JPS6111736A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To prevent stain after development without causing reduction in sensitivity by using at least one kind of sensitizing dye represented by a specified formula. CONSTITUTION:A sensitizing dye represented by formula I such as a compound represented by formula IV is synthesized by a specified means and dispersed directly in an emulsion by 4X10<-5>-1X10<-3>mol per 1mol silver halide. The dye may be dissolved in a proper solvent such as methanol and added to the emulsion in the form of a soln. In the formula I, each of Z<1> and Q is a group of nonmetallic atoms required to form a 5- or 6-membered heterocyclic ring; R<1> is (substituted) alkyl or a substituent represented by formula II; R<2> is H, (substituted) alkyl, (substituted) aryl, a heterocyclic group or a substituent represented by formula III; Y is a group of nonmetallic atoms capable of forming cyclic imido; each of L1 and L2 is (substituted) methine; each of h and i is an integer of 2-5; l is 1 or 2; and m is an integer of 1-4. The resulting emulsion is used in the manufacture of various colors and black-and-white sensitive silver halide materials such as an emulsion for a color positive (negative) and sensitive materials for an engraving, X-ray recording and heat development.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, which is particularly spectrally sensitized with a sensitizing dye, has high sensitivity,
The present invention also relates to a photosensitive material with less staining after development.

(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 extends to the infrared range by selecting the structure of the sensitizing dye according to the required purpose.

Although it has become possible to adjust it arbitrarily, there are various drawbacks and improvements are needed. That is, when applying a sensitizing dye to a silver halide photographic emulsion, 1) the spectral sensitivity distribution is appropriate, and 2) high sensitivity can be imparted in a desired spectral sensitivity range. In addition to the original purpose of 3) not causing capri, Hiroshi)
It is a photographic technology that does not cause changes in sensitivity or increase fog during the production of photosensitive materials or during storage after production, and does not cause undesirable phenomena such as residual residue after development that decomposes into colored matter and does not cause staining. This is important in actually manufacturing and providing photosensitive materials.

In general, it is well known that a method for preventing staining caused by sensitizing dyes after development is to increase the hydrophilicity of the sensitizing dyes. However, increasing hydrophilicity often causes a decrease in the adsorption of sensitizing dyes to silver halide. As a result, although I no longer experience sting, I often experience it when I don't get the desired sensitivity. Therefore, there is a strong desire to develop a technique that prevents staining caused by sensitizing dyes after development without reducing adsorption to silver halide or deteriorating sensitivity.

(Object of the Invention) That is, an object of the present invention is to provide a silver halide photographic light-sensitive material containing a sensitizing dye that does not cause a decrease in sensitivity and does not cause staining after development.

(Structure of the Invention) As a result of intensive research efforts by the present inventors to achieve all of these objects, we unexpectedly discovered that a sensitizing dye represented by the following general formula (I) or general formula (II) It has been found that the objects of the present invention can be achieved by using at least one of them.

General formula (I) In the formula, 21 is! Represents a group of nonmetallic atoms necessary to form a t-membered heterocyclic ring.

For example, a thiazole nucleus (e.g., thiazole, μ-methylthiazole%μm7enyltheazole, ri).

j-dimethylthiazole, 4. j-diphenylthiazole etc.) & benzothiazole nuclei (e.g. benzothiazole, μm chlorobenzothiazole.

j-chlorobenzothiacyl, 6-chlorobenzothiazole, j-nitrobenzothiazole, Hiro-methylbenzothiazole, j-methylbenzothiazole, A-methylbenzothiazole, j-bromobenzothiazole, 6-
Benzothiazole, s-phenylbenzothiazole kj-methoxybenzothiazole, 6-medoxybenzothiazole%!-ethoxybenzothiazole, !-ethoxycarbonylbenzothiazole, j-carboxybenzo Thiazole, j-7enethylbensotheazole, j-fluoro-
<Nzothiazole, j-chloro-&-) If rubenzothiazole, 5,6-dimethylbenzothiazole,! -Hydroxy-t-methyl/soteazole, tetrahydrobenzothiazole, cuphenylbenzothiazole, etc.), naphthothiazole nucleus (e.g. chin) (J, z-(
1) Thiazole.

Nut [l, code d] thiazole, naphtho [2゜3-d
] Thiazole, j-methoxynaphtho [l.

λ-d] thiazole, 7-nitoxynaf) ["J,.

/-d] Thiazole, lr-methoxynaphtho [co.

/, -d) Thiazole,! -Methoxynaphtho [co.

3-d]thiazole, etc.), thiazoline nucleus (e.g., thiazoline, 4A-methylthiazoline, 4A-nitrothiazoline, etc.), oxazole nucleus (e.g.

Oxazole, French-methyloxazole, μ-nitrooxazole, J'-methyloxazole, l-phenyloxazole, a,j-diphenyloxazole, l-
etheroxazole, etc.), benzoxazole core (benzoxazole, j-chlorobenzoxazole, !
-Methylbenzoxazole, t-bromobenzoxazole, j-fluorohe/soxazole, j-phenylbenzoxazole,! -Methoxybenzoxazole1. t-Nitrobenzoxazole! -trifluoromethylbenzoxazole, j-hydroxybenzoxazole 1, j-carboxybenzoxazole,
6-Methylbenzoxazole, 6-chlorobenzoxazole, t-nitrobenzoxazole & t-methoxybenzoxazole, t-hydroxybenzoxazole%j, -dimethylbenzoxazole% ψ
, roudimethylbenzoxazole, j-ethoxybenzoxazole, etc.), naphthoxazole nuclei (e.g.

Nando (2,/-d)oxazole, Natto (/.

j-d) oxazole, naphtho [λ, j-d) oxazole, j-nitronaphtho [λ, /-d) oxazole, etc.), oxazoline nucleus (e.g., French.

% benzoselenazole core (e.g., benzoselenazole, j-, z-lolobenzoselenazole) zol, j-nitrobenzoselenazole, j-methoxybenzoselenazole, j-hydroxybenzoselenazole, t-nitrobenzoselenazole,
j-chloro-6-nitrobenzoselenazole, etc.), naphthoselenazole core (e.g., naphtho[λ,/-d)selenazole, naphthoC/, J-d)selenazole, etc.), J,J-dialkylindolenine nucleus (e.g. % 3
．． 3-dimethylindolenine, 3,3-dimethylindolenine, 3,3-dimethyl-yo-cyanoindolenine,
3.3-dimethyl-6-nitroindolenine, 3.3-
Dimethyl-j-nitroindolenine % 3.3-Dimethyl-j-methoxyindolenine, 3,3. j-) Rimeterindoreni7. J, J-dimethyl-y-chloroindolenine, etc.), imidazole nuclei (e.g. l-alkylimidazole, l-alkyl-μm phenylimidazole, l-alkylbenciimidazole, /-alkyl-y-chlorobenzimidazole).

l-alkyl-j, 6-dichlorobenzimidazole,
l-Alkyl-y-methoxybenzimidazole, l-
Alkyl-j-cyanobenzimidazole, l-alkyl-j-fluorobenzimidazole% l-alkyl-j-)lifluoromethylhencyimidazole, l-alkyl-6-chloro-j-cyanobenzimidazole,
l-alkyl-A-chloro-, t-) IJ fluoromethylbenzimidazole, l-alkylnaphthoC/,
2-d] Imidazole, l-allyl-5,6-dichlorobenzimidazole, l-allyl-j-chlorobenzimidazole% l-arylimidazole, l-arylbenzimidazole, l-aryl-yo-chlorobenzimidazole, l -aryl-j, t-dichlorobenzimidazole, l-aryl-j-methoxybenzimidazole, l-aryl-j-cyanobenzimidazole, l-arylnaph) (/,,?-d]imidazole, the alkyl mentioned above is carbon Those having 1 to 7 atoms, for example, unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, hydroxyalkyl groups (e.g. Eva, λ-hydroxyalkyl, 3-hydroxypropyl, etc.) are preferred. Particularly preferred. is a methyl group or an ethyl group.The above aryl is a methyl group or an ethyl group.

phenyl, halogen (e.g., chloro) substituted phenyl, alkyl (e.g., methyl) substituted phenyl, alkoxy (e.g., methoxy) substituted phenyl, etc.), pyridine nucleus (e.g., 2-pyridine, q-pyridine, !-methelukopyridine) , 3-methyl-μm pyridine, etc.),
Quinoline core (e.g. 2-quinoline, 3-meteruchoquinoline).

j-Ether-λ-quinoline & t-methyl-λ-quinoline, % t-nitro-1-quinoline, r-fluoro-1-quinoline, ru-methoxy-quinoline.

6-Hydroxycorquinoline, Ir-chlorocorquinoline & Hiro-quinoline, 2-ethoxy-Hiro-quinoline, 6-nitro-μmm pheasant 9 flo-μmm pheasant 9 fug-methyl-μm quinoline, t-methoxy- μm quinoline, inquinoline% 6-nitro-twoisoquinoline%
3,l-dihyde er-/~isoquinoline, 6-nitro-3-inquinoline, etc.), imidazo[μ,j-b)quinoxaline core (e.g., l,3-diethylimidazo[μ
, j-1)) Quinoxaline.

6-chloro-/,3-diallylimidazo[<t,5-b
) quinoxaline etc.), oxadiazole core.

Represents thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus, etc.

Q represents a nonmetallic atomic group necessary to form a J- or T-membered heterocyclic ring; examples of the heterocyclic ring include rhodanine nucleus & cortiohydantoin nucleus, monothioquine oxazolidine-hiro-one nucleus, copirazoline-j-one nucleus, Barbyric acid nucleus, λ-thiobarbylic acid nucleus, thiazolidine, λ. ≠-dione nucleus, thiazolidine-hiro-one nucleus, inoxacilone nucleus.

These include hydantoin nucleus and indandione nucleus.

R2 is bonded to the nitrogen atom contained in these nuclei.
, hydrogen atom. Carbon number l~llf% preferably 1~7%%
IC preferably /, l alkyl group (e.g. methyl group, ethyl group, propyl group, isopropyl group, butyl group,
Isobutyl group, hexyl group.

(octyl group, dodecyl group, octadecyl group, etc.)

Substituted alkyl groups (e.g., aralkyl groups (e.g., benzyl group, 2-phenylethyl group, etc.), hydroxyalkyl groups (e.g., -monohydroxyethyl group, 3-hydroxypropyl group, etc.), carboxyalkyl groups (e.g., -
Monocarboxyethyl group.

3-carboxypropyl group, p-carboxybutyl group,
carboxymethyl group, etc.), alkoxyalkyl group (e.g., comethoxyethyl group, 2-(comethoxyethoxy)ethyl group, etc.)% sulfoalkyl group (e.g., 2-(comethoxyethoxy)ethyl group, etc.)
-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, μm sulfobutyl group. 2-C3-sulfopropoxy]ethyl group, non-hydroxy-3-sulfozorobyl group, 3-sulfopropoxyethoxyethyl group, etc.)%
sulfatoalkyl group (e.g., 3-sulfatopropyl group, μm sulfatobutyl group, etc.), heterocyclic-substituted alkyl group (e.g., co-biolidine-co-on-1-yl), ethyl group, tetrahydrofurfuryl group, co- morpholinoethyl group), 2-acedoxyethyl group, carbomethoxymethyl group, comethanesulfonylaminoethyl group, etc.), allyl group, aryl group (e.g. phenyl group, cornaphthyl group, etc.), substituted aryl group (e.g. μ
- Carboxyphenyl group %μ ~ Sulfophenyl group.

3-chlorophenyl group, 3-methylphenyl group, etc.),
A heterocyclic group (for example, &λ-pyridyl group, Co and i represent an integer from Co to j, and Y represents a cyclic imide group (for example, succinimide group, phthalic acid imide group, orthobe/zosulfimide group, maleimide group, etc.). Preferably k represents 2 and i represents ko or 3.

R1 is an alkyl group having preferably 1 to 71 carbon atoms, particularly preferably 1 to 44 carbon atoms, such as methyl, ethyl, propyl, impropyl, butyl.

isobutyl, hexyl, octyl, dodecyl, octadecyl, etc.), substituted alkyl groups (e.g., aralkyl groups (e.g., hensyl, 2-phenylethyl, etc.), hydroxyalkyl groups (e.g., co-hydroxyether, 3-hydroxypropylnato, etc.).

Carboxyalkyl groups (e.g. cocarboxyethyl, 3-carboxypropyl, lA-carboxybutyl,
carboxymethyl), alkoxyalkyl groups (e.g. 2-methoxyethyl, λ-(2-methoxyethoxy)ethyl, etc.), sulfoalkyl M (e.g. tlf, x-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl,
sulfatoalkyl groups (e.g., 3-sulfatopropyl, (e.g. fatobutyl), heterocyclic substituted alkyl□ groups (e.g.!
-(pyrrolidine-coon-l-yl)ethyl, tetrahydrofurfuryl, etc.), λ-acetoxyethyl, carphomethoxymethyl% λ-methanesulfonylamine ethyl), allyl group.

represents. Here, h and i represent integers from co to j, and Y represents a cyclic imide group (for example, a conoriimide group, a phthalic acid imide group, an orthobenzosulfimide group, a maleimide group, etc.). Preferably k represents moss. However, at least one of R1 or R2 is +c)(Sl←
"] or methine group or substituted methine group (alkyl group (e.g. methyl, ethyl etc.), aryl group (e.g. phenyl etc.) or
chloro, bromo, etc.). It may also form a ringtone with other Lf). T is! or moss, and m represents an integer of l-μ.

General formula (II) z2 and Z3 are synonymous with Zl, %W is represented by a sulfur atom, an oxygen atom, or N-R"! R3 and R5 are R
It has the same meaning as 1, R and R - has the same meaning as R2.

However, at least one of R, R, R, and R represents an integer from +CH2←-c-cH3h'I+ 2 to j. nbqbr and s ld
/ or λ. p is synonymous with m. R3, R4.

R5. R6 and R7 are L. and ■, are synonymous with 2. XQ represents an acid anion, and specific examples thereof include a halide anion, an alkyl sulfate anion, and p-toluenesulfonate.

Specific examples of the metal compounds represented by general formula (I) and general formula (II) include the following, but the scope of the present invention is not limited thereto.

ONsu0 C2H5 ■-λ1 l-Jj ■-, 2hiroCH2COCH3c2H5 ■-koj ■-ノ■-1[-J [-1 ■-7 ■-r ■-ta11-IJ 1-IJ 11-/ 4' [-/A [-77 COC)ia ■-it [-/P ■-JO II-CO1 TI-, lλ ■-23 cH2cOcHa ■-λ≠ 2H5 Here, PTSeFip-toluenesulfonate is represented.

The sensitizing dyes represented by general formulas (I) and (II) used in the present invention are @I-1eterl-1etero
cyclicco -Cyanine dFes
andrelated (!OmpOundl -
”, F, M.

Written by Hamer John, Wiley & Sons
(New York, London) Published in 1964.

@Heterocyclic Compounds-
8special topics in hetero
cyclic chemistr7-”chaptsy
■、tJec・■page4'! -~yo/j, D
, M. Sturmer, John Wile)'&
It can be easily synthesized based on the method described in Sons (New York, London), published in 1977.

Synthetic side tones are described for representative compounds.

Synthesis Example-1 <Synthesis of I-/> J-(-2-(z, t-diketopyrrolidyl)ethyl)-
Synthesis of 2-methylthiothiazolinium bromide λ-methylthiothiazoline 4.6t (sxio” mol)
and 2-(2,3-diketopyrrolidyl)ethylbromide 1
2.09 C6 x IO-"mol) 1-/300C on an oil bath with stirring for about 3 hours. After returning the reaction product to room temperature, it was added to acetone jOtd1 and the resulting precipitation tube decane I got it from the station.

The target product was obtained in //, /f (yield 6t%).

The obtained 3-(co(co,!-diteopyrrolidyl)ethyl)-comethelthiotheazolinium bromide3. μF
(/”pclo-2 mol) and 3-ethylrhoda:=7/
, At (/X/17-”T-l)17cetonitrilej
OtlK was dispersed and refluxed with stirring. Triethylamine 3r (3Xto-2 moles) was added dropwise to this over about 3 minutes, and the mixture was stirred and refluxed for 1#.

After cooling with water, the precipitated crystals kF were collected and washed with acetonitrile jOd. This crystallization methanol was 100 td.

The solution was dissolved in 100 d of chloroform and concentrated under normal pressure to about 10 d. Cool on ice, collect the precipitated crystals, and wash with methanol 2031.

The target product was obtained with keko, jf (yield 7 es, λma! (methanol) 3 6 nm).

Synthesis Example 2 Synthesis of I-7> J-(J-(Q-benzosulf, imido)ethyl)-j
-Methoxy-2-methylthiobenzothiazolium, p-
Toluenesulfonate j, P? (lXlO mol) and 3-
Carboxymethylrhodanine/, 99 (lXlO mol)
The mixture was dispersed in careacetonitrile jθd and refluxed with stirring. Triethylamine 39 (3×10 2 mol) was added dropwise to this solution over a period of about 10 minutes, and the mixture was stirred and refluxed for 1 hour. After cooling on ice, the precipitated crystals KF' were collected and washed with 5 tons of acetonitrile.

This crystalline methanol ioOml & chloroform loO
ml VC was dissolved and concentrated under normal pressure to about soml. After cooling on ice, the precipitated crystal kF was collected and washed with methanol λ0tnl.

Purpose @tco, otsu? (Yield: 471 λma! (methanol) a3gnm).

Synthesis Example 3 Synthesis of I-2>! -(N-acetylanilinomethylidene)-3-ethylrhodanine 3.Of(lXlO%#) and J-(J-(co,j-diketopyrrolidyl)-propyl)-λ-methyl-thiazolinium bromide 3.2f (lXlO” moles) of methanol! The mixture was dispersed in Od and refluxed with stirring. Triethylamine 21 (JX/0-2 mol) was added dropwise to the mixture and the mixture was refluxed for about 1 hour. After that, it was cooled with water and the reaction product was evaporated into ether 3
The resulting precipitate was obtained by decantation. Chloroform the obtained precipitate! After dissolving in Oml and filtering, 12 inopropanol was added and concentrated at normal pressure, and about 7'c6 Otrl was expelled, cooled with water, precipitated crystals were collected, and washed with Inpropanol λO-.

The target vJV was obtained at 2.3t (yield: λ□8 engineering (methanol)≠4'/nm).

Synthesis Example 4 Synthesis of <I-/> J, t-diketopyrrolidyl)-propyl)-2-methylthiazolinium bromide J, xt(
ixio mol) IDMsO (dimethyl sulfoxide) jOaJK was dispersed and stirred on a water bath heated to jOoC. To this, DBU (/, J'-')lf bicyclo[s, 4t, o]-7-undecene)3f(λ×
The mixture was added dropwise over a period of 1 θ - 2 mol) and then heated and stirred for about 1 hour. Thereafter, the reaction mixture was poured into Kether 3ootrt, and the resulting precipitate was obtained by decantation.

After dissolving this precipitate in chloroform and filtering it, ethanol was added and concentrated under normal pressure.
I made it to Oml. After cooling on ice, the precipitated crystal kP was collected and washed with 20 ttl of Improper Tools.

The desired product f/, 4A4Lf (yield 33cm, λmax (methanol) A/Jnm) was obtained.

Synthesis Example 5 Synthesis of -2μ>J',J-dichloro-7-ether-3-methylcarbonylmethyl-2-methylbenzidizidazolium chloride 3. cof(/x10 mol) and j-(j-(N-acetylanilino)-2,tA-intadienyritene)-
3.6 t (IXIO mol) of 3-etherrhodanine and 1 (2 x 10 -2 mol) of triethylamine were dispersed in methanol and refluxed with stirring for about 1,000 s hours. After that, it was cooled on ice and the precipitated crystal kF was collected using methanol! Washed with Od. The obtained crystals were dissolved in 200rtl of methanol and 2ooml of chloroform, filtered, and then dissolved at normal pressure to about 1zOt.
It was shrunk to nl. After cooling on ice, one of the precipitated crystals was taken and washed with 5 Otnl of methanol.

Objective 22. off (yield 0% λma (methanol) 7/7 nm).

Synthesis Example 6 <Synthesis of n-/> Compound Example I-Reference tμ, 9? (txto-”mol) and p-
Methyl toluenesulfonate 3. yt(2×io'″″2
The mixture was dispersed in anisole/ILl and stirred for 2 hours on an oil bath at 200C. Thereafter, the mixture was allowed to cool to room temperature, and 200 alf of ether was added thereto. The resulting precipitate was obtained by decantation. This is acetone! The precipitate was dissolved in O1d and added again with ether solution. Comethyl-J-(4A-sulfobutyl)thiazolinium 2.3? (txto-2moh) and engineering p
/ - was added and the mixture was refluxed with stirring.

Triethylamine JIF (jX/+7-2 mol) was added dropwise to the mixture, and the mixture was refluxed for 1 hour. Thereafter, it was cooled on ice, and the precipitated crystals were collected and washed with ethanol aml. Obtained crystalline chemethanol jOml, i% ethanol dissolved in chloroform jO- and filtered! Add Odke and put it under normal pressure for about 5 minutes.
It was concentrated in the trench that became ortrt.

After cooling on ice, the precipitated crystals were collected and washed with 20 Ld of ethanol.

Target rotacyanin dye 'Ig, 4Ay (yield 64L%)
, λmaX(methanol)jt7J11yl).

The following rhodacyanine 411-/ of 11-2 to 1-λμ can be synthesized by using the corresponding merocyanine and quaternary salt.

The sensitizing dye used in the present invention preferably has an amount of /x/Q-6 mol to jxlθ mol per 7 mol of silver halide, and preferably 1xio''-'' mol to 2. ! It is contained in the silver halide photographic emulsion in a proportion of X10-3 mol, particularly preferably 4tX10-5 mol to 1XIO mol.

The sensitizing dye used in the present invention can be directly dispersed into the emulsion. In addition, these can be prepared using suitable solvents such as methyl alcohol and ethyl alcohol.

It can also be dissolved in methylceronelube, acetone, water, pyridine, or a mixed solvent thereof, and added to the emulsion in the form of a solution. Ultrasonic waves can also be used for dissolution. The method for adding this sensitizing dye is to dissolve one dye in a volatile organic solvent and disperse the solution in a hydrophilic colloid, as described in J3-J, Gl, 9Ir7, etc. , a method of adding this dispersion to a whole emulsion, and a method of adding this dispersion to a sonic emulsion, including dispersing it in a water-soluble solvent without dissolving the water-insoluble dye, as described in Tokko Shobutsu T-CoA IZL, etc. :US-J,Ir
x2. A method of dissolving a dye in a surfactant and adding the solution to an emulsion as described in the specification of tJz: JP-A No. 3
A method of dissolving a red-shifting compound using a red-shifting compound as described in No. 1-74AAλμ, and adding the solution into an emulsion: A dye substantially free of water as described in JP-A-Sho, to-rot Jt. A method of dissolving it in an acid and adding it to the solution emulsion is used. Other additions to emulsions include U.S. Patent Nos. 3, 3, and 3.
Tos No., Ko No. 1, Tata T, No. 2 Za 7, No. 3. IIλ
In addition, the method described in No. rJs and the like can 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.

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
, 377, U.S. Patent No. 2,611゜jqj, U.S. Patent No. 3,3riq, oto, U.S. Patent No. J, t/l, 6
No. 31, U.S. Patent No. 3゜tcot, French name Riwa, British Patent No. 1,24t2. ! tt, British Patent No. 1. Rich 3. it
No. 2, Special Publication Showa 43-≠23 No., Special Publication Show μ≠-1 No. 3
Reference No. 30, Showa 4A3-70773, U.S. Patent No. 3. I
Alt, Octopus No. 7, Special Publication No. 13-μ230, U.S. Patent No. 3. L/j, l, 13, U.S. Pat. No. 3.61j, 6
No. 32, U.S. Patent No. 3. Sensitizing dyes described in Otsu No. 77.223, U.S. Pat.

The silver halide used in the present invention is, for example, silver chloride.

Any of silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, etc. may be used. In the present invention,
Among the above silver halides, silver chlorobromide and silver iodobromide are particularly preferred.

Silver halide grains in photographic emulsions can be cubic, octahedral, or
Regular (regula) like 4A-hedron, rhombus/J-hedron
r) Crystal? It may also have an irregular crystal shape such as a spherical shape or a plate shape, or a composite shape of these crystal shapes. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy at least the jO factor of the total projected area. For details, please refer to JP-A-Sho JTL-1279.
21. Same 3g-113'? 27, etc.

The silver halide grains may have different phases inside and on the surface. Further, it may be a particle in which the subsidence is mainly formed on the surface, or a particle in which the subsidence is formed as a king inside one particle.

The photographic emulsion used in the present invention is P, Glafkid
Chimic et PhysiquePhoto by es
ographique (published by Paul Monte 1 in 1967)% Pho by G, F, Duffin
tographic Emulsion Chemi
str7 (The Focal Press, /9
tt), V. L., Zelikman et al. M.
making and coating photogra
phic Emulsion (The Focal
Published by Press, A4 size! It can be prepared using the method described in 2010).

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 halogen tFl may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

A method in which particles are formed in an excess of silver ions (so-called back-mixing method) can also be used.

As one type of simultaneous mixing method, a method of keeping I) Agk constant in the liquid phase in which silver halide is produced, ie, the so-called Chondrald double jet method can also be used.

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

Silver halide emulsions of two or more types formed separately may be mixed together and used.

In the process of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt.

Iridium salt or its complex salt, rhodium salt or its complex salt,
Iron salts or iron complex salts, gold salts or their complex salts, etc.

They may coexist.

The silver halide emulsion may be chemically sensitized or not. For chemical sensitization, for example H, Frleser
Edited by Die Grundlagen der Photo
graphischenprozesse mit
SilberhalogenidenrAkadem
ischeverlags,gesellscMfLl
61) The method described on pages 471-73μ can be used.

That is, sulfur-containing compounds that can react with active gelatin or silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines)? Sulfur sensitization method used: Reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) Reduction sensitization method used: 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 I r b P cl can be used alone or in combination.

The photographic emulsion of the present invention is used in the manufacturing process of light-sensitive materials.

Various compounds can be included for the purpose of preventing IJk during storage or photographic processing, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (% nitro- or halogen substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptove/zoteazole M1 mer; Cazotobenzimidazoles, mercaptotheacyanols, mercaptotetrazoles (especially!-phenyl-monomercaptotetrazole), mercaptopyrimidines: The above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group: Thiocto compounds such as oxazolinthione; azaindenes such as tetraazaindenes (particularly 44-hydroxy tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; Many compounds known as inhibitors or stabilizers can be added.

For more information, see E. J. Birr, rstabi
lization.

of Photographic 5ilver
I(alideEmulsions J(Foc)
al Press, t 974') etc.? Just refer to it.

The photosensitive material made using the present invention contains a water-soluble dye in the hydrophilic colloid layer for the purpose of preventing irradiation and other various purposes. May be included. Such dyes include oquinol dyes, hemioxonol dyes, and styryl dyes.

Included are merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes: hemioquinol dyes and merocyanine dyes are useful.

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

For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes formaldehyde, glyoxal, geltaraldehyde, etc. ') & N-methylol compound (
Dimethylol urea.

methyloldimethylhydantoin, etc.), dioxane derivatives (co,3-dihydroxydioxane, etc.), active vinyl compounds (t,!,!;-) acryloyl-hexahydro-8-triasif% l.

'-vinylsulfonyl-copropanol).

Active halogen compounds (J, 4t-dichloro-6-hydroxy-8-triazine, etc.), mucohalogen acids (
mucochloric acid, mucophenoxychloric acid, etc.), etc. can be used alone or in combination.

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

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates,
polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amide/or amides, polyallenoxide adducts of silicones), glycidol derivatives (e.g. Nonionic surfactants such as fatty acid esters of polyhydric alcohols and alkyl esters of sugars: alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalenes Sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, and phosphate ester groups; Ampholytic surfactants such as amine oxides: alkyl amine salts, aliphatic or aromatic primary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium, imidazolyte, and aliphatic or heterocyclic phosphonium or Cationic surfactants such as sulfonium salts can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention is used for the purpose of increasing sensitivity, increasing contrast, or promoting development.

For example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioetherified 4NM,
It may also contain thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The binder or storage colloid that can be used in the emulsion/l or intermediate layer of the light-sensitive material of the present invention includes:

Gelatinke can be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casei/cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sugar derivatives such as sodium alginate, starch derivatives, etc. Vinyl alcohol, polyhinyl alcohol partial acetal.

Poly-N-vinylpyrrolidone, polyacrylic acid.

A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, which is formed by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative, an amine phenol derivative, etc.) in the color development process. It may also contain a compound that can develop color. For example, as my/ta couplers, j-pyrazolot coupler 1 pyrazolobenzimidazole coupler, cyanoacetyl coumaron coupler.

There are open chain acylacetonitrile couplers, etc.
Couplers include acylacetamide couplers (for example, base/diylacetanilides, pivaloylacetanilides), and cyan couplers include naphthol couplers, phenol rubra, and the like. These couplers are preferably non-diffusive and have a hydrophobic group called a pallast group in the molecule. The coupler may be either di-equivalent or di-equivalent to the silver ion.

In addition, there are colored kazosols, which have color correction effects, and couplers (so-called DI), which release development inhibitors during development.
R coupler) or, with the current trend, coupler agent 2
Emitting couplers (so-called FR casolers) may also be used.

In addition to DIR couplers, there are also colorless DIR couplers in which the product of the coupling reaction is colorless and releases % wrinkle inhibitor.
Coupling compound *? May include.

Various other additives may be used in the silver halide photographic emulsion of the present invention. For example, brighteners, desensitizers, plasticizers,
Slip agent, matte agent, oil, mordant, 1 color antifoggant, 2 ultraviolet absorber, anti-fading agent, etc.

For more information on these additives, please refer to Research Disclosure (RESEARCH DISCLO8URE).
) No. 776, pages 12-31 (RD-/7.g4AJ) (
Dec., /2711) 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 paper emulsions, color negative emulsions, color reversal emulsions (which may or may not contain couplers). (in some cases), emulsions for photosensitive materials for plate making (e.g. lithium film, etc.),
Emulsions used in photosensitive materials for cathode ray tube displays In addition to emulsions used in photosensitive materials for X-ray recording (particularly materials for direct and indirect photography using screen storage), they can also be used in photosensitive materials for heat development.

Exposure Fi for obtaining photograph I# may be carried out using a conventional method. Namely, natural light (sunlight) 1 tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon mark lamp, xenon flash lamp, cathode ray tube flying spot, light emitting diode, laser light (e.g. gas laser,
YAG laser.

Infrared light such as dye lasers, semiconductor lasers, etc.

Any of a wide variety of known light sources can be used, including: 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 the i7i o o that is usually used in cameras.
Exposure times of 0 to 1 second, as well as short exposures of 17iooo seconds) can be used, such as exposure times of 10% //106 seconds using xenon flash lamps or cathode ray tubes, or exposure times longer than 7 seconds can be used. It can also be used. If necessary, the spectral composition of the light used for exposure can be completely adjusted using color filters.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure (Research Disclosure), etc.
re l / No. 76, pages 2r-30 (RD-774
As described in μ3).

Any known method and known treatment solution can be applied. Depending on the purpose, this photo processing may be
Forming photographic processing (black and white photographic processing) or dye I#
Any photographic processing (color photographic processing) that forms the image may be used. The processing temperature is usually no r0(4)-ra, to0C
A temperature lower than /J”C or to
'The temperature may exceed C1.

In some cases, other known development methods (such as thermal development) may also be used.

Next, in order to show the embodiments of the present invention more specifically and in detail, specific examples will be described. However, the present invention is not limited to the following examples.

Example 1 /N silver nitrate aqueous solution and 0.7 mol potassium bromide and 0
．． An aqueous solution containing 3 mol of sodium chloride and Kl)Ag'
Mix by double jet method while controlling
A silver chlorobromide emulsion was obtained. After washing the emulsion with water and desalting, an aqueous gelatin solution was added and gold sensitization and sulfur sensitization were performed to obtain the optimum sensitivity. The grains of this silver chlorobromide emulsion are
The particles were cubic with an average particle diameter of 0.4 At μm.

Weigh each emulsion prepared as described above into a pot and add the sensitizing dyes shown in Table 1. Chilled.

- Add 10% gelatin gel, thickener, and water to 1 volume each.
It was adjusted to be 2of (the amount of silver in this is 3.2t)
t, gelatin j, 4Af).

Separately, t-dichlorotriazine sodium salt, t-(μm nonylphenoxy)-3-
Prepare an aqueous gelatin solution containing oxapentane sulfonic acid sodium salt and a thickener, and make sure that this aqueous gelatin solution, the coating solution containing the admixture emulsion, and the entire emulsion coating solution are on the support side, and then apply the gelatin solution. The amount of gelatin and the amount of emulsion applied are 1.197 m of gelatin and 72.23 V of gelatin, respectively.
m,! : A photosensitive material sample was obtained by simultaneously coating the two materials.

These samples have a color temperature of 5aoo0%...2j
A light exposure of 5 seconds was carried out using tlux light. After exposure, the strips were developed at 300C for 20 seconds using fA+elephant solution having the composition shown below, stopped, and then washed with water to obtain strips with black and white images. The density of this strip was measured to obtain white light sensitivity and fog. The optical density of the reference point used to determine the sensitivity is r fog, jO).

Composition of developer Composition of fixer The sample was fixed at 20°C for 20 seconds using the dust 1 sample solution, stopped at xo'C for 2 seconds, and fixed at 2o0C for 20 seconds without exposing the entire sample, and further /7. A tube was used that had been rinsed with water for 20 seconds under OOC. This sample stain (residual color) was determined by reflectance measurement using a color analyzer model 607 manufactured by Hitachi, Ltd., and the λmax of the remaining sensitizing dye was determined. In the table, the following compounds were used as comparative compounds.

As can be seen from the 03K fgi table, the compound of the present invention has a higher sensitivity than the comparative compound, with the same y value, and less staining after processing.

Like comparative compound (d), a water-soluble substituent? Many attempts have been made so far to introduce and eliminate the sting sound bundle. However, as shown in the results shown in Test AI 2j-27, although the trap stains are reduced, the sensitivity is lower. In other words, the mere introduction of only a water-soluble substituent is aimed at improving the elution property during treatment with a water-soluble group, and in a hydrophilic medium such as a silver halide photographic emulsion, adsorption to silver halide is also difficult. It is thought that this may lead to a decrease in photosensitivity by 1 minute. On the other hand, those in which water-soluble substituents are introduced to an extent that does not cause a decrease in sensitivity are less effective in improving staining.

In comparison, the compound of the present invention does not simply have a water-soluble substituent introduced therein, and there is no sensitivity loss. Moreover, the fact that it has the effect of reducing stain in this way is something that has not been known up to now.

The requirements for stains are particularly strict in the field of reflective materials because stains are easily noticeable.Therefore, attempts are made to improve the whiteness even slightly by mixing white pigments into the support, or by adding brighteners to the support, emulsion, protective layer, etc. Eliminating staining after treatment of 92 spectral sensitizers is a highly desirable technique.

Example 2 Aqueous solution kp containing 7N silver nitrate aqueous solution, 23 mol of potassium bromide and 0.0/j mol of potassium iodide in O4
A silver iodobromide emulsion was prepared in the same manner as in Example 1 by mixing by double jet method while controlling kgk. This emulsion was coated in exactly the same manner as in Example 1 except that the sensitizing dye in Example 1 was changed to the sensitizing dye in Table 2, and a sample was obtained and exposed. I used the following sounds.

The results in Table 2 also show that the sensitizing dye of the present invention exhibits high sensitivity similar to that of the comparative compounds, and has less staining.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Showa! February 2017 Amane

Claims (1)

[Scope of Claims] A silver halide photographic emulsion containing at least one sensitizing dye represented by the following general formula (I) or general formula (II). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z^1, Z^2, Z^3 and Q are each 5
represents a group of nonmetallic atoms necessary to form a 6-membered heterocycle. W represents S, O or N-R^6. R^1,
R^3 and R^5 are alkyl groups, substituted alkyl groups, or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ mathematical formulas,
There are chemical formulas, tables, etc. Represents ▼. R^2, R^4 and R^6 are hydrogen atoms, alkyl groups, substituted alkyl groups,
Represents an aryl group, a substituted aryl group, a heterocyclic group, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. However, at least one of R^1 or R^2 is ▲There is a mathematical formula, chemical formula, table, etc.▼ or ▲There is a mathematical formula, chemical formula, table, etc.▼, and R^3, R^4, R^5 , R^6 is ▲There is a mathematical formula, chemical formula, table, etc.▼ or ▲There is a mathematical formula, chemical formula, table, etc.▼. h and i are 2~
Represents an integer of 5. Y represents a nonmetallic atom group capable of forming a cyclic imide group. L_1, L_2, L_3, L_4, L_5, L_6 and L_7 represent a methine group or a substituted methine group. X represents an acid anion. l, n, q, r and s represent 1 or 2. m and p represent integers of 1 to 4. )