JPH01179143A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain high sensitivity and superior whiteness by incorporating at least one kind of specified compd. and carrying out color sensitization with a specified dye. CONSTITUTION:At least one kind of compd. represented by formula I is incorporated into at least one of constituent layers and the silver halide particles in the emulsion layer are color-sensitized with a panchromatic sensitizing dye. High sensitivity, a fine color tone and superior whiteness of a silver image can be obtd. In the formula I, X<1> is a bivalent connecting group bonding to C through a hetero atom, A is a group bonding to X<1> through a hetero atom in A and regulating the color tone of a silver image, each of R<1>-R<3> is H or a substitutable group, R<1> and R<2> or R<1> and R<3> may bond to each other to form a carbon or hetero ring, Y is a group represented by formula II, cyano or nitro, each of R<4>-R<8> is H or a substitutable group, each of (n) and (m) is 0 or 1, and in case of m=0, a group represented by A bonds to C through a hetero atom in A.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide black-and-white photographic light-sensitive material for observing silver images. , relates to a panchromatically color-sensitized silver halide photographic material. The present invention is particularly effective in silver halide photographic materials for obtaining black and white prints of good image quality (graininess, tone, whiteness) from color-developed negative-tone light-sensitive materials.

(Prior Art) In a silver halide black-and-white photographic material in which a silver image is observed, the color tone of the silver image is an important point. Conventionally, as a method for controlling the color tone of silver images, compounds containing sulfur atoms and easily adsorbed to silver (for example, mercapto compounds and thiazoline-thione compounds) have been well-known. However, these compounds easily adsorb to silver halide, so
Interferes with the adsorption of sensitizing dyes and reduces sensitivity. In order to compensate for this decrease in sensitivity, large amounts of sensitizing dyes or sensitizing dyes with strong adsorption are used, but in this case, some of the sensitizing dyes remain after the development process, resulting in The result was a decrease in whiteness and poor overall appearance. This tendency is particularly noticeable in the case of panchromatic sensitizing dyes. Conversely, reducing the amount of a compound that controls the tone of a silver image results in poorer tone.

As described above, with the conventional techniques, it has been difficult to satisfy both the tone whiteness of the image quality and the sensitivity of the photographic quality, especially in panchromatically color-sensitized photographic materials.

Panchromatic color-sensitized black-and-white photographic paper is available in order to obtain fine-grained black-and-white prints from color-developed negative photosensitive materials, but none of them is fully satisfactory in terms of tone, whiteness, and sensitivity.

(Objective of the Invention) The object of the present invention is to provide a silver nine halide black-and-white photographic light-sensitive material having a white reflective layer for observing a silver image, which has high sensitivity and excellent color tone of a silver image and whiteness of a white background. The present invention provides a silver halide black-and-white photographic material that is chromatically color-sensitized.

(Structure of the Invention) The above object of the present invention is to provide a black and white photographic material for observing a silver image, which has at least one light-sensitive silver halide emulsion layer on a support having a white reflective layer. At least one of the constituent layers of the emulsion layer contains at least one compound represented by the following general formula (1), and furthermore, the silver halide grains of the emulsion layer are colored with a chromatographic sensitizing dye. This was achieved using a silver halide photographic material that is characterized by being sensitized.

General formula (I) In the formula, Xl represents a divalent linking group bonded to a carbon atom via a heteroatom, and A represents a silver image bonded to Xl via a heteroatom of A. It represents a group that adjusts color tone, R1, R2 and R3 represent a hydrogen atom or a substitutable group, and R and R and R2 and R3 may be combined to form a carbocycle or a heterocycle.

R4, R5, R6-H, 7 and R8 each represent a hydrogen atom or a substitutable group. ), where n and m are O or /
represents. When m=O, the group represented by A is bonded to a carbon atom via the heteroatom of A.

The photographic material of the present invention is color sensitized with a panchromatic sensitizing dye. For example, Tokukai Akira! A cyanine dye having a long methine chain can be used.

Panchromatic sensitizing dyes used in the present invention include cyanine dyes, merocyanine dyes, rhodacyanine dyes, etc.
Particularly preferred are compounds represented by the following general formula (II).

General formula (II) (W engineering) 10 In the formula, %Q1 represents a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom, and Q2 represents an oxygen atom, a sulfur atom, or a selenium atom.

L□, R2, R3, R4 and R5 represent methine groups. This methine group may be substituted or may form a ring with another methine group.

P□ and P2 represent alkyl groups which may be the same or different. Also, P is connected to Ll and P2 is connected to L5! Alternatively, a t-membered carbon ring may be formed.

vl, v2. v3. v4. v5. v6. vl and v8
are a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a carboxy group, a cyano group, a hydroxy group, an amine group, an acylamino group, an alkoxy group, an alkylthio group, and an alkyl group, respectively. It represents a sulfonyl group, a sulfonic acid group, an aryloxy group, or an aryl group, or two bonded to adjacent carbon atoms in (1) to (V8) may mutually form a fused ring.

(Wl), 1 represents the charge-balanced counterion, Jl is 0
represents the value necessary to neutralize the above charge.

Next, general formula (1) will be explained in detail.

R1 represents a hydrogen atom or a substitutable group, and examples of the substitutable group include an alkyl group (preferably one with a carbon number of up to 20), an alkenyl group (preferably one with a carbon number of i to 20), an aryl group ( (preferably one with 6 to 20 carbon atoms)
, an alkoxy group (preferably one with a carbon number of lN2O),
Aryloxy group (preferably one with j-20 carbon atoms)
, alkylthio group (preferably one with carbon number/~-〇)
, arylthio group (preferably one having A-20 carbon atoms)
, amine group (unsubstituted amine, preferably carbon number/~-0
represents a secondary or tertiary amine group substituted with an alkyl group or an aryl group having z--0 carbon atoms, a hydrocarbon group, etc.

Furthermore, R1 may be combined with R2 or 几3 to form a carbon mass or a heterocycle (for example, a 7-membered ring). R2,
R3 may be the same or different and each represents a hydrogen atom or a substitutable group, and substitutable groups include a halogen atom (fluorine, chlorine, bromine), an alkyl group (preferably one with a carbon number of 1-0) , aryl group (preferably one with 6 to 20 carbon atoms), alkoxy group (preferably one with 7 carbon atoms)
~CoO), aryloxy group (preferably one with 6 to 20 carbon atoms), alkylthio group (preferably one with 7 to 0 carbon atoms), arylthio group (preferably one with 6 to 20 carbon atoms) , an acyloxy group (preferably one having a carbon number of - to 0), an amino group (an unsubstituted amino group, preferably an alkyl group having 1 to 40 carbon atoms, or a primary or tertiary group substituted with an aryl group having 6 to -0 carbon atoms) amine group),
A carbonamide group (preferably an alkylcarbonamide group with a carbon number of /-JO, an alkylcarbonamide group with a carbon number of 4-20), a ureido group (preferably a carbon number /-JO)
an alkylureido group having 6 to 6 carbon atoms. 20 aryl ureido group], a carbonate group containing a carboxy group (preferably an alkyl carbonate group having 7 carbon atoms, and a carbon number t
an aryl carbonate ester group with a carbon number of N0), an oxycarbonyl group (preferably an alkyloxycarbonyl group with a carbon number of 1N0, an alkyloxycarbonyl group with a carbon number of tN20), a carbamoyl group (preferably a carbon number of 7 ~C0 alkylcarbamoyl group, carbon number 4~coθ-carpamoyl group), acyl group (preferably alkylcarbonyl group having 1 to 20 carbon atoms, arylcarbonyl group having 4 carbon atoms/V20), sulfo group , a sulfonyl group (preferably an alkylsulfonyl group with carbon number/-20, carbon number AN20
arylcarbonyl group), sulfinyl group (preferably an alkylsulfinyl group with carbon number/-20, carbon number 6
~20 arylsulfinyl group), sulfamoyl group (preferably ``alkylsulfamoyl group having 1 to 10 carbon atoms, arylsulfamoyl group having JN20 carbon atoms),
Represents a cyano group and a nitro group.

R4, H,5, R,6, R7 and R8 may be the same or different, and each represents a hydrogen atom or a group capable of being substituted at a position.Specific substituents include an alkyl group (preferably an alkyl group having 7 to 7 carbon atoms). 20), alkenyl groups (preferably those with carbon numbers λ to 0), aryl groups (preferably those with carbon numbers A-20), alkoxy groups (preferably those with carbon numbers /
-20), aryloxy group (preferably one with carbon number A-20), acyloxy group (preferably one with carbon number - to -0), amino group (unsubstituted amino group, preferably one with carbon number 1- a secondary or tertiary amino group substituted with an alkyl group having a carbon number of t-coO),
Carbonamide group (preferably an alkylcarbonamide group having carbon number/N20, alkylcarbonamide group having carbon number j-J7), ureido group (preferably carbon number/-20
alkylureido group, arylureido group having 4 to 20 carbon atoms), oxycarbonyl group (preferably 1 to 1 carbon atoms)
20 alkyloxycarbonyl group, carbon number AN20 alkyloxycarzenyl group), carbamoyl group (preferably a carbon number/~20 alkylcar-ζmoyl group, carbon number AN20 alkylcarpamoyl group) ), acyl group (
Preferably an alkylcarbonyl group having -20 carbon atoms, an alkylcarbonyl group having t-10 carbon atoms), a sulfonyl group (preferably an alkylsulfonyl group having -20 carbon atoms),
arylsulfinyl group with Rx number t to -〇), sulfinyl group (preferably rusulfinyl group in alkali having carbon number / to -〇, arylsulfinyl group having carbon number A-20), sulfamoyl group (preferably carbon number 7 to 20) represents a rusulfamoyl group in alkali, a rusulfamoyl group containing 1 to 20 carbon atoms. Among these, preferable substituents for R and R include an oxycarbonyl group, a carbamoyl group, an acyl group, a sulfonyl group, a sulfamoyl group, a sulfinyl group, a cyano group, and a nitro group.

These substituents may have 7 or more substituents 4, and when there are 2 or more substituents, they may be the same or different, and specific substituents include the same as the substituent for R1 above. can be mentioned. When R and R or R1 and R2 combine to form a carbocycle or a heterocycle, preferred examples include those represented by the following general formulas (1) and (IV).

General Formula (III) General Formula (It/) In General Formula (III), zl represents an atomic group necessary to form a carbocycle or a heterocycle.

Specifically, for example, a j-membered ring, a seven-membered ring, a seven-negative carbon ring, a j-membered ring containing seven or more nitrogen, oxygen, or sulfur atoms, a seven-membered heterocycle, or a seven-membered heterocycle. These carbocycles or heterocycles include those forming a condensed ring at an appropriate position.

Specifically, cyclobentenone, cyclohexenone, cyclohebutenone, benzocyclohebutenone, benzocyclobentenone, benzocyclohexenone, goupyridone, gooquinolone, λ-pyrone, l-pyrone, /-theokorpyrone, /-thio-μm Others include pyrone, coumarin, chromone, uracil, etc. Here, these carbocycles or heterocycles may have seven or more substituents, and when there are two or more substituents, they may be the same or different. Specific substituents include the above R
The same substituents as 1 can be mentioned.

In addition, Z2 in general formula (IV) is general formula (IIT)
It means the same thing as Zl, specifically cyclopentanone, cyclohexano/, cycloheptanone, benzocycloheptanone, benzocyclo means tantanone, benzocyclohexanone, ≠-tetrahydropyridone, V-dihydroquinolone, ≠-tetra Examples include 哄Dropiro/etc. These carbocycles or heterocycles may have seven or more substituents, and when there are two or more substituents, they may be the same or different.

Specific substituents include the same substituents as those for R1 above.

Are R2, R3, Xl, A, and m the general formula (I)? It is the same as mentioned above.

Next, even if A is directly bonded via a heteroatom (e.g. sulfur atom, nitrogen atom, oxygen atom, etc.) in A (m=O
), 6 or X 1 t.

(m=/) Xl represents a divalent linking group, and the heteroatom (
For example, it is bonded via a sulfur atom, nitrogen atom, oxygen atom, etc., and is cleaved as Represents a group that releases A.

Examples of such a linking group include JP-A No. 131 (British Patent Publication No. 010.rlrh), U.S. Pat. , Ri J, No. 2, Dohiro, ao Ri, 3.2
No. 3, British Patent No. 2,091.

713, which releases A by intramolecular ring-closing reaction, British Patent No. 2,072,363, JP-A-Sho t7-/
144. A device that releases A by intramolecular electron transfer as described in the specification of No. 31A, etc., rμλ
Those that release A with the desorption of carbon dioxide as described in No. 1, etc., or JP-A-Sho! Examples include linking groups such as those that release At- with the elimination of formalin, as described in No. PJ4t.

The material to be used as X is selected depending on the timing of release of A, release control, the type of A used, etc.

Examples of compounds that control the color tone of a silver image represented by A include compounds having a mercapto group bonded to a heterocycle;
For example, substituted or unsubstituted mercaptoazoles (specifically /-phenyl-!-mercaptotetrazole,
/-(!-xyphenyl-!-mercaptotetrazole, /-(4t-sulfophenyl)-!-mercaptotetrazole, /-(#-sulfamoylphenyl)-!-mercaptotetrazole, cometertetrazole
-Mercapto-/,! , 4A-thiadiazole, cophenylu! -Mercapto, /, 2. I-Triazole, J-(J-dimethylaminoethylthio)-1-mercapto-/, J, Thiadiazole, Komelkabutobenzoxazole, Komelkabutobenzimidazole, Komelkabutobenzothiazole, Cophenylu! -Merkaft-/, j, 4t-oxadiazole,/
-(j-(3-Jf leureido)phenyl)-t-mercaptotetrazole, etc.), substituted or unsubstituted mercaptoazaindenes (specifically, 4-methyl-l
-Mercapto-/, 3. Ja, 7-tetrazaindene,
t-phenyl-gumercaptotetrazaindene, 4!
, A-dimethyl-11-merkabuto-/, J, Ja, 7-
tetrazaindene, etc.), substituted or unsubstituted mercaptopyrimidines (specifically, 1-mercaptopyrimidine, -1mercaptoμmmethyl-t-hydroxypyrimidine, etc.). Examples of heterocyclic compounds capable of producing iminosilver include substituted or unsubstituted benzotriazoles (specifically, benzotriazole,!
- Nitropenzotriazole,! -methylbenzotriazole, etc.) substituted or unsubstituted imidazoles (
Specifically, indazole! -nitroindazole, 3
-nitroindazole, etc.), substituted or unsubstituted benzimidazoles (specifically, j-nitrobenzimidazole, j-nitropenzimidazole, etc.).

Further, after A is released from the mother nucleus of general formula (I) in the development process, it becomes a compound having the effect of adjusting the color p4f of a silver image. The compound may then be transformed into a compound having substantially no or significantly reduced tone-adjusting effect.

Specific Khl-(J-phenoxycarbonylphenyl)
-! -Mercaptotetrazole, /-(Hiro-)Ninoma dicarbonylphenyl)-3-mercaptotetrazole,
/-(j-maleinimidophenyl)-yo-mercaptotetrazole,! -(phenoxycarbonyl)benzotriazole, cophenokiscarbonylmethylthio!
-Mercapto-/,! , 47-thiadiazole and the like.

Preferable examples of the compound represented by A include compounds having a mercapto group bonded to a heterocycle.

Specific examples of the metal compound represented by the general formula (1) of the present invention are shown below, but the compounds of the present invention are not limited thereto.

(I-/ ) (I--2) O (I-≠) (I-j) (I-7) SO□NH2 (I-,1') (I-ta) (I-//) (I -/1 (1-/j) (I-/1 (1-/7) (I-/r) (1-/ri) C) The blocked photographic reagent represented by general formula (I) is
Tokukai Akira! Turco 010! No. 7, JP-A-Sho t/-41373
It can be synthesized by the known synthesis method described in No. 2, JP-A No. 61-Ta J3 Gua, and the like.

One or more blocked photographic reagents of the present invention may be used in combination.

The compounds defined by the general formula (I) of the present invention include a silver halide emulsion layer, a coloring material layer, an undercoat 9 layer, a protective layer, an intermediate layer, a filter layer, an antihalation layer, a silver halide photographic light-sensitive material, It may be added to any of the injury layer, cover sheet layer, neutralization layer, neutralization timing layer, white reflective layer, and other auxiliary layers.

The compound of general formula (I) of the present invention may be added at any time during the manufacturing process, but is generally preferably immediately before coating.

The compounds of general formula (I) according to the invention can be used in a wide range of ways. Specifically, it depends on the type of A, but 1O mol/m NIO mol/yH.

Particularly preferred is a range of -xlO mol/m2 to coXIO mol/m2.

Next, general formula (It) will be explained in detail.

Q□ represents a nitrogen atom, an oxygen atom, or a sulfur atom, fc represents a selenium atom, and Q2 represents an oxygen atom, a sulfur atom, or a selenium atom.

L□, L2, L3, L4 and L5 represent a methine group, and this methine group is, for example, a substituted or unsubstituted alkyl group (e.g. methyl, ethyl), a substituted or unsubstituted aryl group (e.g. phenyl), or a substituted or unsubstituted aryl group (e.g. phenyl). It may be substituted with a halogen atom (eg, chlorine, bromine). It may also form a ring with other methine groups.

P and P2 represent an alkyl group which may be the same or different, preferably an unsubstituted alkyl group having 7 carbon atoms as shown below (for example, methyl, ethyl, propyl, butyl, intyl, octyl, decyl, dodecyl, octadecyl)
and substituted alkyl groups (substituents such as carboxy groups, sulfo groups, cyano groups, halogen atoms (e.g., fluorine, chlorine, bromine, etc.), hydroxy groups, alkoxycarbonyl groups having up to r carbon atoms (e.g., methoxycarbonyl, ethoxy carbonyl, phenoxycarzenyl, benzyloxycarbonyl), alkoxy groups with a carbon number below (e.g., methoxy, ethoxy, benzyloxy, phenethyloxy), monocyclic aryloxy groups with a carbon number of 10 or less (e.g., phenoxy , p-tolyloxy), acyloxy groups having 3 or less carbon atoms (e.g., acetyloxy, propionyloxy), acyl groups having ♂ or less carbon atoms (e.g., acetyl, propionyl, benzoyl, mesyl)
, carbamoyl groups (e.g. eva, carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbonyl, pivadinocarvinyl), sulfamoyl groups (e.g. sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), An alkyl group 1 having a carbon number of it or less substituted with an aryl group having a carbon number of io or less (eg, phenyl, ≠-chlorophenyl, goomethylphenyl, α-naphthyl), etc. can be mentioned.

Particularly preferred are unsubstituted alkyl groups (eg, methyl, ethyl) and sulfoalkyl groups (eg, cosulfoethyl, 3-sulfopropyl, ≠-sulfobutyl).

Also, Pl is connected to Ll and 1 and/or P2 is connected to L5! Alternatively, a t-membered elementary ring may be formed.

■1・■2・■3・■4・v5・■6・v7 and v8
are hydrogen atoms and halogen atoms (for example,
(chlorine, fluorine, bromine), an unsubstituted alkyl group, preferably an unsubstituted alkyl group (e.g., methyl, ethyl), a substituted alkyl group, preferably a carbon number/♂ or less (e.g. benzoyl, α
-naphthylmethyl, -phenylethyl, trifluoromethyl), acyl groups, more preferably acyl groups having 10 or less carbon atoms (e.g. acetyl, benzoyl, mesyl),
An acyloxy group, more preferably an acyloxy group having io or less carbon atoms (for example, acetyloxy group), an alkylsulfonyl group, more preferably an alkoxy group having 10 or less carbon atoms (for example, methoxycarbonyl,
-1+-cycarzenyl, benzyloxycardonyl), t[or unsubstituted carbamoyl group (e.g., carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), substituted or unsubstituted Sulfamoyl group (e.g. sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl, bi-lysinosulfonyl), carboxy group, cyan group, hydroxy group, amine group, acylamino group, more preferably acylamino group with carbon number r or less groups (e.g. acetylamino), alkoxy groups, more preferably alkoxy groups having io or less carbon atoms (e.g. methoxy, ethoxy, benzyloxy), alkylthio groups (e.g. ethylthio), alkylsulfonyl groups (e.g. methylsulfonyl). ), sulfonic acid groups, aryloxy (e.g.
(phenoxy), oryl group (side light, phenyl, tolyl). Further, two of v□ to v8 bonded to adjacent carbon atoms may be bonded to each other to form a condensed ring. For example, fused rings include benzene rings and heterocycles (eg, pyrrole, thiophene, furan, pyridine, imidazole, triazole, thiazole).

(W□)11 is included in the formula to indicate the presence or absence of a cation or anion when necessary to neutralize the ionic charge of the dye. Therefore,
11 can take an appropriate value of 0 or more as necessary. Whether a dye is cationic, anionic, or has no net ionic charge depends on its auxochrome and substituents. The counterion (W, ), can be easily exchanged after the dye is manufactured. Typical cations are inorganic or organic ammonium ions and alkali metal ions; -10,000 anions can be specifically either inorganic or organic anions;
For example, halogen anions (eg, deep purple ions, chloride ions, bromide ions, iodine ions), substituted arylsulfonate ions (eg, tJf, p-), fluorenesulfonate ions, p-ri.

rubenzenesulfonate ion), aryl disulfonate ion (e.g. l,3-benzenedisulfonate ion, /,j-naphthalene disulfonate ion), alkyl sulfate ion (
Examples include methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonate ion. Preferably it is an iodine ion.

Among the red-sensitive sensitizing dyes represented by general formula (II), more preferable red-sensitive sensitizing dyes are represented by the following general formulas (V) and (Vl).

(w2)12 General formula (Vl) In general formula (V), Q3 represents an oxygen atom or a sulfur atom.

L and L7 represent methine groups.

P3 and P4 are synonymous with P□ and P2 in general formula i) 6P3 is connected to L6 and P4 is connected to L7! Alternatively, a t-membered carbon ring may be formed.

■ v 1v, V 1 v13, V14.9
翫 10 11 12V□5 and ■□6 are V□, v2, v3 of general formula (If), respectively
, ■4, ■5, v6, ■7 and v8. Preferably VV%V
, V %V 13 , V r 4.9 10
11 12■ and V□6 are
Hydrogen atom, unsubstituted alkyl group having 6 or less carbon atoms (e.g. methyl, ethyl, n-propyl, isopropyl, n-
Butyl, 1-dothyl, methyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl), carbon a
The following substituted alkyl groups (e.g. carboxymethyl,
- monocarboxyethyl, benzyl, 7-enethyl, dimethylaminopropyl), hydroxy groups, amino groups (e.g. amino, hydroxyamino, methylamino, dimethylamino, diphenylamino), alkoxy groups (e.g.
methoxy, ethoxy, inpropoxy, propoxy, butoxy, pentoxy), aryloxy groups (eg phenoxy) and aryl groups (eg phenyl).

(W2)l has the same meaning as (Wl)11 in general formula (II).

In the general formula (Vl), Q4 represents an oxygen atom or a sulfur atom, and L8, L8, L1G% Lll and L12 have the same meanings as L1, L2, L3, L4 and L5 in the general formula (If).

P5 and P6 have the same meanings as Po and P2 in general formula (II).

v , ■ , ■ , ■ , V2□, ■2□, ■
At least seven pairs of two bonded to adjacent carbon atoms in 23 and v24 are bonded to each other to form a benzene ring or a heterocycle (e.g., pyronyl, thiophene, furan, pyridine, imidazole, triazole, thiazole). Form. These rings may be further substituted. Other (17 to (28) not related to this) have the same meanings as (2) and -v8 in general formula (If).

(W3)13 has the same meaning as (W□)11 in general formula (If).

Specific examples of the dyes used in the present invention, particularly dyes represented by general formulas (II), (Vl and (l), are shown below, but the invention is not limited thereto.

C2H5 C2H5■e (CH2)4SO3゜C2H5 θ HN(C2H5)3 C・H・He 2H5 2H5 (CH2)4CH3 e (II-//) (II-/ko) HN(C2H5)3 CH2C00HC2H3 Ie (CH2) 2NH802CH3c2H5 Engineering (II-/j) Engineering e CTI-/r) (II-/RI) (CH2)4CH3C2H5 Ie (■-KO) (■-Col) (Cll2), 803(:) (CH2) 4803e
Na"' (If-here) (■-23) (If-24A) (I[-27) ■- (II--21 (Ti-30) Knee (II-J/) (■-32) This invention The dye represented by the general formula (II) used in Chapter 27
ON page 217, John Wiley & Sump (J
Ohn Wiley and 5ons) Publishing (19
bu≠year) D, M, Starmer (D, M.

``Heterocyclic Compounds'' in Chart Topics in Heterocyclic Chemistry J.
licCompounds-8special Top
ics 1nHeterocyclic Chem
istry) Chapter 1, sec, ■, μ! 2~jノ! page,
John Wiley Life and Sevens
It can be easily synthesized based on the method described in ``Ey and Sons'' (1977).

In order to incorporate the spectral sensitizing dyes represented by the general formulas (I[), (V) or (■) into the silver halide emulsion of the present invention, they are prepared, pre-ripened, post-ripened etc. It may be added at any stage of emulsion preparation, may be added before or after coating, or may be added in combination with the above-mentioned addition method.

The spectral sensitizing dye used in the present invention can be directly dispersed in an emulsion or a hydrophilic colloid solution. In addition, these are suitable solvents, such as methyl alcohol, ethyl alcohol, flobyl alcohol, methyl cellosolve, JP-A-1996-17734, and US Pat. r30
It can also be added to the emulsion in the form of a solution dissolved in a halogenated alcohol, acetone, water, pyridine, etc., or a mixed solvent thereof, as described in the above. Other addition methods include Special Publication Akihiro T-Cog/rJ-No., U.S. Patent 3.
．． T-co, 13! No., same J, J Otsu 0, 10/No., same co,
R/Co, 3g No. 3, Same Ko, Tata J, Jlr No. 7, Same J
, 1A29.1rjj, same J, tjr.

The method described in Oyugo can be used. It is also possible to use the method described in German Patent Application No. 1017, Cot.3, and the method described in U.S. Pat.

The amount of the sensitizing dye added varies depending on the desired purpose and the effect of the compound, but is 10 to 10@-2 mol per mol of Ag, preferably 1ONIO mol. Further, supersensitization using a combination of dyes can also be carried out as desired.

When the present invention is applied to a photographic material for obtaining black and white prints with good image quality (graininess, tone, whiteness) from a color-developed negative photosensitive material, in addition to the above panchromatic sensitizing dye, orthomatic sensitizing dyes may be used. It is preferable to use a sensitizing dye and, if necessary, a regular sensitizing dye.

Since the color tone of a support having a white reflective layer is severely evaluated, the present invention uses a support having a white reflective layer...The effect is particularly noticeable in silver halide photographic materials. It is.

In the present invention, the support is preferably a water-impermeable support. A water-impermeable support refers to a support to which water does not penetrate at all or only to a limited extent. Examples of such a support include a whitened plastic film prepared by coating a transparent plastic film of cellulose triacetate or polyethylene terephthalate with a white pigment such as titanium white dispersed in pie/goo such as gelatin, or a highly hydrophobic film such as polyethylene. There are paper supports laminated on both sides with molecules.

The silver halide in the silver halide photosensitive material used in the present invention has high solubility in the developer and does not contain any iodine, such as silver chloride, silver chlorobromide, or silver bromide, which progresses quickly in development. In particular, the present invention is directed to an emulsion containing silver chlorobromide or silver bromide having a silver bromide content of not more than 0.1 mol %. is preferred. The average particle size of the silver halide grains is not particularly limited, but it is preferably not larger than μ. Preferably - is lμ to 0. It is between λμ.

The particle size distribution may be broad or narrow. The latter is known as a so-called monodisperse emulsion, and has a dispersion coefficient of 20% or less, more preferably l! ≦ or less is better. (
The dispersion coefficient here represents the standard deviation divided by the average particle size. ) Known silver halide solvents can be used during grain formation.

As the silver halide emulsion, a so-called primitive emulsion which is not chemically sensitized may be used, but it is usually chemically sensitized. For chemical sensitization, sulfur sensitization using compounds such as thiosulfates, thioureas, thiazoles, and rhodanines, and activated gelatin, stannous salts, amines, hydrazines, formamidine sulfinic acid, It can be used alone or in combination with a reduction sensitization method using a silane compound or the like, a noble metal sensitization method using a complex salt of a metal in Group I of the periodic table such as platinum, iridium, palladium, etc. in addition to a total complex salt.

In addition, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, thioether compounds, thiomorpholines, urethane derivatives, urea derivatives, imidazole derivatives,
It may also contain 3-pyrazolidones and the like.

In the present invention, it is advantageous to use gelatin as the binder or protective colloid in the photographic emulsion, but hydrophilic colloids other than gelatin such as dextran, polyacrylamide, polyvinylpyrrolidone, etc. can also be used.

Generally, when forming a silver image on a support having a white reflective layer, a fluorescent whitening agent is sometimes used to increase the whiteness. It has the disadvantage of reduced sensitivity.

However, it has been found that the system using the compound of general formula (I) of the present invention has the unexpected effect of being able to reduce the decrease in sensitivity caused by a fluorescent brightener.

The fluorescent brightener used in the present invention includes Ve
enkataramanWa″The Chemis
Try of 8ynthetic Dyes”
Compounds described in Volume V, Chapter ♂ can be used. More specifically, stilbene-based compounds, coumarin-based compounds, biphenyl-based compounds, benzoxacylyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, carbostyryl-based compounds, etc. may be mentioned, with stilbene-based compounds and coumarin-based compounds being preferred. Examples include compounds.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration,
Various known surfactants may be included for various purposes such as high contrast, sensitization, etc.

Nonionic interfaces such as saponins, polyoxyethylene compounds, glycidol derivatives (e.g., alkenylsuccinic acid polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and urethanes or ethers. Activators; tritylinoid saponins, alkyl cardonates, alkylbenzene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines,
Anionic surfactants such as sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, diamino acids, aminoalkylsulfonic acids,
Ampholytic surfactants such as aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine imides, and amine oxides; Cationic surfactants such as high grade ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. Fluorine-containing surfactants are preferably used for the purpose of preventing static electricity.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, a polymer containing as a monomer component alkyl (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. can be used.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts, aldehydes, N-methylol compounds, active vinyl compounds ('+3,!-triacryloyl-hexahydro-S-triazine, bis(vinylsulfonyl)methyl ether, etc.), active halogen compounds (!,
≠-dichloro-6-hydroxy-8-) IJ azinato), muco-rogenic acids, etc. can be used alone or in combination.

It is extremely preferable to use a conventionally known toning agent in combination with the compound of general formula (I) in the light-sensitive material of the present invention for fine adjustment of color tone. Examples of color toners used in combination include l-phenyl-j-mercaptotetrazoles, ≠-phenyl-3-mercaptotriazoles, Komelkabuto/,
3. Mercapto compounds bonded to a heterocycle such as ≠-thiadiazoles are preferred.

The photosensitive material of the present invention contains water-soluble dyes (such as oxonol dyes, hemioquinol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes) as filter dyes in the hydrophilic colloid layer or for various purposes such as preventing irradiation.

May contain.

The silver halide photographic material of the present invention may contain a known antifoggant or stabilizer. Antifoggants or stabilizers that may be contained include mercapto compounds, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chloropenzimidazoles, bromobenzimidazoles, aminotriazoles, benztriazoles, and nido-0. Benztriazoles, benzenethiosulfones [1, benzenesulfinic acids, benzenesulfonic acid amides, azaindenes [e.g. triazaindenes, tetraazaindenes (especially 4(-hydroxy-substituted
/ + ' + 3'' + 7) Tetraazaindenes)].

For the photographic processing of the light-sensitive material of the present invention, any known development processing method for forming a silver image can be used. A known treatment liquid can be used. The processing temperature is usually chosen between /r''c and to''c, but it may also be below ir'c or above 00C1. Developers used in black-and-white photographic processing can include known developing agents. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. l-phenyl-3-pyrazolidone)
, aminophenols (N-methyl-p-aminephenol), l-phenyl-3-pyrazolines,
ascorbic acid, and as described in U.S. Patent No. D67.172/J, J.

Heterocyclic compounds in which a μm tetrahydroquinoline ring and an intrene ring are condensed can be used alone or in combination. In particular, it is preferable to use pyrazolidones and/or amine phenols together with dihydroxybenzenes. The developer generally contains other known preservatives, alkaline agents, pH buffers, antifoggants, etc., and, if necessary, solubilizers, color toners, development accelerators, surfactants, antifoaming agents, etc. water softener, hardener,
It may also contain a viscosity-imparting agent. The photosensitive material of the present invention is
Usually, sulfite ion as a preservative is used as O0/! mole/1
Processed with a developer containing the above.

Further, a part of the developing agent may be included in the sensitive material.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to this.

Example 1 (1) Preparation of photosensitive silver halide emulsion An aqueous solution consisting of potassium bromide and sodium chloride was added to an aqueous silver nitrate solution and an aqueous gelatin solution in an acidic state (pH=1) by the double jet method with vigorous stirring, and the average particle o
A cubic monodisperse emulsion (silver bromide 50 mol %, dispersion coefficient/Hiro %) of 4 Iμ was prepared. After that, it is washed with water by the usual precipitation method, and then sulfur sensitized to form a photosensitive silver chlorobromide emulsion λ.
I got it.

(2) Preparation of coating sample Paper support laminated on both sides with polyethylene (thickness 20
Samples l to f were prepared by sequentially applying each layer of the following formulation on the substrate (0μ) from the support side.

(Emulsion layer) Binder: Gelatin, 'yf/m2 coating silver amount: /, zt/m2 Sensitizing dye:
Listed in Table 1 Coating aid Sodium Nidodecylbenzenesulfonate 7~/m2 Fluorescent whitening agent: o, if/m2 NH Polymer latex: Polyethyl acrylate Cot/m2 Color preparation: Listed in Table 1 (Surface protection layer) ノζinder: gelatin ko, 0? /m coating aid sodium nidodecylbenzenesulfonate to ■/m2 colloidal silica (average o,.

! μ) o, 3t 7m 2 hardener:
l-dichloro-≦ monohydroxy/,! ,! -1 Reazin natrirum salt o, ory7'm2 (3) Evaluation of coated samples After coating these samples at a temperature and humidity of 5i0ctt%RH 7
Stored for days. Each sample was evaluated by the following method. The results of photographic properties are shown in Table 1.

(A) Sensitivity evaluation Each sample was passed through a continuous wedge and the color temperature
After exposure to K, 1700 lux tungsten light for 7 seconds, use Fuji 7 with Pitol developer (manufactured by Fuji Photo Film).
Using a developer diluted with water to /:/, develop at 2o 0C for 0 seconds, stop, and then use Fuji Fix (manufactured by Fuji Photo Film ■)! After fixing for minutes, washing with water, and drying, the photographic sensitivity of each sample was evaluated using the same method using the exposure amount that gave a constant density (optical density of 0.4) higher than the fog density.

(B) Evaluation of whiteness Each sample was mixed with Fuji Babitol developer (Fuji Photo Film f
R) at 200C for 90 seconds, stopping, fixing, washing with water, drying, and evaluating the whiteness.

(C) Evaluation of color tone Exposure, development, stopping, and
After fixing, washing with water and drying, the color tone was evaluated.

(D) Grain evaluation suite t'e-HR, aOO (manufactured by Fuji Photo Film ■) These coated samples were printed through a color negative image obtained by subjecting a color negative photosensitive material to color negative processing, and then developed with Fuji Pavitol. Liquid (manufactured by Fuji Photo Film)
Using the present liquid diluted with water to
Develop for seconds, stop, and then use Fuji Fix (manufactured by Fuji Photo Film)! The graininess was evaluated by fixing for a minute, washing with water, and drying.

○: Practically acceptable range.

×: In a range that poses a practical problem.

From the results shown in Table 1, it is clearly seen that Samples 7 to 1 of the present invention have high sensitivity and good image quality (whiteness, color tone, graininess).

Example 2 Using the same emulsion A as in Example 1, Samples/~Sample 7μ of the following formulations were prepared in the same manner as in Example/.

(Emulsion layer) Binder: Gelatin ≠, 7? /rn2 Coating amount of silver: /, jf/m2 Sensitizing dye: Listed in Table 2 Coating aid Sodium nidodecylbenzenesulfonate 7/m2 Fluorescent brightener: 01lf/m2 Polymer latex: Polyethyl acrylate cot /m2 + Color toning agent: those listed in Table λ and t (surface protective layer) rl Binder: gelatin, Ot/m2 Coating aid: dodecylbenze, but sulfonic acid 1 thorium
to■/m2 Colloidal silica (average o,.

jμ) o, 3t7m2 Hardener: ≠-dichloro A-hydroxy/, J, s-t 1 riazine sodium sea urchin salt. , 0197m'' Similar to Example 1, (A) sensitivity, (B) whiteness, (C)
Color tone and (D) graininess were evaluated. Furthermore, (E) stability over time was evaluated by the following method. The results are shown in Table 2.

(E) Evaluation of stability over time Two sets of each sample were prepared, one set was ao”cr.

It was aged for 3 days at a temperature and humidity of %RH (A). Well...the other 7 sets were sealed and stored in the refrigerator (mouth).

Three days later, (A) and (-) were exposed to light in the same manner as in (A), developed, stopped, fixed, washed with water, and dried, and the sensitivity difference between (A) and (B) was determined [each fog density] The difference in the logarithm of the exposure amount that gives a higher constant density (optical density of 0.4) was determined and evaluated.

From the results shown in Table 2, the sample of the present invention! It can be seen that sample Iu has high sensitivity and good image quality (whiteness, color tone, graininess). Furthermore, it can be seen that Samples 7 to ≠ using more preferable panchromatic sensitizing dyes also have excellent stability over time.

X-/X-2 Patent applicant Fuji Photo Film Co., Ltd. Showa t3 J/F/D

Claims (2)

[Claims] (1) In a black-and-white photographic material for observing a silver image having at least one photosensitive silver halide emulsion layer on a support, at least one of the constituent layers of the photographic material has the following general formula (I). 1. A silver halide photographic light-sensitive material containing at least one compound represented by the following formula, and further comprising silver halide grains in the emulsion layer color-sensitized with a panchromatic sensitizing dye. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X^1 represents a divalent linking group bonded to a carbon atom via a hetero atom, represents a group that adjusts the color tone of a silver image bonded to X^1, R^1, R^2 and R^3 represent a hydrogen atom or a substitutable group, and R^1, R^2 and R^2 and R^3 may be combined to form a carbocycle or a heterocycle. Y is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas ,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, cyano group, or nitro group (where R^4, R^5, R^6, R^7 and R^8 represent a hydrogen atom or a substitutable group) ), and n and m represent 0 or 1. However, when m=0, the group represented by A is bonded to the carbon atom via the heteroatom of A. (2) The panchromatic sensitizing dye has the following general formula (II)
The silver halide photographic light-sensitive material according to claim 1, which is selected from the group of compounds represented by the following. General formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, Q_1 represents a nitrogen atom, oxygen atom, sulfur atom, or selenium atom, and Q_2 represents an oxygen atom, sulfur atom, or selenium atom. L_1, L_2, L_3, L_4 and L_5 represent methine groups. This methine group may be substituted or may form a ring with another methine group. P_1 and P_2 represent alkyl groups which may be the same or different. Further, P_1, L_1 and P_2 may be linked to L_5 to form a 5- or 6-membered carbon ring. V_1, V_2, V_3, V_4, V_5, V_6, V
_7 and V_8 are a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a carboxy group, a cyano group, a hydroxy group, an amino group, an acylamino group, an alkoxy group, an alkylthio group, respectively. group, an alkylsulfonyl group, a sulfonic acid group, an aryloxy group, or an aryl group, or two of V_1 to V_8 bonded to adjacent carbon atoms may form a fused ring with each other. (W_1)_l__1 represents a charge-balanced counterion, l
_1 represents a value necessary to neutralize charges of 0 or more.