JPS61275836A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To obtain a silver halide emulsion high in sensitivity and spectrally sensitized with a trimethine cyanine dye by incorporating a combination of at least one of specified sensitizing dyes and at least one of specified compounds in the emulsion. CONSTITUTION:The silver halide emulsion layer contains at least one of the sensitizing dyes represented by formula I in an amt. of 1X10<-8>-1X10<-2> mol, preferably, 1X10<-5>-2.5X10<-3> mol per mol of silver halide, and at least one of compounds represented by formula II, preferably, in a spectrally sensitizing amt., especially advantageously, in an amt. of 1X10<-8>-1X10<-2> mol per mol of silver halide in the silver halide emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a spectrally sensitized silver halide photographic emulsion.

(Prior art) One of the seven manufacturing technologies for photographic light-sensitive materials is the technology to extend the sensitive wavelength range to longer wavelengths by adding a certain type of cyanine dye to a silver halide photographic emulsion, that is, the spectral sensitization technology. It is well known that this applies. In this case, the sensitivity obtained by spectral sensitization, that is, the spectral sensitivity, is affected by the chemical structure of the sensitizing dye, various properties of the emulsion, such as the halogen composition of silver halide, crystal habit, crystal system, silver ion concentration, hydrogen ion concentration, etc. It is also known that Furthermore, this spectral sensitivity is affected by stabilizers, antifoggants, and
It is also influenced by photographic additives such as coating aids, sedimentation agents, color couplers, and hardeners.

Generally, seven sensitizing dyes are used in photosensitive materials to sensitize a predetermined spectral wavelength range. On the other hand, it is known that the presence of a second, specifically selected dye or other organic substance in addition to this dye significantly increases the efficiency of spectral sensitization; It is known as feeling.

In general, the addition of a second dye or the addition of an organic substance often does not increase the sensitivity or even reduces the sensitivity, so supersensitization is a unique development. Extremely strict selectivity is required for the compound and the second sensitizing dye. Therefore, what appears to be a seemingly minor difference in chemical structure significantly affects this supersensitizing effect, and it is difficult to obtain a supersensitizing combination simply by predicting from the chemical structural formula.

When applying supersensitization to a silver halide photographic emulsion, the sensitizing dye used is required to have a high spectral sensitivity.

It is well known that styryl bases exhibit excellent supersensitizing effects on the spectral sensitization of silver halide by monomethine cyanine dyes. For example, T. H. James (
The Theory of the Photographic Process (ed.)
f the PbotographicProcesses
s)” 1st edition, Macmillan Macmi II a
Published by N Company (New York), page 2 ≠ (/1977) K.

It is also known that styryl base exhibits an excellent supersensitizing effect on the spectral sensitization of silver halide by not only monomethine cyanine dyes but also various cyanine dyes. (For example, U.S. Patent No. 2゜3/3,9--) However, in any of the above cases, the long methine chain connecting the heterocycle and the benzene ring as shown in the following general formula (I) is used as the styryl base. Two types of sagas are used.

General Formula (N) However, the spectral sensitization obtained with the silver halide photographic emulsion supersensitized by this method is still not sufficient.

In particular, the present inventor has discovered that trimethine cyanine dye and the general formula (I
) We have discovered a method for obtaining high sensitivity in the spectral sensitization region that could not be obtained with conventional emulsions that were supersensitized using a compound represented by the following formula.

Incidentally, an example using pentamethine cyanine and a compound represented by the general formula (n) is shown in US Pat. No. 21,! ;,23
gK, but compared to that case, the sensitivity increase is particularly remarkable due to the combination of trimethine cyanine and the compound represented by the general formula (n).

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide photographic emulsion that is spectrally sensitized with a trimethine cyanine dye and has a high sensitivity that has not been previously available. be.

(Means for Solving the Problems) The object of the present invention is to obtain at least one type of sensitizing dye represented by the following general formula (I) and at least one type of compound represented by the general formula (H). This could be achieved by using a combination of two types.

General formula (I) (Xo) (wherein, Zl and Z2 may be the same or different from each other,
Represents a group of nonmetallic atoms necessary to form a j-membered or 6-membered heterocycle, and these rings may have a substituent or be fused with another ring. λ, m may be the same or different and represent 0 or /, 1%,
R2 represents a substituted or unsubstituted alkyl group which may be the same or different from each other, R3 represents a hydrogen atom, substituted or unsubstituted alkyl alkoxy or aryl group, X○ represents an anion, and n represents 0 or / and is 0 when the dye forms an inner salt. ) General formula (II) (wherein, Z3 represents a group of nonmetallic atoms necessary to form a j-membered or 6-membered heterocycle, and these rings may have a substituent, and other It may be fused on the ring. q is 0 or /.

R4 and R5 may be the same or different from each other and do not represent substituted or unsubstituted alkyl groups. ) then the general formula (
I) will be explained in detail.

As Zl and Z2 of the compound represented by general formula (I), the following are preferred. That is, Zl and Z2 may be the same or different from each other, and include a thiazole nucleus (e.g., thiazole, goomethylthiazole, gouphenylthiazole, dimethylthiazole, +, , 1-diphenylthiazole, etc.), Benzothiazole core (e.g., benzothiazole, goochlorobenzothiazole,
t-rioobe7zofTzole, ot-chloropensothiazole, j-nitrobenzothiazole, goomethylbenzothiazole,! -Methylbenzothiazole, O-Methylbenzothiazole, j-) Bromobenzothiazole, O-Fromobenzothiazol, t-iothohenzothiazole, j-7enylbenzothiazole, j-
Methoxybenzothiazole, methylbenzothiazole, j-ethoxybenzothiazole, j-ethoxycarbonylbenzothiazole, j-carboxybenzothiazole 1, f-7, i, thylbenzothiazole, terfluorobenzothiazole, ochloro- Methylbenzothiazole, t-dimethylbenzothiazole, j-hydroxy-t-methylbenzothiazole,
trihydrobenzothiazole, ≠-phenylbenzothiazole, etc.), naphthothiazole nuclei (e.g., naphtho[:,2, /-d]thiazole, nat(/,2
-d) Thiazole, Natsuto [! , 3-d]thiazole,
j-methoxynaphtho(/,,2-d)thiazole, 7-
Nitokina 7 [! , /-ter-d) Thiazole, ♂-methoxynaphtho [! , /-d)
Thiazole, j-methoxynaphtho [! , 3-d) thiazole, etc.), thiazoline nucleus (e.g., thiazoline, goomethylthiazoline, goonitrothiazoline, etc.), oxazole nucleus (e.g., oxazole, goomethyloxazole, goonitrooxazole, j-methyloxazole, cuphenyloxazole, g, t-diphenyloxazole, gouethyloxazole, etc.), benzoxazole nucleus (benzoxazole, terchloropenzoxazole, j-methylbenzoxazole, j-
Bromo is terfluorobenzoxazole, j-phenylbenzoxazole,! -Methoxybenzox M7'-l, j-nitrobenzoxazole, J-trifluoromethylbenzoxazole,!
-Hydroxybenzoxazole, j-carboxybenzoxazole, Otsu-methylbenzoxazole, Otsu-
Chloropenzooxazole, O-nitrobenzoxazole, O-methoxybenzoxazole-/S, O-hydroxybenzoxazole, 3-1 O-dimethylbenzoxazole, 7. O-dimethylbenzoxazole,
j-ethoxybenzoxazole, etc.), naphthoxyl@
Nazole nuclei (e.g., naf l-(,?, /-(I
) Okinozoru, Naft [/.

--d] oxazole, naphtho(j, 3-d) oxazole, 5-nitronaphtho(,!,/-d) oxazole, etc.], oxazoline nuclei (e.g., g.

goo dimethyl oxazoline, etc.), selenazole core (e.g. Eva, ≠-methyl selenazole, go nitro selenazole, go phenyl selenazole), benzoselenazole nucleus (e.g. benzoselenazole, 3; -/) loropenzo selenium Zol, j-nitrobenzoselenazole, S-methoxybenzoselenazole, j-hydroxybenzoselenazole, O-nitrobenzoselenazole, j
-chloro-6=nitrobenzoselenazole, etc.), naphthoselenazole core (e.g. naph1-(u,/-d)
selenazole, nut (/, 2-d) selenazole, etc.), 3,3-dialkylindolenine core (e.g., 3
, 3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-j-cyanoindolenine,
3,3-dimethyl-ot-2l loindolenine, 3,3
-dimethyl-yo-di-loindolenine, 3,3-dimethyl-j-methoxyindolenine, 3,3.3--trimethylintorunine, 3,3-dimethyl-j-chloroindolenine, etc.), imidazole nucleus (For example, /-alkylimidazole, /-alkyl-gophenylimidazole, /-alkylbenzimidazole, /-alkyl-j-chloropensoimidazole, /-alkyl-l, /-alkyl-j-methoxybenzimidazole, /-alkyl-j-cyanobenzimidazole, /-
Alkyl-j-fluoropenzimitasole, /-alkyl-, t-1 1J fluoromethylhensoimitasole, /-alkyl-chloro-y-cyanobenzimidazole, /-alkyl=6-chlorot I
J fluoromethylbenzpaimidazoleimidazole, /-aryruta, O-cyclopensoimitasole, /-allyl-1-chlorobenzimidazole, /~ruarylimidazole/-arylbenzimidazole, /-aryl-! -chlorobenzimidazole, /-aryl-j, dichlorobenz'imidaso-), /-aryl-j-methoxybenzimidazole, /-aryl-j-cyanobenzimidazole, /-arylnaphtho[/,,2 -d] imidazole,
The alkyl group mentioned above has 7 to g carbon atoms, for example, an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, or a hydroxyalkyl group (e.g., 2-hydroxyalkyl group). , 3-hydroxypropyl, etc.) are preferred. Particularly preferably a methyl group,
It is an ethyl group. The aforementioned aryl is phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg evamethyl)! represents substituted phenyl, alkoxy (eg methoxy) substituted phenylnato. ), pyridine nucleus (for example!
-Pyridine, goupyridine, j-methyl-! -pyridine, 3-methyl-goupyridine, etc.), quinoline nuclei (e.g., noquinoline, 3-methyl-noquinoline, j-ethyl-!-quinoline, O-methyl-noquinoline, O-
Nidro! -quinoline, g-fluoro-noquinoline,
O-methoxy-noquinoline, O-hydroxy-l-quinoline, do-chloro-noquinoline, goo-quinoline, o-ethoxy-goo-quinoline, o-nidro-goo-quinoline, do-chloro-goo-quinoline, g-fluoro-goo-quinoline, z-methyl-goo-quinoline , methoxy-guquinoline, (O-methyl-guquinoline, O-methoxy-guquinoline, 6-chloro-couquinoline)-inquinoline, O-nidro/-isoquinoline, 3.41-dihydro-/-inquinoline, Otsu-2 quinoxaline, imidazo(+,tb)quinoxaline (e.g. /,3-diethylimidazo(4,,tb)quinoxaline, ot-chloro-/,3-diallylimidazo [≠
、． t-b) quinoxaline, etc.), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, p/l-rimidine nucleus, etc.

More preferably, one of Zl and Z27 has a benzothiazole nucleus (for example, benzothiazole, terchlorobenzothiazole, o-chlorobenzothiazol, j-methylbenzothiazole, o-methylbenzothiazole, ta,
O-dimethylbenzothiazole! -methoxybenzothiazole, 6-medoxybenzothiazole, dimethoxybenzothiazole, etc.), and the other is a quinoline nucleus (e.g., μm quinoline, g-chloro-μm quinoline, g-methyl-j-quinoline, Ryo-methoxy-μm quinoline, 6-methyl-μm quinoline, Z-methoxy-μm
quinoline, o-chloro-gu quinoline).

Further, R1 and R2 may be the same or different from each other, and each has an unsubstituted alkyl group having 7 g or less carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a decyl group, a dodecyl group). , octadecyl group, vinylmethyl group, cyclohexyl group, etc.) or a substituted alkyl group (as a substituent, for example, a carboxy group, a sulfo group,
Cyan group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom), hydroxy group, alkoxycarbonyl group having carbon number of g or less (for example, me-1-oxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group,
benzyloxycarbonyl group, etc.), alkoxy groups with carbon atoms of gram or less (e.g., methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), monocyclic aryloxy groups with carbon number of 10 or less (e.g., phenoxy group,
p-trinioxy group), acyloxy group having 3 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), acyl group having ♂ carbon number or less (e.g. acetyl group,
propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, Pi is lysinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N- dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.),
An alkyl group having a carbon number/f or less substituted with an aryl group having a carbon number of 70 or less (for example, a phenyl group, a goochlorophenyl group, a goomethylphenyl group, an α-naphthyl group, etc.) is preferable.

In particular, R,, R2 are unsubstituted alkyl groups (carbon number/
~j) are preferred.

R3 is a hydrogen atom; a substituted or unsubstituted alkyl group having 7 to 20 carbon atoms (for example, a methyl group, an ethyl group, etc.)
, carbon number/~, 20 substituted or unsubstituted alkoxyl groups (e.g. methoxy group, ethoxy group, etc.), carbon number ~
/≠ substituted or unsubstituted aryl groups (eg, phenyl group, naphthyl group, etc.), and the like.

In addition, as the phosphor 3, a hydrogen atom or an unsubstituted alkyl group is particularly preferable.

Specifically, XO may be an inorganic anion or an organic anion, such as a halogen ion (e.g., fluorine ion, chlorine ion, bromide ion, iodide ion, etc.), substituted arylsulfonate ion (e.g. p
-toluenesulfonic acid ion, etc.), thiocyanate ion, perchlorate ion, etc. Among these, iodine ion, p-toluenesulfonate ion, and perchlorate ion are preferable.Next, general formula (I) I will explain K in detail.

Specifically, the nonmetallic atomic group represented by Z3 is Zl,
The same ones as shown in Z2 can be mentioned.

Preferably, a benzothiazole nucleus (e.g. benzothiazole, j-chlorobenzothiazole, o-chlorobenzothiazole, j-methylbenzothiazole, o-methylbenzothiazole, !, o-dimethylbenzothiazole, !-methoxybenzothiazole, 6-methylbenzothiazole, ta,z-dimethoxybenzothiazole, etc.).

R4 and R5 may be the same or different from each other, and may be an unsubstituted alkyl group having less than or equal to the number of carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a decyl group, a dodecyl group, -/za- octadecyl group, vinylmethyl group, cyclohexyl group, etc.) or substituted alkyl group (substituents include carboxy group, sulfo group, cyan group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom)) , hydroxy group, alkoxycarbonyl group with carbon number of g or less (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.)
, an alkoxy group having the following carbon number (e.g. methoxy group,
ethoxy group, benzyloxy group, phenethyloxy group), monocyclic aryloxy group having 10 or less carbon atoms (e.g. phenoxy group, p-1-Unioxy group, etc.), acyloxy group having 3 or less carbon atoms (e.g. acetyloxy group), oxy group, propionyloxy group, etc.), acyl group having a carbon number of g or less (e.g. acef) L' group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group) , morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N.

N-dimethylsulfamoyl group, morpholinosulfonyl group, pyharidinosulfonyl group, etc.), aryl groups having 70 or less carbon atoms (e.g. phenyl group, goochlorophenyl group, goomethylphenyl group, α-naphthyl group, etc.), etc. A substituted alkyl group having 7 g or less carbon atoms) is preferred.

More preferred are methyl and ethyl groups.

Typical examples of the compounds represented by the general formulas (I) and Nl) are listed below, but the compounds are not limited thereto.

I-/ 2FI5 Shizuku “C3HI+ 2H5 ■ CH2C02H 2H5 〇2H5 −,22− C2I-1゜ C2■15 C2■(5 2H5 2H5 ; C2■]5 2H5 −. Otsu J- 2H5 2H5 12≠− 2H5 ■ 2H5 −λotsu− 02H5 2H5 2H5 2H5 2H5 2H5 2H5 2H5 T-? Otsu ■-37 -, 2 ter -3g ■-39 ■-G0 J-4/ I-≠l ■-113 ■−≠V -4tJ- 1-g Otsu -4f ■−≠7 1-s.

1-J-/ 1-, t, z ■-ta 3 1-, t4t -J-t TI Otsuichi 3'A- ■-Off I 5g 1-jri■=Otsu O ■-Otsu/ (CH2)3SO31 -LN(C2H5)3■-62 (CH2)3SO3HN(C2H5)s(CH2)3S
O3■1N(C2H5)32H5 ■-Otsuta3g- ■-70 1-7.2 ■-73 ■-77 ■-72 ■-g/ ■-,! i', 2 (CH2)3SOa -11.2- 1-, r4t ■-doj I-4'7 C2H5I○ C2I-16 ■-taO ■-77 ■-72 1μj- 1μμm -≠Otsu- ■-Tazo (CH2)4SO3Na ■-10 Otsuichi ≠ Tar-10g 1-#)ri II-/ +1-. 2 jO- ■-3 ■-g ■-j ■-Otsu■-ta■-10 Ji■-// ■-/2 ■-73 1-/g1-/J- I[-/Otsu-yo3 − ■−/7 −1g Ir−/ri■−,20 n−,2/ It−1,2 If−,23 ■−2≠ 2H5 Represented by general formulas (I) and (II) used in the present invention The compounds used are known compounds, and are manufactured by F.M.
Bar 7- (F, M, Hamer) “
Heterocyclic Compound Cyanine Dies
And Related Humpounds (Hetero)
cyclic compounds-Cyanine
dies and relatedcompo
unds-) J Chapter TV ~ VT Chapter Chapter Doot ~ / ri page 2 (John Willie and the Kings) J o b n Will
ey & 5ons Inc. - New York, London-1
/91. μ Annual L.D.M. Starmer (D, M,
Inheterocyclic Chemistry (Heterocyclic Compounds)
-5special topics in hetero
cyclic chemistry-)” Part g
Chapter, Section 1, Pages 1g2-j/j (John Willie
And ψ Sons John Wiley & 5ons
It can be synthesized based on the method described in 1977, New York, London, 1977.

The sensitizing dye of general formula (I) used in the present invention is halogenated in a proportion of 1 mole of silver halide/x70 mol to /x10'' mol, preferably /x70' mol to λ, 5x70 mol. Contained in photographic emulsions.

The sensitizing dye used in the present invention can be directly dispersed into the emulsion. In addition, these can be prepared using a suitable solvent, such as evaporated methyl alcohol, ethyl alcohol, methyl cellosolve,
It can also be dissolved in acetone, water, pyridine, or a mixed solvent thereof, and added to the emulsion in the form of a solution. It is also possible to use ultrasonic waves for dissolution. The method of adding this sensitizing dye is described in US Patent No. 3. li
tri.

Dissolve the dye in a volatile organic solvent and disperse the solution in a hydrophilic colloid, as described in No.
, Method of adding this dispersion to an emulsion, Special Publication Shogu Otsu-2
1111? ! 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 US Pat. 2. A method in which a dye is dissolved in a surfactant and the solution is added to an emulsion as described in No. 2133; A method of dissolving a red-shifting compound as described in No. g, and adding the solution to an emulsion; JP-A ShojO-Do01?2
A method of dissolving a dye as described in No. 3 in an acid substantially free of water and adding the solution to an emulsion is used. Other additions to emulsions include U.S. Patent No. 2. ? /, 2.
3≠3, same No. 3, 311-. 2, ZOS issue, same number, 2,5;'? The methods described in No. 7, No. 3.11.2, and No. 3 of the same may also be used. The sensitizing dyes may also be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but can of course be dispersed at any stage of the preparation of the silver halide emulsion.

It is preferable to use the compound represented by the general formula (II) used in the present invention in an amount capable of supersensitizing, particularly from /x10 mol to /x7 per mol of silver halide in the emulsion.
A proportion of 0 mol is advantageously used.

-jd- The ratio (molar ratio) of the sensitizing dye represented by the general formula (I) and the compound represented by the general formula (n) is the dye represented by the general formula (I)/-the general formula It). Compound represented -
The range from 10// to //100 is preferably used, in particular the range from 2// to //10.

The compound represented by the general formula (II) used in the present invention can be dispersed in an emulsion, and can also be dispersed in a suitable solvent (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. It can also be added to the emulsion by dissolving it in the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes.

They can also be dispersed and added into the emulsion by the method described in JP-A No. 2003-010003.

The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes. For example, U.S. Patent No. 3.703.3
No. 77, U.S. Patent No. 2,6.8'g.

j≠j, U.S. Patent No. 3,377.0 O, U.S. Patent No. 3. Otsu/O, A3! No. 3, U.S. Patent No. 3, No. 2, No. 2, British Patent No. 7. ! I7. No. SGG, British Patent No. 12.2, 3. It, No. 2, Special Public Show 13-≠23 No. 2, Special Public Show Gu'&-/'1030, Special Public Show'l-3-
No. 10773, U.S. Patent No. 3. II-/Otsu, No. 927,
Special Publication No. 3-11730, U.S. Patent No. 3. Otsu/J, Otsu No. 73, U.S. Patent No. 3. Otsu/j, No. 632, U.S. Patent No. 3. Otsu No. 77.293, U.S. Patent No. 3, 1.33;
, No. 72/, etc. can be used.

The silver halide emulsion that can be used in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. Preferred silver halides are silver bromide, silver chlorobromide, silver iodobromide, or silver iodochlorobromide.

The silver halide grains in the photographic emulsion may have regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like.
It may have a crystalline form (egular ') or a composite form of these crystalline forms. It may also consist of a mixture of particles of various crystalline forms.

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

It may also be a grain in which a latent image is mainly formed on the surface (for example, a negative emulsion), or a grain in which a latent image is mainly formed inside the grain (for example, an internal latent image emulsion, a pre-fogged direct reversal emulsion). It may be.

The silver halide emulsion used in the present invention has a thickness of 0,j microns or less, preferably 0.3 microns or less, a diameter of preferably 0.6 microns or more, and an average aspect ratio of 5.
The above-mentioned grains may be tabular grains that occupy more than j0 times of the total projected area. Further, the emulsion may be a monodisperse emulsion in which particles having a particle size within ±10% of the average particle diameter account for Pj% or more of the number of particles.

The photographic emulsion used in the present invention is B. gelafchides (
Written by Chimie et-Z Glafkides
/- Physique Photographique
)J (Paul Montel
Published by 1 company, /9/7 years), G.F.
, F. Duffin) [Photographic Emulsion Chemistry (Photographic E.
mulsionChemistry) J (published by The Focal Press, / 2018), V, L, Ze
likman etal) [Making and Coating Photography Emulsion (
Making and Coating Photogr
aphicEmulsion) J
It can be prepared using the method described in 2010).

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, H Freezer (
H, Fr1eser) ed.
er PhotographischenProze
sse mit Silver-halogeni
den) J
emi scheVerlagsgesellscha
Method 7 described in pages 7 to 734 can be used.

The photographic emulsion 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 light-sensitive material, or for stabilizing photographic performance. i.e. azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzo-lyazoles, benzimidazoles (especially nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles. , mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotrazoles (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. ; Thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (especially μm hydroxy-substituted (/, 3, 3a, '7') tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; Many compounds known as inhibitors or stabilizers can be added.

The silver halide photographic emulsion of the present invention has a cyan coupler, a magenta coupler, and a yellow coupler.
Coupler and coupler 1-dispersing compounds can be included.

That is, it may contain a compound that can develop color by oxidative coupling with an aromatic 7th class amine developer (for example, a phenylene diamine derivative, an amine phenol derivative, etc.) in a color development process.

For example, as a magenta coupler! - There are pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g., Ever<nzoylacetanilides, pivaloylacetanilides), etc. 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 g-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 development 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.

The photographic emulsion of the present invention may contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, for the purpose of increasing sensitivity, increasing cloudiness, or promoting development.
It may also contain thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

- To the silver halide photographic emulsion of the present invention, known water-soluble dyes other than the dyes shown in the present invention (for example, oxonol dyes; hemioquinol dyes and It may be used in combination with merocyanine dye). Further, as a spectral sensitizer, it may be used in combination with known cyanine dyes, merocyanine dyes, and hemicyanine dyes other than the dyes shown in the present invention.

The photographic material used in the present invention includes a binder (for example, gelatin such as lime-treated gelatin, acid-treated gelatin, derivative gelatin, polyvinyl alcohol, etc.), a development accelerator (for example, polyalkylene oxides, thioether compounds, etc.), hardening agents (e.g., 3.r-triacryloyl-hexahydro-5-
) riazine, /, 3-vinylsulfonyl-λ-pronoq
Knoll, 2. gauge chlor-6-hydroxy-8-triazine, etc.), coating aids, antistatic agents, developing agents, plasticizers, matting agents, lubricants, ultraviolet absorbers, optical brighteners, air fog prevention agents, etc. may contain.

As for these additives, known additives can be used, and they are also described in Research Disclosure magazine Re5e.
arch Disclosure Volume 17, P.
Those described in 12-P, 3/ can be used.

The silver halide emulsion layer and/or other constituent layers are coated on the support. The coating method is described in Research Disclosure, Volume 77, P27-2g [coating
The method described in procedures J can be used.

The sensitizing dye of the general formula (I) and the compound of the general formula (I) of the present invention are used in silver halide photographic emulsions for various color and black-and-white sensitive materials.

More specifically, color positive emulsions, color paper emulsions, color negative emulsions, color reversal emulsions (which may or may not contain couplers), photosensitive materials for printing plates (e.g. lith film, lith du Emulsions used in photosensitive materials for X-ray recording (especially materials for direct and indirect photography using screens), emulsions used in photosensitive materials for cathode ray tube displays, silver salt diffusion transfer processes (Silver 5alt, etc.) diff
emulsions used in color diffusion transfer processes; emulsions used in color diffusion transfer processes;
tie transfer process
emulsions used in silver dye bleaching methods, emulsions used in materials for recording print-out images, photo-developable emulsions Bakeout Dlrect Pri
emulsions used in photosensitive materials (black and white, color), emulsions used in photosensitive materials for physical development (for example, as described in British Patent No. 20, No. 277, etc.) Used with etc.

Exposure to obtain a photographic image may be carried out using a conventional method.

That is, any of a variety of known light sources can be used, such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, and cathode ray tube flying spots. The exposure time is from 171,000 seconds normally used in cameras to 7
Exposure times shorter than 17iooo seconds, such as xenon flash lamps or cathode ray tubes, as well as exposure times shorter than 17iooo seconds;
Exposures of 4-77106 seconds can be used, or exposures longer than 7 seconds can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure.

Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like.

Photographic processing of light-sensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure).
Di 5 closure) / 7 Otsu No. λg ~ 3
As described on page 0 (RD-/7g<zJ),
Any known method and known treatment liquid can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. Processing temperatures range from normal to 0C! ;O0C, but the temperature may be lower than /♂0C or higher than 5o0C.

(Example) Next, specific examples used in the present invention will be shown. However, the invention is not limited to these specific examples.

Example: A cubic AgClBr emulsion with an average particle size of 0.35 μm was formed by the usual double-jet method while controlling pAg, washed with water, desalted, and sulfur-sensitized to obtain the optimum sensitivity. Br: OmoIV, q6, Ag
Amount: 0.3 mol/T'p emulsion, gelatin concentration j%) (60y each) [Weighed, added the sensitizing dye shown in Table 1, and added a thickening and spreading agent! liquid solution, -monohydroxiagu,
Otsu-Dichlorotriazine sodium salt, 2% liquid, 10q
6 gelatin gel and water were added to adjust the total amount/θOy (gelatin concentration 3φ). Separately, an aqueous solution mainly consisting of gelatin is prepared, and this gelatin solution and a solution containing the above-mentioned emulsion are mixed so that the emulsion solution is on the support side,
And the applied amount of gelatin liquid and emulsion liquid are gelatin/μy/m 2 and gelatin 2.117 m, respectively.
A photographic material was obtained by coating the film on a 110 μm polyethylene terephthalate film so that the film had the following properties.

These samples have color temperature j≠00°KS3000i u
Light exposure was carried out by passing x light through a 5c-4o filter Z manufactured by Fuji Photo Film per second.

After exposure, development was carried out at 20° C. for 7 minutes using a developer having the composition shown below, followed by stopping and fixing, followed by washing with water to obtain a strip star with a black and white image. Measure the concentration of this strip,
White light sensitivity and fog were obtained.

The optical density of the reference point used to determine the sensitivity is [fog +
0.20].

Composition of developer and composition of fixer Comparative example As can be seen from the results shown in Table 1, the combination of the compounds of the present invention provides higher sensitivity than when added alone. Further, in the combination with a known comparative example, the increase in sensitivity was smaller than in the case of the combination of the present invention, but on the contrary, a decrease in sensitivity was observed.

Example Cop Cubic particles A, g with an average particle diameter of 0.2 Jltm were formed by the usual double jet method while controlling the Ag, washed with water, desalted, and sulfur sensitized to obtain the optimum sensitivity. (:lBr emulsion (B r :f Q m O
°C, Ag amount: Q. 1 m o fl / Kp emulsion, gelatin concentration 7%) was weighed into a pot, and the sensitizing dyes and/or compounds shown in Table 1 were added to the pots, followed by a thickening and spreading agent, 2 liquids, -1 Hydroxyg, Otsu-
Add 2 dichlorotriazine sodium salt solutions, 10% gelatin gel and water to make a total volume of 100y each (gelatin concentration 4
L%). Separately, an aqueous solution mainly consisting of gelatin was prepared, and this gelatin solution and a solution containing the above-mentioned emulsion were mixed so that the emulsion solution was on the support side, and the coating amount of the gelatin solution and the coating amount of the emulsion solution were respectively gelatin/4ty. /m'' and gelatin, !, Iy/m2.5 was coated on a /♂0 μm polyethylene terephthalate film to obtain a photographic effect.

These samples have a color temperature of ≠00°, 3;000fl
II X light by Fuji Photo Film SC-,/-o
A light exposure was performed for 3 seconds through a filter.

After exposure, RO using the same developer as shown in Example/
The strips were developed for 7 minutes under OC, stopped, fixed, and washed with water to obtain strips with black and white images.

-77=F As is clear from the results in Table 2, the combination of the compound of the present invention was able to significantly improve sensitivity compared to the comparative example.

Example 3 An aqueous solution of silver nitrate, an aqueous solution of potassium bromide of O, tamol, and an aqueous solution of sodium chloride of 0.3 mol were mixed with good stirring to form particles, and after washing and desalting, particles were prepared so as to obtain the optimum sensitivity. Sulfur-sensitized cubic AgαBr emulsion with an average grain size of 0.3 μm (Br:!; Omo 1%, Ag!:
0.7mo f! Weigh out 4 tries of each of the sensitizing dyes and/or compounds shown in Table 3 into a pot, add a 2% thickening and spreading agent solution, λ-hydroxy-j, and O. -Dichlorotriazine sodium trifium f- 2% rum salt solution, 70% seratin gel, and water were added to each to make a total volume of 100y (gelatin concentration: 4t%). Separately, an aqueous solution mainly consisting of gelatin is prepared, and this gelatin solution and a solution containing the above-mentioned emulsion are mixed so that the emulsion solution is on the support side, and the coating amount of the gelatin solution and the coating amount of the emulsion solution are respectively gelatin/lly A photographic material was obtained by coating 7 g of 0 μm polyethylene terephthalate film in such a manner that gelatin was 2.y/m” and gelatin was 2.y/m!.

These samples have a color temperature of ≠00'! 000λux
The light was exposed to light for λ seconds through a 5c-so filter manufactured by Fuji Photo Film.

After exposure, the same developer as shown in Example/20
It was developed at 0C for 7 minutes, stopped, fixed, and washed with water to obtain strips with black and white images.

-♂0- As is clear from the results in Table 3, the combination of the compound of the present invention was able to significantly improve sensitivity compared to the comparative example.

Example μ A 7N silver nitrate aqueous solution and an aqueous solution containing 7.1 mol of potassium bromide were mixed by a double jet method while controlling pAg to obtain a silver bromide emulsion.

This emulsion was washed with water, desalted, and then subjected to gold sensitization and sulfur sensitization to obtain optimum sensitivity. The grains of this silver bromide emulsion were approximately cubic with an average grain size of 0 μm.

30 y of each of the silver bromide emulsions prepared as described above were weighed into a pot, and the sensitizing dyes and/or compounds shown in the table were added thereto to obtain 2-hydroxy-t.

Otsu-2 solution of dichlorotriazine sodium salt, -♂
/-10 Tigelatin gel, water was added and the total amount of each was /20y, and the amount of silver in this was 3. /, 27, gelatin was prepared so that it was t, do 1. Separately, an aqueous solution mainly consisting of gelatin is prepared, and this gelatin solution and a solution containing the above-mentioned emulsion are mixed so that the emulsion solution is on the support side, and the coating amount of the gelatin solution and the coating amount of the emulsion solution are respectively gelatin/3; y/m2
And gelatin! .

A photosensitive material was obtained by simultaneously applying the coatings so that j y /m 2 was obtained.

These samples have a color temperature of 2dj4t'! ;000 lux light for 2 seconds light wedge exposure.

Simultaneous development was carried out under the same development processing conditions as shown in Example.

-g2=-do3-L As is clear from the results in the table, the combination of the compound of the present invention was able to significantly improve sensitivity compared to the comparative example.

Example j Gelatin aqueous solution (gelatin 20o in water Otsu00IIri)
An aqueous solution (■ solution) containing potassium bromide/II-,,2j/ and potassium iodide 0.2/Oml and 0172 mol of silver nitrate were added to An aqueous solution (Liquid II) containing 1yOd was added over 20 minutes. After leaving it in that state for 2 minutes, an aqueous solution containing potassium bromide and potassium iodide -yg=liquid (■liquid')u! rOrxl and a rtr aqueous solution (■ solution) *101 containing silver nitrate 0, 4L7 mo/l/wo were added over 30 minutes by a controlled double jet method while keeping the pAgu constant, and the iodine content was jmolti and the average particle size was 0, jμ. /prohedral silver iodobromide grains were prepared.

Weigh 30y of each of the silver iodobromide emulsions prepared as described above into a pot, add the sensitizing dyes and /-1: or compounds shown in Table 9J, and! -Hydroxy-4,A-2% solution of dichlorotriazine sodium salt, 10% gelatin gel, and water were added and the total volume was 720F, and the amount of silver in this was 3.72
1. Gelatin is j.

It was prepared so that it would be 4ty. Separately, an aqueous solution mainly consisting of gelatin is prepared, and this gelatin solution and a solution containing the above-mentioned emulsion are placed so that the emulsion solution is on the support side, and the coating amount of the gelatin solution and the coating amount of the emulsion solution are respectively gelatin/emulsion-containing.
,! ; f/m2 and gelatin were simultaneously coated at 2.3 f/m2 to obtain a photographic material.

These samples were exposed to light wedges for 50 seconds at a color temperature of 21 J'KS 300 lux.

gs- -doot- Comparative Example As is clear from the results in Table 5, the combination of the compound of the present invention was able to significantly improve sensitivity compared to the comparative example.

Example 6 A /N silver nitrate aqueous solution and an aqueous solution containing O9 red mol potassium bromide and 0.0/2 mol potassium iodide were mixed by a rub jet method while controlling pAg. A silver iodobromide emulsion was obtained. This emulsion was washed with water, desalted, and then subjected to gold sensitization and sulfur sensitization to obtain optimum sensitivity. The grains of this silver iodobromide emulsion had an average grain diameter of o, t μm and were (I00)-faced, containing ♂&%/g-hedron.

307 of each of the silver iodobromide emulsions 7 prepared as described above were weighed into a pot, and the sensitizing dyes and/or compounds shown in Table 4 were added to 2+ of the 2-hydroxy-t, O-dichlorotriazine sodium salt. % solution, 70% ceratin gel,
Add water to each total amount/20y, and the amount of silver in this is 3. /, 2
f, gelatin is evening.

It was prepared so that it became /. Separately, an aqueous solution mainly consisting of gelatin is prepared, and this gelatin solution and a solution containing the above-mentioned emulsion are placed so that the emulsion solution is on the support side, and the coating amount of the gelatin solution and the coating amount of the emulsion solution are respectively gelatin/,
! ;f/m2kichi gelatin-1,,3'f/rn2t
: A photographic material was obtained by simultaneously applying the two.

These samples had a color temperature of 2♂j' and 3-0θrutzgg- -g9- Comparative Example As is clear from the results in Table 6, compared to the comparative example, those using the compound of the present invention in combination with We were able to significantly improve sensitivity.

Patent applicant: Fuji Photo Film Co., Ltd. = 90-

Claims (1)

[Scope of Claims] A silver halide photographic emulsion comprising at least one sensitizing dye represented by the following general formula (I) and at least one compound represented by the general formula (II). General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. R_1
, R_2 represents a substituted or unsubstituted alkyl group which may be the same or different from each other, R_3 is a hydrogen atom,
It represents a substituted or unsubstituted alkyl alkoxy or aryl group, X^■ represents an anion, n represents 0 or 1, and is 0 when the dye forms an inner salt. ) General formula (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z_3 represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle, and these rings have no substituents. or may be fused with another ring.q
is 0 or 1. R_4 and R_5 may be the same or different from each other and represent a substituted or unsubstituted alkyl group. )