JPH0485531A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the sensitivity and shelf stability of a sensitive material and to suppress dye stain by incorporating a specified sensitizing dye polymer. CONSTITUTION:This sensitive material contains a dye polymer represented by formula I, wherein A,B1 and B2 are polymerized monomeric untis, J is 4-15C combining group, V1 and V2 are groups separating Z and A,(a) is 10-100 mol%, (b) is 0-50mol%, (d) is 0-50mol%, Z is a residue of a methine dye represented by formula PI or III,Dp,Dq and Dr are electron donative basic heterocyclic groups, La and Lb are bonding groups each having a conjugate chain, E is an electron withdrawing group having an acidic nucleus, X is an ion, (l) is the number of X and each of (m) and (n) is 0 or 1. A compd. represented by formula IV may be used as the polymer represented by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an improvement in a silver halide photographic material, and more particularly to a silver halide photographic material with improved color sensitization sensitivity and stability over time.

[Background of the invention]

In silver halide photographic materials, a sensitizing dye is added to silver halide in order to form images by sensing desired light. In particular, in color photographic materials, it is desired that the spectral sensitivity of the sensitizing dye be higher than the inherent sensitivity of the silver halide itself, and the structure of the sensitizing dye itself,
Adsorption to the surface of silver halide grains, state of aggregation on the surface of silver halide grains, etc. have been studied.

Is it known that high color sensitization sensitivity can be obtained by forming a certain aggregation state of sensitizing dyes on the surface of halogenated grains? The problem is how to form them, and how to maintain their agglomerated state during storage over time.

A proposal to polymerize a sensitizing dye to facilitate the formation of an aggregated state was proposed in US Pat. No. 2,393.351 or R.Bean.
.

W, 5hepard, R, Kay, E, Wal.
urck: J, Phys, Chem, ,
69(12).

4368 (1965), or a favorable aggregation state cannot be obtained. Furthermore, JP-A-2-113239 proposes a sensitizing dye polymer consisting of a coiled polymer main chain, but although the J aggregation property is improved compared to conventional polymers, the color of silver halide photosensitive materials during storage over time is This is not satisfactory due to a decrease in sensitization sensitivity.

Furthermore, due to the large molecular weight of conventional sensitizing dye polymers, decolorization during development is insufficient.
Current gj! A disadvantage was that the image after processing was contaminated with stains caused by the sensitizing dye polymer.

[Purpose of the invention]

The object of the present invention has been achieved by a silver halide photographic material containing a dye polymer represented by the following formula C1.

Formula [I] In the formula, A, B, and B2 each represent a polymerized monomer unit, and J represents a linking group having 4 to 15 carbon atoms.

Vl and V2 each represent a group that can be cleaved to separate Z and A during processing. a is 10 to 100 mol%, b
represents 0 to 50 mol%, and d represents 0 to 50 mol%.

2 represents a methine dye residue represented by the general formula CA, ) or [B].

General formula (A) Numerical formula [B] (Dr=Lb-E, + Uni, Dp, Dq and Dr each represent an electron donating basic heterocyclic group, La and Lb each represent a conjugated chain binding group and E represents an electron-withdrawing acidic nuclear group.pp-La"
At least one of Dq and Dr-Lb=H is bonded to the v2 group. X represents the ions necessary to cancel the charges within the molecule, and Q represents the number of ions necessary to cancel the charges within the molecule.

m and n represent 0 or l, and m+n≠0.

- In the formula [■], the methine dye represented by Z is, for example, "Heterocyclic Compounds, Cyaninated and Related Compounders" by F.M. Herma (published by Interscience Publishers, 1964). Examples of the dyes include cyanine dyes, merocyanine dyes, composite cyanine dyes, complex merocyanine dyes, and holopolar dyes represented by the following general formulas.

- 2 in the formula CI) represents a cyanine dye, and the following - formula (
Compounds represented by A-I), [:A-II) or [:A-1[[] are preferred.

one mathematical formula CA-I) (x+.)k+ one mathematical formula CA-ff) general formula (A-III) (xse)ks where z , , z , , z , z , , z , and Z
, each represents an atomic group necessary to form a 5- to 6-membered nitrogen-containing heterocycle.

L ,,L ,,L ,,L ,,LS S,L a,L
, , L , , L , and Ll. each represents a methine group. Y represents an oxygen atom, a sulfur atom, a selenium atom or a -NR group.

Rl, R2+Rs, 'Rs and R6 represent an alkyl group, and R4 and R7 represent an alkyl group, a cyclic alkyl group, a heterocyclic group or an aryl group.

At least one of R5 and R2, R1 and R6 is a sulfo group,
Preferably, it is an alkyl group substituted with a carboxyl group or a hydroquine group.

x, e, x2e and X3' each represent an ion that cancels charges within the molecule. k+, kz and ni are each,
Represents the number of ions/ion required to cancel the charge within the molecule, (1
+, 02. Qs, Qs and Q are each an integer of 0 or 1, and m (+ m 2 + n 1 and R2 are each an integer of 0 to 2).

However, the sum of R2 and R2 is 2 or less.

Z ,,Z 2. The heterocycle formed by Z 3 and Z4 is a 5- to 6-membered heterocycle commonly used in cyanine dyes, or a condensed ring of these and a benzene ring or a naphthalene ring. That is, cyanine heterocyclic rings comprising, for example, a thiazole ring, a selenazole ring, an oxazole ring, a tetrazole ring, a pyridine ring, a pyrroline ring, or an imidazole ring, and which have a substitution on the ring, are also included.

Specifically, thiazole type (e.g. thiazole, 4-methylthiazole, 4-7dynylthiazole, 5-methyldeazole, 5-phenyldeazole, 4.5-somethylthiazole, 4.5-diphenylthiazole) ,
Benzothiazole, 5-70 Lohenzothiazole, 5-
Chlorobenzothiazole, 6-chlorobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-promohenzothiazole, 5-carpoxyhenzothiazole, 5-ethoxy/carbonylbenzothiazole, 5-hydroxy Benzothiazole, 5-phenylbenzothiazole, 6-phenylbenzothiazole,
5-methquinebenzothiazole, 6-methquinebenzothiazole, 5-iodobenzothiazole, 6-nitoquinebenzothiazole, tetrahydrobenzothiazole, 5
6-dimethylbenzothiazole, 5.6-dimethoquinopenzothiazole, 5.6-cyoxymethylenebenzothiazole, 6-nitoquine-5-methylbenzothiazole,
5-Phenethylbenzothiazole, naphtho[1,,2-
dl thiazole, na7tho[2,1-d]thiazole, naphtho[2,3-d]thiazole, 5-methoquinonaphtho[1,,2-dl thiazole, 8-methoxynaphtho[2,1,-d]thiazole , 7-methoxynaphtho [
2,1,-dl thiazole, 5-methoxythionaphtheno [6,7-dl thiazole, 8,9-sohydronaphtho [1,2-dl thiazole, 4,5-dihydronaphtho [2゜1-d1 thiazole, etc.] Oxazole type (e.g. 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4.5-dimethyloxazole, 5-phenyloxazole, 5.6-diphenyloxazole, benzoxazole, 5-chlorobenzoxazole, 5- methylbenzoxazole,
5-phenylbenzoxazole, 6-methylbenzoxazole, 5.6-dimethylbenzoxazole, 5
-Methquin benzoxazole, 5-ethoxybenzoxazole, 5-7enethylbenzoxazole, 5-
Hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole, 5-bromobenzoxazole, 5-methyl-6-chlorobenzoxazole, naphtho[1,2-d]oxazole, naphtho f2,1-d cooxazole, na-y [2,3-dl oxazole, etc.), selenazole series (e.g. 4-methylselenazole, 4-phenylselenazole, benzoselenazole, 5
-talolobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, tetrahydrobenzoselenazole, naphtho [1,2-dl selenazole, naphtho [2,1-d] selenazole, etc.),
Tetrazole ring (e.g. 4-phenylterrazole, 4
-Methyltelllazole, penzotelllazole, 5-methylbenzotelllazole, 5-methoxybenzotelllazole, 5,6-dimethylbenzotelllazole, naphtho[2
.
pyridine, etc.), quinoline series (e.g. 1f2-quinoline, 6
-methyl-2-quinoline, 5-ethyl-2-quinoline,
6-chloro-2-quinoline, 8-chloro-2-quinoline, 6-medoxy-2-quinoline, 8-ethoxy-2-quinoline, 6-methyl-2-quinoline, 8-fluoro-2
-quinoline, 5-7methylamino-2-quinoline, 4-
Quinoline, 6-medoxy-4-quinoline, 7-methyl-
4-quinoline, 8-chloro-4-quinoline, etc.), 3.
3-Dialkylindolenine series (e.g. 3,3-dimethylindolenine, 3,3.5-trimethylindolenine, 3゜3~dimethyl-5-(·dimethylamino)indolenine, 3.3-diethylindolenine etc.), imidazono groups (e.g. imidazole, 1-alkylimidazole, 1-alkyl-4-phenylimidazole,
1-alkyl-4,5-dimethylimidazole, l-alkylbenzimitazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-alkyl-5-cyanobenzimidazole, ■-alkyl-5-chlorobenzimidazole , ■-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-chloro-6-cyanobenzimidazole, 1-alkyl-5-triple olomethylbenzimidazole, l-alkyl-5-methylsulfonylbenzimitazole , 1-alkyl-5-
Methoxoluponylbenzimidazole, 1-alkyl-5-acetylbenzimidazole, 1-alkyl-5
-(N,N-dimethylamino)sulfonylbenzimidazole, l-alkylnaphtho[1,,2-d]imidazole, 1-alkylnaphtho[2,1-d] imidazole, l-alkylnaphtho[2,3-d ] imidazole, etc.).

The 1-alkyl group is an alkyl group having 1 to 10 carbon atoms (if it has a substituent, the number of carbon atoms in the substituent is not included), an alkoxy group having 1 to 6 carbon atoms, Alcoquine having an alkoxy group having 1 to 4 carbon atoms also includes those substituted with a carbonyl group, a carbonyl group, a carbamoyl group, a cyano group, a halogen atom, a sulfo group, a phenyl group, a substituted phenyl group, a vinyl group, etc. ( Specific examples of the substituent include methyl, ethyl, cyclohexyl, butyl, delene, 2-methoxyethyl, 3-butoxypropyl, 2-hydroxy-ethoxyethyl, ethquincarbonylmethyl, carboxymethyl, 2-carboxyethyl, 2-cyanoethyl, 2-carbamoylethyl, 2-hydroquinethyl, 2-fluoroethyl, 2.
2.2-trifluoroethyl, 2-sulfoethyl, 3-
sulfopropyl, 4-sulfobutyl, phenethyl, benzyl, sulfo-7ethyl, carboxyl benzyl, allyl, etc.).

2. 2. The nucleus formed by 23 and Z is further oxazoline-based (e.g., oxazoline, 4,4-dimethyloxazoline), thiazoline-based (e.g., thiazoline, 4-methylthiazoline), and inoxazole-based (e.g., isoxazole, benzisoxazole). , 5-chlorobenzisoxazole, 6-methylbenzisoxazole, 7-methylbenzoxazole, 6-medoxybenzoxazole, 7-medoxybenzisoxazole, etc.), 1,3.4-thiadiazole (e.g. 5- Methyl-1,3,4-thiadiazole, 5-methylthio-
1,3,4-thiadiazole, etc.), chenothiazole series (e.g. cheno[2,3-d]thiazole, cheno[
3,2-a]thiazole, cheno[2°3-e]benzothiazole, cheno[3,2-e]benzothiazole, thiazolo[4,5-b]benzothiophene, etc.), tetrazole type (e.g. 1-alkyl tetrazole), imidazoquinoxalines (e.g. 1-alkylimidazo[4,
5-bl Quinoxaline, 6,7 dichloro-alkylimidazo[4,5-b]quinogisaline, 6-chloro-1
-arylimidazo [4,5-bl quinoxaline, etc.), imidazoquinoline series (for example, 1-alkylimidazo [4,5-bl quinoline, 6,7-dichloro-alkylimidazo [4,5-bl quinoline, etc.)], Pyrrolopyridine series (e.g. 3,3-dialkyl-3H-pyrrolo[
2,3-bl pyridine), pyrrolopyrazine-based (eg pyrolo[2,3-bl pyrazine)], pyridopyridine-based (eg pyrido[2,3-bl pyridine), and the like.

The heterocycle formed by Z5 and Z6 is a 5- to 6-membered heterocycle used as a mother nucleus of a desensitizing dye, or a condensed ring of these and a benzene ring or a naphthalene ring; 2. Specifically, the heterocycle formed by thiazole type (for example, 5-nitrobenzothiazole, 5-nitronaphtho [
2, l-d] thiazole, etc.), oxazole series (e.g. 4-nitrooxazole, 5-nitrobenzoxazole, etc.), selenazole series (5-nitrobenzoselenazole), 3,3-dialkylindolenine series (e.g. 3
．． 3-dimethyl-5-benzoylindolenine, 3.
3-dimethyl-5-methanesulfonylindolenine, 3
．． 3-dimethyl-6-aneanoindolenine, 3.3-
; methyl-5-cyanoindolenine, 3,3-dimethyl-5-ditroindolenine, etc.), thiazoloquinolines (for example, thiazolo[4,5-b]pyridine, thiazolo[
5,4-bl pyridine, etc.), imidazoquinoxalines (e.g. 1-argylimidazo [4,5-bl quinoxaline, 6,7-dichloro-1-alkylimidazo [
4,5-bl quinoxaline, 6-chloro l-arylimidazo[4,5-b]quinoxaline, etc.), pyrrolopyridine series (e.g. 3,3-dialkyl-3H-pyrrolo[2
,3-bl pyridine), pyrrolopyrazine series (e.g. pyrrolo[2,3-bl pyrazine), pyrroloisoquinoline series (e.g. 2-phenyl-pyrrolo[2,1-a] isoquinoline, 2-tolyl-5,6- Citrahydrovirolo [
2゜1-a]inquinoline, etc.), pyridopyridine type (for example, pyrido[2,3-bl pyridine), and the like.

The nitrogen-containing heterocycle formed by Z6 is a 1-H indole group (for example, fly-alkyl-2-phenyl-5-nitro-3-indole, 1-aryl-2-(4-nitrophenyl)-3- Indole, l-alkyl-2-(2
-pyridyl)-3-indole, 1-alkyl・2-phenyl-5-benzoyl-3-indole, etc.), pyrazolobira sin (e.g. 2-phenyl-6,7-synthylvirasolo[1,5-a]pyrazoline, pyrrolo Isoquinolines (e.g. 2-phenyl-5,6-titrahydrovirolo [2,1-a] isoquinoline, 2-ph true 5,6-titrahydrovirolo [2,1a] isoquinoline, etc.), pyrazolo Pyridine type (e.g. 2-pyrazolo [
1,,5-a] pyridine), pyrazolopyri non-type (e.g. 2-phenylpyrazolo[1,5-a1 biritazine), imidazopyridine type (e.g. methyl-2(4-
phenylazophenyl)imidazo[1,,2a,] pyrazoline l-methyl-2~phenyl1) I-imidazo[
1,,2-alpyridinium, etc.).

L +, R2, L 3. L 4. L s, L 6+
L y, L a, L s and. Examples of substituents for methine groups, including those having substituents represented by, include lower alkyl groups having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, isobutyl, etc.), aryl groups (for example, phenyl, p-tolyl, p-chlorophenyl, etc.), alkoxy groups having 1 to 4 carbon atoms (e.g., methquine, ethquine, etc.), aryloxy groups (e.g., phenoxy/etc.), aralkyl groups (e.g., pen-nor, 7-ethyl etc.), heterocyclic groups (e.g., thienyl, furyl, etc.), substituted amino groups (e.g., dimethylamino, tetramethyleneamino, anilino, etc.), alkylthio groups (e.g., methylthio), and acidic nuclear groups (e.g., malononitrile, alkylsulfonylacetonitrile, cyanogen). Methylbenzofuranylketone or cyanomethylphenylketone, 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidacillin-5-one, hydantoin, 2- or 4-thiohydantoin, 2-
iminooxazoline-4-one, 2-oxazoline-5
-one, 2-thioxazolidine-2,4-dione, inxacillin-5-one, 2-thiazolin-4-one,
Thiazolidin-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, inrhodanine, indan-1,3-dione, thiophene-3-one, thiophene-3-1,,1-dioxide ,
Indolin-2-one, Indolin-3-one, Intazolin-3-one, 2-oxoindasilinium, 3-
Oxoindacillinium, 5.7-thioxo6.7-
Cyhydrothiazolo [3゜2-a] pyrimidine, fuclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barhylic acid, 2-thiobarhylic acid, chroman-2,4-dione, indacillin-2one or pyrido [
1,2-a] pyrimidine-1,3-dione), and substituents of the methine group may form 4- to 6-membered rings (for example, 2-hydroquine-4-oxo/clobutene ring,
cyclopentene ring, 3,3-dimethylcyclohexene ring, etc.).

The alkyl group represented by Rl+R2, R3, Rs and R6 is preferably an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, butyl, isobutyl, etc.), and the alkyl group may have a substituent. included. Examples of the substituent include an alkokino group, an alkoxycarbonyl group, an aryl group, a hydroquine group, a cyan group, a vinyl group, a halogen atom, a carbamoyl group, a sulfamoite group,
Examples include carboxyl group, sulfo group, and sulfato group.

The alkyl group represented by R1 and Ra is preferably an alkyl group having 1 to 6 carbon atoms (eg, methyl, propyl, propyl, etc.), and the alkyl group includes those having a substituent. Examples of the substituent include an alkoxy group, an alkylthio group, an aryleoquine group, an aryl group, a hydroquine group, a cyano group, a hinyl group, a halogen atom, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, and a carboxyl group. Can be mentioned.

The cyclic alkyl group represented by R2 and R7 is a 5-membered,
A 6-membered cyclic alkyl group (eg, cyclopentyl, cyclohexynyl, etc.) is preferred.

Examples of the heterocyclic group represented by R4 and R7 include a pyridyl group (e.g., 2-pyridyl, 3-pyridyl, 4-pyridyl, etc.), a 2-thiazolyl group, and examples of the aryl group include a phenyl group, Examples thereof include a 2-naphthyl group and a substituted phenyl group (eg, p-1-lyl, p-chlorophenyl, p-carboxyphenyl, etc.).

X+. The acid anion represented by +
Examples include yosito, perchlorate, perfluoroborate, and the like. When the dye forms an inner salt, kl
+k 2 and ni are 0.

The general formula [B] in the present invention represents a merocyanine dye, and the following formulas CB-I), CB-n) or [B-II
Compounds represented by I) are preferred.

-Math CB-I) General formula CB-1f) R2 General formula CB-1 [I] In the formula, Z 1. Z s, Z s, Y, L 2. Ls
, L 4+L s, L a.

L? , L s, L 10. Rl, R3, R4, R6,
Ql, Qs, Q6. m I+nl+m2 and R2 have the same meanings as the general formulas CA-I), (A-I) and [A-nl). E represents an acidic nuclear group.

-E in formula 1'B-1) to general formula B-nl)
The acidic nucleus represented by is either cyclic or non-cyclic, and examples include those shown below (display was performed using a single limit resonance structure).

In the formula, Ra, Rb, Re and Rd are each a monovalent substituent, such as a hydrogen atom, an alkyl group (including those having an It substituent, such as methyl, ethyl, octyl). , dodecyl, 5ec-octyl, 2- and droxyethyl, etc.)
, aryl group (including those having substituents, e.g. p-
hryl, phenyl, etc.), or heterocyclic groups (including those having substituents, such as benzofuryl).

In the case of a cyclic group> In the formula, R is a monovalent substituent, such as a hydrogen atom, an alkyl group (e.g. methyl, ethyl, etc.), an alkyl group having a substituent (e.g. methoxyethyl, hydroxyethyl, carboxyethyl) , sulfoethyl, carbamoylethyl, etc.),
Mention may be made of aryl groups (eg phenyl), heterocyclic groups (eg pyridyl, benzothiazolyl, etc.).

Further, the ring may have a substituent such as a methyl group or a phenyl group.

General formula (A-I), (A-If), CA-
DI]CB-I), CB-I[) and [:B-I
The methine dyes shown in II) are Zr, Zz, Z3.
As a substituent of Z4+ 25.26°E, or R+
-R2,Rs, R4゜R3,R5,R, or as a substituent thereof, is bonded to V2 or directly to J via a heteroatom.

Polymer backbone repeating units useful as A-, -B, - and -82- can be any units derived from - that are capable of addition polymerization. Such salts include amino acids such as lysine and ornithine, or acrylic and methacrylic esters (e.g. methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl acrylate, 2-ethylhexyl methacrylate, methacrylate). 2-hydroxyethyl acid, 2-acrylic acid
ethylenically unsaturated monomastyrenes and styrene derivatives (e.g. vinyltoluene, vinylbenzene, cyhinylbenzene, 4-tert-butyl styrene and 2-chloromethylstyrene), vinyl ethers, vinyl esters, and maleic anhydride.

The -he-unit is preferably a polymerized monomer unit having pendant amino or hydroxyl groups linked to the methine dye.

Such monomers having pendant amino groups include lysine, vinylamine, 2-aminoethyl methacrylate, and 3-aminopropylmethacrylamide.

The linking group J is any known linking group, preferably a substituted or unsubstituted alkylene group, a substituted or unsubstituted aralkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted alkenylene group having 4 to 10 carbon atoms. ■1 or 7 units A
is bonded to via a heteroatom.

V, and ■2 are V IJ ! during processing. V z)n Z
(m; 1) or cleaved as V2-Z (m=O.

n=1), a group that releases a methine dye, and examples of such a linking group include those described in JP-A-54-145135 (British Patent Publication No. 2,010,818A) and U.S. Patent No. 4,248.
．． No. 962, No. 4,409,323, British Patent No. 2,0
A group utilizing an intramolecular ring-closing reaction described in No. 96,783,
British Patent No. 2,072.363, JP 57-1542
A group that utilizes intramolecular electron transfer as described in JP-A-57-179842, etc., a group that utilizes carbon dioxide elimination as described in JP-A-57-179842, etc., or a group that utilizes formalin elimination as described in JP-A-59-93422. A group that utilizes separation, Special Publication No. 17369, 1983.
(U.S. Patent No. 3,888,677), No. 55-969
No. 6 (U.S. Patent No. 3,791,830), No. 55-34
No. 927 (U.S. Patent No. 4,009,029), JP-A-5
No. 6-77842 (U.S. Pat. No. 4,307,175),
A group utilizing the so-called reverse Michael reaction described in No. 59-10564.2 and No. 59-105640,
No. 4-39727, U.S. Patent No. 3,674.478, U.S. Pat. No. 3,932,480, U.S. Pat. A group that utilizes the production of quinone methide or quinone methide compounds through intramolecular electron transfer as described in JP-A-55-53330 and JP-A-59-218439
Utilizing the intramolecular ring-closing reaction described in JP-A No. 1983
-76541 (U.S. Patent No. 4,335,200), U.S. Patent No. 57-135949, U.S. Patent No. 57-179842, U.S. Patent No. 5
No. 9-137945, No. 59-140445, No. 59
-219741, those utilizing 5- or 6-membered ring cleavage described in No. 60-41034, or JP-A-59
-201057, 61-43739, 61-9
Examples include groups that utilize the addition of a nucleophile to an unsaturated bond as described in No. 5347.

The structural formulas of the typical V1 and V mentioned above are shown below together with the released group W.

Shil FlS YSO2CH3 (Tomo YCH2’W CH, -N people W CH.

In the formula, W--J-(V, book Z Or represents -Z.

Preferably, it is a polymer backbone.

The coiled polymer main chain in the present invention is, for example, H,
LawThe Organic Chemistry
of Peptides J (1950, J, Wile
y, 5ons), G, FasmanrPoly a −
Amin.

Ac1dsJ (1967, Marcel Dekke
r, Inc.), G. Zubayr Biochemis
tryJ (1983, Addison Wesley
Publ, Co,), E, Selegny ropti
Cally Active PolymersJ (1
979°D, Reidel Publishing), R
,B.Martinrlntroductionto
Biophysical Chemistry J (19
64, Mc Gray Hill.

Preferred are helitu-coiled polymer backbones such as the polyamino acids described in, et al.
1-lysine) and poly(1-ornithine) are preferred.

These poly backbones have repeating units ranging from 5 to s, ooo
Preferably something that you own.

Specific examples of the sensitizing dye polymer of the present invention are shown below.

S-9 S-11 (CH2), C0NH-QHe CH2C0OH The sensitizing dye represented by the formula [■] according to the present invention is, for example, (J, Am, Chem, Soc, 67, .1875-1
899 (1945)), F.M. Palmer, The Chemistry of Heterocyclic Compounders
eterocyclic compounds) 1st
Volume 8, The Cyanine Soybeans and Related 1
Combounds (The Cyanine Dyesan)
d Re1ated Compounds) (A,
Weissberger ed.

Published by Interscience, New York 1
964), U.S. Pat. No. 3,483.196, U.S. Pat.
No. 41,089, No. 3,541.089, No. 3,59
No. 8,595, No. 3,598,596, No. 3,632
, No. 808, No. 3,757.663, JP-A-60-7
Those skilled in the art can easily synthesize it by referring to the method described in No. 8445 and the like.

Synthesis example (manufacture of dye polymer S-1) Intermediate synthesis 6-chloro-1-methyl-uracil (6.4 g) and potassium carbonate (6.8 g) in dimethylformamide (60 m
12) Add a solution of bromoacetic acid in dimethylformamide to the solution and stir at 90°C for 4 hours.

After the reaction solution was allowed to cool, it was poured into water acidified with hydrochloric acid, and the precipitated crystals were collected by filtration.
2), N-chlorosuccinimide (3.9g
) was added and reacted at 35°C for 2 hours.

The reaction solution was poured into water, and the precipitate was collected by filtration, washed with water, and dried.

A dimethylformamide solution (20++++2) of the obtained crystals (3.8 g) was added to 5,6-dichloro-2 (3-(5
,6-dichloro-1-ethyl-3-(3-sulfonatopropyl)-2(3H)penzimidazolinylidene if
-propenyl) -1-ethyl-3-(4-hytomixyphenyl)benzimidazolium salt (10,1 g) and 1
．． A solution of 8-diazabicyclo[5,4,0]undec-7-ene (2,5 g) in dimethylformamide (50 m4
) and heat the reaction at 90°C for 2 hours.

After cooling, the reaction solution was poured into water, and the precipitated crystals were collected by filtration and washed with ethanol. Recrystallization was performed using a mixed solvent of chloroform and methanol to obtain crystals with a wavelength of λwax (MeOH) of 518 nm.

5,6-dichloro-2(3-(5,6-dichloro-1-ethyl-3-(5,6-dichloro-1-ethyl-3-
(3-sulfonatopropyl)-2(3H)penzimidazolinylidene)-1-propenyl)-1-ethyl-3
-[4-(5-chloro-3-carboxymethyl-1-methyl-6-uracil)oxyphenyl]propenyl]benzimidazolium salt (0.9 g), pyridine (0-5
g) and poly-lysine (0.15 g) were added and mixed.

A dimethylformamide solution of 2-chloro-1,3-dimethylimidazolinium hydrochloride (0.2 g) was added to the mixed solution (
1,m+2) was added and stirred at room temperature for 6 hours, followed by the addition of poly-lysine hydrochloride (0.23 g).

After the reaction was continued for 24 hours, the reaction solution was filtered, and the filtrate was poured into methanol to cause precipitation. Filter the precipitate,
After drying, the desired product S-1 was obtained.

λmax (MeOH) 580nm.

The amount of the sensitizing dye added in the present invention is not particularly limited, but is 2 x 1 sensitizing dye units per mole of silver halide.
It is preferable to use 0-@mol to I x 10-'' mol, more preferably 5X to' mol-5X 10-3 mol.

Sensitizing dyes can be added to the emulsion using methods well known in the art. For example, these sensitizing dyes can be directly dispersed in the emulsion or dissolved in water-soluble solvents such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, fluorinated alcohols, dimethylformamide, or mixtures thereof. Alternatively, it can be diluted with water or dissolved in water, and added to the emulsion in the form of a solution. Ultrasonic vibrations can also be used during the dissolution process.

Alternatively, the dye can be prepared by dissolving the dye in a volatile organic solvent, dispersing this solution in a hydrophilic colloid, and adding this dispersion to an emulsion, as described in U.S. Pat. No. 3,469,987. As described in Japanese Patent Publication No. 46-24185, a method is also used in which water-insoluble dyes are ground in a solid state without being dissolved, dispersed in an aqueous solvent, and this dispersion is added to an emulsion. It will be done. The dye can also be added to the emulsion in the form of a dispersion by the acid dissolution and dispersion method. Other additions to emulsions include U.S. Pat.
No. 5, No. 3,342゜605, No. 2,996.287
No. 3,425,835, etc. can also be used.

The sensitizing dye represented by formula (1) used in the present invention can be added to the emulsion at any time during the manufacturing process from the time of silver halide grain formation to just before coating on the support. can be added to.

Specifically, before the formation of silver halide grains, during the formation of silver halide grains, after the completion of silver halide grain formation until the start of chemical sensitization, at the start of chemical sensitization, during chemical sensitization, and during chemical sensitization. Any time selected from the end of chemical sensitization and the time of application may be used. Alternatively, it may be added in multiple portions.

- The dyes represented by the formula CI) can be added by dissolving each dye in the same or different solvents and mixing the solutions before adding them to the emulsion, or adding them separately to the emulsion. However, it is more preferable to mix the dye solution before adding it to the emulsion.

The sensitizing dye according to the present invention may further be used in combination with other sensitizing dyes other than the present invention or compounds that provide supersensitizing action.

The silver halide grains contained in the silver halide photographic light-sensitive material of the present invention may be any of silver bromide, silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide.

In particular, silver iodobromide is preferred from the standpoint of obtaining high sensitivity.

In the case of silver iodobromide, the average silver iodide content in the silver halide grains is preferably 0.5 to 10 mol%, more preferably 1
~8 mol%.

The crystals of the /10 silver halide emulsion used in the present invention may have a uniform internal silver halide composition, but the core inside the grain may be coated with a shell having a composition different from that of the core. Preferably one with structure.

In the grains having a core/shell structure, the shell may be uniform, but it is particularly preferable that the coated shell is further coated with shells having different silver halide compositions, so that the shell has a multilayer structure.

In a silver halide crystal having a core/shell structure made of silver iodobromide (silver chloroiodobromide), the silver iodide content of the core is preferably 2 to 40 mol%. More preferred is 10-4
0 mol%, more preferably 15 to 40 mol%.

In /S silver halide crystals consisting of silver iodobromide (silver chloroiodobromide), the ions may be added as an ionic solution, such as a potassium iodide solution, and may be added to the silver halide grains during growth. Although it may be added as a grain with a small solubility product, it is more preferable to add it as a silver halide grain with a small solubility product.

The silver halide grains used in the present invention have a shape such as cubic, octahedral, tetradecahedral, or spherical.
It may be a so-called normal crystal or a crystal containing twin planes.

The method for producing normal crystal silver halide grains is known, for example J
, Phot, Sci., 5, 332 (1961), Be
r, Bunsenges.

Phys, Chem, 67.949 (1963), In
tern, Con, Gress Photo.

Sci, Tokyo (1967), etc.

Tabular grains with aspect ratios greater than 1 can also be used in the present invention. Tabular grains are disclosed in U.S. Pat.
No. 6, No. 4,414.310, No. 4.433,048
No. 4°439.520 and British Patent No. 2,112.
It can be easily prepared by the method described in No. 157 and the like.

Tabular grains having an aspect ratio of greater than 1 are preferably from 2 to 100, more preferably from 2 to 20.

The circular diameter of the flat plate grains is preferably 0.2+1 m to 30 μm, more preferably 0.4 μm=10 μm. Further, the thickness thereof is preferably 0.5 μm or less, more preferably 0.3 μm or less.

The silver halide emulsion used in the present invention includes:
Although polydisperse emulsions can be used, monodisperse emulsions are more preferred.

The monodisperse emulsion referred to herein is, for example, The PhoLo
-Graphic Journal, 79, 330-3
38 (1939).

In the method reported by Sm1th et al., the average particle yjL
At least 95 particles in number or weight when measured in diameter
% of particles within ±40% of the average particle diameter, preferably ±
A silver halide emulsion with a content of 30% or less.

The above-mentioned silver halide grains used in the silver halide photographic material of the present invention include, for example, T and H grains.

James, “The Theory of the
Photographic Pro-c e s s
"The neutrality method described in literature such as 4th edition, published by Macmillan Fan (1977), p. 38-1.04,
It can be produced by applying methods such as an acid method, an ammonia method, forward mixing, back mixing, a double jet method, a Chondrald-double jet method, a conversion method, and a core/shell method.

Known photographic additives can be used in the silver halide photographic emulsion of the present invention.

Examples of known photographic additives include compounds described in Research Disclosure (RD) RD-17643 and RD-18716 shown in the table below.

Additives RD-17643 page Classification 23 llI 29 XX 24 Vr Chemical sensitizer Development accelerator Antifoggant Stabilizer Color stain inhibitor 25 Image stabilizer 25 Ultraviolet absorber 25-26 Filter dye // Brightener 24 Hardening agent 26 Coating aid 26-27 Surfactant 26-27 Plasticizer 27 Slip agent Static inhibitor 27 Matting agent 28 Binder 26 ■ ■ ■ ■ N ■ RD-18716 Page Classification 648- Top right 648- Upper right 649 - Lower right left - Right 649 Right ~ 650 Left 651 Left 650 Right 650 Right 650 Right 651 left When applying the present invention to a silver halide color photographic light-sensitive material, couplers described in the Research Disclosure below may be used. Can be used.

[Item] (page of RD308119) Yellow coupler 1001 ■-D section magenta coupler 1001 ■-D-0 uncoupler 1001 ■-D section colored coupler 1
002 ■-G term DIR coupler 1001
■-F section BAR coupler 1002 ■-F
Section CPD17643] (RD18716) ■C-G ■C-G ■C-G ■G ■F Alkali-soluble coupler 1001 ■-E The additives used in the present invention are described in RD308119XIV. It can be added by a dispersion method etc.

In the present invention, the above-mentioned RD], page 764328, R
D18716647-8 pages and RD308119 (7)
X1ll i: The retail support described can be used.

The photosensitive material of the present invention can be provided with auxiliary layers such as the filter layer and intermediate layer described in the above-mentioned RD308119-.

The photosensitive material of the present invention includes the aforementioned RDI764328-29,
I? DI8716647 page and RD308119 X
Development processing can be carried out by the usual method described in Section I.

Examples of light-sensitive materials to which the silver halide photographic light-sensitive material of the present invention can be applied include color negative film for photography, color reversal film, color photographic paper, color positive film,
It can be used for color reversal photographic paper and other photosensitive materials such as printing plates, X-ray photography, direct positives, heat development, and silver dye bleaching.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In the following examples, the amount added in the silver halide photographic material is expressed in grams per 1 m z unless otherwise specified.

Furthermore, silver halide and colloidal silver are shown in terms of silver.

Sensitizing dyes are expressed in moles per mole of silver.

Example 1 (Preparation of Sample No., Iol) Ideal for a monodispersed silver iodobromide emulsion with an average grain size of 0.65 μm and an internal silver iodide core of 8 mol% and an average silver iodide content of 8 mol%. was subjected to total sulfur sensitization to produce sensitized dye polymer S-1.
was added in an amount of 0.24 g per mole of silver to spectral sensitize to green sensitivity.

Then 4-hydroquine-6-methyl-1,3,3a,
7-Citradesign and l-7enyl-5-mercaptotetrazole were added for stabilization.

Furthermore, the following magenta coupler = (M-1) was dissolved in ethyl acetate and a high boiling point solvent (Oil-1), and a dispersion obtained by emulsifying and dispersing it in an aqueous solution containing gelatin, and a general photographic addition of a spreading agent and a hardening agent. A coating solution is prepared by adding a coating agent, which is coated on a subbed triacetyl cellulose support by a conventional method, and dried to produce a photosensitive material Js (preparation of sample No. 102) Sensitizing dye polymer in sample No. 101 Comparative sample No. 102 was prepared in the same manner except that 0.12 g of the following sensitizing dye was added instead of S-1.

(Creation of sample No. 103) Instead of the sensitizing dye polymer S-1 in sample No. 101, the dye polymer DP-4 described in the example of JP-A-2-113239 (however, m: n = 40: 6) was used.
0) Comparative sample No. 103 was prepared in the same manner except that 0.19 g was added.

Sample No. 1O1-103 was exposed to blue light to determine the intrinsic sensitivity and exposed to an interference filter to determine the sensitivity at the maximum color sensitization portion.

Subsequently, the following development treatment was performed.

Processing process Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water Wash 3 minutes 15 seconds Fixed arrival time: 6 minutes 30 seconds Water Wash 3 minutes 15 seconds Stabilization 1 minute 30 seconds drying drying The composition of the treatment liquid used in each treatment step is shown below.

(Color developer) 4-amino-3・methyl-N-(β-hydroxy/ethyl)aniline sulfate anhydrous sodium sulfite hydroxylamine l/2 sulfate anhydrous potassium carbonate potassium bromide nitrilotriacetic acid trisodium salt (L water salt) Add potassium hydroxide water to make 1Q (Bleach solution) Ethylenediaminetetraacetic iron iron (n[) Ammonium salt ethylenediaminetetraacetic acid 2 Ammonium chloride Ammonium bromide Add glacial acetic acid water to make IQ 6.0 Adjust to.

10.0 g 150.0 g 1.0.0 g pH using ammonia water 4.75 g 4.25 g 2.0 g 37.5 g 1.3 g 2.5 g 1.0 g 100.0 g (Fixer) Ammonium thiosulfate 175.0 g Anhydrous ammonium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to 1f
2 and adjust the pH to 6.0 using acetic acid.

(Stabilizing liquid) Formalin (37% aqueous solution) 1.5 m
QConidax (manufactured by Konica Corporation) 7.5mQ
Evaluation of car color sensitization efficiency by adding water to obtain II2.The color sensitization sensitivity is shown as a relative value when the intrinsic sensitivity is set to 100.

The evaluation sample for storage stability over time was left naturally for 18 hours (A), and the sample (B) was left for 24 hours under constant temperature and humidity at a relative temperature of 75% and deteriorated forcibly. The sensitivity to light passing through the filter was expressed as a relative value when the sensitivity of sample (A) was set as 100.

The larger the value, the better the storage stability over time.

Evaluation of dye staining Visual evaluation was performed according to the following criteria.

There is almost no contamination due to residual O sensitizing dye.

△ Slight staining due to residual sensitizing dye is observed.

× There is clearly contamination due to residual sensitizing dye.

The results are also shown in Table-1.

Table 1 As is clear from Table 1, the photosensitive materials containing the sensitizing dye polymer of the present invention have superior storage stability over time and color sensitization compared to those containing ordinary sensitizing dyes and conventional polymers. It is also highly efficient. In addition, almost no dye staining is observed.

Example 2 On both sides of a subbed polyethylene terephthalate support, each layer having the composition shown below was sequentially formed from the support side to obtain X-ray photosensitive material sample No.

201 to 203 were obtained.

Additives other than silver halide are shown in amounts per mole of silver halide unless otherwise specified.

1st layer: Crossover cut layer dye (A I-3) 3mg/m”
Mordant (Cpd-1) 0.2g/m”
Gelatin 0.2 g/m" Second layer: Emulsion layer average grain size 0.57 μm, AgBr containing 2 mol% AgI
Core/shell type monodisperse emulsion consisting of + coating silver amount 4.5 g/m" Sensitizing dye (listed in Table 2) 4-Hydroxy-6-methyl-1,3,3a-7-titrazaindene 3.0 gt-
Butylcatechol 400mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0g Styrene-maleic anhydride copolymer 2.5g Trimethylolpropane diethylene glycol p-nitrophenyl root IJ Phenylphosphonium chloride 1.3-dihydroquinebenzene-4 Ammonium sulfonate 2-mercaptobenzimidazole 5-sodium sulfonate 10 g g 0 mg g 1.5 mg I,■-dimethylol-1-bromo 1-nitromethane gelatin 3rd layer: Protective layer polymethyl methacrylate (average particle size 5 μm) Colloidal silica 0 g 2 g /m” 7mg/m2 (average particle size 0, 01.3μm) 70mg
/m”So, Na (n is a mixture of 2 to 5) Gelatin Ig/m2 Hardener C
H2” CH30zCH20CHzSOzCH-CHz
Each sample was exposed to light through a step wedge and subjected to the following processing, and sensitivity and fog were measured. The sensitivity was expressed as the reciprocal of the exposure amount that gives a density of fog + 0.5. On the other hand, the storage stability over time was evaluated using a sample that was left at 40° C. and 70% relative humidity for 2 days, and the sensitivity immediately after the sample was prepared was taken as 100 and expressed as I: relative sensitivity.

(Processing process) Insert 1.2 seconds developer Transition 35℃ 14.6 seconds fixing + Transition
33℃ 8.2 seconds Washer Crossing 25℃
7.2 seconds squeeze 40'C5,7
Second drying 45℃ 8.1 seconds (Developer) Hydroquinone 25.0g Phenidone 1.2g Potassium sulfite 55.0g Boric acid
10.0g Sodium hydroxide 21.0g Triethylene glycol 17.5g 5-nitroimidazole
0.10g 5-nitrobenzimidazole 0. lOg glutaraldehyde bisulfite 15.0g glacial acetic acid
Add 16.Og potassium bromide triethylenetetramine hexaacetic acid water to make IQ.

(Fixer) ammonium thiosulfate anhydrous sodium sulfite boric acid Acetic acid (90wt%) Sodium acetate (trihydrate) Aluminum sulfate (18 hydrate) Sulfuric acid (50wt%) Add water and make to 112.

The results are shown in Table-2.

4.0g A-1 2.5g HN(C2H6)3 130.9g 7.3g 7.0g 5.5g 25.8g 14.6g 6.77g A-2 Dye described in Examples of JP-A-2-113239 Polymer DP-4 (m: n = 60+40) Table-
2, it is clear that the photosensitive material containing the sensitizing dye polymer of the present invention has high sensitivity, excellent storage stability over time, and little dye staining.

However, the number of moles added was the number of moles of the dye unit.

Moreover, 5A-1 and 5A-2 are as follows.

Claims (1)

[Scope of Claims] A silver halide photographic material containing a dye polymer represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, A, B_1 and B_2 each represent a polymerized monomer unit, and J represents a linking group having 4 to 15 carbon atoms. V
_1 and V_2 each represent a group that can be cleaved to separate Z and A during processing. a is 10 to 100 mol%,
b represents 0 to 50 mol%, and d represents 0 to 50 mol%. Z represents a methine dye residue represented by the general formula [A] or [B]. General formula [A] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [B] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Here, Dp, Dq, and Dr each represent an electron-donating basic heterocyclic group. , La and Lb each represent a conjugated chain bonding group, and E represents an electron-withdrawing acidic core group. Dp-La=
At least one of Dq and Dr=Lb=E is bonded to the V_2 group. X represents the ions necessary to cancel the charges within the molecule, and l represents the number of ions necessary to cancel the charges within the molecule. m and n represent 0 or 1, and m+n≠0. ]