silver iodobromide with an aspect ratio of 1.5:l and Table 1
A low-sensitivity green-sensitive emulsion layer containing a coupler dispersion of 1.3 g of the silver halide emulsion shown in Table 1 and a magenta coupler dispersion [(M-3). H-a: o, yellow filter single layer containing 1 g yellow colloidal silver and 1.5 g gelatin - containing 9 nmol% silver iodide, average grain size 0.6 μm
A low-speed blue-sensitive emulsion layer containing 0.91 silver iodobromide and a coupler dispersion [(Y-17) with an aspect ratio of 1.5:1 and an average of 10:8 mole % silver iodide. Particle size 1.3μm
3m aspect, 5:1 high-sensitivity blue-sensitive emulsion layer containing silver iodobromide 0.99 and coupler dispersion [(y-2)]-11: protective layer side containing 1.5 g of gelatin; The red-sensitive layers of Layer-3 and Layer-4 contain anhydro-5,51-dichloro-3,3'-di(γ-sulfopropyl-9-ethylthiacarpositin hydroxide) per mole of silver. Pyridinium salt 6 x 10 mol and anhydro-9
-ethyl-3,31-cy(γsulfopropyl) -4
, 5,4', 5'-dibenzothiolcarpositin hydroxide triethylamine salt (1.5XIO mol) was added to perform spectroscopic sensitization.

In addition, the green photosensitive layers of layer-6 and layer-7 (j for 1 mole of silver,
anhydro-9-ethyl-3,31-cy(γsulfopropyl J-5,51-dichlorooxycarpositin sodium salt 7×10 mol and anhydro-5,6
, 5', 6'-tetrac IJ rho]-1'-diethyl-3,3'-di(r-sulfobrohydryl hydroxide sodium salt 1.6X1
Spectral sensitization was performed by adding 0 mol.

Next, the composition of the coupler dispersion used in this example is shown below.

Coupler dispersion [(0-1)] Cyan coupler (0-170,08
Mol, colored cyan coupler (00-1) 0.01 mo A/and rJ D x R Cub 5- (D-1) 0.0
03 moles were dissolved in tricresyl phosphate (hereinafter referred to as TOP) of the same weight as the coupler and acetic acid (hereinafter referred to as 111A) of 3 times the weight of the coupler, and sodium triisopropylnaphthalene sulfonate was added as an emulsifier. The heated gelatin solution was mixed and emulsified using a colloid mill.

Coupler dispersion [<0-2)] Prepared in the same manner as in the other day [(OIJ) except that (0-1) was replaced with cyan coupler (PO-2).

Coupler dispersion [(0-3)] Cyan coupler (0-1) 0.015 per mole of silver
Mol, colored cyan coupler (00-1, J0005
The mole was dissolved in TOP of the same weight as the coupler and KA of 3 times the weight of the coupler, added with sodium triisopropylnaphthalene sulfonate, mixed with a heated gelatin solution, and emulsified in a colloid mill.

Coupler dispersion [(M-1)I Magenta coupler (M-IJ008 mol, colored magenta coupler (OM-1) 0.01 mol and DIR coupler (D-2) 0.001 mol are added as couplers per mol of silver. The mixture was dissolved in the same weight of TCP and KA of 3 times the weight of the coupler, added with sodium triisopropylnaphthalene sulfonate, mixed with a heated gelatin solution, and emulsified in a colloid mill.

Coupler dispersion [(M-1)] was prepared in the same manner as [(M-1)] except that magenta coupler (PM-9) was used instead of Noko (M-1).

Coupler dispersion amount [(M-3 Magenta coupler (M-IJ0018 for 1 mole of saw silver)
Mol, colored magenta coupler (OM-1J0.00
6 mol of coupler and the same weight of TOP and 1 yen weight of FA
Sodium triisopropylnaphthalene sulfonate was added thereto, mixed with a heated gelatin solution, and emulsified using a colloid mill.

Coupler dispersion [(Y-1)] Dissolve 0.3 mol of yellow coupler (Y-1) per mol of silver in 1/2 weight of coupler dibutyl phthalate (hereinafter referred to as DBR) and 3 times the weight of KA. Then, sodium triisopropylnaphthalene sulfonate was added, mixed with a heated gelatin solution, and emulsified using a colloid mill.

Coupler dispersion [(Y-2)] Except for changing (Y-1) to 0.15 mol, [(Y-1)
] Adjusted in the same way.

(Y-1) a/ (M-1) (OM-17 l Next, a method for preparing the silver halide emulsion used in this example will be described.

Silver halide A (containing 7 mol% silver iodide, average grain size 3μ)
Silver iodobromide emulsion with m1 average aspect ratio of 0:l) Prepared by the same method as described in JP-A-58-113928. That is, potassium bromide 59.5,! 0.8% gelatin solution containing i+5. 8.33 g of potassium bromide was heated to 80°C [t' by the tuple jet method.
58.3 ml of water bath solution and 11.9 g of silver nitrate
The added aqueous solutions 5 B and 3 rsl were added at the same flow rate.

Then a solution containing 17.6% phthalated gelatin 80
0 ml was added. Next, the silver nitrate bath solution was diluted with PBr or 4
It was added until it reached 0. Then 38.7g of potassium iodide
To an aqueous solution 2.61 containing 340 g of potassium bromide was added an aqueous solution 2.61 containing 525 g of silver nitrate at an equal flow rate by the tuple jet method. During this time, PBr was maintained at 1.40. After setting the temperature to 40°C and washing the precipitate with water, gelatin was added, redispersed, and coagulated at 20°C. An emulsion was prepared.

Silver halide B (silver iodobromide emulsion with average grain size 2.8 μm, average aspect ratio 7:1, internal silver iodide 10 mol%, outer 1 m silver iodide 2 mol%) Contains 10.7 g of potassium chloride. Aqueous solution 11.917 of 1.5% gelatin aqueous solution 31 was stirred at 70°C and pH 5.8, and 2.54.9 g of potassium bromide was added, and 3.96 g of silver nitrate was added to P.
It was added at a constant flow rate by a double jet method while maintaining Br09. Next, 2.8e of an aqueous solution containing 33.7 g of silver nitrate, 214 g of potassium bromide, and 33 g of potassium iodide were added.
．． An aqueous solution containing 2.81 g of the aqueous solution was added at equal flow rates by the tuple jet method while maintaining PBrl of 2.

Next, 1.9 J of an aqueous solution containing 224.9 g of silver nitrate, 155.5 g of potassium bromide, and 4.421 g of potassium iodide! An aqueous solution of 1.91 μm in diameter was added at an equal flow rate by the double jet method while maintaining PBrl of 2.
Tabular grains having a m1 thickness of 0.4 μm and an aspect ratio of 7:1 were precipitated. After that, desalination treatment was performed at 40°C, gelatin was added, redispersed, and then cooled to 20°C to solidify.
A silver halide emulsion B of 1.5111 was obtained.

A silver iodobromide emulsion containing 0 silver halide (average grain size 2.6 μm, 1 average aspect ratio 7:), 2 mol % internal silver iodide, 10 mol % external silver iodide, containing 50.69 mol potassium bromide. 2.5 g of a 1.5% aqueous gelatin solution was stirred at 65°C and then mixed with 4 flg of water (bath liquid) containing 5.70,q of silver nitrate while maintaining a pBr of 0.81 -. A)1
Water containing 1 co and 4.0 g of potassium nitride fN @ #4 liquid B) 11. After adding oo with a droplet, add silver nitrate,
pBr was adjusted to 1.4.

Next, a solution containing nitric acid @ 4590 fl (bath solution 0) 2
．． 51 and potassium iodide 14.19 and potassium bromide 33
A solution (bath solution D) 21 containing 0g of potassium iodide was added using a double jet method at a rapid rate while maintaining pBr at 1.5, and after the addition was completed, solution 0 and potassium iodide 11.3. Lit and a solution 50017 containing potassium bromide 'i' 3.09 were added at a rapid rate using a double jet method while maintaining the pBr at 15. The temperature was set to 40'C, 1. After washing the precipitate with water, gelatin was added, redispersed, and solidified at 20'C.
kg of emulsion was prepared.

These multilayer coating samples were then exposed to white light through a wedge and processed in the following processing steps.

Processing process (38°C) Processing time Color development 3 minutes 15 seconds White 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixation
Wash with water for 6 minutes and 30 seconds Stabilize for 3 minutes and 15 seconds
The composition of the treatment liquid used in each treatment step was as follows: 1 minute 30 seconds.

Composition of color developing solution; Composition of bleaching solution; Composition of theorem solution; Composition of stabilizing solution; Next, residual silver in the highest concentration area of the sample after processing was measured using the fluorescence X@ method.

The results obtained are shown in Table-1.

From Table 1, the aspect ratio is 3: I J: J-J-
It can be seen that the desilvering properties of the tabular grains are poor when conventional couplers are used, whereas the samples containing the polymer couplers of the present invention have excellent desilvering properties. or,
In the case of tabular grains, the desilvering property is specifically improved by combining with a polymer coupler in the case of heterogeneous grains in which the silver iodide content is different inside and outside, rather than in the case of uniformly containing silver iodide. It is shown.

Example 2 Samples 8 to 15 shown in Table 2 were prepared by coating the following layers in multiple layers on a support made of subbed cellulose triacetate film.

Layer-1: Anhydro-9-ethyl-3,31-di(r-sulfopropyl)- in silver halide A described in Example-1
Spectral sensitization was carried out by changing the amount of 4,5,4',6'-dibenzothiolcarpodihydroxide triethylamine salt added as shown in Table 2, and the amount of coated silver was 2g/7FI.
The IS coating was applied and dried to a thickness of 3 μm.

A comparative sample was prepared by replacing silver halide A with silver halide and performing the same spectral sensitization.

The method for preparing silver halide is shown below.

Halogenated #D (silver iodide 7 mol%, average grain size 1.OAm
s average aspect ratio 1.5:1) Solution 7 containing 41.65 g of potassium bromide, 13.9 g of potassium iodide and 34.63 g of potassium thianophosphate, Ol (containing 1.25% of heptalated gelatin) While stirring the mixture at 80°C, 26.5% of potassium iodide was added to it by a double jet method.
8 fl and 2.45 g of a solution containing 387 g of potassium bromide
1 and a solution containing 594.69 silver nitrate 2.45/! were added at equal flow rates. Next, the temperature was lowered to 40°C, and after washing the precipitate with water, gelatin was added and redispersed with λ1, and then coagulated at 20°C to prepare an emulsion weighing 2.0 kg.

Pigeon-2: A coating solution containing the coupler dispersion shown in Table 2 was coated and dried so that the amount of gelatin applied was 29/g.

Coupler dispersion [(M-4)] Dissolve 20 g of PM-10 in coupler + 7) l/2 weight of DOP and 3 times the weight of KA, add I1, sodium triisopropylnaphthalene sulfonate and mix with heated gelatin solution. l. Emulsified in a colloid mill.

Color dispersion [(Y-3)] Except for replacing (PM-9) with (PY-8), [(M-4)
] Adjusted in the same way.

Coupler Dispersion 1 (M-5)] Prepared in the same manner as [(M-a)] except that PM-9 was replaced with M-1.

The obtained sample sample 1 was passed through a sensitometric wedge with neutral ash and a yellow filter that cuts blue light so that only the aperture of the spectral sensitizer can be fixed. Ta.

The exposed sample was then subjected to only the first development, water washing, fixing, water washing, and drying of the h-transfer treatment described below.

Regarding 1 [), what is the source of the silver image created? Perform prayer level measurement. Sensitivity was determined from the reciprocal of the exposure required for -) 0.2 of fog. Furthermore, color contamination in the minimum density area was measured. The results are shown in Table 2. However, sensitivity is expressed as relative sensitivity.

Processing process Special product (minutes) Dryness 1st development 6 38℃ Water washing 2N Fixing 4 Water washing 4 Drying 1st development 1ψ Liquid water
food sodium tetrapolyphosphate
2g sodium sulfite
20p hydroquinone monoflu 7one) 301
Sodium carbonate 30g]-phenyl-4-methyl-4-methoxy-3-pyrazolidone 2g Potassium bromide
2.5g potassium thiocyanate
1.2g potassium iodide (0.1% solution)
Add 2d water 1
000+j 97 constant liquid water
800 ammonium gothiosulfate
80.11g sodium sulfite
5.0g Sodium bisulfite 5.0
Table 9 Table 2 From Table 2, tabular grains with an aspect ratio of 3=1 or more have the advantage of significantly increasing sensitivity as the amount of photosensitive dye increases, compared to conventional grains, but have the disadvantage of increased color staining. However, it can be seen that the increase in color staining can be effectively suppressed by providing a layer containing the polymer coupler according to the present invention.

Example 3 The film sample used in Example 1 was exposed to light in a conventional manner and subjected to the following treatments.

Processing process Processing temperature (°C) Processing time 1, color development 38 3 minutes 15 seconds 2, bleach-fixing
38 8 minutes 5, water washing 30-34 2 minutes 4,
Stable 30-34 1 minute 5,
Drying 40-60 The following color developing solution, bleach-fixing solution and stabilizing solution were used.

U color developer 1 [Bleach-fix solution] [Stabilizer] Add water to make it 1/1.

Next, measure the amount of residual button in the highest concentration part of the sample after treatment.
Measured by ytX-ray method. The results obtained are shown in Table 3.

Table-3 fxO, mn'rA-yθ, ethylenediaminetetraacetic acid iron(ro)ammonium, OyDTA4Fe
i: i 1 , 2-cyclohexanediaminetetraacetate iron 0
11) Ammonium, HEDTA-7! θ represents iron(2) ammonium hydroxyethylethylenedi-1,02-minetriacetate.

Table 3 shows that samples 6 and 7 of the comparative example had an extremely large amount of residual silver and could not be put to practical use when a bleach-fix solution was used, whereas the samples according to the present invention contained various iron silicate @ ) It can be seen that the desilvering property is extremely excellent even when salt is used.

Also, when using a bleach-fix solution, in the case of non-uniform grains in which the silver iodide content is different inside and outside, rather than uniformly containing silver iodide, in combination with a polymer coupler, residual copper plating can be particularly reduced and desilvered. It has been shown that the quality is good.

Example 4 Coating samples &24 to 29 were prepared in the same manner as in Example 1. Table 4 shows the silver halide emulsion and coupler dispersion used in sample preparation. Further, the method for producing silver halide emulsion E-G according to the present invention used in this example is shown below.

Silver Halide E A polydisperse seed emulsion having a silver iodide content of 2.0 mol % was prepared using the five solutions shown below.

(1665 atl” KB with distilled water
r 19'1gη When the addition of 35g/min is finished, it will be aoa+j/min. When the silver halide crystals in this emulsion were observed using an electron microscope, they were found to be a polydisperse emulsion consisting of multiple twin crystals with an average grain size of 0,630 μm and a chair distribution of 25%.

Next, using this seed, tabular grains of the present invention were grown using the solution shown below.

Solution 0-2 and solution B-2 were added to solution 0-8 stirred at 75° C. by a double jet method to grow silver iodobromide with a silver iodide content of 9 mol %.

Addition is at an initial rate of 104 yd/min @final rate of 25
The pE was gradually increased to 0d/min during this period.
r was kept at 1.36.

Subsequently, double jet method melted 111F c-3
and Solution B-3 were added to grow pure external silver. Attachment 111
Eye J initial speed 91. , 3 rRe/min s final velocity 91. -3 m//', 'lli, n, and pBr was maintained at 1.0 during this time.

When the obtained grains were observed under a total electron microscope, a tabular emulsion was obtained with an average grain size of 1.5 μm, an average aspect ratio of 5:1, and a size distribution coefficient of variation of 32%.

Silver halide 7 1 liter of 5% ossein gelatin solution was stirred at 75°C, 150 d of a 4.7M water bath solution of silver nitrate and ammonium iodide was added over 40 minutes using the double jet method, and then 5 liters of the same solution was added.
25 ml was added over 20 minutes to form a silver iodide emulsion. At this time, pAg was maintained at 11.5. Next, 230 g of this emulsion was added to a 5% ossein gelatin solution 11 stirred at 750° C., and 500 ml of a 4.7 M silver nitrate and ammonium bromide solution was added over 10 minutes using the double jet method.

PAg at this time was kept at 60. This emulsion was added to pAg9
．． 5G adjustment 17.28% 8% ammonia 301/ was added and aged for 15 minutes.

The pH of the emulsion thus obtained was adjusted to 5.8,
750 yr of 4.7M solution of silver nitrate and ammonium bromide
1 was added over 15 minutes using the double jet method. During this time, the pAg was kept at 9.5, and the addition rate was initially 33.
at/ml-n, final a 7 ml/min
It was gradually increased so that After the addition was completed, washing with desalinated water was carried out in a conventional manner.

The silver iodide content in the core of the emulsion thus obtained was 9 mol%, the volume of the core was 42%, the coefficient of grain size variation was 20%, and the average grain size was 1.40 μm1.
The average aspect ratio was 5:1.

Silver Halide G A monodisperse spherical seed emulsion consisting of silver iodobromide containing 1.4 mol % of silver iodide was prepared using the solution shown below.

1 potassium iodide 8g 1 water
2.41 rSilver nitrate 30o9 B] (Add water and add 2g of dissolved iB1 to solution AI stirred at 40°C for 20 seconds to make a core emulsion consisting of polydisperse multiple twins. Next, fI solution B2 IA 11111. with 20 seconds of music, then 1 minute] I11 was aged. p B r at the time of aging.
l:jl, 2 ammonia yield 0.63 M, pHi
:j] was 1.0.

After ripening, the pH was adjusted to 60, and demineralization and washing with water were carried out using a conventional method. When the emulsion grains were observed under an electron microscope, they were found to be monodisperse spherical grains with an average grain size of 028 μm and a distribution of 23%.

Next, using this seed, tabular grains according to the present invention were grown using the solution shown below.

It was a polydisperse emulsion consisting of multiple twins.

Next, using this seed, tabular grains of the present invention were grown using the solution shown below.

Solution 0-2 and solution B-2 were added to solution A-2 stirred at 75° C. by a double jet method to grow silver iodobromide with a silver iodide content of 9 mol %.

The addition was increased sequentially to an initial rate of 104 III/min and a final rate of 250i++/min, during which time the pBr was maintained at 1.36.

-1,09- Subsequently, solution 0-3 and solution B-3 were prepared using the double jet method.
was added to grow pure silver bromide. Addition is done at an initial rate of 91.
3 III/mim, final speed 91.31RI
/mln, and during this time pBr
was kept at 1.0. The obtained particles were observed with an electron microscope and found to have an average particle diameter of 1.5 μm and an average aspect ratio of 6.
:1, a tabular emulsion with a size distribution coefficient of variation of 18% is shown.
- -ill - The coated samples 24 to 29 thus obtained were exposed and developed by the method described in Example 1, and the amount of residual silver in the highest density area was measured by fluorescent X-ray method. . The results are shown in Table-5.

Table 5 From Table 5, it can be seen that the sample comprising an emulsion layer comprising tabular grains with an aspect ratio of 3:1 or more and a layer containing a polymer coupler according to the present invention has excellent desilvering properties. It was also found that emulsions with good monodispersity were more effective.

(3) Effects of the Invention The desilvering property and dye staining of a multilayer color photographic material having tabular silver halide grains whose silver halide composition is essentially silver iodobromide are improved.

Improvement of dye staining has great practical value, especially in color reversal.

Agent Patent Attorney No 1) Written amendment to parent-in-law proceedings September 1985 268 2 Name of invention Copper halide multilayer photosensitive material 3 Relationship with tenancy of the person making the amendment Patent applicant address 1-26 Nishi-Shinjuku, Shinjuku-ku, Tokyo Number 2, 1 Sakura-cho, Hino-shi, Tokyo Konishiroku Photo Industry Co., Ltd. ([Call number 0425-83-152
1) Patent Part 5 Column 6 of ``Detailed Description of the Invention'' in the Specification Subject to Amendment Contents of Amendment 1) The following is corrected for ``Detailed Description of the Invention.''

= 2- Attachment Table-2

Claims (1)

[Claims] The aspect ratio is 3:1 or more, and mainly (111
) A silver iodobromide emulsion having at least one silver halide emulsion layer containing tabular grains and a layer containing a polymer coupler latex, the emulsion layer being spectrally sensitized with a trimethine dye. A silver halide multilayer photosensitive material comprising: