JPH0235444A - Silver halide emulsion - Google Patents

Abstract

PURPOSE:To improve the spectral sensitivity of the title emulsion against a flashing exposure, and to lessen the deterioration of the sensitivity of the emulsion after preserving it at high temp. and humidity environments by sensitizing the emulsion with a specified methine dye. CONSTITUTION:The emulsion is composed of the emulsion for the flashing exposure of a laser ray, etc., and comprises a nucleus substd. one or more of carbon atoms among 10C azulene nucleus with a chalcogen atom or nitrogen atom, and the emulsion is sensitized by a methine dye (such as a compd. shown by formula I) substd. with a methine bind having an auxochrome capable of forming a conjugate and resonance chromophore with a 10pi electron system of a nucleus contd. in the 7 membered ring part of the azulene nucleus, at an end group. In the formula, V1-V5 are each hydrogen or halogen atom, etc., Y and Z are each carbon, nitrogen or a chalcogen atom, L1-L5 are each methine group, Q1 is an atomic group necessary for forming a 5-6 membered ring, R2 is alkyl group, (l) is 0-3, (n1) is 0 or 1, M is a pair ion, (m) is a necessary number. The pigment is composed of a compd. shown by formula II wherein Y is nitrogen group, Z is N-CH3 group, V1 is OCH3 group, Z<1> is sulfur atom, R<2> is C2H5 group, (l1) is 0, M is I<-> atom, (m) is 1, X is CH3 group at 6-position of a benzene nucleus, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a spectrally sensitized silver halide photographic emulsion, in particular a silver halide emulsion for flash exposure which has improved spectral sensitivity. It concerns silver emulsions.

(Prior Art) In recent years, new system technologies for quickly transmitting information have been rapidly developed. In other words, it senses electrical signals,
This is a method of visually purifying image information such as photographs, letters, or numbers by converting it into electric light onto a light material. Fields that utilize this system technology include facsimiles, computer phototypesetting systems, character typesetting systems, scanner halftone image formation, and holography-IC photomasks.

The light source used in these devices for rapid information transmission systems must have a signal current that faithfully changes the illuminance according to the change in current, and is usually a xenon flash light, glow discharge light, or an arc light source. light, high pressure mercury lamp,
Xenon lamps, flying spots of phosphor from cathode ray tubes, and even laser light are used, and a light source device is constructed by combining these high-intensity light sources with high-speed shutters.

Particularly in the field of facsimile, laser light is being used in place of glow discharge light because the glow discharge light that has been conventionally used has various drawbacks. In addition, coherent (Co) laser beams are also used in other fields.
For example, laser light is used in the field of holography for reproducing and recording object images.

Laser beams include those that use helium-neon gas, argon gas, krypton gas, carbon dioxide gas, etc. as the laser oscillation medium, as well as lasers that use solids such as ruby and cadmium as the oscillation medium, and other liquid lasers.
There are semiconductor lasers and the like, and among these, helium-neon lasers, which have a relatively long life and are inexpensive, are the most popular.

Unlike the light used for normal illumination, these laser lights are coherent lights with a single frequency, uniform phase, and sharp directionality. Silver photographic materials are required to have spectral characteristics that match the emission wavelength of the laser used.

(Problems to be Solved by the Invention) As described above, there has been a desire for a spectral sensitizing dye that can sufficiently improve reciprocity law irregularity in flash exposure and also has high stability over time.

It is therefore an object of the present invention to provide a silver halide photographic emulsion having improved spectral sensitivity to flash exposure.

Furthermore, another object of the present invention is to provide a silver halide photographic emulsion for flash exposure which has improved stability over time.

In the present invention, "Flash exposure J (!:" means high-intensity short-time exposure suitable for the above purpose. Short time here means 10-3 seconds or less, preferably 10-3 to 10-9 seconds. do.

Silver halide photographic materials used when the exposure time is thus short are required to have improved reciprocity law irregularities.

Sensitization of silver halide photographic emulsions used in light-sensitive materials, particularly to flash exposure, is achieved by I)Ag of the emulsion.

It is greatly influenced not only by halogen composition, particle size and crystal habit, but also by chemical sensitization method or chemical ripening conditions. Dye sensitization with respect to flash exposure was previously said to be primarily dependent on the photosensitivity properties of the silver halide itself contained in the emulsion; has also been found to be highly dependent (see, for example, the description in British Patent No. 1330t Tata).

(Means for Solving the Problems) The above aspects of the present invention are such that at least 7 of the 10 carbon atoms of the azulene nucleus are chalcogen atoms (for example, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms) or nitrogen atoms. The 7-membered ring part of the nucleus is replaced by a methine bond with an auxochrome at the end that forms a conjugated resonance chromophore with the 10π electron system of the nucleus. This was achieved using a silver halide emulsion characterized by containing at least seven methine dyes.

This methine dye acts as a sensitizing dye, a sensitizer, a desensitizing dye, or a desensitizing agent.

The present invention will be explained in more detail below.

In the methine dye containing a complex azulene nucleus used in the present invention, a preferable complex azulene nucleus is /.

Since this is a nucleus in which at least seven of the carbon atoms at the 3rd position are replaced with chalcogen atoms or nitrogen atoms, this nucleus will be explained as a representative example.

The dye of the present invention can be expressed in an alternating resonance form as shown in the following general formula (1).

In the formula, E represents an auxochrome, LFi represents a methine bond, and v1, v2, v3, v4, and v5 each represent a hydrogen atom, a hydrogen atom, an alkyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, Represents a carbamoyl group, sulfamoyl group, carmexyl group, cyano group, hydroxy group, amino group, acylamino group, alkoxy group, alkylthio group, alkylsulfonyl group, sulfonic acid group, or aryl group, or The two carbon atoms bonded to each other may form a fused ring. In addition, an alkyl group, an acyl group, an acyloxy group,
The alkoxycarbonyl group, carbamoyl group, sulfamoyl group, amino group, acylamino group, alkoxy group, alkylthio group, alkylsulfonyl group, and aryl group may be further substituted.

■ Y and ZFi carbon atoms (-C===-, ;ThriL,
VdV1, v2, v3, v4 and v5)
, a chalcogen atom (such as an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, etc.) or a nitrogen atom (-N-1R1
may or may not be necessary to form a nucleus; when R1 is necessary, R1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. ). However, both Y and Z are not carbon atoms. Furthermore, when Y and Z are represented by a chalcogen atom or a nitrogen atom, at least one of them is a nitrogen atom. Further, when one represents a chalcogen atom and the other represents a carbon atom or a nitrogen atom, Z represents a chalcogen atom and Y represents a carbon atom or a nitrogen atom.

M represents a charge-balancing counterion and is a number greater than or equal to 0 necessary to balance the mFi charge.

In formula (1), the bonding position of the methine bond is represented as the 6th position as a representative, but other positions (μ position, 3rd position, 7th position, r position) are also represented in the same way. However, preferably the μ position, the 6th position,
The r position, more preferably the Fia position and the 6th position.

The auxochrome E will be explained in detail.

E can take any common form found in methine dyes. Typically, auxochromes are composed of nitrogen or chalcogen atoms that resonate between charged and uncharged states in the dye. For example, it can be in the form of any of the auxochromes found in cyanine, merocyanine, oquinol, pyrylium or chiapi171Jum dyes. However, there is no need to limit auxochromes to these classes.

Less commonly, auxochromes composed of other atoms, such as phosphorus or boron, are considered. Example: L
td, 2-)liphenylphosphoro-7°3-cyclopenkdief-3-yl.

Among the dyes represented by the general formula (1), preferred are those represented by the following general formulas (II) to (IX).

General formula (If) In the formula, (1) to V5, Y, Z, M, and m1j have the same meanings as in general formula (1). Further, as in general formula (I), the methine bond may be located at any of the μ, 3, 6, and 7 positions.

Ql is! Alternatively, it represents an atomic group necessary to form a t-membered nitrogen-containing ring.・L1, R2, R3, R4, and R5
represents an optionally substituted methine group.

R2 represents a substituted or unsubstituted alkyl group. ll
represents an integer between θ and 3. nl represents O or l.

General formula (III) are synonymous.

R3 represents a substituted or unsubstituted alkyl group.

12 represents an integer from θ to 3. R2 represents O or l.

General formula (IV) In the formula, v0 to V5, YXZ, MXmtti General formula (1)
is synonymous with Further, as in the general formula (1), the methine bond may be located at any of the j-position, the j-position, the 6th-position, and the 7th-position.

Q2 represents an atomic group necessary to form a golden nitrogen ring. R6, L1, R8, R9 and Llo are L
1, R2, R3, R4 and R5 and in the formula, ■1 to v5,
Y, Z, M, and m have the same meanings as in general formula (1). Y', Z
' is synonymous with YSZ. Further, as in general formula (1), the position of the methine bond may be any of the j-position, the j-position, the 7-position, and the 2-position.

Vl-Vs has the same Mf as UVx-Vs.

Lll % I' 12, and Ll3 is L1%"2\
It has the same meaning as L3, R4 and R5. 13 represents an integer from θ to 3.

General formula (V) General formula (Vl) In the formula, (1) to v5, Y, Z, M, mn have the same meaning as general formula (1). Further, as in the general formula (2), the methine bond may be located at any of the j-position, j-position, 6-position, and 7-position.

Dl and Dl represent an atomic group necessary to form an acidic nucleus, and may be acyclic or cyclic.

Ll4, Lts, Ll6, and Ll7 are L 1 %L
2, R3, R4 and R5. 14 is θ~3
represents an integer. R3 is O or/.

In the formula, ■1 to v5, Y% ZS M% m is the general formula (1
) is synonymous with Further, as in the general formula (1), the position of the methine bond may be any of the j-position, the j-position, the 6th-position, the 7th-position, and the j-position.

R4 and R5 represent substituents known in general tertiary amines. R4 and R5 may form a ring.

Ll8 and Ll9 are L1%"2, R3, R4 and R
It is synonymous with 5. 15 represents an integer between θ and 3.

General formula (■) In the formula, E and E'FiE1 or R2 have the same meaning.

However, at least seven of j=E and E' are El.

(2) 1 to v5, YXZ, M, and m have the same meanings as in general formula (I). Also, as in general formula (1), in El, the position of the methine bond is ≠, ! Place, 6th, 7th, or any other place is fine.

Wl represents an atomic group necessary to form a j-membered or t-membered heterocycle.

R6 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group.

Q3 and R7 are each Q 1 %R3 of general formula (II)
is synonymous with

R20\L21% ”22%” 231L24%
”25 and R26 are synonymous with L1%L'2, R3, R4 and R5.

16 and ltV'i is an integer from 0 to 3.

R4 is O or /.

In the formula, (1) to v5, Y, Z, and MXm have the same meanings as in general formula (1). Further, as in the general formula (N), the position of the methine bond may be any of the μ, !, 7, 7, and 7 positions.

W2 is synonymous with Wl. R8 has the same meaning as R6.

Dl and Dl have the same meanings as Dl and Dl in general formula (V).

R27\L28 XL'29\L'ao to L31 and R32 are synonymous with L1% R2, R3, R4 and R5.

18 and 19 are integers from O to 3.

R5 represents 0 or l.

General formula (■a) General formula (]Xb) In the formula, ■1 to v5, Y, Z, M, and m have the same meanings as in general formula (1). Furthermore, as in the general formula (1), the methine bond may be located at any of the hi-position, 5-position, and 6-position.

R33 and R34 are L1, R2, L3 to L4 and R
It is synonymous with 5.

Ar represents an aromatic group.

11o represents an integer from θ to 3.

General formulas (I) to (DO) will be explained in detail below.

R1 is preferably a hydrogen atom, an unsubstituted alkyl group having carbon number/r or less (for example, methyl group, ethyl group, propyl group, butyl group, methyl group, octyl group, decyl group, dodecyl group, octadecyl group), or substituted Alkyl groups (as substituents, for example, carboxy groups, sulfo groups, cyano groups, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms), hydroxy groups, alkoxycarbonyl groups with the following carbon atoms (for example, methoxycarbonyl groups) , ethoxycarbonyl group, phenoxycarzenyl group, benzyloxycarbonyl group), alkoxy group with carbon number of g or less, (
For example, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group), monocyclic aryloxy group having up to 10 carbon atoms (e.g. phenoxy group, p-tyloxy group), acyloxy group having up to 3 carbon atoms (e.g. acetyloxy group, bronyloxy group), acyl group with carbon number r or less (e.g. acetyl group, propionyl group, benzoyl group, mesyl group), carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group) group, Pi is a lysinocarbonyl group), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, Pi is a lysinosulfonyl group), an aryl group having a carbon number/θ or less (e.g. phenyl group, Hiro-chlorophenyl group, μm methylphenyl group, α-su7tyl group), aryl group (e.g. phenyl group, 2-naphthyl group), substituted aryl group ( Examples include Hiroki rpoxyphenyl group, ≠-sulfophenyl group, 3-chlorophenyl group, 3-methylphenyl group), and heterocyclic groups (e.g., copyridyl group, coachazolyl group).

Particularly preferred are unsubstituted alkyl groups (e.g. methyl group,
ethyl group), and a sulfoalkyl group (eg, cosulfoethyl group, 3-sulfopropyl group, and hiro-sulfobutyl group). More preferred is a methyl group.

Furthermore, as the metal atom that can form a salt with R1, an alkali metal is particularly preferable, and as the organic compound that can form a salt with R1, pyridines, amines, etc. are preferable.

v1, v2, v3, V4, v5, ■1', ■2', ■3
', v, 1, ■5' are hydrogen atom, halogen atom (for example, chlorine atom, fluorine atom, bromine atom),
An unsubstituted alkyl group having 10 or less carbon atoms (e.g. methyl group, ethyl group), a substituted alkyl group having 10 or less carbon atoms (e.g. benzyl group, α-naphthylmethyl group, cophenylethyl group, trifluoromethyl group), Acyl group with carbon number IO or less (e.g. acetyl group, benzoyl group, mesyl group)
, an acyloxy group having a carbon number of lθ or less (e.g. acetyloxy group), an alkoxycarbonyl group having a carbon number of IO or less (
For example, methoxycarbonyl group, ethoxycarbonyl group,
benzyloxycarbonyl group), substituted or unsubstituted carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), substituted or unsubstituted sulfamoyl group (e.g. sulfamoyl group, N , N-dimethylsulfamoyl group, morpholinosulfonyl group, lysinosulfonyl group), carboxy group, cyano group, hydroxy group, amino group, acylamino group with carbon number r or less (e.g. acetylamino group), carbon number lQ The following alkoxy groups (
For example, methoxy group, ethoxy group, benzyloxy group),
Preferred are alkylthio groups (eg, ethylthio group), alkylsulfonyl groups (eg, methylsulfonyl group), sulfonic acid groups, and aryl groups (eg, phenyl group, tolyl group). Moreover, λ bonded to adjacent carbon atoms among (1) to V5 may bond to each other to form a benzene ring. Further, they may be bonded to each other to form a heterocycle (eg, pyrrole ring, thiophene ring, furan ring, pyridine ring, imidazole ring, triazole ring, thiazole ring).

V2, V3, v4, v5, v2, v3, v4 and v5
The preferred one is a hydrogen atom.

Preferred examples of Vl and vl are a hydrogen atom, a chlorine atom, an alkoxy group (eg, methoxy group), an alkylthio group (eg, methylthio group), and an aryl group (eg, phenyl group).

Mm 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. Whether a dye is cationic, anionic, or has a net ionic charge depends on its auxochromes and substituents. Counterions can be easily exchanged after the dye is manufactured.

Typical cations are ammonium ions and alkali metal ions, while anions may specifically be either inorganic or organic anions, such as halogen anions (e.g. fluoride, chloride,
Bromine ion, iodine ion), substituted arylsulfonate ion (e.g. p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (e.g. 1,3-benzenedisulfonate ion, 1,j-naphthalene) disulfonic acid ion, λ, O-naphthalenedisulfonic acid 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.

The nucleus formed by Ql and Q3 includes a thiazole nucleus (e.g. thiazole, ≠-methylthiazole, Hiro-phenylthiazole, Hiro, j-dimethylthiazole,
! , j-diphenylthiazole), benzothiazole nucleus (e.g., benzothiazole, Hiro-chlorobenzothiazole, !-chlorobenzothiazole, 2-chlorobenzothiazole, j-nitrobenzothiazole, ≠-methylbenzothiazole, !-methylbenzo Thiazole, t-
Methylbenzothiazole, r-7' lomobenzothiazole, 6-bromobenzothiazole,! -Iodohenzothiazole! -Phenylbenzothiazole,! -methoxybenzothiazole, 6-methylbenzothiazole,!
-Ethoxy and inzothiazole! -Ethoxycarbonylbenzothiazole,! -carboxybenzothia/-r,
j-7enethylbenzothiazole! -fluorobenzothiazole, j-chloro-6-methylbenzothiazole,! , t-dimethylbenzothiazole, j,6-simethoxybenzothiazole, ! -Hydroxy-4-methylbenzothiazole, tetrahydrobenzothiazole, ψ-
phenylbenzothiazole), naphthothiazole core (e.g., naphtho[co, t-d)thiazole, naphtho[1,
Code d] Thiazole, Nando (u, J-d)thiazole, j-methoxynaphtho[1,2-d]thiazole, 7-
Nitoxynaphtho[x,/-d:]thiazole, r-methoxynaphtho[λ,/-d:]thiazole,! -methoxynaf) (: J, J-d) thiazole, etc.)), thiazoline nuclei (e.g., thiazoline, ≠-methylthiazoline, ≠-
Nitrothiazoline), oxazole nucleus (e.g., oxazole, Hiro-methyloxazole, Hiro-nitrooxazole, !-methyloxazole, ≠-
phenyloxazole, μ, j-diphenyloxazole, hiro-ethyloxazole), benzoxazole nucleus (e.g., benzoxazole, j-chlorobenzoxazole, j-methylbenzoxazole, !-bromobenzoxazole, j-fluoropenzoxazole, j-phenylbenzoxazole, !-methoxybenzoxazole, !-dirobenzoxazole, t-
17 Fluoromethylbenzoxazole! -Hydroxybenzoxazole, j-hydroxybenzoxazole, 6-methylbenzoxazole, A-chloro0-<
nzoxazole, t-nitrobenzoxazole, 6
-Medoxybenzoxazole, 6-hydroxybenzoxazole,! , t-dimethylbenzoxazole,
Hiroshi, 6-dimethylbenzoxazole,! -ethoxybenzoxazole), naphthoxazole core (e.g.
naphtho [co, 1-d) oxazole, naphtho [/.

Code d]oxazole, naphtho[co, J-d]oxazole, j-nitronaphtho[J,/-d]oxazole, etc.)), oxazoline nucleus (e.g., ≠, ≠-dimethyloxazoline), selenazole nucleus (selenazole nucleus ( For example, hiro-methylselenazole, ≠-nitroselenazole, ≠-phenylselenazole), benzoselenazole core (e.g., t-benzoselenazole, j-chlorobenzoselenazole, !-12-benzoselenazole), Zor,!-
Methoxybenzoselenazole! -Hydroxybenzoselenazole, t-nitrobenzoselenazole,! -dichloro-6-nitrobenzoselenazolej.

t-dimethylbenzoselenazole, etc.), naphthoselenazole core (e.g. naph) lj, /-d:) selenazole, naphtho[1,2-d]selenazole)), selenazoline core (e.g. selenazoline, ≠-methyl selenazoline), telllazole core (e.g. telllazole, Hiro-methyltelllazole, Hiro-phenyltelllazole), penzotelllazole nucleus (e.g. penzotelllazole, j-chlorobenzotelllazole, !-methyl benzotelllazole, j,4-dimethylbenzotelllazole, t-methoxybenzotelllazole), naphthotelllazole core (e.g., naphtho(J,/-d)telllazole, naphtho[1,,2-d)telllazole, etc.)
), tellazoline core (e.g. tellazoline, t-methyltellazoline), 3,3-dialkylindolenine nucleus (e.g. !, 3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl=! -cyanoindolenine, 3.3-dimethyl=m=troindolenine, 3.3-dimethyl-!-12loindolenine, 3.
3-dimethyl-j-methoxyindolenine, 3,. 3.
j-) Limethylindolenine, 3,3°! -Dimethyl! -lyroindolenine), imidazole nucleus (e.g. /-alkylimidazole, /-alkyl-gouphenylimidazole), benzimidazole nucleus (e.g. /-alkylbenzimidazole, l-
Alkyl! -chlorobenzimidazole, / furkyl-z, g-dichlorobenzimidazole, l-alkyl-yo-methoxybenzimidazole, / -alkyl-yo-cyanobenzimidazole, /-alkyl!
-fluorobenzimidazole, l-alkyl-j-)
Lifluoromethylbenzimitasole, l-alkyl-
6-chloro-7-cyanobenzimidazole, l-alkyl-6-chloro-! -trifluoromethylbenzimidazole, l-allyl-j, t-dichloroinciimidazole, /-allyl-t-chlorobenzimidazole,
/-aryl-1,+-dichlorobenzimidazole, /-aryl-j-methoxybenzimidazole, /-aryl-1,+-dichlorobenzimidazole, /-aryl-j-methoxybenzimidazole, /-aryl-1,+-dichlorobenzimidazole, /-aryl-j-methoxybenzimidazole
-aryl-y-cyanobenzimidazole), naphthoimidazole nucleus (e.g. co-alkylnaphtho[1,λ
-d]imidazole, /-arylnaphthoC1, coded]imidazole), the alkyl group mentioned above is a carbon atom /~
For example, unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and hydroxyalkyl groups (eg, cochtoxyethyl, 3-hydroxypropyl) are preferred. Particularly preferred are methyl group and ethyl group.

The aforementioned aryl groups represent phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. ), pyridine nucleus (e.g., copyridine, Hiro-pyridine, !-methyl-J-pyridine, 3-methyl-≠
-pyridine), quinoline nucleus (e.g., coquinoline, 3-methyl-2-quinoline, j-ethyl-λ
-quinoline, 6-methyl-choquinoline, 6-nitrochoquinoline, t-fluoro-choquinoline, 6-medoxy-coquinoline, t-hydroxy-coquinoline,
t-chlorochoquinoline, hiro-quinoline, 6-nitoxy≠-quinoline, 2-nitro-hiro-quinoline, ? -chloro≠-quinoline, t-fluoro-μm quinoline, t
-Methyl-μm quinoline,! -methoxy-hiro-quinoline, 6-methyl-μm quinoline, t-methoxy-μm quinoline, 2-chloro-μm quinoline), inquinoline nucleus (
For example, 6-nitro-/-inoquinoline, 3゜≠-dihydro-1-isoquinoline, 6-nitro-3-inquinoline)), imidazo[Hiroshi, r-b) quinoxaline core (e.g., 1,3-diethylimidazo[ ≠, r-b:l quinoxaline, 6-chloro-1,J-diallylimidazo[ge,
j-b) quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, and pyrimidine nucleus.

More preferred are benzothiazole core, benzoxazole core, and indolenine core.

R2, R3 and R7 can take the form of a μ-classification substituent for the basic core of any cyanine dye.

For example, preferably an unsubstituted alkyl group having 7 g or less carbon atoms (e.g., methyl group, ethyl group, propyl group, dityl group, k-methyl group, octyl group, decyl group, dodecyl group, octadecyl group) or substituted alkyl group (substituted Examples of the group include a carboxy group, a sulfo group, a cyano group, and a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom).
, hydroxy group, alkoxycarbonyl group with carbon number r or less (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group), alkoxy group with carbon number less than r (e.g. methoxy group, ethoxy group, benzyloxy group) group, phenethyloxy group), monocyclic aryloxy group with carbon number/θ or less (
For example, phenoxy group, p-tolyloxy group), carbon number 3
The following acyloxy groups (e.g. acetyloxy group, propionyloxy group), acyl groups having up to r carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, mesyl group), carbamoyl groups (e.g. carbamoyl group, N, N-
dimethylcarbamoyl group, morpholinocarbonyl group, bilysinocarbonyl group), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group,
morpholinosulfonyl group, piperidinosulfonyl group),
An alkyl group having a carbon number/r or less substituted with an aryl group having a carbon number of IO or less (for example, a phenyl group, a goochlorophenyl group, a goomethylphenyl group, an α-naphthyl group) is preferable. ) can be mentioned.

D1, D1' and D1, Dl represent atomic groups necessary to form an acidic nucleus, but they can take the form of the acidic nucleus of any general merocyanine dye. In a preferred form, Dl and Dl are cyano, sulfo or carbonyl groups, and D1' and Dl represent the remaining atomic groups necessary to form the acidic nucleus.

When the acidic nucleus is acyclic, i.e. Dl and Dl
Or when Dl and Dl are independent groups, the terminus of the methine bond is a group such as malononitrile, alkylsulfonylacetonitrile, cyanmethylbenzofuranyl ketone or cyanmethylphenylketone.

D1,Dl or D1,Dl - together with carbon, nitrogen and chalcogen (typically oxygen, sulfur,
forms a j- or 6-membered heterocycle consisting of selenium, tellurium) atoms. Preferably DllDl Also FiD
2. Dl together completes the next nucleus.

Kovirazoline - 1 1, pyrazolidine - 3°! -Zion, imidacillin-! -one, hydantoin, Komata Fi≠-thiohydantoin, λ-iminooxazolidine-Hiro-one, cooxazoline! -one, cochoxazolidine, gudion, isoxazoline-yo-
on, cochiazoline-μm on, thiazolidine-μm
on, thiazolidine-j, IIt-dione, rhodanine, thiazolidine-co, terzithione, inrhodanine,
Indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,/-dioxide, indolin-2-one, indolin-3-one, indacillin-3
-one, co-oxoindazolinium, 3-oxoindasilinium,! , 7-thioxo6.7-cyhydroteazolo(j,J-a)pyrimidine, cyclohexane-1
, 3-dione, 3. ≠-dihydroisoquinoline-guone, 7.3-dioxane-Hiroshi, 6-dione, pulpy-
#L λ-thiobarbic acid, chromanco.

Hiro-dione, indacillin-λ-one, or pyrido [
1,2-a]pyrimidine-1,J-dione core.

More preferably, 1,3-dialkylbarbyl L
/+3-dialkyl-cotchobarbituric acid, 3-alkyl rhodanine (preferably the alkyl group is an unsubstituted alkyl group).

The substituent bonded to the nitrogen atom contained in the nucleus is a hydrogen atom, an alkyl group having a carbon number of /~/♂, preferably 1~7, particularly preferably /~≠ (for example, a methyl group, an ethyl group, a propyl group) , isopropyl group, butyl group, inbutyl group,
hexyl group, octyl group, dodecyl group, octadecyl group), substituted alkyl groups (e.g. aralkyl group (e.g. benzyl group, λ-phenylethyl group), hydroxyalkyl group (e.g. tld', x-hydroxyethyl group, 3-hydroxypropyl group) group), carboxyalkyl group (e.g. cocarboxyethyl group, 3-carboxypropyl group, ≠
-carboxybutyl group, carboxymethyl group), alkoxyalkyl group (e.g. λ-methoxyethyl group, λ-
(,2-methoxyethoxy)ethyl group), sulfoalkyl group (e.g., cosulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, gousulfobutyl group, 2-[
3-sulfopropoxy]ethyl group, -monohydroxy=3
-sulfopropyl group, 3-sulfopropoxyethoxyethyl group), sulfatoalkyl group (e.g., 3-sulfatofurovir group, Hiro-sulfatobutyl group), heterocyclic-substituted alkyl group (e.g., 2(hyrolidine-1- On-7-
yl)ethyl group, tetrahydrofurfuryl group, comorpholinoethyl group), 2-acetoxyethyl group, carbomethoxymethyl group, comethanesulfonylaminoethyl group), allyl group, aryl group (e.g. phenyl group, λ-naphthyl group) , a substituted aryl group (eg, gucarboxyphenyl group, Hiro-sulfophenyl group, 3-chlorophenyl group, 3-methylphenyl group), and a heterocyclic group (eg, copyridyl group, cochiazolyl group) are preferred.

Since R4 and R5 are substituents for the tertiary amine used in the synthesis, they may be any substituents for general tertiary amines.

R4 and R5 may be the same or different from each other, and are preferably unsubstituted alkyl groups having carbon number/♂ or less (for example, methyl group, ethyl group, propyl group, butyl group, methyl group, octyl group, decyl group) , dodecyl group, octadecyl group) or substituted alkyl group (substituents include, for example, carboxy group, sulfo group, cyan group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom), hydroxy group, carbon number r or less an alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarmenyl group, phenoxycarbonyl group, benzyloxycarbonyl group), an alkoxy group having the following carbon atoms (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyloxy group), Monocyclic aryloxy group with 10 or less carbon atoms (e.g., phenoxy group, p - IJ ruoxy group), acyloxy group with 3 or less carbon atoms (e.g., acetyloxy group, propionyloxy group), number of carbon atoms! The following acyl groups (e.g. acetyl group, propionyl group, benzoyl group, mesyl group), carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), sulfamoyl group (e.g. sulfamoyl group) group, N, N dimethylsulfamoyl group, morpholinosulfonyl group, pi, 111J dinosulfonyl group),
Aryl group having 10 or less carbon atoms (e.g. phenyl group, μm
An alkyl group substituted with a chlorphenyl group, ≠-methylphenyl group, α-naphthyl group and having a carbon number/r or less is preferable. ) cyano group, alkoxy group (eg, methoxy group, ethoxy group), aryloxy group (eg, phenoxy group), and alkoxycarbonyl group (eg, ethoxycarbonyl group).

Furthermore, R4 and R5 can be combined with each other to form a heterocycle excluding aromatic heterocycles.

For example, pyrrolidi1, py is preferably lysine, morpholine, py is radiine, tetrahydropyridine, dihydropyridine and tetrahydroquinoline.

More preferably R4 and R5 are ethyl groups.

Preferred examples of the heterocycle formed by Q2 include a pyrrole nucleus, a carbazole nucleus, an indole nucleus, a pyrazole nucleus, a pyrazolo(1,j-1)benzimidazole nucleus, a pyrazolo[1,tb)quinazolone nucleus, and an indazole nucleus.

Also formed by W11W2! Alternatively, the t-membered heterocycle is one in which an oxo group or a thioxo group at an appropriate position is removed from the cyclic heterocycle represented by D1, Dl and D2, D2.

R6 and R8 are preferably the same as those mentioned above as substituents bonded to the nitrogen atom contained in the nucleus of the cyclic heterocycle represented by D1, D1 and D2, D2.

Ar represents an aromatic group, preferably an aryl group (e.g.
phenyl group, 3-chlorophenyl group, naphthyl group)
can be mentioned.

L1, R2, R3, R4, R5, R6, L1, L as
L 9 X L 10% ” 11%
” 12% L 13 S ”14%
L'ts 翫 L16＼ ” 17 s L 18
\ L 19 s L 20% 521%R22
~ L 23% L 24s l 25
%L 26 ~ "27%" 2
8 ~” 29 s R30\L31~L32\1La
a and R34 are substituted with a methine group (substituted or unsubstituted alkyl group (e.g. methyl group, ethyl group), substituted or unsubstituted aryl group (e.g. phenyl group) or halogen atom (e.g. chlorine atom, bromine atom)) ), and may form a ring with another methine group, or may form a ring with an auxochrome.

Next, specific examples of methine dyes used in the present invention will be shown, but the present invention is not limited thereto.

(Example of compound represented by general formula (II)) Example of compound (
I)-/~(II)-/Ite for cod, y, z, v,, Z1, R2, /1, M, m,
X is specifically shown.

(U)-ko0 (n) +27 Compound example (n)-22~( ■) -26 Using, v1, Y1, Y2 is specifically shown.

Compound Examples (1)-27 to (2) Specific examples of compounds v1, R1, Z, R2, 11, M, m, and X are shown below.

(II)-j/[)-33 (Example of compound represented by general formula (III)) Using compound example (III)-/~(III)-7, Y% 2%
71% 12, M, m, heterocycle is specifically shown.

(III)-r (I[I)-ta (compound represented by general formula (II/)) Compound example (I
Y, Z, v1, 13, M, m are specifically shown using V)-/~(fV)-1 m.

Compound examples (IV)-7 to (IV)-/ / Using, Y, Z, V1, 13.M. Make m concrete Shown below.

<■)-i (IV)-/J (f'/) (compound represented by general formula (V)) Using compound example (V)-/~(V)-j, Y, Z, V1, 14, M, m, acidic nuclei are specifically shown.

Compound example (V) l/~(V)-/7 l Using YSZ.

”　1　s 14, M, m, acidic nucleus Specifically shown.

(Compound represented by general formula (M)) y, z, v, , R4, R5, M, and m are specifically shown using compound examples (■) / to (M) -3.

Compound example (M) t～(■) using Y, Z.

v1, R4, R5, M, m Be specific.

(Compound represented by general formula (■)) (■) (■) / (Compound represented by general formula (■)) (■) λ (■) (■) (■) (■)-3 (IX) -,? (Compound represented by general formula (■)) (IK)-/ (IK) λ U) i3 α The methine dye used in the present invention can be used as a photographic sensitizing dye, a sensitizer, a desensitizing dye, and a desensitizing agent. Can be used.

In particular, when used as a sensitizing dye or desensitizing dye, the performance and sensitivity of a certain dye depend on the dye's energy level (which can be evaluated by its oxidation potential and reduction potential). T. H. James (T. H.)

James) The Theory of the Photographic Process
Photographic Process), J edition, Macmillan:/ (Macmillan), /977.
It is well known for chapter 10, pages 26/-201, etc.

By changing the heterocycles and substituents of the dyes represented by formulas (II) to (■), the energy level of the dye can be changed, and both sensitizing dyes and desensitizing dyes can be obtained.

The methine dye of the present invention is disclosed in Japanese Patent Application No. 24137! r, can be synthesized by the method described in Japanese Patent Application No. 62-Glu rtg.

General formula (■) (preferably general formula (n), (1), (I)
V), (V), (Vl), (■), (■), (■)) are used as photographic sensitizers and sensitizing dyes (hereinafter referred to as sensitizing dyes) or desensitizers. and when used as a desensitizing dye (hereinafter referred to as a desensitizing dye), jX10-7 to jX10-1 mol, preferably jXlo-6 to 2x10, per mol of silver halide in the silver halide emulsion. -2 Use. Optimal lil: C. Depends on the chemical structure of the methine dye used, the crystal habit of the silver halide emulsion, and the grain size. Furthermore, these methine dyes may be added during any process of preparing silver halide photosensitive materials, such as grain formation, physical ripening, and chemical ripening, or may be added to the coating solution before coating. May be used in conjunction with law.

The methine dye used in the present invention can be directly dispersed into a photosensitive material or a hydrophilic colloid solution. They can also be used in suitable solvents, such as methyl alcohol, ethyl alcohol, flobyl alcohol, methyl cellosol,
JP-A Showat-Tough/j, U.S. Patent No. 3.7jtlr, 1
It can also be added to the photosensitive material in the form of a solution dissolved in a chlorinated alcohol, acetone, water, pyridine, etc. described in No. 30, or a mixed solvent thereof.

Other addition methods include Tokuko Sho≠Otsu-λ≠/♂j, US Patent 3. rco2.133, P3,1rtO.

10/No., Same, Ri/Co, 3≠No.3, Same λ, Tata t, 2
No. 17, 3, 1t29. l'33, 3°/r! I
,! The method described in Kou No. 2 can be used. It is also possible to use the method described in German patent application λ, 10≠, 2r3 and the method described in US Pat.

The silver halide emulsion used in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. Preferred silver rodanides include silver bromide, silver chlorobromide, silver iodobromide, or silver iodochlorobromide. Silver chlorobromide with a high α content is preferable when handling in a bright safelight is important, and silver bromide or silver iodobromide is preferable when high sensitivity is important.

The silver halide grains may have a regular crystal structure such as a cube, an octahedron, a /4-hedron, a rhombic dodecahedron, or an irregular crystal structure such as a spherical shape or a plate shape. It may have a crystal form or a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms.

Further, the non-rodanized silver grains used in the present invention preferably have an average grain diameter of 0.0/-.lambda. microns, but preferably 0.02-1 micron.

In addition, particles having a thickness of 0.3 microns or less, preferably 0.3 microns or less, a diameter of preferably 0.1 micron or more, and an average aspect ratio of 5 or more account for 50% of the total projected area.
They may be tabular grains that account for 0% or more. It may also be a monodisperse photosensitive material in which particles having a particle size within ±μO of the average particle diameter, preferably within V'iro%, account for 0%, preferably 1% or more of the number of particles.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.

In addition, particles in which the latent image is mainly formed on the surface (for example, a negative-tone photosensitive material), particles in which the latent image is mainly formed inside the particle (for example, an internal latent-type photosensitive material),
The particles may also be pre-fogged particles (for example, direct positive photosensitive material).

Silver rhodide emulsions having the seven-rod composition, crystal habit, intragrain structure, shape and distribution of the strains described above are used in light-sensitive photographic elements for a variety of applications. Therefore, the methine dye of the present invention can be used as a sensitizer, sensitizing dye, desensitizer, or desensitizing dye in light-sensitive materials for the following uses. These dyes can be added to desired layers such as intermediate layers, protective layers, and pack layers in addition to the light-sensitive material layers.

The methine dye of the present invention is used in silver rhodanide photographic materials for various color and black and white sensitive materials.

For details on ζ et al., please see photosensitive materials for color positives, color...
♀-Negative photosensitive materials for color negative photosensitive materials, color reversal photosensitive materials (which may or may not contain couplers), halogenated steel photosensitive materials for direct positives, photosensitive materials for plate making (e.g. lithium film) photosensitive materials for use in photosensitive materials for cathode ray tube displays, photosensitive materials for use in X-ray recording (especially materials for direct and indirect photography using screens), Silver salt diffusion transfer process (SilverSal
tdiffusion transfer proc
photosensitive materials used in color diffusion transfer processes, die transfer processes,
x, (imbibition transfer p
It is used together with photosensitive materials used in silver dye bleaching methods, photosensitive materials used in heat development photosensitive materials, etc.

The photographic light-sensitive material used in the present invention is described in "Chimie et Ph.
ysique Photographique)J
(Ball Monte/l/Published by Paul Monte1,/Rei Otsu 7th year), G.F. Defein G, F,
"Photographic Emulsion Chemistry" by Duf in
ulsionChemistry) J (Safaukarp v, x, published by The Focal Press, /
(2006), Gui L., T. x Likman et al. V, L.
“Making and Coating Photographic Emulsions” by Zelikman et al.
making and coating photogra
phic Emulsion) J (7oh fJk
Pv, x, published by The Focal Press, /
It can be prepared using the method described in (2011).

In addition, during the formation of silver halide grains, ammonia, rhodanpotash, rhodanammonium, thioether compounds (for example, U.S. Pat. No. 3,271,137, U.S. Pat.
．． j7g, tλ♂ No. J, No. 1011.130,
Same No. ≠l Kota 7. Hiroshi No. 32, Hiroshi No. 274.37≠, etc.) Thione compounds (e.g. JP-A Sho! 3-/Hiroshi≠, 3)
/ri issue, same number 53-rs! /Lor No. jj-77
, No. 737, etc.), amine compounds (for example, JP-A No. 4!
-1007/7, etc.) can be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

Examples of the internal defect type photosensitive material used in the present invention include US Patent No. 2. 2. Ko! θ No. 3゜106,313
No. 3. g4t7. Octopus No. 7, same! , 761,276
No. 3, and 3. Conversion type photosensitive materials, core/shell type photosensitive materials, photosensitive materials incorporating different metals, etc., which are described in 33.0/Hiroshi No. 33, etc., can be mentioned.

Next, the prefogged direct positive photosensitive material used in the present invention includes a direct positive silver halide photographic photosensitive material that has been fogged with light or with a chemical fogging agent.

Generally, this photosensitive material is classified into the following two types.

One type of crystal has a nucleus capable of trapping free electrons inside the silver halide crystal, and its surface has been chemically fogged in advance. The feature of this type of light-sensitive material is that it directly gives a positive image by itself, and by adding a sensitizing dye, it can not only increase the sensitivity through spectral sensitization but also sensitize the intrinsic absorption region. can also be given. In this type of photosensitive material, the halogen composition must be adjusted so that the chemical sensitizer used to provide free electron trap nuclei can easily incorporate Group I metal salts into the silver halide. . Furthermore, by adding an organic desensitizer, it is possible to improve dropout, and in particular to prevent "reinversion". Further, by adding bromine ions or iodine ions, it is possible to increase the maximum concentration, increase sensitivity, and improve omission.

Another cool photosensitive material is a photosensitive material in which free electron trap nuclei are not provided inside the silver halide, but the surface of the silver halide is chemically fogged.

This light-sensitive material is a silver halide light-sensitive material containing as few crystal defects as possible, preferably pure silver bromide, and consisting of regular crystals without twin planes.

This photosensitive material itself does not directly give any positive image.

However, if an organic desensitizer is adsorbed onto the silver halide of this light-sensitive material, a direct positive acid with high sensitivity can be obtained.

Either photosensitive material can be used in the present invention. In other words, both types of light-sensitive materials can be effectively sensitized using methine dyes.

The direct positive silver halide photographic material will be described in detail below.

The direct positive silver halide used in the present invention is an inorganic desensitizer (i.e., noble metal atoms contained in silver halide grains, etc.)
It can also contain an organic desensitizer or a desensitizing dye that adsorbs on the silver halide surface, singly or in combination.

In order to incorporate the inorganic desensitizer used in the present invention into silver halide grains, a water-soluble noble metal compound such as iridium,
Chlorides of group R metals of the periodic table such as rhodium per mol of silver halide/0-7 to 10-2 mol, preferably 10
-5 to 10-3 mol may be added as an aqueous solution during preparation of silver halide grains.

The organic desensitizer used in the present invention is a substance that has the ability to capture free electrons generated in silver halide grains by radiation irradiation, and is a substance that adsorbs to silver halide. Furthermore, it is defined as a substance having the lowest vacant electron energy level, which is lower than the electron energy level of the conduction band of silver halide grains. Preferably, the compound has a highest occupied electron energy level lower than the valence band of the particles.

The organic desensitizer used in the present invention is, for example, U.S. Pat.
No. 023,102, No. 313/≠, No. 72, No. 2
．． British Patent No. 72.3,0/ri, British Patent No. z9g, 371, British Patent No. 691,376, British Patent No. 311,139, British Patent No. 4
67.201, 74th tr, tr1, 75th
'J, J'77, same No. 173, 1rlr No. 7, same No. 9
0yo, No. 237, No. 207,367, No. 0 tag,
No. 712, French Painting Patent No. 1. jkoo, rko≠ No. 1.
j/r, No. 09'1, No. 1. ! /No. 1,096, No. 1.620,119, No. 1,! No. 20.123,
Same 1st. ! λ0,12/No. 1,123°6, Belgian Patent No. 722. Da! No. 7, No. 7 λ,! Specifications of ≠ issues, Tokko Akihiro 3-/3167, ≠ 3-
/≠zoo issue, etc.

Examples of organic desensitizers or desensitizing dyes that can be used in the present invention include dimethine cyanine dyes containing a co-substituted phenyl)-indole nucleus, bis-(/-alkyl-cophenyl)-indole-3- trimethine cyanine dye, cyanine dye containing an aromatic substituted indole nucleus, imidazoquinoxaline dye, asymmetric cyanine dye containing a carbazole nucleus, trimethine cyanine dye containing an aromatic substituted indole nucleus 1.2-J-3-) Realkyl-3H - Cyanine dyes containing a nitroindole nucleus, cyanine dyes containing a complex fused pyrimidinedione nucleus, 2-inoxazoline-yone nucleus, q-classified with a kobyrazoline-thorn nucleus or a complex fused pyrimidinedione nucleus merocyanine dyes, cyanine dyes containing a λ-allylimino (or alkylimino)-l-allyl (or alkyl)-3-thiazoline nucleus, merocyanine dyes having a 3-allyl-amino or 3-lower fatty acid amide substituted monobirazolin-j-one; μ-class ammonium salt dyes, biryllium, thiapyrylium, selenapyrylium salt dyes, cyanine dyes having a nitro-substituted 2-arylindole nucleus, bipyridinium salt dyes, cyanine dyes containing a pyrrole nucleus bonded at the carbon atom in the co-position, 1. 2
- Diaryltrimethine indole dye, cyanine dye containing a goopyrazole nucleus, polymethine dye containing an imidazole nucleus, dimethine cyanine dye containing a cophenyl-substituted indole nucleus, trimethine cyanine dye consisting of two indole nuclei, l-cyanoalkyl lucor Cyanine dyes containing an arylindole nucleus, cyanine and merocyanine dyes in which two nuclei have desensitizing substituents such as nitro groups, cyanine dyes containing an /-alkyl-J-phenyl substituted indole nucleus, /-alkoxyl 2-arylindoles Nuclear-containing cyanine dye, imidazo [Hiroshi].

1, +1 Cyanine dyes having a quinoxaline nucleus, dyes containing a cycloheptanetriene ring, dimethine cyanine dyes containing an indole nucleus, pyrazolo[1,j-a'3: cyanine dyes containing an nzoimidazole nucleus, pyrazolo (t, / −
b) Cyanine dye containing a quinazolone nucleus, pyrrolo [co, J
-b) dimethine cyanine dyes containing a pyridine nucleus, cyanine dyes containing a pyrrole nucleus, dyes containing a pyrrolo[co,/~b]thiazole nucleus, containing an indole or indolenine nucleus containing a hensoylic or haphenylsulfonyl substituent; Cyanine dye US patent J4! Nitrostyryl-type compounds described in lj, pinacryptol yellow j-metanitrobenzylidene rhodanine, etc., Special Publication Showa 4'r-/30! Bis-pyridyram compound described in Japanese Patent Publication No. 1987-147,
The phenazine compounds described in r7≠6 are useful.

More preferred organic desensitizers are compounds represented by the general formula (X) or the general formula (X[l) spanning the general formula (X).

General formula (X) r1 In the formula, Zl represents an atomic group necessary to form a nitrogen-containing heterocycle.

Tl is a halogen atom, an alkyl group, a norodane atom,
Acyl group, acyloxy group, acylamino group, alkoxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carbonyl group, cyan group, hydroxy group, amine group, alkylthio group, alkylsulfonyl group,
It represents a sulfonic acid group, a sulfonamide group, an aryl group, or a condensed ring, which may further have a substituent.

ql represents 1, ko or 3.

rl represents 0, 1, ko, or 3.

General formula (XI) In the formula, R9 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. These may further have a substituent.

T2 has the same meaning as T1.

q2 represents 1, ko, or 3.

T2 represents θ, '%, or 3.

General formula (XA) In the formula, it has the same meaning as R10ViR9.

It is synonymous with T3hT1.

q3 represents 1, 2 or 3.

T3 represents θ, 1, ko, and fcn3.

General formulas (X), (XI) and (Kari) will be explained in more detail. Specific examples of the nitrogen-containing heterocyclic nucleus completed by Zl include 1, 2. +-triazole, 1,3.4t-oxadiazole, 1,3. ≠-Thiadiazole, tetraazaindene, pentaazaindeno, triazaindene, benzothiazole, benzimidazole, benzoxazole, pyrimidine, triazine, pyridine, quinoline, quinazoline, phthalazine, quinoxaline, imidazo [ta,
5-1) Quinoxaline, tetrazole, and 1,3-diazaazulene may be mentioned, and these rings may further have a substituent or may be further fused.

T1, T2 and T3 are halogen atoms (e.g. chlorine atom, fluorine atom, bromine atom), unsubstituted alkyl groups having carbon numbers of θ or less (e.g. methyl groups, ethyl groups), substituted alkyl groups having carbon numbers of 7 g or less (e.g. cyclohexyl group, allyl group, benzyl group, α-naphthylmethyl group, cophenylethyl group, trifluoromethyl group), acyl group with 10 or less carbon atoms (e.g. acetyl group, benzoyl group, mesyl group), 10 carbon atoms The following acyloxy groups (e.g. acetyloxy group), alkoxycarbonyl groups having 10 or less carbon atoms (e.g. methylsulfonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), substituted or unsubstituted carbamoyl groups (e.g. carbamoyl group) ,
N,N-dimethylcarbamoyl group, morpholinocarbonyl group, hyberidinocarbonyl group), substituted or unsubstituted sulfamoyl group (e.g. sulfamoyl group, N.

N-dimethylsulfamoyl group, morpholinosulfonyl group, pyharidinosulfonyl group), carboxy group, cyan group, hydroxy group, amine group, acylamino group with carbon number r or less (e.g. acetylamino group), carbon number/θ or less alkoxy groups (e.g. methoxy, ethoxy, benzyloxy), alkylthio groups (e.g. ethylthio)
, an alkylsulfonyl group (eg, methylsulfonyl group), a sulfono acid group, a sulfonamide group, and an aryl group (eg, phenyl group, tolyl group).

One bonded to an adjacent carbon atom may be bonded to each other to form a benzene ring. In addition, heterocycles (e.g., pyrrole ring, thiophene ring, furan ring,
pyridine ring, imidazole ring, triazole ring, thiazole ring).

R9 and RIO represent a hydrogen atom, an alkyl group having 7 to 1♂ carbon atoms, preferably 7 to 7 carbon atoms, particularly preferably 1≠ (e.g., methyl group, ethyl group, propyl group, isopropyl group, methyl group, isobutyl group) , hexyl group, octyl group, dodecyl group, octadecyl group), substituted alkyl groups (e.g. aralkyl group (e.g., t is benzyl group, λ-phenylethyl group), hydroxyalkyl group (e.g. co-hydroxyethyl group, 3-hydroxy propyl group), carboxyalkyl group (e.g. λ-carboxyethyl group, 3
-carboxypropyl group, carboxydutyl group, carboxymethyl group), alkoxyalkyl group (e.g.
λ-methoxyethyl group, Co(Comethoxyethoxy)
ethyl group), sulfoalkyl group (e.g. cosulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group,
≠-sulfobutyl group, λ-[3-sulfopropoxy]ethyl group, cohydroxy-3-sulfopropyl group, 3-
sulfopropoxyethoxyethyl group), sulfatoalkyl group (e.g., 3-sulfatopropyl group, ≠-sulfatobutyl group), heterocyclic-substituted alkyl group (e.g., co(pyrrolidin-2-on-/-yl)ethyl group, Tetrahydrofurfuryl group, co-morpholinoethyl group), co-acetoxyethyl group, carbomethoxymethyl group, co-methanesulfonylaminoethyl group), allyl group, aryl group (e.g. phenyl group, co-naphthyl group), substituted aryl group ( For example, preferred are a glucarboxyphenyl group, a ≠-sulfophenyl group, a 3-chlorophenyl group, a 3-methylphenyl group), and a heterocyclic group (eg, a copyridyl group, a cortiazolyl group).

Fog can be applied to the direct positive type silver halide used in the present invention by a conventionally known technique after water-soluble salts generated after precipitation of the silver halide are removed. Fog can be imparted by using a fogging agent (reducing agent) alone or by combining the fogging agent with a gold compound or a useful metal compound that is more electrically positive than silver.

Representative fogging agents useful in making such emulsions include, for example, formalin, hydrazine, polyamines (e.g., triethylenetetramine, tetraethylenepentamine, etc.), thiourea dioxide, tetra(hydroxymethyl)phosphonium chloride, acineborane hydrogen. These include boron compounds, stannous chloride, tin(n) chloride, etc. Typical useful metal compounds that are more electrically positive than silver include gold, rhodium, platinum, radium,
Included are soluble salts such as iridium, such as potassium chloroaurate, chloroauric acid, ammonium palladium chloride, sodium iridium chloride, and the like.

The fogging agent is generally 1.0× per mole of silver halide.
It is used in a range of 10-6 to 1,0 x 10-1 mol.

Typical gold compounds include chloroauric acid, sodium chloroaurate, sulfur compounds, selenium compounds, etc., and generally contain 1,0x10-6 to 1,0x10-4 per mole of silver halide.
It is preferable to contain it in a molar range.

The degree of fogging of the pre-coupled direct positive silver halide emulsions used in the present invention can be varied over a wide range. The degree of fogging depends on the silver halide composition and grain size of the silver halide emulsion used, as well as the type and concentration of the fogging agent used, as is well known to art technicians.
Emulsion PH% pAg% at the time of fogging
Related to temperature, time, etc.

The direct positive silver halide thick photosensitive material of the present invention contains a selenium compound as described in JP-A No. 6-≠Corco, and a sensitizing dye such as a dimethine trimethine cyanine dye, a halogen-substituted hydroxyl phthalate, etc. Rhine dyes, phenazine dyes, benzothiazole, cyanine dyes containing benzoselenazole nuclei, cyanine dyes containing naphthoxazole nuclei, triphenylmethane dyes, cyanine dyes containing indolenine nuclei,! - a cyanine dye containing a pyridine-rhodanine nucleus, a cyanine dye containing a thiazole nucleus,
High sensitivity can be provided by containing a substance such as at least one sensitizing dye selected from asymmetric cyanine, quinoline, meso-substituted cyanine dye, cyanine dye containing a rhodanine nucleus, and polymethine dye having three nuclei. be.

The direct positive silver halide photographic light-sensitive material of the present invention can be applied to various uses. For example, for duplicating,
Various photosensitive materials for printing such as reproductions and offset masters, special photosensitive materials such as X-ray, flash photography, and electron beam photography, and for general copying, microcopying, direct positive color, and quick stabilized printing. It is used in light-sensitive materials for direct positive photography, such as for diffusion transfer, color diffusion transfer, and bath fixation.

The following is a description of common silver halide photographic materials.

Silver halide photosensitive materials are usually chemically sensitized. For chemical sensitization, for example H Freezer H,Fr
1eser) edition De 4-Krando 5-'y'n der.
Photography photographer Mitsut Zilbelhalogeniden (DieGrundlagen d
er Photography Prozes
se mit Silberhalogeniden
(Akademische Verlagsgesell)
schaft.

/4r) The method described on pages A7j to 734L can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, reduction sensitization using noble metal compounds (e.g., total complex salts,
pt.

A noble metal sensitization method using complex salts of metals of group (I) of the periodic table such as Ir and Pd can be used alone or in combination.

The photographic material used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the material, or for stabilizing photographic performance.

i.e. thiazoles such as benzothiazolium salts,
Nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles ode (especially /-
phenyl-j-mercaptotetrazole), mercaptopyrimidines: The above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group: Thioketone compounds such as oxazolinthione; Azaindenes such as tetraazaindenes (especially ≠-hydroxy-substituted (1,3゜3a,y)tetraazaindenes);
Many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acids: benzenesulfinic acid; and the like.

It may also contain water-soluble inorganic salts such as carbon dioxide, cadmium, cobalt, nickel, manganese, gold, thallium, and zinc. Hardening agents include formalin, glyoxal, aldehydes such as mucochloric acid, S-triazines, epoxies, aziridines, vinyl sulfonic acid, and coating aids such as saponin, sodium polyalkylene sulfonate, and lauryl polyethylene glycol. Alternatively, it may contain oleyl monoether, amylated alkyl taurine, a fluorine-containing compound, or the like.

Further, the silver halide photographic light-sensitive material of the present invention may contain color couplers such as cyan coupler, magenta coupler, yellow coupler, and compounds that disperse the couplers.

That is, it may contain a compound that can develop color by oxidative coupling with an aromatic/grade amine developer (eg, phenylenediamine derivative, aminophenol derivative, etc.) in color development treatment.

For example, as a magenta coupler! - Pyrazolone couplers There are pyrazolobenzimidazole couplers, cyanoacetyl coumaron couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides,
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either ≠ equivalent or di-equivalent to the silver ion. It may also be a colored coupler that has a color correction effect or a coupler that releases a gap inhibitor during development (so-called DIR coupler).

In addition to the DIR coupler, the coupling reaction product may include a colorless DIR coupling compound which is colorless and releases a development inhibitor.

Further, the silver halide photographic material of the present invention can contain a so-called filter dye, which absorbs and cuts visible light so that it can be handled under a fluorescent lamp that cuts off ultraviolet light using an ultraviolet light source. .

The dye used in the present invention has a main absorption in the visible wavelength range of the wavelength range of inherent sensitivity of the silver halide emulsion used. There are no particular restrictions on the chemical structure of the dye, and oxonol dyes, hemioxonol dyes, merocyanine dyes, cyanine dyes, azo dyes, etc. can be used, but water-soluble dyes are advantageous in terms of eliminating residual color after processing. It is.

Specifically, for example, Tokko Akira! Pyrazolone dyes as described in U.S. Patent No. λ, 2714°7g; Diarylazo dyes described in U.S. Pat. No. 3, No. 177 and US Pat. ≠23,207, 3.3♂≠, and the styryl dyes and butadienyl dyes described in U.S. Patent No. 4J'7, and U.S. Pat. ! 27. Merocyanine dye described in U.S. Patent No. 3゜≠6. rri No. 7, same No. 3.1. ! 2. merocyanine dyes and oxonol dyes described in US Pat. 76°A
Enaminohemioxonol dyes described in No. A/ and British Patent No. ZRP, tori No. 7,177.1A29
Issue, JP-A-4'r-1! /No. 30, same≠Tatata 620
No., Koter//'71720, U.S. Patent No. 2,33
3. Hiroshi No. 72, same No. 3. ／≠? .

/♂No.7, same No.3. /77.071, same No. 3゜2≠7
．． No. 127, same No. 3. ! '10,117, same number 3.6
7! , No. 1011, No. 3. tjf3. ? OJ',
The dye described in is used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
It may contain various compounds for various purposes such as (promotion of phenomena, enhancement of contrast, sensitization), etc.

For example, thioether compounds, thiomorpholines, urethane derivatives, imidazole derivatives, 3-pyrazolidones, etc. may be included.

Also, for example, saponins (steroids), alkylene oxide derivatives (such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, Non-ionic materials such as alkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates , sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc., carboxy groups,
Anionic surfactants containing acidic groups such as sulfo groups, phosphosulfate ester groups, and phosphate ester groups; Ampholytic surfactants; cationic interfaces such as alkylamine salts, aliphatic or aromatic tertiary ammonium salts, heterocyclic cylindrical≠grade ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles. Activators can be used.

In particular, the surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more, which are described in Japanese Patent Publication No. 2003-11212.

Polyalkylene glycol aryl ethers (alkylaryl) ethers, polyalkylene glycol esters, polyalkylene glycol fatty acid amides, polyalkylene glycol amines, polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, and the like can be used. The molecule f needs to be 100 or more.

The number of polyalkylene oxides is not limited to one, and two or more may be included in the molecule. In that case, the side polyalkylene oxides may consist of less than IQ alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least 10. When there is more than one polyalkylene oxide in the molecule, each of them may consist of different alkylene oxide units, such as ethylene oxide and propylene oxide. The polyalkylene oxide compound used in the present invention preferably contains alkylene oxide units from /g to lOO.

Specific examples of the polyalkylene oxide compounds used in the present invention are as follows.

Polyalkylene oxide compound example (Xln)-/ (XI[I)-2 (X[[[)-j (Xnl)-Hiro(X[I)-j (Xlll)( )IO(CH2CH20)9oH C4H90(CH2CH20 )15H C12H250 (CH2CH20)15HC18H31
0(CH2CH20)15HC18H310(CH2C
H20) 40HC8H17CH:CHC8H160(C
H2CH20)15H(XI[+)-IOC11H23
COO(CH2CH20)80H(Xllll)-//
C11H23C00 (CH2CH20) 2400C1
1H23(XIII)-/7 H(CH2CH20)a(CH2H20)b(CH2C
H20)cHsaH3 a-)-b-4-c = 30 b:a+c=10? (XI)-/r (X In) i 3c Engineering IH23CONH (CH
2CH20) 15H(XI[I)-/ri(XIn)/! C14H2gN(CH3)(C
H2CH20)2C14H2[I)-/1 CH2-0-CH-CH2α? nHz3H(OCH2C
H2) 140-CH-CH-CH-(CH2CH20h
4H(XI[[)-20 HO(CH2CH20)a(CH2CH2CH2CH2
0)b(CH2CH20)cHa-)-c=J(7,b
=/1. t o (CH2CH20), 4H (XI[r)-2/ b=♂+ a+c=Even 0 (XII[)-Jλ (XI[I)-23 (X Ill) -j II HO+cH2cH
20 sho-H etc. JP-A-30-1361423, JP-A-Sho! Polyalkylene oxide compounds described in No. 2-101130 and JP-A-Sho, t3-32/7 can be used. These polyalkylene oxide compounds may be used alone or in combination of two or more.

When these polyalkylene oxide compounds are added to a silver halide emulsion, they are dissolved in an aqueous solution of an appropriate concentration or in a low boiling point organic solvent that is miscible with water.
It can be added to the emulsion at any suitable time before coating, preferably after chemical ripening. It may be added to non-photosensitive hydrophilic colloid layers, such as intermediate layers, protective layers, filter layers, etc., instead of being added to the emulsion.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, polymethyl methacrylate, etc. in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate),
Acrylonitrile and the like can be used alone or in combination.

The emulsion used in the present invention mainly uses gelatin as a protective colloid, and it is particularly advantageous to use inert gelatin. Instead of gelatin, photographically inert gelatin derivatives (eg, phthalated gelatin), water-soluble synthetic polymers (eg, polyhinyl acrylate, polyvinyl alcohol, polyvinylpyrrolidone) are used.

Other additives may be used in conjunction with the photographic material or other hydrocolloids in accordance with the present invention, such as antifading agents, brighteners, preservatives, inorganic or organic hardeners, antifogging agents, etc. agents, ultraviolet absorbers, mordants, plasticizers, latex polymers, matting agents, etc.Specifically, research disclosure (Re
5earchDisclosure) Vol.
/7t (/7r, XI), D-77&4L3, etc.

The novel emulsions of the present invention can be applied to any suitable photographic support, such as glass, film bases such as cellulose acetate, cellulose acetate butyrate, polyester [
For example, poly(ethylene terephthalate) baryta paper,
Resin coated paper, synthetic paper, etc. are used.

Photographic processing of light-sensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure).
Disclosure) z No. 76, pages 2r-30 (R
D-7rglI3), any of the known methods and known treatment liquids can be applied. Depending on the purpose, this photographic processing may be either photographic processing that forms a silver painting (black and white photographic processing) or photographic processing that forms a dye group (color photographic processing).

As the developing solution used in the present invention, a so-called Lith type developer having a low concentration of sulfite ions can be used, or a sufficient amount of sulfite ions as a preservative (specially KO, / jmol/1
above) can be used, and also has a pH of 7
, 5 or more, especially 10. It is also possible to use a developer of 93.

There are no particular restrictions on the developing agents that can be used in the method of the invention, such as dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg /-phenyl-3-pyrazolidone, ≠).

(Hiro-dimethyl-7-phenyl-3-pyrazolidone) and amine phenols (for example, N-methyl-p-aminophenol) can be used alone or in combination.

The developer also contains alkali metal sulfites, carbonates,
Contains pH buffering agents such as borates and phosphates, bromides, iodides, and antifoggants or antifoggants such as organic antifoggants (particularly preferably nitroindazoles or benzotriazoles). be able to.

If necessary, water softeners, solubilizing agents, color toning agents, phenomenon accelerators, surfactants (especially preferably the aforementioned polyalkylene oxides), antifoaming agents, hardeners, film silver stain preventive agents ( For example, λ-mercaptobenzimidazole sulfonic acids) and the like may be included.

Specific examples of these additives can be found in Research Disclosure/
It is described in No. 74, /7tμ3, etc.

The processing temperature is usually selected between /♂'C and zo 0c, but it may also be lower than lr 0c or higher than so''C.

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 also contain a water-soluble aluminum salt or the like as a hardening agent.

(Examples) The present invention will be explained in more detail with reference to Examples below, but the embodiments of the present invention are not limited thereto.

Examples/(Negative Emulsion) A silver chlorobromide emulsion was obtained by the usual double jet method. The halogen composition of this particle is Br ion ♂ tamorti, and in the precipitation composition process, per mole of silver ion, 1002000 parts/(weight ratio) solution/(weight ratio) of rhodium(III) chloride/
, jcc and Rodin Mercury (II) io, ooo, o
oo min/(weight ratio) solution≠, Jcc was contained. The resulting silver chlorobromide emulsion was sulfur sensitized with a gold sensitizer by using a 10% solution of gold(II[) chloride per mole of silver ion, 2,7 C'(!). mode ii 0.7 micron.The resulting emulsion was
This agreement/.

It contained 2 moles of silver ions.

300 g of water was added to 100 g of the obtained silver chlorobromide raw emulsion to give a total weight of 100 g/kg. Melt this at jOoC≠O
Stored at 0C and stirred each methine dye in Table 1! A 10-3 molar methanol solution was added. Furthermore, 20 cc of a 2% aqueous solution of λ,t-dichloro2-hydroxy-3-triazine and 20 cc of a 2% aqueous solution of nonyl(sodium sulfonate) were added to the cellulose triacetate film so that the dry film thickness was approximately μ microns. Coated.

This sample was cut into strips and treated with Sensitome I.
I did J-. The photosensitive needle used was a flash photometer (E, G-G
・Manufactured by the company). Obtain a single light color using an interference filter,
The exposure amount was determined using both physical photometry using a photometer and photographic photometry.

The exposed strips were heated to θ0C using the following developer.
After developing for 3 minutes, it was fixed, washed with water, and dried. The density of the thus treated strips was measured using an S-type densitometer manufactured by Fuji Photo Film Co., Ltd., and a photographic characteristic curve was determined.

The amount of exposure necessary to give an optical density of [Cub +) + 1,0] is determined, and the relative value of its reciprocal (this is defined as relative sensitivity) is used to express the sensitizing effect of the dye.

[Composition of developer]

The results are shown in Table 1.

In addition, The following dye (A) was used as a comparison dye. of Using.

Comparative dye (A) The ratio (A) is a value defined as follows.

Dye (II)-μ from Jikkenya 3 is dye (A) (A-2
), the spectral sensitization (
It can be seen that in this case, a monochromatic exposure with a narrow band width of t o nm is provided. Also, the dye (It) −≠
It can be seen from the comparison with additive-free (Y/) that the high illuminance failure for light in the characteristic sensitivity wavelength range (in this case, due to monochromatic light exposure with a narrow band width of 3♂/nm) is rather improved. Experimenter μ! From dye (It)-co-1, (II)
It can be seen that -, 2≠ gives high intrinsic sensitivity and spectral sensitivity at 7-6 second exposure.

Example 2 (Negative Emulsion) The same silver chlorobromide emulsion as used in Example 2 was used. Add water colog to emulsion cozog and melt it≠o
' Saved in C. Add the methine dye shown in Table 2 and finals as in Example/ in the same manner as in Example/,
A sample was obtained by coating and drying.

Scanning exposure was performed using a commercially available He--Ne laser oscillation unit, and the sample was exposed for /x10-5 seconds.

A menu that tests the stability of each sample under high temperature and high humidity conditions.
jO0C±, 2°C and relative humidity 10%±! ≠ was incubated for a time.

Comparative Dye (B) Each sample was prepared according to Example 1, scanning exposure was performed using a commercially available Ar laser oscillation unit, and the sample was exposed to light for /×10 −5 seconds to cause a phenomenon.

The results obtained are shown in Table 3.

The results obtained are shown in Table 2. Comparative dye (B) gives only low sensitivity and desensitizes under storage conditions of high humidity and high temperature, whereas dye (It)-2 of the present invention provides only low sensitivity.
, (II)-23, (V) -1, (V) -// is
It can be seen that it has high sensitivity and can maintain high sensitivity even under storage conditions of high humidity and high temperature.

Example 3 (Negative Emulsion) A silver iodobromide emulsion was obtained by a conventional method. The halogen composition of these particles is 1 mole of silver ion, and 1 mole of gold chloride and 0.0 mole of potassium hexachloroplatinate (F/) per mole of silver ion. /% solvent/, 7 cc was used for noble metal sensitization. The average particle diameter was o, og microns.

Comparative dye (C) Comparative dye (C) gives only low sensitivity and desensitizes under storage conditions of high humidity and high temperature.
Dye of the present invention (It)-7, (It)-33, (1-1
, (1-4tFi high sensitivity, and it can be seen that high sensitivity can be maintained even under storage conditions of high humidity and high temperature.

Example 4L (negative emulsion) A commonly known method (1 photoj.
7 pages 330 pages (1 and 3) TrivelliSrn
A silver chloroiodobromide emulsion/silver iodobromide emulsion in which the average grain size of silver halide crystal grains is about 0.36 croms prepared by
kg was added with a certain amount of a methanol solution of the dye used in the invention as exemplified above. This silver halide photographic emulsion was coated on a cellulose triacetate film base and dried to prepare a sample.

The above sample was produced using a commercially available neon-helium laser oscillator with an output of 0. /♂mW neon-helium laser light, using a neutral gray gelatin filter instead of a light wedge, and exposing for 7/100,000 seconds, using a phenomenon solution with the following formulation. The sensitivity of the sensitizing dye H used (the reciprocal of the exposure required to give density = ko, !) is 10
The relative sensitivity is expressed as 0.

Table ≠ lists the dyes used in the present invention exemplified above and the sensitizing dyes exemplified as comparative dyes: E, F, G, H1.
The chemical structures of the sensitizing dyes shown for comparison are as follows, showing relative sensitivities when D, J, and K are added to the silver halide photographic emulsion used in the present invention.

Dye G Dye E Dye H Dye F Dye J As is clear from the numerical values in the table, the photographic emulsion containing the dye of the present invention has significantly higher sensitivity than the comparative one.

EXAMPLE (Negative Emulsion) A silver chlorobromide gelatin emulsion containing 3 mol of silver bromide was prepared by a simultaneous mixing method at 110C for 0 minutes. The emulsion thus prepared was desalted and redispersed, with an average grain size of 0.
A 2 μm cubic monodisperse emulsion was obtained.

To each of these samples, sodium thiosulfate irmg and 2.0 mg of chloroauric acid were added per mole of silver rhodide, and chemical ripening was performed at t, o 0 c for 10 minutes.

These samples were coated with dye at an amount of r, o mg/m2.
In addition, 6-methyl-μ is added as a stabilizer.
m-hydroxy-1,3,311.7-titrazye/dene was added, and in addition to these, saponin and formalin were added. These samples were then placed on a support with silver amounts of J and l, respectively.
A film was prepared by applying the solution at rg/m2.

Each of the films thus obtained was subjected to scanning exposure using a commercially available semiconductor laser (laser wavelength: 7 r Onm) oscillation unit, giving an exposure of /x10-5 seconds. Furthermore, use the following developer solution at 20°C.
The phenomenon occurred for I minutes.

Sensitivity in Table 5 is expressed as relative sensitivity, where the reciprocal of the exposure amount necessary to give density λ, j is 100 of the sensitivity of the sensitizing dye used for comparison.

The results obtained are shown in Table 5.

Comparative Dye (L) As is clear from the values in Table 5, it can be seen that the dye of the present invention has higher sensitivity than the comparative dye (L).

Example t (direct positive emulsion) 1 mole of silver in an aqueous gelatin solution maintained at
)y×10−7 mol/Ag mol of iridium salt and l×
In the presence of 10-5 moles of rhodium chloride, a mixed aqueous solution of silver sulfate, sodium chloride and potassium bromide,
At the same time, add at a constant rate for 30 minutes to obtain an average particle size of 0.
．． A 2μ silver chlorobromide monodisperse emulsion was prepared. (α composition 20
(mol %) This emulsion was desalted by the flocculation method, and 2 mg of thiourea dioxide and 0.2 mg of thiourea dioxide were added per mole of silver. Add 1 mg of potassium chloraurate, and
A ripening stain was produced until the highest performance was obtained at C.

These emulsions were divided and the methine dye of the present invention and the following organic desensitizer (A) (per mole of silver/X1
0-3 mol) per mole of silver ≠ × 10-4
Mol of polyalkylene oxide compound (XIII)-
7.10% KBr aqueous solution and Cohydroxy Hiroshi as a hardening agent.

6-dichloro-1,3. ! An emulsion was prepared by adding -4 lyazine sodium salt and /13-divinylsulfonyl-2-propanol, containing a dispersion of silica and ethyl acrylate as a matting agent, and sodium dodecylbenzenesulfonate as a surfactant. Coating was carried out on a polyethylene terephthalate film at the same time as the gelatin protective layer containing silver in an amount of 3.0 g and 7 m 2 .

Organic desensitizer (A) Using the commercially available laser oscillation unit If shown in Table 6 on the obtained sample, Scan Jung l1H1 row A, /x on the sample.
A 10-5 second exposure was given.

Table 2 shows the results of developing with a developing solution having the following composition at 3r 0c for 20 seconds, stopping, fixing, washing with water, and drying.

(Photographic characteristics/) Photographic characteristics are for each film to 0c phase relative dust 7! The photographic properties were evaluated in the same manner as in 1 after being left for 3 days under the conditions described above.

Here, the relative sensitivity is the relative value of the reciprocal of the exposure amount that gives the density 1,j in the JI 0C 20 second phenomenon, and assuming that the value of the photographic characteristic l of sample / is 10θ, sample A2.3,
The relative sensitivity of II and if was determined.

Similarly, the value of the photographic characteristic l of samples A&, /1, /j is set to 10
The relative sensitivity was determined by setting it to 0.

A phenomenon liquid having the following formulation was used.

Current liquid formulation comparative dye (M) Comparative dye (0) Comparative dye (N) From the table below, it can be seen that the dye of the present invention has high sensitivity and the decrease in sensitivity after storage at high humidity and high temperature is small.

Example 7 (Direct positive emulsion) A gelatin aqueous solution containing 0-r g/l of potassium bromide was maintained at 7θ0C, and per mole of silver! x 10-6 mol/Ag mol of rhodium salt and tX 10-7 mol/A
adding an aqueous solution of silver nitrate and an aqueous solution of potassium bromide simultaneously at a constant rate over a period of 25 minutes in the presence of g moles of iridium salt,
By keeping the potential between them at +AOmV, the average particle size is 0.2! A silver bromide cubic monodisperse emulsion of μ was prepared.

This emulsion was desalted by the flocculation method,
Add 10 mg thiourea dioxide and t mg potassium chloroaurate per mole of silver and t! The aged turnips were grown at 0C until the best performance was obtained.

These emulsions were divided and the methine dye of the present invention and the organic desensitizer (B) (per mole of silver/xl0-3) were divided as shown in Table 7.
1 mole) per mole of silver, 1) 1, ) I×10−4 mol of polyalkylene oxide compound (XI[l−7) and 1
After adjusting the PAg with 0% KBr and adding 1,3-divinylsulfonyl-coprobanol as a hardening agent, a protective layer containing silica mat and gelatin with the addition of sodium dodecylbenzenesulfonate as a surfactant was simultaneously applied to polyethylene. Silver amount J, 2g/ on terephthalate film
Coating was carried out in a total of m2.

Organic Desensitizer (B) (1) A backing layer and a pack protective layer were coated on the opposite side of the emulsion layer and protective layer with the support sandwiched therebetween.

The backing layer contains ta-[r-oxo-3- as a dye.
Methyl-a (ta-N, N-dimethylaminophenyl)
Methylene-2-pyrazolinyl]be/zenesulfonic acid potassium salt and μ-[3-carboxy-! −Hydroxy≠−
(j-(3-carboxy-!-oxol-(t-sulfophenyl)-2-pyrazoline-gooylidene)-i,
J--: ntadienyl)-/-pyrazolyl] Contains potassium salt of benzenesulfonate, contains ethyl acrylate polymer to improve film quality, and is coated with a surfactant, a charge control agent, and a hardening agent together with gelatin. Ta. In the pack protective layer, a polymer of polymethyl methacrylate was added in gelatin as a surfactant and a matting agent and was coated on top of the back layer (on the opposite side of the support).

The obtained sample was irradiated with the commercially available laser shown in Table 7! Scanning exposure is performed using the unit, and /×l0
A -5 second exposure was given.

Thereafter, the same evaluation as in Example t was performed. The results obtained are shown in Table 7.

Note that, as in Example 6, the relative sensitivity was determined by setting the value of photographic property / of sample A1, j to 100.

Table 7 shows that the dyes of the present invention have high sensitivity, and the decrease in sensitivity after storage at high humidity and high temperature is small.

Patent applicant: Fuji Photo Film Co., Ltd. 1゜ 2゜ 3゜

Claims (2)

[Claims] (1) The azulene nucleus consists of a nucleus in which at least one of the 10 carbon atoms is replaced with a chalcogen atom or a nitrogen atom, and the 7-membered ring part of the nucleus forms a conjugated resonance chromophore with the 10π electron system of the nucleus. A silver halide emulsion for flash exposure, characterized in that it contains at least one methine dye substituted with a methine bond having an auxochrome formed at its end. (2) The methine dye consists of a nucleus in which at least one carbon atom at the 1st and 3rd positions of an azulene nucleus is replaced with a chalcogen atom or a nitrogen atom, and the 7-membered ring part of the nucleus is a 10π electron system of the nucleus. It is substituted with a methine bond with an auxochrome at the end that forms a conjugated resonance chromophore, and the 1,3
2. The silver halide emulsion for flash exposure according to claim 1, wherein when both of the two carbon atoms at the position are replaced with heteroatoms, at least one of the heteroatoms is a nitrogen atom.