JPH0248652A - Photographic sensitive silver halide emulsion - Google Patents

Abstract

PURPOSE:To increase the sensitivity of an emulsion to exposure with He-Ne laser by incorporating a specified hypercolor sensitizer and a spectral sensitizing dye. CONSTITUTION:The title emulsion contains a compd. (A) or a salt thereof and a spectral sensitizing dye. The compd. A renders <=1.0X10<5> molecular extinction coefft. at 624nm to an aq. soln. prepd. by mixing 2ml. soln. contg. 4.0X10<-4>mol/l anhydro-5, 5'-dichloro-9-ethyl-3, 3'-bis (3-sulfopropyl) thiaca rbocyanine hydroxide.pyridinium salt with 1ml aq. soln. contg. 1.0X10<-1>mol/l KCl, adding 4ml aq. soln. contg. 8.0X10<-2>mol/l of the compd. A to the mixed soln. and diluting them with water to 10ml in total. A compd. represented by the formula may be used as the compd. A.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to silver halide photographic emulsions with improved sensitivity and methods for increasing the sensitivity of silver halide photographic emulsions.

``Prior Art'' In the field of technology for producing photographic emulsions, there is a strong desire to develop a technology that suppresses the occurrence of fog and further improves the sensitivity of emulsions. Regarding factors governing photographic sensitivity, Jou
T, Tan published in rnal of Imaging Science, Kota Volume, No. 3, 23-Tatabeji
Paper by 1 [Analysis of Factors
Influencing Photography
c8sensitivityj. Among these, the technique of increasing the efficiency of spectral sensitization, that is, superchromatic sensitization, is one of the most important techniques for increasing the sensitivity of photographic emulsions. Regarding supersensitization, see “The Theory of the Photographer” edited by T. H. James.
aphic ProcessJ (μth edition, Macmi
llan, New York, /ri77) 1st O
Chapters (co-authored by W. West and P. B. Gi1man). Among them, emphasis is placed on hole capture type supersensitization and exciton capture type supersensitization.

Many of the cyanine dyes widely used as sensitizing dyes form J-aggregates in photographic emulsions, but when the J-aggregates grow too large, the efficiency of spectral sensitization decreases. This is because if the aggregate is large, excitons (dye molecules in an excited state) simply move around quickly within the aggregate, making it difficult to inject electrons into the silver halide and cause spectral sensitization. It's for a reason. In such cases, when the aggregate is divided into smaller pieces, excitons are captured at the ends of the aggregate, and electrons can be easily injected from the excitons into the halogen compound, increasing the efficiency of spectral sensitization. I can't stand it. The above-mentioned supersensitization is called exciton capture type supersensitization, and the +S ability required of the supersensitizer is to be reduced by dividing it on the aggregate of the sensitizing dye.

[Problem to be Solved by the Invention] Other sensitizing dyes, antifoggants, stabilizers, and the like are known as compounds that can split the J-aggregate of sensitizing dyes. However, other sensitizing dyes are often unusable because they lack the ability to resolve aggregates or have sensitivity delayed to undesirable wavelength ranges. In addition, antifoggants and stabilizers often lack the ability to split the J-aggregates of sensitizing dyes or cause undesirable photographic effects such as inhibition of development, so they are often unusable.

1. Means for Solving the Problems However, when the present inventors added a compound satisfying the following conditions to the emulsion as a supersensitizer, the ability to split the J-aggregate of the sensitizing dye was sufficiently high. We have found that the efficiency of spectral sensitization can be improved to significantly increase sensitivity without the above photographically undesirable side effects.

That is, the present invention is a silver halide photographic emulsion containing at least one compound or a salt thereof satisfying the following conditions and a spectral sensitizing dye.

Conditions/: Anhydro-j+j'-cyclorotaethyl-j
, ≠ of 3'-bis(3-sulfovir)theacarbocyanine hydroxide pyridinium salt.

OX/0-'mol/ft water frj liquid λ shoulder j and potassium chloride l.

A 1 mol/2 aqueous solution of OX/O-2 is mixed with a 1 mol/2 aqueous solution of OX/O-1, and to this mixed solution, the compound ♂ and an aqueous solution of 10-2 mol/2 OX are added and diluted with water to give a total amount of 10 g.

The molecular extinction coefficient at A2llnm of this aqueous solution is i,
Must be oxio5 or lower.

In the light of conventional knowledge, such a compound'mt
What happened was completely unexpected and surprising.

In addition, the efficiency of spectral sensitization is 19≠ according to the Jou printed in 2010.
rnal of Physical and Co
J, 5pence and B,) i, ear published in volume 52 of lloiCo11oidChe magazine, page 1oto
It can be measured according to Tadaaki Tani and Hitoshi Tobe's paper published in Volume 7, page 3λ of the Journal of the Photographic Society of Japan, published in 2010.

Although there is a wide range of compounds that satisfy the condition 1 of the present invention, cyclic compounds are preferable, and the following general formula (1), general formula (IN
, general formula CIIN], or general formula (IV), or a Vi- to μ-cyclic heterocyclic compound, all of which have a molecular weight of tOO or less, but particularly 2- to μ-ring heterocyclic compounds are most preferred.

General formula [1] where k and R%l ( may be the same or different, hydrogen atom, halogen atom, -0M(M) hydrogen atom or monovalent gold fA (e.g. Na, K, Li)), a substituted or unsubstituted alkyl group, an unsubstituted or unsubstituted aryl group, a substituted or Fi unsubstituted alkoxy group, a substituted or unsubstituted alkoxy group, an unsubstituted ami7 group, a sulfo group , fit-substituted or unsubstituted 7-aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted aminothiocarbonylthio group.

The alkyl group in % preferably has 20 or less carbon atoms, for example, methyl group, ethyl group, λ-hydroxyethyl group, cordiethylaminoethyl group, propyl group, isopropyl group, 3-dimethylami/propyl group, methyl group , an isopentyl group, a hexyl group, a heptyl group, a heptyl group, a benzyl group, an octadecyl group, and the like. The alkoxy group preferably has a carbon number of 20 or less, and includes, for example, a methoxy group, an ethoxy group, a propyloxyl group, a butoxy group, an octadecyloxy group, and the like. The @-substituted amino group preferably has a carbon number of λ or less, such as a dimethylamino group, a diethylamino group, a hydroxyamino group, a --human mixyethylamino group, a cosulfoethylamino group, a cordiethylaminoethylamino group, an anilino group, Examples include β-su7tylamino group. The aryloxy group preferably has 20 or less carbon atoms, and includes, for example, a phenoxy group, a ≠-sulfophenoxy group, and a β-naphthyloxy group.

The alkylthio group preferably has a carbon number of 20 or less, such as a methylthio group, an ethylthio group, a cohydroxyethylthio group, a codiethylaminoethylthio group,
Examples include dodecylthio group. The arylthio group preferably has 20 or less carbon atoms, and includes, for example, a phenylthio group, a β-su7tilteo group, a Hiro-sulfophenylthio group, and the like. i! The substituted aminothiocarbonylthio group preferably has a carbon number lj or less, and examples thereof include a dimethylaminothiocarbonylthio group, a diethylaminothiocarbonylthio group, and a phenylaminothiocarbonylthio group.

General Formula (It) A+L Layer B Here, A and BFi may be the same or different and represent an ft-substituted or unsubstituted hetea-ring residue. L is a covalent linking group'! ! I-Represent. n represents Q or /.

The heterocyclic residue represented by A%B is preferably a j-membered, 6-membered, or #'i7-membered ring, and may be a condensed ring formed by these rings. Further, the substituent may be placed above.

The linking group represented by L is an aliphatic or aromatic divalent organic residue which may have a substituent, or an oxygen atom,
A sulfur atom or a selenium atom is preferred.

Examples of the heterocyclic residue represented by A include furyl group,
thienyl group, biOlyl group, triazinyl group, triazolyl group, imidazolyl group, pyridyl group, pyrimidinyl group,
Pyrazinyl group, quinazolinyl group, purinyl group, quinolinyl group, acridinyl group, indolyl group, thiazolyl group,
Examples include oxasilyl group and 7-lazanyl group.

Examples of the organic residue of the linking group represented by L include methylene group, ethylene group, phenylene group, buOpyrene group, /-
Examples thereof include oxocarbonyl-/, 3-dyne group, p-xylene-α, α'-diyl group, ethylenedioxy group, succinyl group, malonyl group, and the like.

General formula CIn) where R11 12, 13, R, 14, 15, 1
6几17 and 几18 may be the same or different.

Hydrogen atom, halogen atom, -(JM (M represents a hydrogen atom or a monovalent metal (for example, Na, %L)), or unsubstituted alkyl group, 11-substituted or unsubstituted aryl group, rt-substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, cyano group, Nido 03
% Sulfo group, carboxyl group, substituted or unsubstituted aryloxy group, unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted acyl group, substituted or unsubstituted represents an aminosulfonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted aminocarbonyl group.

The alkyl group preferably has 20 or less carbon atoms, such as methyl group, ethyl group, λ-hydroxyethyl group, λ-diethylaminoethyl group, propyl group, isopropyl group, 3-dimethylaminoyl group, pentyl group, etc. group, impentyl group, hexyl group, cyclohexyl group, heptyl group, benzyl group, octadecyl group, etc. There are as many carbon atoms as an aryl group! The following are preferred, such as phenyl group, tolyl group, sulfophenyl group,
Examples include carboxyphenyl group, naphthyl group, and sulfonaphthyl group. The alkoxy group preferably has less than 0 carbon atoms, such as a methoxy group, an ethoxy group,
Examples include a butyloxy group, a butoxy group, an octadecyloxy group, and the like. The number of carbon atoms for the substituted amino group is 20
The following are preferred, such as dimethylamino group, diethylamino group, hydroxyamino group, 2-hydroxyethylamino group, -mono-sulfoetheramino group, Kodi-modified tylaminoethylamino group, anilino group, β-naphthylamino group, etc. can be mentioned. The aryloxy group preferably has a carbon number of −θ or less, such as a phenoxy group,
Examples include Hiro-sulfophenoxy group and β-naphthyloxy group. The alkylthio group preferably has 20 or less carbon atoms, such as methylthio group, ethylthio group,
Examples include a cohydroxyethylthio group, a codiethylaminoethylthio group, and a dodecylthio group. The ruthio group preferably has a carbon number of 0 or less, such as a phenylthio group, a β-naphthylthio group, a μm sulfophenylthio group, and the like. The acyl group preferably has 20 or less carbon atoms, and examples thereof include an acetyl group, a propionyl group, a butyryl group, a stearyl group, a benzoyl group, and the like. rjIr, the substituted aminosulfonyl group preferably has less than 0 carbon atoms, such as diethylaminosulfonyl group, di(2-hydroxyethyl)aminosulfonyl group, anilinosulfonyl M, 2-sulfoethylami/carbonyl group, dodecylaminosulfonyl group Examples include groups. As an alkoxycarbonyl group, the number of carbon atoms is -
It is preferably 0 or less, and examples thereof include methoxycarbonyl group, ethoxycarbonyl group, methoxyethoxycarbonyl group, diethylaminoethoxycarbonyl group, and benzyloxycarbonyl group. The aryloxycarbonyl group preferably has a carbon number of λO or less, and examples thereof include a phenoxycarbonyl group, a Hiro-sulfophenyloxycarbonyl group, and a tolyloxycarbonyl group. [8Aminocarbonyl group preferably has carbon atoms of -θ or less, dimethylaminocarbonyl group, diethylaminocarbonyl group, butylaminocarbonyl group,
Examples include octadecylaminocarbonyl group and λ-sulfoethylaminocarbonyl group.

Here, 几21. B22 B23, R24, B25
, 几261(,27, and H,28 may be the same or different, hydrogen atom, halogen atom, -0M (M
is a hydrogen atom or a monovalent metal (e.g. Na, Li
) i represents. ), substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, direct substituted or unsubstituted alkoxy group, substituted or unsubstituted amine group, mercapto group, cya/group, nitro group, sulfonate group. group, carboxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, lit or unsubstituted acyl group, substituted or unsubstituted aminosulfonyl group , +!! represents a substituted or unsubstituted ami7carbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted aminocarbonyl group.

Also, B21 and B 22, R22 and B 23, R23 and B 24, 几24 and B25, B25 and B 26, B2
6 and R27, or R28 and R28 may form a substituted or unsubstituted fused benzene ring.

In particular, the alkyl group preferably has 20 or fewer carbon atoms, such as methyl group, ethyl group, cohydeoxyethyl group, codiethylaminoethyl group, propyl group, isopropyl group, 3-dimethylamitube avir group, benzalyl group, Examples include pentyl group, hexyl group, cyclohexyl group, heptyl group, pencil group, and octadecyl group. The aryl group preferably has a carbon number/J'' or less, and examples thereof include phenyl group, tolyl group, sulfophenyl group, carboxyphenyl group, naphthyl group, and sulfonaphthyl group.Alkoxy As a base, the number of carbon atoms is 2
It is preferably 0 or less, and examples thereof include methoxy group, ethoxy group, propyloxy group, butoxy group, octadecyloxy group, and the like. Substituted amino group has 2 carbon atoms
0 or less are preferred, such as 7 dimethylamino groups, diethylamino groups, hydroxyamino groups, etc. Examples include -human oxyethylamino crystal, λ-sulfoethylamino group, cordiethylaminoethylamino group, anilino group, and β-7teramino group. The aryloxy group preferably has 20 or less carbon atoms, and examples include evaphenoxy group, ≠-sulfophenoxy group, and β-naphthyloxy group. As an alkylthio group, the number of carbon atoms is 2.
It is preferably 0 or less, and includes, for example, a methylthio group, an ethylthio group, a 2-hydroxyethylthio group, a 2-diethylaminoethylthio group, a dodecylthio group, and the like.

The arylthio group preferably has carbon 11,120 or less, such as phenylthio group, β-naphthylthio group,
Examples include Hiro-sulfophenylthio group. The acyl group preferably has 20 or less carbon atoms, and includes an acetyl group, a butyryl group, a butyryl group, a stearoyl group, a benzoyl group, and the like. The substituted ami/sulfonyl group preferably has carbon atoms of 2θ or less, such as diethylaminosulfonyl group, di(,2-hydroxyethyl)aminosulfonyl group, anilinosulfonyl group, λ-sulfoethylami7carponyl group, dodecylami/sulfonyl group Examples include. The alkoxycarbonyl group preferably has a carbon number of 2θ or less, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a methoxyethoxycarbonyl group, a diethylaminoethoxycarbonyl group, and a benzyloxycarbonyl group. The aryloxycarbonyl group preferably has 20 or less carbon atoms, such as phenoxycarbonyl group, ≠-sulfophenyloxycarbonyl group, tolyloxycarbonyl group, and the like. The hjm aminocarbonyl group preferably has 20 or less carbon atoms, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a propylaminocarbonyl group, an octadecylaminocarbonyl group, a cosulfoethylaminocarbonyl group, and the like.

Compounds satisfying the conditions/all may also be in the form of inorganic or organic acid salts. Preferred examples of inorganic or organic acids include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, hydroiodic acid, perchloric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc. can be mentioned.

Furthermore, the molecule t of the compound that satisfies the conditions/total grooves is preferably 600 or less, more preferably 300 or less.

Specific examples of compounds of the present invention that satisfy condition 1 are shown below, but the present invention is not limited to these compounds.

(riH2N)i((,:)12)2(JH Table 1 shows the molecular extinction coefficients at 62 μn of the aqueous solutions of the compounds shown in these specific examples obtained according to the conditions/procedure. show.

Table 1 As shown, an aqueous solution of any compound has a molecular extinction coefficient of 7.
0x/θ5 or less, and the molecular weight of any compound is j
It is below OO.

There are many compounds that are commercially available or can be easily derived from commercially available products, such as the compounds shown in the specific examples described in "Heterocyclic Comparins-8-Triazine and Derivative “
Interscience Publishing (/Rijri Annual) (8mol
in andRapoport,')1eteroc
yclic Compounds-8-'I'riaz
ine and Derivatives”Int.
erscience Publishers (/ri!ri). ), Temple's 1 Heterocyclic Conno (unzutriazol/, 2.l/L", John Willie and Fists (/rit/annual) ('l'em
p 1 e.

”) leterocyclic compounds
Triazine/ , , 2s 44',
Joho W eyes & 5ons (/ri♂/). ),
Hoffmann's ``Heterocyclic Connovation'' imidasols and derivatives 1. Interscience Publishing (/3 years) ()lofmann, @)lete
rocyclic Compounds-Imidaz
"Ole and Derivatives" (llij3).), Metzger 6 Hete O Cyclic Compounds Thiazoles and Their Conductors", John Wiley & Sons
ger, “Heterocyclic Compound
s'l'biazo1e and ItsDe
rivetives', John Wile
y & 5oz (/9'72). ) and Klinsberg, ``1 Hete a Cyclic Compound - Pyridine and 4 Bodies'', published by Interscience Publishing (/ 1940) (Klinsberg, ``Heierocyc
licCompounds-Pyridine an
dDerivatives” Interscie
ncePublishers (/ri60). ), etc., and some of them are commercially available.

Preferred examples of the 2-μ ring heterocycle include benzothiazole, benzoxazole, benzimidazole,
Penzotellazole, benzimidazole, indole, isoindole, indolenine, indoline, indazole, chromene, chroman, isochroman, qui/phosphorus, isoquinoline, quinolidine, cinnoline, phthalazine, quinazoline, quinoxaline, na7tisazi7, purine,
pteridine, indolizine, benzofuran, isobenzofuran, benzothiophene, ben/pyran, benzazepine, benzoxazine, cyclopentapyran, cycloheptaisoxazole, benzothiazepine, virazolotriazole, tetraazaindene, naphthothiazole, naphthoxazole, Naphthoselenazole, naphthotellazole, naphthoimidazole, carbazole, xanthine, 7-enanthrizine, acridine, perimidine,
Fenanto-O-phosphorus, thianthrene, phenoxathiin,
Phenoxazine, phenothiazine, phenazine, and these heterocycles are further combined with cyclic hydrocarbons such as benzene and naphthalene, furan, thiophene, virole, pyran, thiopyran, pyridine, oxazole, isoxazole,
Preferably, the compound is fused with a heterocycle such as thiazole, inthiazole, imidazole, pyrazole, pyrazine, pyrimidine, or pyridazine to form a nine-polycyclic compound.

In the present invention, those having a petro ring as shown below are particularly preferred.

Further, these polycyclic compounds may have a substituent, and preferred substituents are halogen atoms, -
(JM (M is a hydrogen atom or a monovalent metal (e.g. Na
, K, L i ). ), substitution or a
t-substituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or Vi-free
l'amino group, cyano group, nitro group, sulfo group, carboxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted tIL￥18 furkylthio group, substituted or unsubstituted ruthio group, substituted' Alternatively, examples thereof include an unsubstituted acyl group, a substituted or unsubstituted aminesulfonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, and a II-substituted or unsubstituted ami7carbonyl group.

In particular, the alkyl group preferably has 20 or fewer carbon atoms; for example, a methyl group, an ethyl group, a cohydroxyethyl group, a -diethylaminoethyl group, a propyl group, an isoprobyl group, a 3-dimethylaminobutyl group, and a methyl group. Examples of the group and iso include methyl group, hexyl group, cyclohexyl group, heptyl group, benzyl group, and octadecyl group. The aryl group preferably has carbon number/j or less, such as phenyl group, tolyl group, sulfophenyl group,
Examples include carboxyphenyl group, naphthyl group, and sulfonaphthyl group. The alkoxy group preferably has 20 or less carbon atoms, such as a methoxy group, an ethoxy group,
Examples include a pyloxy group, a butoxy group, an octadecyloxy group, and the like. The substituted amino group preferably has less than 0 carbon atoms, such as dimethylamino group, diethylamide 7 group, hydroxyamino group, --hydroxyethylamino group, λ-sulfoethylamino group, cordiethylaminoethylamino group, anilino group. , β-naphthylamide 7 groups, and the like. The aryloxy group preferably has 20 or less carbon atoms, and includes, for example, a phenoxy group, a Hiro-sulfophenoxy group, and a β-naphthyloxy group. The alkylthio group preferably has 20 or less carbon atoms, such as methylthio group, ethylthio group,
2-hydroxyethylthio group, λ-diethylaminoethylthio group, dodecylthio group, cosulfoethylthio group,
3-sulfopropylthio group, Hiro-sulfobutylthio group,
Examples include. Arylthio group has 20 carbon atoms
The following are preferable, and examples thereof include phenylthio group, β-naphthylthio group, and ≠-sulfophenylthio group. The acyl group preferably has 20 or less carbon atoms, and examples thereof include an acetyl group, a propionyl group, a butyryl group, a stearyl group, a benzoyl group, and the like. The substituted aminosulfonyl group preferably has 20 or less carbon atoms, and examples thereof include diethylaminosulfonyl group, di(2-hydroxyethyl)aminosulfonyl group, anilinosulfonyl group, cosulfoethylamide/carbonyl group, dodecylamide/sulfonyl group, and the like. I get vignetted. The alkoxycarbonyl group preferably has 20 or less carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a methoxyethoxycarbonyl group, a diethylaminoethoxycarbonyl group,
Examples include benzyloxycarbonyl group. The aryloxycarbonyl group preferably has a carbon number of 2θ or less, and includes, for example, a phenoxycarbonyl group, a ≠-sulfophenyloxycarbonyl group, and a tolyloxycarbonyl group. The substituted aminocarbonyl group preferably has carbon B, 2o or less, and includes dimethylaminocarbonyl group, diethylaminocarbonyl group, propylamine/carbonyl group, octadecylaminocarbonyl group,
Examples include cosulfoethylamino carbonyl group.

Further, the polycyclic compound may be in the form of an inorganic or organic acid salt. Preferred examples of inorganic or organic acids include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, hydroiodic acid, perchloric acid, oxalic acid, p-++-luenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc. can be mentioned.

Specific examples of the compounds of the present invention are shown below, but the present invention is not limited to these compounds.

-43゜When measuring the molecular extinction coefficient at &, 2≠nm of an aqueous solution of the compounds shown in these specific examples obtained according to the procedure under conditions/, all of them are O, and the molecular weight of all the compounds is 600 or less. .

In addition, uninvented compounds include, for example, Messenger hete a cyclic compound theazole and its derivatives 1. John Wiley & Sons (Metzger) letterocyclic
Compounds-Thiazoleand Its
1) eratives', John VV
Condensed Pyridazine Containing Ginoline and Phthalazine John Wiley
& Sons (published in 1973) (Castle, ”
)ieterocyclic Compounds-Co
ndensed PyridazinesInclu
ding C1nnolines and Phth
alazines', John Wiley &3
ons (/ri73),) and Botutsu lW1 Comprehensive Heterocyclic Chemistry [Vol.'
, a-Gammon Press <ivy≠ annual publication) (Potts
,”ComprehensiveHeterocycle
ic Chemistry vol,t'Per
It can be easily synthesized by the method described in gamon Press (/ri♂4'), ).

The compound or compound satisfying the conditions used in the present invention is preferably contained in an amount of 10@-4 to 10@-1 mole per mole of silver halide. Further, it is preferable to add it to the silver halide emulsion before adding the fractional sensitizing color X't IIN.

As the spectral sensitizing dye used in the present invention, compounds represented by the general formula [V] shown below are preferred. This will be explained below.

General formula (1 In the formula, YB2 and Y32#-t represent a sulfur atom and a selenium atom +-, respectively. (However, Y31% and Y32 are both selenium atoms at the same time.) R31 and 32 are lower alkyl groups (for example, methyl groups) , ethyl group, propyl group, butyl group, etc.), alkyl groups having a sulfo group (e.g. β-sulfoethyl group, r-sulfobutyl group, γ-sulfophthyl group, δ-sulfoptyl group,
represents a sulfoalkoxyalkyl group (eg, sulfoethoxyethyl group, sulfopropoxyethyl group), etc.

``33 represents a lower alkyl group (eg, ethyl group, propyl group).

A, BVi naphthothiazole ring, benzothiazole ring,
Represents a group of nonmetallic atoms necessary to form a naphthoselenazole ring or a benzoselenazole ring. These rings each contain a lower alkyl group (e.g. ethyl group, methyl group, etc.) or an alkoxy group (e.g. methoxy group, ethoxy group, etc.)
, a human mixyl group (Shioshi's phenyl group), an alkoxycarbonyl group (Shioshi IJ's methoxycarbonyl &), a halogen atom (for example, a chlorine atom, a bromine atom, etc.), and a hydrogen atom. Furthermore, lower alkyl groups include cases where they are 11-substituted.

Examples of the naphthothiazole ring, benzothiazole ring, naphthoselenazole ring, and benzoselenazole ring completed by a nonmetallic atom group that replaces these substituents with fl are α-naphthothiazole, β-naphthothiazole, β, β-naphthothiazole, Thiazole, benzothiazole! -Methylbenzothiazole,! -chlorobenzothiazole, j-methoxybenzothiazole,! -bromobenzothiazole,! ,6
-Simethylbenzothiazole,! -cyanobenzothiazole, j-phenylbenzothiazole, j-human Oxybenzothiazole,! -Hydroxy-6-methylbenzothiazole, j-ethoxy-6-methylbenzothiazole, j-ethoxy-6-methylbenzothiazole,!
-Ethoxy-6-methylbenzothiazole, j-hydroxypenzothiazole, α-naphthoselenazole, β
-naphthoselenazole, β, β-naphthoselenazole,
Benzoselenazole! -methylbenzoselenazole,
! -riOroben°Selenazole,! -Methoxybenzoselenazole, j-phenyl-benzoselenazole,!
, 6-dimethylbenzoselenazole, and hydroxybenzoselenazole.

X is an anion C example commonly used in cyanine dyes, t
Haha Q ')' ion, benzenesulfonate ion,
p-Toluenesulfonic acid ion, etc.

m stands for O, and when it is an inner salt, m=o'(+
-Represent.

Next, specific examples of sensitizing dyes represented by the general formula [V] are shown in Table 2.
It is not limited only to these.

The sensitizing dyes used in the silver halide photographic material of the present invention are disclosed in U.S. Pat.
If you refer to the specification of the issue, Tokuko Sho ≠ 0-23 ≠,
It can be easily synthesized by related engineers.

In the photographic emulsion of the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used.

The silver halide grains in the photographic emulsion may be so-called regular grains having regular crystal structures such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical shapes. Crystal defects such as twin planes ff: having
Tabular grains or their composite form may be used.

The tabular grain aspect ratio is given by the ratio of the average diameter of a circle having an area equal to the projected area of each tabular grain to the average thickness of each tabular grain. In the present invention, the preferred grain form in the case of tabular grains is an aspect ratio of J to less than IO, more preferably j to less than IO. Further, the thickness of the particles is preferably 0.3μ or less, particularly preferably 0.2μ or less.

The tabular grains are preferably present in an amount of 10% by weight of the total grains, more preferably 0% by weight or more.

The grain size of the silver halide may be a monodisperse emulsion with a narrow distribution, or a polydisperse emulsion with a wide distribution.

The halide photographic emulsion that can be used in the present invention can be produced by a known method, such as Re5earchLlisclo
sure116/ 76173 (/271/February)
, pp. 2.2-23, “■, Emulsion production (Emulsion
preparation and types)'
It is possible to follow the method described in the same publication, /%/za 7/6 (/17/17), page 1.

The photographic emulsion used in the present invention is the one described in "Chemistry and Physics of Photography" by Graf Kide, published by Paul Montell (P.
kids, Chimie et Physiqu
ePhotographique Paul Mont
el, /ri67), "Photographic Emulsion Chemistry" by Duffin,
Published by Focal Press (G, F, Duffin.

Photographic Emulsion Ch
emistry(Focal Press, /riA
A), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelikman
et al, Makingand Coati
ng Photographic Emulsion
.

Focal Press, / 9 A II) using the method described in v! 41A.

During the formation of silver halide grains used in the present invention, halogen-related solvents such as ammonia, Odankali, rhodanammonium, and thioether compounds (for example, U.S. Pat. No. 3,27/, 13
No. 7, No. 3. ! 741゜i,, No. 2, f53.7
01A, No. 130, No. 1 Hiroshi.

λ71μ32, same ≠, 27t, 374, etc.)
, thione compounds (for example, JP-A-33-/'I-μ).

3) No. 2, No. 33-12. '1-01, same number j-
77,737, etc.), amine compounds (e.g., JP-A No. 3
≠-100, 7/7, etc.) can be used.

In the present invention, a water-soluble O dihydrium salt or a water-soluble iridium salt can be used.

In the present invention, the soluble salt and the soluble halogen salt may be reacted by any one-sided mixing method, simultaneous mixing method, or a combination thereof.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method of keeping pAgt' constant in the liquid phase in which silver halide is produced, that is, the so-called Chondrald double jet method, can be used. According to this method, the crystal form is regular and A halogen ratio emulsion with near uniform grain size is provided.

The halogen ratio emulsion used in the method of the invention is preferably chemically sensitized.

In the case of chemical sensitization, ordinary sulfur sensitization, reduction sensitization, noble metal sensitization, and combinations thereof are used.

More specific chemical sensitizers include Allyl thiocarbamide,
Sulfur sensitizers such as thiourine, thiosulfate, thioether and cystine; Botashiwamuku 00 oleate, auras, thiosulfate and potassium chloride (Potassium chlor).

Examples include noble metal sensitizers such as tin chloride, reduction sensitizers such as phenylhydrazine, and reductone.

The silver halide emulsion used in the present invention is spectrally sensitized with a known spectral sensitizing dye, if necessary. The spectral sensitized color chart used is, for example, Hamer, 'Heterocyclic Compounds of Cyanine Soybeans and Related Compounds', John Wiley & Sons (published in 6≠) (F, M ,Ha
mer.

“Heterocyc Iic Compound
s-TheCyanine Dyes and R
John Wi
ley & 5ons (15;' An, Starmer, 1 Heterocyclic Compounders) Swiss Topics in Heterocyclic Chemistry John Wiley & Sons (1977) (D, M, 8turmer, @)ieter
cyclic compounds & special
Topics 1n) 1eterocyclic
Chemistry', John Wiey &
Cyanine, merocyanine, rhodacyanine, styryl, hemicyanine, oxonol, benzylidene, holopolar, etc., described in 5ons (/ri77), etc.
Although cyanine and merocyanine are preferable.

Examples of sensitizing dyes that can be preferably used in the present invention include JP-A No. 1sO-/33≠≠2, JP-A No. 6/-7J''33, JP-A No. 62-t2!/, and JP-A No. 62-t2!/Koza! No. 27, 60-
/ Kokota 2 issue, same! Tarl♂O7! ! Examples include cyanine dyes and merocyanine dyes represented by the general formulas described in No. 3 and the like. Specifically, JP-A-60-/33≠l
AJ issue, pages (♂) to (/l), JP-A-1. /-7!3
No. 32, pages ri to (7), pages 2≠ to (koj),
Pages (10) to (is) of JP-A No. 62-623/1980, pages (j)-(7) of JP-A-1986-2/21 core issue, JP-A No. 30-/22 Octopus R The blue region, edge region, red region, or infrared spectrum of the spectrum described in pages (7) to (ri) of JP-A No. 0! Examples include sensitizing dyes that spectrally sensitize halogenated regions.

Most preferred are cyanine dyes represented by the general formula [V].

The above sensitizing dye is per mole of silver halide! ×/ 0-
7 moles! x/0-2moh, preferably lX/(7-
6 mol ~/X/0-3 mol, particularly preferably coX
It is contained in the silver halide photographic emulsion in a ratio of 10-6 mol to jX/0-4 mol.

The sensitizing dyes described above can be dispersed directly into the emulsion layer. They can also be added to the emulsion in the form of a solution by first dissolving them in an i4-based solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof. Ultrasonic waves can also be used for dissolution. Further, as a method of adding the sensitizing dye, US Pat. No. 31 μm, 9
．． A method of dissolving a dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding Km to the emulsion with this dispersion, as described in Japanese Patent Publication No. 6-2
A method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion, as described in ≠LTJ issue; Japanese Patent Publication No. 6/-μ! Mechanically pulverizing a water-insoluble dye in an aqueous solvent as described in No. 277,
dispersing and adding the dispersion to an emulsion; dissolving the dye in a surfactant and cooling the solution into an emulsion, as described in U.S. Pat. No. 3,122,731;
A method as described in JP-A No. 51-7 Ko1s2II- in which a red-shifting compound is used to dissolve the solution and the solution is added to an emulsion; as described in JP-A-3'0-♂0126. A method is used in which the entire dye is dissolved in an acid substantially free of water and the solution is cooled into an emulsion. Other additions to emulsions include U.S. Pat. tsos issue, same No. 2. Tawa 6.2♂fu,
Same @3. The method described in ≠-ta, t3, etc. can also be used. The sensitizing dyes described above may also be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but can of course also be dispersed during any step in the preparation of the silver halide emulsion. .

The above-mentioned sensitizing dyes may be used in combination with other sensitizing dyes. For example, U.S. Patent No. 3°703.377
No. 2. t♂za, No. 5411, No. 3.327, 0
No. 1, 0, No. 3. ls/j, ls3! No. 3. l
s, 2g, No. 26≠, British Patent No. 1, Ko≠2. J Zaza No. 1. λri3. r6ko, Tokko Akihiro 3-≠23, 4L Hiro-7 Hiro 030, ≠3-10773, U.S. Patent No. 3. IL/Otsu, Octopus No. 7, Special Publication Sho≠3-1IL No. 30, U.S. Patent No. 2. t/J-, t/, No. 3, same@j
, A/j, No. 432, same No. 3. Sensitizing dyes described in ls/7, 2ri No. 5, ls/3, 63, t, 72/, etc. can be used.

Suitable supports that can be used in the photographic light-sensitive material having the photographic emulsion of the present invention include, for example, the above-mentioned RD, A/7&≠2
6≠♂ from the right column of page g and 6≠7 of rot1r7it
It is written in the left column of the page.

Photographic materials to which the photographic emulsion of the present invention can be applied include:
Mention may be made of various color and black and white photosensitive materials.

For example, color negative film for photography (general use, movie use, etc.)
, color reversal film (for slides, movies, etc., or may or may not contain couplers), color photographic paper, color positive film (for movies, etc.), color reversal photographic paper, color photosensitive materials for heat development , color photosensitive materials using the bride dye bleaching method, photosensitive materials for plate making (lith film, scanner film, etc.), X-ray photosensitive materials (
(direct/indirect medical use, industrial use, etc.), black and white negative film for photography, black and white photographic paper, sensitive material for microphone A (for CCJM, micro film, etc.) Color diffusion transfer photosensitive material (DT film)
, Kaburashio amended transfer photosensitive material, printout photosensitive material, and the like.

Exposure for obtaining a photographic image using a photographic light-sensitive material using the photographic emulsion of the present invention may be carried out using a conventional method.

Namely, natural "yt < sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, light emitting diode, laser source (e.g. Heliwa Moon neon laser, YAG laser - Any of a variety of known light sources including infrared light can be used, such as lasers, dye lasers, semiconductor lasers, etc.Also, radiation from phosphors excited by electron beams, X-rays, γ-rays, α-rays, etc. can be used. The photographic emulsion of the present invention is suitable for use as a helium-neon laser light source.

g Light time Vi I/ioo as well as exposure time of 7 seconds from 771000 seconds used in normal cameras.

Exposures shorter than a second, such as xenon flash lamps or cathode Ivi
fc using i tube, //104 to //106 seconds om51
or exposures longer than 7 seconds can be used. If necessary, the original spectral composition used for exposure can be adjusted using color filters.

The photographic light-sensitive materials to which the photographic emulsion of the present invention can be applied include the above-mentioned paper, /16/7A Ko 3, pages 2 to λ, and the same, /1.
The development process can be carried out by the usual method described in the left column to the right column of the tri page of 6/17/1.

"Example" Next, specific examples of the present invention will be shown, but the present invention is not limited thereto.

Example 1 Hehedral silver fluoride emulsion (circle radius 0) produced by rA according to a conventional method
, II μm, AgBr-containing -30,76ma1
1. /KP, pH=ls, 3, I) Ag=J', J'u
)', aliquot 10AJF each, keep at 70℃ and stir.
A known amount of a methanol solution of lo-2mOfL/λ of the following compound was added.

(Compound/) (Compound ko) (Compound 3) (Compound 1A) Furthermore, 5 minutes after adding all of the above compounds, 0°002λ
A methanol solution of mOλ/2 of dyestuff jd was added, and the mixture was further stirred for 20 minutes, and then the temperature was lowered.

(Dye A) A coating aid was added to the above emulsion and coated on a TAC film base. The spectral sensitization efficiency/v of dye A was measured using the above coated film in a conventional manner. The exposure time Fi during measurement was 100 seconds, and the developing Fi surface developer MAA
-/ for 70 minutes at 0°C. The measurement results are shown in Table 3. Further, the reflection spectrum of the coated film was measured, and the absorption maximum wavelength and half-value width of the J band are shown in No. 35A.

From the results of the third experiment, compound 7~μ splits the J-aggregate of dye A, shifts the J band to shorter wavelengths and broadens it, and significantly increases the efficiency of spectral sensitization of dye A by $V. I know that I did it.

The same octahedral silver bromide emulsion t101. IO”-2mo of compound 3 was collected in portions and stirred at 70°C.
fl/I! A known amount of a methanol solution of , was added.

After another 5 minutes, 0.022 moJl/n of methanol solution of dye A (j ml) was added, and more! 0.00 for public bonds
1% sodium thiosulfate aqueous solution was added with ILt (appropriate amount of Nk) and further aged for 73 minutes for sulfur sensitization.A coating aid was then added to the above emulsion and coated on a TAC film base.

The blue light sensitivity (sensitivity obtained by photoexciting with beautified silver) and minus blue light sensitivity (sensitivity obtained by photoexciting dye A) of the above coated film were measured as follows. That is, the coated film is passed through a color filter and a continuous wedge to give a tungsten bulb (color temperature 21!
Exposure for seconds.

For the color filters, I used Fuji Gelatin Filter BPN≠2 to obtain blue light sensitivity, and the same (SCj2) to obtain M9 minus blue original sensitivity. Performed at 0℃ for 70 minutes,
After fixing and drying, the optical density was measured using a Fuji self-recording densitometer. Sensitivity was determined as the reciprocal of the exposure amount at which the developed film had an optical density of 100,/. The obtained friendliness values are shown in Table μ.

It can be seen that Compound 3 particularly suppressed negative blue sensitivity.

Example 3 The coated film of Example 1 was treated with a helium neon laser light source and subjected to the same treatment as Example 3. The measurement results are shown in Table 3.

Thus, it can be seen that according to the present invention, high sensitivity can be achieved, especially when exposed with a helium-neon laser.

Claims (4)

[Claims] (1) A silver halide photographic emulsion containing at least one compound or salt thereof that satisfies Condition 1 below and a spectral sensitizing dye. Condition 1: Anhydro-5,5'-dichloro-9-ethyl-3,3
'-Bis(3-sulfopropyl)thiacarbocyanine hydroxide pyridinium salt (4.0 x 10^-^4 mol/l aqueous solution of 2 ml and potassium chloride 1.0 x 10^
- Mix 1 ml of an aqueous solution of 1 mol/l of the compound, add 4 ml of an aqueous solution of 8.0 x 10 ^-^ 2 mol/l of the compound, and dilute with water to make a constant volume of 10 ml. do. The molecular extinction coefficient of this aqueous solution at 624 nm is 1.0.
×10^5 or less. (2) Claim (1) characterized in that a compound satisfying the above condition 1 is added to the spectrally sensitized silver halide photographic emulsion before adding a spectral sensitizing dye. emulsion. (3) Silver halide photographic emulsion according to claim 1, characterized in that the spectral sensitizing dye is a compound represented by the following general formula [V] General formula [V] ▲ Numerical formula, chemical formula, There are tables, etc.▼ In the formula, Y_1 and Y_2 represent a sulfur atom and a selenium atom, respectively. (Except that Y_1 and Y_2 are both selenium atoms.) R_3_1 and R_3_2 represent a lower alkyl group and an alkyl group having a sulfo group, respectively. R_3_3 represents a lower alkyl group, and A and B represent a group of nonmetallic atoms necessary to form a naphthothiazole ring, a benzothiazole ring, a naphthoselenazole ring, or a benzoselenazole ring. (4) The silver halide photographic emulsion according to claim 1, wherein the silver halide photographic emulsion uses a helium-neon laser as a light source.