JPS60205442A - Photographic silver halide emulsion - Google Patents

Abstract

PURPOSE:To obtain a photographic silver halide emulsion contg. a sensitizing dye which does not cause stain after development without reducing the sensitivity by using at least one kind of specified sensitizing dye. CONSTITUTION:A sensitizing dye represented by formulas I -III is used as a sensitizing dye for photography by 1X10<-6>-5X10<-3>mol per 1mol silver halide. The dye has a substituent represented by formula IV or V. The dye is directly dispersed in an emulsion or it is added to the emulsion in the form of a soln. after dissolution in methanol, water, pyridine or a solvent mixture of them. In the formulae, each of Z<1>-Z<3> is a group of nonmetallic atoms required to form a 5- or 6-membered heterocyclic ring; R<2> is substitutable alkyl or a group represented by the formula IV or V; each of L1-L5 is substitutable methine; W is halogen, cyano or the like; u is 0, 1, 2 or 3; each of X1 and X2 is an acid anion; each of R<1> and R<3> is a group represented by the formula IV or V; each of l, n, k, p and r is 1, 2 or 3; each of m and q is 1, 2, 3 or 4; Y is a group of nonmetallic atoms capable of forming cyclic imide; and each of s and t is 2, 3, 4 or 5.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide '#A: emulsion, which is spectrally sensitized with a sensitizing dye, has good sensitivity, and has a high sensitivity after development. This relates to an emulsion with less stain.

(Prior Art) Spectral sensitization is a known and important technique for expanding the spectral sensitivity of silver halide photographic emulsions from the inherent sensitivity range of silver halide to the longer wavelength side. The sensitive wavelength range can be extended to the infrared range by selecting the structure of the sensitizing dye according to the required purpose. Although it has become possible to make adjustments, there are still various drawbacks and improvements are needed. That is, when applying a sensitizing dye to a silver halide photographic emulsion, 1)
In addition to the original objective of having an appropriate spectral sensitivity distribution, 2) being able to provide high sensitivity in the desired spectral sensitivity range, 3)
4) There is no change in sensitivity or increase in fog during the production of the photosensitive material or during storage after production, and 5) There is no possibility of staining as a colored substance that remains or decomposes after processing. It is important to avoid such phenomena in actually manufacturing and providing photographic materials.

In general, it is well known that increasing the hydrophilicity of the sensitizing dye is a method for preventing staining caused by the sensitizing dye after development. However, increasing hydrophilicity often causes a decrease in the adsorption of sensitizing dyes to silver halide. As a result, although the sting no longer occurs, I often experience that I am unable to obtain the desired sensitivity. Therefore, 1 to 18! without decreasing adsorption to silver halide or sensitivity! There is a strong desire to develop a technology that prevents staining caused by sensitizing dyes after processing.

(Object of the Invention) That is, an object of the present invention is to provide a silver halide photographic emulsion containing sensitized color water that does not cause a decrease in sensitivity and does not cause staining after development.

(Structure of the Invention) The present inventors have worked hard to achieve this objective. +jT
As a result of all our efforts, we unexpectedly discovered that at least the sensitizing dye represented by the following general formula (I) -Jli and/or the general formula (lla) or the sensitizing dye represented by Shikke (]I b ) It has been found that this can be achieved by using at least one color of the dye.

General formula (1) General formula (Ha) 3 General formula (nb) In the formula, Zl, Z2 and Z3 are! represents a group of nonmetallic atoms necessary to form a 6-membered heterocycle (which may be fused). R2 is an optionally substituted alkyl group, +CH2→
--c-UH3 or 1i 1 ++ L 3 , L 4 and L6 represent an optionally substituted methine group, -□. W is a halogen atom, a cyan group, an alkoxycarbonyl group, a substituted -C optionally carbamoyl group, an optionally substituted sulfamoyl group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or a substituted Represents a good acyno group. U represents an integer from 1 to 3. Xl and X2 represent acid anions. R1 and R3 represent ÷C112→-Cney (lJ3 or 9 1 ++), p and r represent integers of /~3, Ill and q represent integers of ~l, and Y can form a cyclic imide. Represents a nonmetallic atomic group. S and t represent integers from λ to j.

The sensitizing dyes represented by the general formulas (1), (lla) and (Llb) have a novel substituent 1fC112→-C-C as a substituent used in photographic sensitizing dyes.
With H3 or S i ++, remarkable effects such as prevention of staining after processing could be achieved without impairing the color sensitization effect.

Next, each general formula will be explained in detail.

In general formula (I), Zl and z2 are each! or represents a group of nonmetallic atoms necessary to form a t-membered heterocycle,
They may be the same or different. Examples of the heterocycle include a thiazole nucleus (eg, thiazole, l-methylthiazole, gouphenylthiazole, p, t-dimethylthiazole, Hiroshi).

j-diphenylthiazole, etc.), benzothiazole nucleus (eg ij', benzothiazole, cuchlorobenzothiazole, j-chlorobenzothiazole, t-chlorobenzothiazole, j-nitropenzothiazole, μm
m-methylindithiazole! m-methylindithiazole, t-methylbenzothiazole,! -bromobenzothiazole, t-bromobenzothiazole,! -iodobenzothiazole, j-phenylbenzothiazole, j-methoxybenzothiazole, t-methoxybenzothiazole, j-ethoxybenzothiazole,! -Ethoxycarbonylbenzothiazole, j-carbogysibenzothiazole, j-phenylbenzothiazole, j-fluorobenzothiazole, terchloro-t-methylbenzothiazole, j,A-dimethylbenzothiazole,! -Hydroxy-6=methylbenzothiazole, tetrahydrobenzothiazole, Hiro-phenylbenzothiazole, etc.)
, naphthothiazole nucleus (e.g. naphtho[λ,/-d]
Thiazole, natto(/,j-d)thiazole, naphtho[co,3-d)thiazole, J-methoxynaphthoquinaphtho[λ,/-d)thiazole, g-methoxynaphtho[λ,/-d,)thiazole , j-methoxynaphtho(2,3-+1)thiazole, etc.), thiazoline nuclei (e.g., thiazoline, μm methylthiazolin, p-nitrothiazoline, etc.), oxazole nuclei (for example, oxazole, hiro-methylthiazole, hiro -Nitrooxazole, !-Methyloxazole, Hiro-Phenyloxazole, ≠.

! -diphenyloxazole, ≠-ethyloxazole, etc.), benzoxazole core (hanzoxazole,
j-chlorobenzoxazole! -Methylbenzoxazole, j-bromobenzoxazole, j-fluorobenzoxazole,! -Phenylbenzoxazole,! -methoxybenzoxazole, t-nitrobenzoxazole, j-)lifluoromethylbenzoxazole, j-hydroxybenzoxazole, s-, /
J ruboxybenzoxazole, t-methylbenzoxazole, t-chlorobenzoxazole, 2-nitrobenzoxazole, 6-methylbenzothiazole, t
-hydroxybenzoxazole, j, A-dimethylbenzoxazole, da, t-dimethylbenzoxazole,! ), naphthothiazole nuclei (e.g. naph) (u,/-d) oxazole, naphtho C/, 2-d) oxazole, naphtho [λ,
J-d) Oxazole,! - Nitronaft [λ, /-d
)oxazole, etc.), oxazinone nucleus (e.g., Ri1
μm dimethyloxazoline, etc.), selenazole core (e.g., ≠-methylselenazole, μm nitroselenazole, μm phenylselenazole), benzoselenazole core (e.g., I' at c, -”nzoselenazole, !-chlorobenzo Selenazole, !-Nitrobenzoselenazole, j-Methoxybenzoselenazole, !-Hydroxybenzoshiroxole, 6-Nidropensoselenazole A
/, j −, 10 rho (e.g., ditrobenzoselenazole), naphthoselenazole nucleus (e.g., naphtho [λ, /
-d) Selenazole, Naphtho [/.

λ-d] selenazole, etc.), J, J-dialkylindolenine core (e.g., 3,3-dimethylindolenine,
3.3-diethylindolenine, 3゜3-dimethyl-j
-Cyanoindolenine, 3.3-dimethyl- to -ditroindolenine, 3.3-dimethyl-! -nitroindolenine, 3,3-dimethyl-! -Methoxyindolenine- 3,3. r-trimethylindolenine, 3,3-dimethyl-y-chloroindolenine, etc.), imidazole nuclei (e.g. /-alkylimidazole, /-alkyl-l-phenylimidazole, /-alkylbenzimidazole, nopurkyl-5-chloro Benzimidazole, l-alkyl-j, 6-dichlorobenzimidazole, l-alkyl-!-methoxybenzimidazole,
/-Alkyl-! -cyanobenzimidazole, /-furkyl-5-fluorobenzimidazole, /-alkyl-j-)lifluoromethylbenzimidazole, l-
Alkyl-4-chloro-j-cyanobenzimidazole, l-alkyl-4-chloro-! -trifluoromethylbenzimidazole, /-alkylnaphtho[/,,2-
d] Imidazole, l-allyl-! , t-dichloroinciimidazole, /-allyl-j-chlorobenzimidazole, /-arylimidazole, /-arylbenzimidazole, l-aryl-! -chlorobenzimidazole, l-aryl-j, l-dichlorobenzimidazole, l-aryl-yo-methoxybenzimidazole, l-ori-rouocyanobenzimidazole,
/-Ding reelnaft [/,, 2-d] imidazole,
The alkyl group mentioned above has /~r carbon atoms, for example, an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, or a hydroxyalkyl group (e.g.
co-hydroxyalkyl, 3-hydroxypropyl, etc.)
etc. are preferred. Particularly preferred are methyl group and ethyl group. The foregoing groups include phenyl, halogen (e.g. chloro) substituted phenyl, alkyl (e.g. methyl) i! Represents substituted phenyl, alkoxy (eg methoxy) #, substituted phenyl, etc. ), pyridine nuclei (e.g., λ-pyridine, Hiro-pyridine, j-methyl-1-pyridine, 3-methyl-μm-pyridine, etc.), quinoline nuclei (e.g., co-quinoline, J-71 tyl-λ-quinol), )hmm,! -ethyl-2-quinoline, t-methyl-λ-quinoline, t-nitro-λ-quinoline, r-fluoro-λ-quinoline, t-
Methoxycoquinoline, t-hydroxy-λ-quinoline, g-chloro-λ-quinoline, v-quinoline, 6-ethoxy μm guinoline, t-nitro-μm quinoline, r
-chloro-guinoline, r-fluoro-guinoline, g-methyl-l-quinoline, g-methoxy-t-guinoline, isoquinoline, t-nitro-l-isoquinoline,
3. goudihydro-7-isoquinoline, 6-=draw 3
-isoquinoline, etc.), imidazo[μ, j-11) quinoxaline nucleus (e.g., l,3-diethylimidazo[≠,
t-b) Quinoxaline, t-chloro-/, j-thia 1
1 imidazo (4(,t-b)quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus,
Represents a pyrimidine nucleus, etc.

The alkyl group represented by R2 is a carbon atom /-/
I preferably / ~ 7 particularly preferably 1 to 1 alkyl group (unsubstituted alkyl group (e.g., methyl, ethyl, propyl, impropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl, etc.), substituted alkyl group, For example, aralxy71 (91t is benzyl, iophenylethyl, etc.), hydroxyalkyl group (for example,
-monohydroxyethyl, 3-hydroxyalkyl), carboxymerkyl groups (e.g. λ-carboxyethyl, 3-carboxypropyl, V-carboxymethyl, carboxymethyl), alkoxyalkyl groups (e.g. ethyl, λ-(,2-methoxyethoxy)ethyl, etc.), sulfoalkyl groups (e.g. yosulfoethyl, 3-sulfopropyl, 3-sulfobutyl, ≠-sulfobutyl, 2-[J-sulfopropoxy]ethyl, λ- hydroxy-3-sulpopropyl, 3-sulfopropoxyethoxydiethyl, etc.), sulfatoargyl/11' (B!l, 3-sulfatopropyl,
l-sulfatobutyl, etc.), heterocyclic-substituted alkyl groups (
λ-(pyro-11din-λ-one-7-yl)ethyl, tetrahydrofurfuryl), -2-acetoxyethyl, carbomethoxymethyl, comethanesulponylaminoethyl) or allyl group represents. Ll, 1,
2, I, and 3 are methine groups (unsubstituted or alkyl groups (e.g., methyl, ethyl, etc.), aryl groups (e.g., phenyl, etc.), or...rogen (e.g., chloro, bromo, etc.)
may be substituted with, or may form a ring with another L.

xl is an inorganic or organic acid anion (e.g. chloride, soromide, iosito, p-toluenesulfona F, I)-nitrobenzenesulfonate, ipsulfonate, methylsulfate, ethylsulfate, /(- chlorate, etc.). k represents 1 or -2, and in the case of / forms an inner salt. ! , n represents/or 2. m represents an integer from 7 to Hiroshi.

S in R1 and R2 in the general formula is preferably λ.

Examples of the cyclic imide group (preferably a !-membered ring) formed by Y include a succinimide group, a phthalic imide group, an orthobenzosulfoimide group, and a maleimide group.

In the general formula (Ha) and the general formula (11b),
z 3 huff, 1 > j and synonymous with Z2, R”FiR
Synonymous with l, JJ 4, L6 is synonymous with Ll, L2, L3,
X2 has the same meaning as Xl.

Examples of groups represented by W--C include the following: That is, chlorine atom, bromine atom, fluorine atom, cyano group, methoxycarbonyl group, ethoxycarbonyl group, carbamoyl group, methoxycarbamoyl group, ethoxycarbamoyl group, sulfamoyl group, methylsulfamoyl group, ethylsulfamoyl group, methyl group , ethyl group, methoxy group, ethoxy group, amine 7 group, dimethyl amine 7 group, amino group including heterocyclic group, etc.

General formula (1) and general formula (IIa) or (llb
Specific examples of the compound group represented by ) include the following, but the scope of the present invention is not limited thereto.

1-/ ■−λ 1 -J Knee≠ υ　l 1-j (c) α -a ■-7 -r I ■-2 1-i.

I -// l-/　λ J-/3 1 ■−／μ ■-／j -/4 1-/7 1-/za B 5r 1-. 23 ■−ko knee 27 ■-2I (J l I-λri ■-30 r ■-37 C1l　2　CL:Il　3(L-H2)3>t+31 ■-darl I-≠3 ■−Hiromu ■−Gua θ r ■-G ■-10C2H5 I-tλ CH3 1-4.3 C21151 1 1 1j4'n-C3kI7T book 1-ss C2115■ -zA　UzHs 17 IJP C2515 ■ 1-6OC2J45 -62 -63 (-7/1 1-7+2I [-7JI -7ri 7l -7J C2) (.

-g3 0 H-rt, t C:214° [-/ ■-ko11-g C2115 +1 I -j ii -, < [-7 υ -r N3 1-10 1 11-// IJ-/, 2 ■-73 11-/ PiC2)' 5 31-/ 4 C2its 1 J-77 υ ]1-1g Loaf 2 1-Jo General formula (I) used in the present invention, (lJa) and (
The sensitizing dye represented by
rdr specification, J1eterocyc order Ccompo
unds -Uyanine dies andrel
ated compounds −“cliapter”
V.

page/ / A~/ 4' 7, F, M, 1
4θmer, John.

Wiley & Sons (New York, London)
Don) company/? A4 yearly, ') Ieterocycle
icCompounds -5special topi
cs 1nheterocyclic cbemist
ry-“chapter ■, sec, lVpage Q
-12~313, D, M.

Jolln Wiley & So, by Sturmer
It can be easily synthesized by following the method described in Def.

Synthesis examples of representative compounds will be described.

O formation FJ1 t, A-cycloa-/-ethyluko 74
-Lou J- Synthesis of (,2-oxopropyl)benzimidazolium chloride! , A-cyclo/-ethyl-1-methylbenzimidazole, 2g, and chloroacetone were placed in a 300rr flask equipped with a stirrer and a reflux condenser, heated to 1/30" and placed in an oil bath. The mixture was heated and stirred for 2 hours. After that, 20 tttl of anisole was added, allowed to cool, and 10θ-ethyl acetate was added. 3
After stirring under reflux for 0 minutes, the mixture was cooled with water. The crystals were separated, washed with ethyl acetate, and then dried at 100C for 5 hours. yield! 0.0 fl (yield: 3) Synthesis Example 2 Synthesis of Compound Example (I-j/)
-anilinovinyl)benzoxacilio3]-butanesulfonate/, 11. i and acetic anhydride! - into a JOO three-necked flask equipped with a stirrer and a reflux condenser;
Heat on a steam bath for 71 minutes. After this,! , 6-dichloro7-ethyl-2-methyl-J-(2-oxopropyl)benzimidazolium chloride t, ttg and N
, N-dimethylformamide zonelf was added, and further 7 tnl of triethylamine was added. This mixture was heated and stirred on a steam bath for 20 minutes. Next is Innoproper Tools
Add all Oml and cool on ice. The stray crystals were collected and washed with isozolopanol. The crystals were purified using methanol and chloroform and dried under reduced pressure for 70 hours. Yield λ.

319 (yield g3 times) 111 points 23.2-233°C Synthesis Example 3 Synthesis of N-, -(2-bromoethyl)cono-phosphoric acid imide Succinimide, Ri and N, N-dimethylformamide! Oml was placed in a 200 ml three-tube flask equipped with a stirrer and a thermometer. Additionally, potassium carbonate/4tgf
The mixture was added and stirred at room temperature for 30 minutes. After this, 2-dibromoethane was added to +y-i, and the reaction was carried out at ≠0,300C for 2 hours. The reaction mixture was then poured out hydraulically and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was crystallized from hexane.

The crystals were taken out of the oven, washed with hexane, and then air-dried. Yield/4
゜7jiC Yield rlqII) Melting point 66~It 0C Synthesis Example 4 j, t-dichloro-7-nityl-comethyl-J
-Synthesis of (2-succinimidoethyl)benzimidazolium bromide! lt-dichloro/-ethyl-λ-methylbenzimidazole ii, j'g and N-(copromoethyl)
Succinimide, 20. Place in a 20θml three-necked flask equipped with a t9f stirrer and reflux condenser, and boil at /300C.
Heated on a Vc heated oil bath for 2 hours. After adding the anisole No. 101 and allowing it to cool, add the ethyl acetate of JOynl and reflux for 30 minutes. After cooling to room temperature, the crystal 'i' was taken, washed with acetone, and washed with jo 0c for 5
Let dry for a while. Yield i/l', 7. ! i+ (yield IT section)
Synthesis Example 5 Synthesis of Compound Example [-j, 7-dichloro-7-ethyl-methyl-J-(J
-succinimidoethyl)benzimidazolium bromide//, Ofl and N,N'-(J,!'-dichlorodiphenyl)formamidine 13.3! The mixture was placed in a 10 oyd three-way flask equipped with a stirrer and a reflux condenser and heated on an oil bath heated to 7700 C for an hour. Innoproper tool after cooling! Onl was added and refluxed for 30 minutes. It was cooled on ice, and the precipitated crystal tF was collected and washed with Improper Tool. This was recrystallized from methanol using activated carbon. Yield 12.3g (yield 1) Melting point λ 3
°C (decomposition) Synthesis M, Example 6 Synthesis of N-(,2-bromoethyl)-orthobenzosulfimide Orthobenzosulfimide 3. t9 and N,N-dimethylformamide were placed in a 100 ml three-way flask equipped with a stirrer and a thermometer. Furthermore, 8 gg of potassium carbonate was added, and the mixture was stirred at room temperature for 30 minutes. After this, add 7 g of 7.2-diolomoethane and add ao,,to
The reaction was carried out at °C for 1 hour.

The reaction mixture was then poured into water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure at 7 tVt to obtain the desired product in the form of an oil. Yield 1, da I (yield 7j) Synthesis Example 7 z, Synthesis of A-dichloro-7-ethyl-,2-methyl-j-(2-orthobenzosulfimidoethyl)benzimidazolium bromide J, A-Dichlororo/
-Ethyl-co-methylbenzimidazole, 31! i
+ and N-(λ-duromoethyl)-orthobenzosulfimide λ, 2 g, was added to a l liter equipped with a stirrer and a reflux condenser.
The mixture was placed in an oowrl Mitsuro flask and heated on an oil bath heated to lλOQC for 3 hours. After that, the oil bath was removed and the mixture was allowed to cool, and then acetone and θd were added to precipitate and loosen the crystals.

After leaving it at room temperature for 2 hours, the crystals were collected, washed with acetone, and dried for 5 hours in a 10" tube. Yield a, ig (
(Yield to %) Synthesis Example 8 Compound Example ■ -Synthesis of -jO j, &-dicrow/-ethyl-comethyl-3-(2-
orthobenzosulfimidoethyl) benzimidazolium bromide o, rzgb yohifu-[λ-(-monoanilinovinyl)benzoxacilio3]-butanesulfonate/, O9 and acetic anhydride 0.7 g and acetonitrile 3
1ootrl equipped with stirrer and reflux condenser
The mixture was placed in a Mitsuro flask and heated on a steam bath for 5 minutes. After this, triethylamine λ,jd was added. This mixture was heated and stirred on a steam bath for 1 hour. After cooling with water, the precipitated 1^ was collected with P and washed with acetonitrile.

The crystals were purified using methanol and chloroform and dried under reduced pressure for 70 hours.

Yield/, Og (yield 77%) Melting point λ? θ~, 2P1C The sensitizing dye used in the present invention is /x10 mol to jx10 mol, preferably, per 1 mol of silver halogenide.
/×lO mol~λ8. t×73 θ mol, particularly preferably Fi≠X10 mol ~/x10
It is contained in the emulsion in molar proportions.

i-combined VC using cyanine dye and hemicyanine dye together
11, Cyanine dye/Hemicyanine dye (N Kai ratio) =
The range / / F - / 00 / / is advantageously used, and the range from 2 to II O / / is advantageously used.

The sensitizing dye used in the present invention can be dispersed in the 1a emulsion. First, use a suitable solvent, fllf
It can also be dissolved in 1Cm in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and added to an emulsion in the form of a solution. Alternatively, ultrasound can also be used for dissolution. However, the method of adding this sensitizing dye is U3-3. a
A method of dissolving a dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 217, etc.,
Water-insoluble dye f as described in t-, 2≠/1j, etc.
A method of dispersing dye 1 in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion: Dissolving dye 1 in a surfactant as described in US-3, rλ Co., No. 131,
Method of adding the solution to the entire emulsion: JP-A-Shoj/-7gax
A method of dissolving a red-shifting compound as described in No. e and adding it to the IAA liquid whole emulsion: JP-A-1 No. 1
O-10t, 21. A method of dissolving a dye as described in the above-mentioned No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 3, No. 1, No. 1, No. 1, No. 1, No. 1, March 2006, and the like, in which a dye is dissolved in an acid substantially free of water, and the resulting solution is added to an emulsion, is used. Other additions to emulsions include U.S. Patent Nos.
No., No.-, 2F4. -17, 3.4'2, l
The method described in VCl, No. 2, such as No. 'Jj, is also used. The sensitizing dye may also be uniformly dispersed in the preparative silver halide emulsion coated on a suitable support, but can of course be dispersed at any stage of the preparation of the silver halide emulsion. .

The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes. For example, U.S. Patent No. J, 703
, No. J77, U.S. Special Issue "No. 2. ttrr.

No. 1171, U.S. Pat. No. 3.327, 01.0, U.S. Pat. t/j, No. 633, U.S. Patent No. 3°628
', 91, No. 14, English tit special ti'r No. 1, 2U
, 2. It1 No. 1, British sex 1' 1st and 2nd 31g 6th No., Tokko Akihiro 3-Hori 36, 11 ￥ Kosho 4Lμ-Nohiro 0
No. 30, Japanese Patent Publication No. 3-10773, U.S. Patent @3. u
/4.7.27, -11 Kosho 4ZJ-4230, US Patent tα3,1/j, 1! l/3, U.S. Patent No. 3,
1/, t, AJ, No. 2, U.S. Special M'F No. J, A/7.
Sensitizing dyes described in λri No. 5, US Pat. No. 3.1,33,72/, etc. can be used.

The silver halide used in the present invention may be, for example, any one of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and the like. In the present invention, silver halides mentioned above, particularly silver chlorobromide and silver iodobromide, are preferred.

Silver halide grains in photographic emulsions can be cubic, octahedral, or
&Hedron, rhombus/, regular like dihedron
r) It may have a crystalline form, or it may have an irregular crystalline form such as spherical or plate-like, or it may have a composite form of these crystalline forms. "C" consisting of a mixture is also good.

Further, an emulsion may be used in which ultratabular silver halide grains having a diameter of at least j times the grain thickness occupy 604 or more of the total projected area. The details are described in the specifications of JP-A No. 1992-/λ7 Tako/, JP-A No. 61-//J-27, and the like.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particle.

The photographic emulsion used in the present invention is P, Glafkid
es'l Cbimic et Physique Yen+
otographique (published by Pant Monte1 - /9'47), Pbot by G. F. Duffin
ograpl+ic Emulsion Chemises
try (The Focal Press, 1266
), V.L., Zelikman et al. Ma.
king and coating PI+otogra
phic Emulsion (The Focal P
It can be prepared using the method described in VC (Res., 1996).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble silver salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. It's okay.

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

As one type of simultaneous mixing method, a method in which pAgt and pAgt in the liquid phase in which silver halogenide is produced can be kept constant, that is, a so-called Chondral double jet method.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, gold salts or their complex salts, etc. , may coexist.

Silver halide emulsions can be chemically sensitized or not. For chemical sensitization, see for example Die Grundlagen der Photog, edited by H, Fr 1eser.
raphischcnProzesse mit Si
lberhalogeniden (Akademisc
be Verlagsgesellschaft.

/ri61)67! The method described on page 73μ can be used.

That is, a sulfur sensitization method using sulfur-containing compounds (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines) that can react with active gelatin and silver; reducing substances (e.g., stannous salts, Reduction sensitization method using amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds);
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 emulsion of the present invention can contain various compounds for the purpose of preventing IJ=i from turning over during the manufacturing process, storage or photographic processing of the light-sensitive material, or for stabilizing the photographic performance. Namely, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercazoto compounds such as mercaptothiazoles, mercapto(nzodiazoles, mercapto); Indimidazoles, mercaptothiadiazoles, mercaptotetrazoles (¥NC/-Phenyl!-Mercaptotetrazo-
A), mercaptopyrimidine@i + the above-mentioned heterocyclic mercapto compounds containing water-soluble foundations such as carlyxyl and sulfone groups; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (especially ≠-hydroxy Replace (/, 3.3a, ?)
A large number of compounds known as antifouling agents or stabilizers can be added, such as tetraazaintenes) + -'zenthiosulfones (7zenesulfinic acids); and the like.

For more information, see E. J. Birr, [5tabiliza
tionof Photographic 5ilve
r Halide Emulsjons J (Foca
1 Press, /27 years), etc.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for the purpose of preventing irradiation or other purposes. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, this oxynol dye;
Hemioxonol dyes and merocyanine dyes are useful.

The photographic light-sensitive material of the present invention may contain 1'a-free or organic hardeners in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, rIr+ chromium acid, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxyphosphorus nln form (2,3 -dihydroxydioxane, etc.), active vinyl compounds (/, 3
, j-triacryloyl-hegisahydro s-triazine, l.

3-vinylsulfonyl-λ-pronotol), active halogen compounds (λ,4A-dichloro-t-hydroxy-5-triazine), mucohalogen acids (mucochloric acid, mucophenolic acid, etc.), etc. F can be used alone or in combination.

Photosensitive emulsion layer of the present invention or other hydrophilic colloid I? #KVi coating aid, antistatic, improved slipperiness, emulsification and dispersion, prevention of adhesion, and improved photographic properties (for example, the current 1ψ
Various surfactants may be included for various purposes such as enhancement, contrast enhancement, and sensitization.

For example, saponins (steroids), alkylene oxide conductors (e.g. &11 ethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters) , polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Nonionic surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphate esters M, N-acyl-N-alkyl taurines, Acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants such as diamino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or Nisderl phosphates, alkyl betaines, amine oxides; amphoteric surfactants such as argylene salts, aliphatic or aromatic Cationic surfactants such as μ-class ammonium salts μm, monocyclic V-class ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, evapolyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholine, etc., for the purpose of increasing sensitivity, increasing contrast, and promoting practicality. , quaternary ammonium salt compounds, urethane derivatives,
Examples include urea derivatives, imidazole derivatives, 3-pyrazolidones, etc.

As a binder and a protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, gelatin can be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose visiting conductors such as hydroxyethyl cellulose, carboxyl methyl cellulose, cellulose sulfates, etc.; sugar derivatives such as sodium alginate and starch derivatives; Various synthetic hydrophilic compounds such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, bo-1-acrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Polymeric substances can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, that is, a color-forming coupler that develops color by oxidative coupling with an aromatic 7th class amine developer (for example, a phenylene diamine derivative or an amine phenol derivative) during a color development process. It may also contain a compound that absorbs water. For example, assume a magenta coupler 'C1! - Virazolone coupler, Virazoloinraimidazole coupler, Cyanoacetylcoumaron Kab 5
-1 open chain acylacetonitrile couplers, etc., -
(Yellow couplers include C1 acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilide 7J'l), etc.; cyan couplers include naphthol couplers, phenol couplers,
etc. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either μ-equivalent or mono-equivalent to silver ions.

There are also colored couplers that have the effect of color correction, or couplers that release a phenomenon suppressor (also called a phenomenon V).
It may also be a so-called 1) In coupler).

In addition to the D I It coupler, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a disorder inhibitor.

Various other additives may be used in the silver halide photographic emulsion of the present invention. For example, brighteners, desensitizers, plasticizers,
Slip agents, matting agents, oils, mordants, color fog prevention agents, ultraviolet absorbers, anti-fading agents, etc.

Regarding these additives, please refer to Research Disclosure (RESEAft(,:)I DISCL).
O8URE)/76 No. 22-31 (RD-/74≠
3) Described in CDeC, /971) etc.7t4ノ'
can be used.

The emulsion of the present invention can be used in various color and black and white silver halide sensitive materials. For example, color positive emulsions, color E/MO emulsions, color negative emulsions, color reversal emulsions (which may or may not contain couplers),
Emulsion
In addition to emulsions used in photosensitive materials for mAQ recording (materials for direct and indirect photography using a screen), it can also be used in photosensitive materials for heat development.

Exposure to obtain a photographer may be carried out using conventional methods. i.e. natural light (sunlight), tungsten electric light,
Fluorescent lamps, mercury lamps, xenon arc lamps, carbon mark lamps, xenon flash lamps, cathode ray tube flying spots, light emitting diodes, laser lights (e.g. gas lasers, YA
Any of various known light sources including infrared light, such as G laser, dye laser, semiconductor laser, etc., can be used. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, r-rays, α-rays, or the like. The exposure time is 171090 which is usually used in cameras.
In addition to exposure times of 1/100 seconds to 7 seconds, exposures shorter than 1/100 seconds, such as //10 to 17 io seconds using a xenon flash lamp or cathode ray tube, can be used, or exposures longer than 7 seconds can be used. You can also do that. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter.

For photographic processing of the light-sensitive material of the present invention, for example, research disclosure
re ) / 7 A whistle λr ~ page 30 (RD-z7t
, a3), any of the known methods and known treatment liquids can be applied. This photographic processing may be either a photographic processing for forming a silver image (black and white photographic processing) or a photographic processing for forming a dye image (color photographic processing), depending on the purpose. Processing temperature Fi
Usually chosen between /g 'C and evening o 0C, /f
The temperature may be lower than f'U or higher than tma 0c.

In some cases, other known development methods (for example, thermal development) may be used.

Next, the present invention will be explained in detail using representative examples.

Example 1 Silver halide grains were formed using ammonia by a conventional double jet method, and after physical ripening and desalting treatment,
Chemically matured by gold sensitization method and sulfur sensitization method, silver iodobromide (': 3-de containing I2.0 mol, average grain diameter 0
, 67 microns) emulsion was obtained.

The emulsion contained 5 to 9 moles of silver halide.

Weigh out the emulsion 10017 and add gelatin water ≠θ
The molten mixture was heated using VC.The sensitizing dyes shown in Tables 1, 2, and 3 were added while stirring.

After that, a hard 111 agent and an anion l” as a coating aid are added.
f, face activity t'lE A1. 1. A thickener was added, and the polyethylene and paper were coated onto a polyethylene paper support of Lamiauto L7-C with gelatin as the main component.
Make it in the upper layer, li''1!r'p- is J, f -1
-, 0, / Apply nail Iro to make it a micron, * attack v! Let's try it out.

The sample was cut into strips and subjected to hinge tometry. Exposure was done using a tungsten light source. 1. Ta. i
6-light strips (300 mL) using the following solution
C for 20 seconds, and then washed and dried at 3θ0C with the following acidic hardening fixer (fixed for 7 seconds). The optical density standard for determining the fr-0 sensitivity is [Fog 10,
! θ].

Developer composition/-Phenyl-3-pyrazolidone o, ay Sodium sulfite 1) Rum (anhydrous) 67g Hydroquinone, 23g Potassium hydroxide //9 Sodium carbonate - hydrate //fl Potassium bromide 3g! -Methyl-(zotriazole/33~Add water to make Il.

Fixer composition CA) Ammonium thiosulfate 770g Sodium sulfite (anhydrous)/j9 Boric acid 7g Glacial acetic acid! I Ethylenediaminetetraacetic acid o, ig Tartaric acid 3.39 Glacial acetic acid iog Kali Aken Koog In addition to Mizukura, Il and 1-L.

After processing, Sudein was prepared by using the above-mentioned inertia without exposing the cut sample to dust 1*, fixing, washing with water, and drying.
The skin is displayed as the reflectance measured using a Hitachi Color Analyzer with a sample without sensitizing dye set on the reference side.

Reflectance is measured at the maximum absorption wavelength (λmax) of the sample being measured.

The obtained results are shown in Tables 1 to 3.

Comparative compound (A) (13) 03 (D) :E) 7p) C2H5 ((3> Cll5 1 (■T) 2115 (J) zl15 ■ As can be seen from Tables 1 and 2, 1 of the present invention While exhibiting sensitivity comparable to that of the corresponding sensitizing dyes with excellent sensitizing properties, staining is reduced.

The stain measured by the measurement method of the present invention differs depending on the absorption wavelength, but for example, a sensitizing dye whose λmax is about t-tnm)
-! In /, stain is no longer visible to the naked eye when the reflectance is higher than rzeir, and when the reflectance is higher than 70%, there is a slight Kg noticeable tO=
Below S, it will be recognized as a significant stain. Therefore, it is determined that the sting changes significantly between the to-chi and tj coefficients, so even a few chis have great significance.

On the other hand, simply introducing a water-soluble group as described above, such as dye (G), reduces staining (Table 1 Aλt%)
In such cases, as shown in Table 1, the sensitivity is also significantly reduced. The main reason for this is that it is difficult to be adsorbed by silver halide. For this reason, if the adsorption reinforcement means is used in this way, the sensitivity will be restored, but as a result, the stain will usually increase as well.

From Table 3, further sensitizing dye (I) K sensitizing dye (11)
Not only did the combination of the corresponding compounds show similar increases in sensitivity as the combination of the corresponding compounds, but surprisingly, the combination of the corresponding compounds also showed the same degree of stain hydration as when used alone. In contrast, the combination of the present invention has even fewer stains.

There are no known patents or documents that predict that the sensitizing dye of the present invention will exhibit such ambiguous effects.

Therefore, the compound of the present invention is original and exhibits extremely effective effects for the production of silver halide photographic materials.

Example 2 Formation of spherical particles of silver iodobromide (silver iodide J, j mol %) by double jet method in the presence of ammonia, average particle size O0 (j tt m), chloraurate and sodium thiosulfate After chemical sensitization with fC0, the sensitizing dye 'f-' shown in Table 1 was added.

Furthermore, the anti-capri agent l-phenyl-j-mercaptotetrazole bi-hydroxy-4-methyl-/, J, Ja
, 7-chitrazaindene, a coating aid dodecylbenzenesulfonate, and a thickener do11 potassium p-vinyl to prepare a coating solution. At this time, the weight ratio of silver/gelatin is 1. -It was 〇.

A hardening agent is added to the above-mentioned tabular silver halide emulsion and spherical silver halide emulsion, and a surface protective layer and a Vc layer are coated on a polyethylene terephthalate support at the same time and dried.
All photographic materials were created. In addition to gelatin, the surface protective layer contains polystyrene sulfonate, polymethyl methacrylate fine particles (average particle size 3.0BrrL),
A low % gelatin aqueous solution containing saponin and the like was used. At this time, the coating amount of silver in the silver halide emulsion layer was 3.0
9/@2 Ash, the amount of gelatin applied in the surface retention layer is 7.3
g/WL2 and the thickness was i, oμm.

Photographic material created as above; jy4AI'InmK
After exposure to 3TO, AgonM blue light with peak intensity, all the following treatments were carried out.

Processing: 3j 0C:, 2j seconds with the following developer, then 30'C,, 2, with the following fixer.
The sample was left in place for j seconds, washed with 300C1 water for 2j seconds, and then dried.

Developer/-Phenyl-3-pyrazolidone i,rg Hydroquinone 3θI! - Nitroindazole o,,2zgKBr 3,7
g Anhydrous sodium sulfite sog Potassium hydroxide 20I! i+ Boric acid 1017 2 glutaraldehyde aqueous solution 20rnl Add water to make the total view /71.

(pH adjusted to 10, 2011C?A) Fixing n & ammonium thiosulfate 200. Ojj Sodium sulfite (anhydrous) 0. Og position ir, og Disodium ethylenediaminetetraacetate o, ip Aluminum sulfate /j, 09 Sulfuric acid ko, ol Glacial acetic acid λλ, OI Add water i, ol (pH is ≠,,2 (adjust to 17) Sensitivity measurements of the processed photographic materials were carried out and the results are shown in Table ψ.Here, the sensitivity value was determined as the logarithm of the reciprocal of the exposure amount required to obtain a degree of blackening of fog value + 1.0. It is the relative value of something.

The stain after processing was measured in the same manner as in Example 1, using a photographic material that was not exposed to light but developed, fixed, washed with water, and dried under the conditions described above.

As can be seen from Table ≠, the sensitizing dye of the present invention was able to significantly suppress stain while exhibiting a sensitivity comparable to that of the corresponding sensitizing dye (2), which had excellent sensitization properties.

Patent applicant Fuji Photo Film Co., Ltd. Procedural Amendment Showa! Mr. Rikuma Yuzukishiro, Commissioner of the Patent Office 1, Indication of the case: Showa Juri 2013 Patent Application No. 47AA4 2, Title of the invention: Silver halide photographic emulsion 3, Relationship with the person making the amendment case: Personality of the watch applicant: Place: Nakanuma, Minamiashigara City, Kanagawa Prefecture 210 address name (52
0) Fuji Photo Film Co., Ltd. Contact information 〒106 bundles 5 Nipart 2'l'l, Nishi-Azabu, Minato-ku] 26-30 No. 4, subject of amendment Column 5 of "Detailed description of the invention" of the specification, amendment The statement in the "Detailed Description of the Invention" section of the Description of Contents is amended as follows.

ti+ page 53, lines 2-3 ``Specification of Japanese Patent Publication No. 3 B-7828,'' shall be deleted.

(2) page 53, lines 5-6 rchapterV, pagel 16-l 47
Delete J.

Procedural Amendment Statement Cow 5 Dear Commissioner of License Agency 1 ・(Representation of Matter G) (1955 Patent Application No. A#AA 2, Title of Invention Silver Halide Photographic Emulsion 3, Relationship with the Supplementary Person Case) Patent applicant address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact address: 1
() 6 Tokyo Minato 1 Me Nishiazabu 2-J'1126-30 Gino 4, Subject of amendment Column 5 of "Detailed explanation of the invention" in the specification, Contents of amendment "Detailed explanation of the invention" in the specification The following amendments have been made to the section.

ill Insert "(These may be substituted with a halogen atom, hydroxy group, carboxy group, carbamoyl group, sulfamoyl group, acylamino group, etc.)" after "maleimide, etc." in line 7 on page 11. .

Procedural Amendment Document 1985 Yachi” r Japan, 1 1 j Mr. Commissioner ■, “Table 14 of 1 < 1985 Patent Application No. 4/46
4 No. 2, Name of the invention Silver halide photographic emulsion 3, Relationship to the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamihigara City, Kanagawa Prefecture Name (52)
0) Minoru Ohnishi, Representative of Fuji Photo Film Co., Ltd. 4. Subject of amendment: ``Detailed Description of the Invention'' column 5 of the specification, ``Detailed Description of the Invention'' section 1 of the description of the contents of the amendment. Correct everything as below.

1) Page 7, line 7 "77 no" all "Amin" and correct it.

2) 7th page line 1-/~3'' "lN2" and correct it.

3) Page 7, line 12 1-Represent. "After the 1 also k, ``ga/'' and chobadai form an inner salt.

” Insert grapes.

4) Line 13 on page 13 1-alkyl” 1-ethyl” and correction °J-ru.

5J　7r Negative/Table sample horse λ0 11-3ri” grapes 1-1-II-≠” and correct it.

6) The tabular silver halide emulsion of 1-upper FI+2 in the r6th row and "1-deletion-1-".

Claims (1)

[Scope of Claims] At least one sensitizing dye represented by the following general formula (I) and/or a sensitizing dye represented by the following general formula (Haton or (nb
A silver halogenide photographic emulsion characterized by containing at least one type of sensitizing dye represented by ). General formula (I) General formula (Ha) General formula (nb) represents a group.R2 is an optionally substituted alkyl group, +cH
2) -c-C113 or a-1°() L3, L4 and L5 represent an optionally substituted methine group. W is a halogen atom, a cyano group, an alkoxycarbonyl group, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted alkoxy group Represents an acyno group. I] represents O or an integer from 1 to 3. Xi and X2 represent acid anions. R1 and R3 are ・(C112U-c-Cl3 or "11ks p and r represent integers of / to 3.
represents an integer from 7 to ≠. Y represents a nonmetallic atomic group capable of forming a cyclic imide. S and t represent integers from λ to j. )