JPS6289038A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To obtain the titled emulsion in which the reduction of the sensitivity of the coloring matter is improved, and the capturing amount of a light increases and a stain of an image due to a residual coloring matter is reduced by adding and mixing 3 kinds of the specific sensitizing coloring matters to the silver halide emulsion made of silver chloride, silver bromide and silver iodide, etc. CONSTITUTION:The silver halide emulsion sensitized with a sulfur and contg. 70mol% silver chloride, 29.5mol% silver bromide, and 0.5mol% silver iodide is prepared. The mean particle size of the silver halide particles contg. in the emulsion is 0.35mu, and 1.03mol the silver halide is incorporated in 1kg the emulsion. And then, 1kg of the emulsion is weighted in each pot and then 3 kinds of the sensitizing coloring matters contg. the compds. shown by the formulas and a sulfinic acid compd. are added to each pot in order followed by mixing at 40 deg.C while agitating and then 4-hydroxy-6- methyl-1,3,3a,7-tetrazaindene, etc., is added to each pot. The obtd. mixture is coated on a base made of a polyethylene terephthalate film. Thus, the reduction of the sensitivity of the coloring matter is improved, and the capturing amount of the light increases, and the stain of an image due to the residual coloring matter after a development may be prevented.

Description

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

(Prior Art) Spectral sensitization technology is an extremely important and essential technology for producing photosensitive materials with high sensitivity and excellent color reproducibility. In order to provide highly sensitive light-sensitive materials, various spectral sensitizers have been developed, and many technical developments have been made to use them, such as supersensitization methods and addition methods. The spectral sensitizer has the function of absorbing light in a long wavelength region that is not substantially absorbed by the silver halide photographic emulsion and transmitting the light absorption energy to the silver halide. Therefore, the use of a spectral sensitizer to capture light 1 is advantageous in increasing photographic sensitivity. For this reason, attempts have been made to develop spectral sensitizers with high light absorption coefficients and to increase the amount added to silver halide emulsions to increase the amount of light-trapping type sensitizers. However, there is an optimum addition range for the amount of spectral sensitizer added to the silver halide emulsion, and if it is added beyond this range, a large desensitization will result. This is generally due to a phenomenon called dye desensitization, which lowers the sensitivity of the silver halide specific photosensitive range. In particular, if the dye desensitization is large, the overall sensitivity will be low even though there is a spectral sensitization effect. These things are C and E.

K. Mees, “The Theory of the
Photographic Process (The Theoryo)
f the Photographic Pro
cess)”10t7~1O4P Sada (Macmillan/
? 4t2 edition), it is mentioned in 11.

What is the best way to increase sensitivity by reducing dye desensitization? Tokikai Akira! 7-2r, P/A, same 1t9-IA4,731,
614-//r, 234. US license a, O//,
013, is known. However, the above-mentioned techniques are limited in the number of sensitizing dyes that can be used, and their effects are still unsatisfactory.

As a result of examining various methods, the present inventors discovered that a certain type of sulfinic acid compound is useful for improving dye desensitization. Moreover, it was found to be useful for sensitizing dyes with a wide range of chemical structures.

(Disadvantages to be Solved by the Invention) The first object of the present invention is to provide a silver halide photographic emulsion with improved dye sensibility. The purpose of the λth is to provide a silver halide photographic emulsion with increased light trapping f. The third object is to provide a silver halide photographic emulsion with less staining due to residual dye after development.

(Means for Solving the Problems) The object of the present invention is to provide at least one sensitizing dye represented by the following general formula (1) and/or at least one sensitizing dye represented by the general formula (II). and the general formula (I[I)
This could be achieved by containing in combination at least /a of the compound represented by.

General formula (1) In the formula, Z□ and z2 may be the same or different and each represents an atomic group necessary to form a heterocycle.

However, when m is /, it represents only a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a selenazoline nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, and a quinoline nucleus.几0 and R2 may be the same or different and each represents an alkyl group, an aryl group, an alkenyl group, or an aralkyl group. R3 represents a hydrogen atom, and R4 and R5 may be the same or different and each represents a hydrogen atom, an alkyl group having a carbon number of μ or less, a phenethyl group, or a phenyl group. R3, R, and may be connected to each other to form an alkylene bridge. m represents/or λ. ps qs n may be the same or different and each represents O or /.

Xe represents an acid residue.

General Formula (n) In the formula, z3 represents an atomic group necessary to form a heterocycle. Q represents a rhodanine nucleus, a corchioselenazolidine nucleus, a corchioselenazolidine nucleus, a kochioxazolidine nucleus, or a corchioxazolidine nucleus, a 2° μm dione nucleus.几. , R7 may be the same or different and each represents an alkyl group, an aryl group, an alkenyl group, or an aralkyl group. R8 and R9 may be the same or different and each is a hydrogen atom,
represents an alkyl group, an aralkyl group, or an aryl group,
R8 and R9, R and Ra (in the case of r≧2), or R and R9 (in the case of r≧λ) may each form a ring.

e represents O or /. r represents l, 2, or 3.

General formula (I [[) % formula % In the formula, 几,. represents a phenyl group or a naphthyl group. M is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom,
Or represents an organic base.

Next, the present invention will be explained in detail.

In the general formula (I), the atomic groups forming the heterocycle represented by Z and Z2 may be the same or different, and specifically include an oxazoline nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus (for example, a nut (/, 2
-d) Oxazole, naphtho[co, /-d) Oxazole, naphtho[co.

3-d]oxazole), thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus (e.g. naphtho[/, code d]thiazole, naphtho[co,/-d)
Thiazole, naphtho[λ, 3-d)thiazole, r, P
-dihydronaphtho [/.

λ-d]thiazole], selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus (e.g. naphtho(/, code d)selenazole, naphthoC2,
/-d) selenazole, na7) (x, J-d) selenazole), imidazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus (e.g. 7) (7,2-d) imidazole, naphtho (J, J-d) ) imidazole), pyridine nucleus, and quinoline nucleus. However, m is /no@%Z
1 and Z2 represent only a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a selenazoline nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, and a quinonine nucleus. The above-mentioned nucleus may have/or two or more substituents on its ring. As the nucleus, a benzimidazole nucleus is particularly preferred.

Preferred examples of such substituents include hydroxy groups, halogen atoms (e.g., fluoro atoms, chlorine atoms,
bromine atom), unsubstituted and substituted alkyl groups (e.g. methyl, ethyl, propyl, isoflovir, tethyl, dobucl, hydroxyethyl, carboxymethyl, ethoxycarbonylmethyl, trifluoromethyl, chloroethyl,
Examples include methoxymethyl, and the total number of carbon atoms is preferably equal to or less than 2, and the total number of carbon atoms is preferably 2 or less. The following are particularly preferred. ), AIJ
+ or substituted aryl groups (e.g. phenyl, tolyl, phenyl, chlorophenyl, /-naphthyl, 2-f
Methyl, carboquinphenyl, 2-thenyl, λ-furyl, copyridyl, etc. The number of carbon atoms is preferably 1 or less. ), aralkyl groups (e.g. benzyl, phenethyl,
- monofurylmethyl, etc.

The number of carbon atoms is preferably 10 or less. ), alkoxy groups (e.g. methoxy7, ethoxy, butoxy7, defluoroxy7)
(preferably 5a10 or less carbon atoms, particularly preferably j or less carbon atoms), carboxyne group, alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, etc.), carbon of the alkyl component Particularly preferred are those having j or less atoms), aceceamino groups (eg, acetylamino, propionylamino, benzoylamino, etc.).

The number of carbon atoms is preferably tr1r or less. ), methine/dioxy group, tetramethylene group, cyano group, acyl group (e.g. acetyl, propionyl, benzoyl, etc. The number of carbon atoms is preferably r or less), alkylsulfonyl group (
fltu methylsulfonyl, ethylsulfonyl, etc. The number of carbon atoms is preferably t or less c. ), alkylsulfinyl groups ILtfd'methylsulfinyl, ethylsulfinyl, etc. The number of carbon atoms is preferably 2 or less.

几0 and R2 may be the same or different and each represents an alkyl group, an aryl group, an alkenyl group, or an aralkyl group, which may be unsubstituted or substituted. These substituents have 2 carbon atoms in the alkyl and alkylene moieties.
The carbon number of the aryl component is /j or less, preferably phenyl, naphthyl, and derivatives thereof.

Specific examples of R, R2 include methyl, ethyl, propyl, butyl, isopropyl, inthyl, hexyl, octyl, dobufur, cohydroquiquethyl, 3-hydroxypropyl, co(cohydroxyethoxy)ethyl,
Carboxymethyl, -carboxyethyl, 3-carboxypropyl, cosulfoethyl, 3-sulfopropyl, 3-sulfobutyl, Hiro-sulfobutyl, -hydroquine-3-sulfozolopyl, λ-chloro-3-sulfopropyl, co(3-sulfopropyl) propyloquine) ethyl, λ-
Chloroethyl, λ, J,! -) IJ fluoroethyl, 2. Tip 3,3-tetrafluorodea pill, l
-cyanoethyl, 3-7anoethyl, λ-carbamoylethyl, 3-carbamoylethyl, cyclohexyl, cyclohexylmethyl, methquinethyl, ethoxyethyl, methoxypropyl, allyl, benzyl, phenethyl,
Examples include p-sulfo7enethyl, m-sulfo7enethyl, p-carboxycuphenethyl, and the like.

Among these, a carboxy group, a sulfo group, and an alkyl group substituted with a heptad atom are preferred.

The alkyl group represented by R4, 几, is a methyl group,
Examples include ethyl group, propyl group, and butyl group.

Furthermore, m is particularly preferably .

Further, when m=2, the silver halide emulsion is particularly preferably a silver chlorobromide emulsion or a silver chloroiodobromide emulsion.

In the general formula (n), z3 has the same meaning as 21 and Otsu2 in the general formula (I), and represents an atomic group necessary to complete the pyrrolidine nucleus and the tetrazole nucleus. Q is rhodanine nucleus, cortiohydantoin nucleus, 2-thioselenazolidine-21hiro-
The atomic group t-i is necessary to form a dione nucleus, a cotto-oxitezolidine-2,4-dione nucleus. In the case of the coachiohydantoin nucleus, the nitrogen atom at position 7 may be substituted, and preferred substituents include an alkyl group (e.g. methyl,
Ethyl, propyl, butyl, alkoxyalkyl group (
(e.g., methoxyethyl, ethoxyethyl, methoxypropyl, etc.), human mixalkyl A4 (e.g., hydroxyethyl, -monohydroxybutyr, 2,3-dihydroxy7)
proyl, etc.), carboxyalkyl groups (e.g. t is carboxymethyl, carboxymethyl l, alkoxycarbonylalkyl groups (e.g. ethoxycarbonylmethyl), human aky7alkoxyalkyl groups (e.g. λ-(cohydroxyethoxy7)ethyl), hydroxy Examples include alkylaminocarbonylalkyl groups (for example, N-(x-hydroxyaminocarbonylmethyl)), and the number of carbon atoms in the alkyl component of these substituents is particularly preferably z or less. R6,
The symbol represents an alkyl group, an aryl group, an alkenyl group, or an aralkyl group, which may be unsubstituted or substituted. The number of carbon atoms in the alkyl and alkylene moieties is -M/Q or less, preferably! The number of carbon atoms in the aryl component is /! In the following, preference is given to phenyl, naphthyl, pyridyl, furyl, chenyl and derivatives thereof.

Le. Specific examples of , 几 include methyl, ethyl, propyl, butyl, isopropyl, pentyl, hexyl, octyl, -monohydroquinethyl, 3-hydroxypropyl, co(cohydroxyethoxy)ethyl, carboxymethyl, and λ-carboxyethyl. , 3-carboquinpropyl, ethoxycarbonylmethyl, cosulfoethyl, 3
-Sulfopropyl, 3-sulfobutyl, ≠-sulfobutyl, cochloroethyl, co, co, 2-toIJ fluoroethyl 1,2,2,3. J-tetrafluoropropyl, 2-cyanethyl, 3-cyanethyl, -carpamoylethyl, methoxyethyl, ethquinethyl, methquinopropyl, he-λ-hydroxyaminocarbonylmethyl, allyl, cyclohexyl, cyclohexylmethyl,
Coffrifrylmethyl, phenyl, tolyl, chlorophenyl, aniflu, carboquinphenyl, sulfophenyl, naphthyl, sulfonaphthyl, benzyl, phenethyl,
p-sulfophenethyl, m-sulfophenethyl, p-carboxyphenyl, -1pyridyl, 3-pyridyl, 3-
Examples include chloro-2-pyridyl, caufuryl, 2-chenyl, and the like.

几 and 几 may be the same or different, each hydrogen atom, alkyl and alkoxyalkyl group (e.g. methyl, ethyl, propyl, butyl, methoxyethyl), aralkyl group (e.g. phenethyl group, etc.)
or represents an aryl group (e.g., phenyl, tolyl, carboxyphenyl, naphthyl with a total carbon number of 10 or less),
R8 and RR7L-Rs (r≧-)'' or R9 and R9
(r≧ko) in a row! , represents the atoms necessary to complete the alkylene bridge forming the membered ring.

When r=/, the emulsion is preferably a silver iodobromide emulsion, and when r=2 or 3, a silver chlorobromide emulsion or a silver chloroiobromide emulsion is particularly preferred.

In general formula (III), ):Ll. represents a phenyl group or a naphthyl group which may be redeemed. Phenyl group, naphthyl-! &,! i It may be substituted with a plurality of substituents, and the substituent may be one unit of the polymer. For example, as shown in Compound Examples 11i-/A, -77, and m-tr, which may be polymerized, Hammett (Hammet t t ) is used as the substituent for the phenyl group and naphthyl group, which may be polymerized. It is preferable that the total sum is O or less (-80
2M is not included in the total).

Next, specific examples of compounds used in the present invention are shown below.

However, the compounds used in the present invention are not limited to these.

Specific examples of compounds represented by general formula (1) ■-/ (1f12)3ゝU3 0H2CH2(J
H■-μ ((,:t-12)3S(J37 C2H3I-+ ■-/.

1-/ko 21-1.

(Ci-12) 3su3- -73 ■−／≠ C21(.

C2) 15 ■-77 1-/r 2H5 1-7ri C2) i5 I-λO ■-ko/ P1'1 -
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General formula (
A specific example of the compound represented by II) "-/ ■-Kokori sannin ■-Gl-z ■-U3Na 1-, r し2F"5 ]1-/.

[-// 1-/ko (CH2) 41s, enter C2H.

11-/Hiroshi■-/! 11-/& [-/7 [-/r ■-79 ■-22 ■-23 (C)12) 38 (■-2 to J3! ■-λt ■-core [-ur ■-2? [-30 #
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Book of books
...Specific examples of compounds represented by general formula (III) 1l-j S (J 2 Na [[-l/ ■-/3 α II[-/ nu1l-is 1[-/A ■-/7 ilI -tr 8 C) 2 tN a The compounds used in the present invention represented by general formulas (I), (n), and (ilI) are known compounds.

For example, the compounds represented by general formula (I) and general formula (II) are disclosed in JP-A-Sho! /-/24. /μ01 JP Shoj/-/3
? , 3λ3, % Kaisho t/-/IA, 3/3, JP Kaisho 1l
-Jt, Jtt, Tokukai Akira! --10r, octopus! ,% Kaisho! ! -/J! , 32, West German Open Patent (OLS) λ, /
! I,! ! 3, Tokuko Shoj 2-2, 4/Takao, Tokukai Sho≠7-
2♂, details such as Deloitte and F, M, )lam
a r , The Chemistry of
Heterocyclic Compounds, Vol.
, /♂, The Cyanine Dyes and
kRelated Compounds, A.

Weissberger ed., Intersci.
ence.

New York, / 5'6 II,, D, M, 8
turmer.

The Chemistry of t(etero
cyclic compounds, VoI,
30% A, Weissbergerand E, C
, Taylor, eds, John Wiley.

New York, / P77, p, IAII/
0, etc., and can be synthesized by referring to them.

In order to incorporate the sensitizing dyes represented by the general formulas (I) and (n) and the compound represented by the general formula (II) used in the present invention into a silver halide emulsion, these are directly dispersed in the emulsion. Alternatively, D may be dispersed in an emulsion directly in water or a hydrophilic colloid or together with a surfactant, an amino acid, a hydrophilic compound such as sorbitol, or a suitable solvent such as methyl Alcohol, ethyl alcohol, propyl alcohol, methylcellosolve,
Tokukai Shoμr-tough/! , U.S. Patent 3,7j B.

Halogenated alcohol described in r30, acetone, water,
Pyridine and the like can also be dissolved in a mixed solvent thereof and added to the emulsion in the form of a solution. Other addition methods include Tokuko Sho≠6-21711j, US patent! , 112, /Jr, 3゜1.1,0,10/
, same co, ri/co, 3ILL3, same 2゜ri94,217,
same! , 112F, lr! ! , 3°4'lG1. ? r7
,same! , 611, 714, same 3゜rkoλ, /3!
The method described in can be used. Also, the method described in German Patent Application No. 10≠, Cor.3, US Patent No. 3. z≠
2, 2! The method described in Section 1 can also be used.

Still, the sensitizing dye described above may be uniformly dispersed in the silver halide PL agent before being coated on a suitable support, but of course it can be dispersed at any stage in the preparation of the silver halide emulsion (during grain formation, chemical ripening, etc.). (at the start, before application, etc.): f can also be dispersed.

The sensitizing dyes represented by the general formulas (I) and (n) are used for spectral sensitization, and specifically silver halide 1
Contained in silver halide photographic emulsions in an amount of 1) z IO mol to tX 10-3 mol, preferably 1 x 10 mol to 2X IO mol, preferably /x 70 mol to /x 10 mol per mole. .

The compound represented by the general formula ([) is /
It is contained in the silver halide photographic emulsion in a ratio of x10 mol to 10 mol, preferably / x 10 mol to 1 mol.

Further, the ratio of the sensitizing dye of general formula (I) to the sensitizing dye of general formula (if) is preferably (I)/(n)=l
/lO~10 (molar ratio).

However, the ratio with the sensitizing dye of general formula (III) is as follows:
Preferably (■1).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide in the photographic emulsion of the present invention. Preferred silver halides are silver bromide, silver iodobromide,
Silver chlorobromide and silver iodochlorobromide.

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

It is also possible to use grains in which the latent image is mainly formed on the surface (for example, negative-tone emulsions), or grains in which the latent image is mainly formed inside the grain (for example, internal a-image emulsions, pre-fogged direct reversal emulsions). It's okay.

The photographic emulsion used in the present invention is P. gelafchides (
"Chimie etPhy Photography" by P. Glafkides)
sique Photographique)J (
Paul Monte A/Paul Monte1, 7967), G, Z7, D7F (G, F, D
uffin) “Photographic Emulsion Chemistry (Photographic gmul
sionChemistry)J (Focalbe V
Published by The Focal Press, /ri4! ), Gui L, YP Erikman et al. (V, L, Ze
! '4 f' Making and Coating Photographic Emulsion
otographic Emulsion)J(Focal Pres)//CThe Focal Pres
Published by s company, /91. 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 salt may be the monofilament mixing method, the simultaneous mixing method, or a combination thereof. good.

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 the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

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

One or more silver halide emulsions formed separately may be used in combination.

The particle size distribution may be narrow or wide. In the present invention, a so-called monodisperse silver halide emulsion having a narrow grain size distribution in which 0% or more of the total grains, especially 0% or more of the total grain size is within ±4 cots of the average grain size in terms of grain number or weight, is used in the present invention. I can do it.

In addition, ultra-tabular silver halide grains whose diameter is more than 5 times their thickness occupy the entire projected area! An emulsion that occupies 0 or more cells may be used. The particle size is O1j~1
0μ is preferred. (Here, particle size is expressed as the diameter of a circle with an area equal to the projected area, and thickness is expressed as the distance between λ parallel planes.) For details, see JP-A-Sho! l'-/2792/
,same! It is described in Mei 1 field books such as r-//3927.

In addition, during the formation of silver rhodanide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (for example, U.S. Pat.
．． Tough Hiromu, Bu Jr, same 3゜70≠, /JO, same μ, 29
7,μ3! P, same≠.

core 6.37 hiro etc.), thione compounds (e.g. JP-A-Shoj)
j-/1411-,3/? ,same! ,! -1r21AOr
.

same! ! -77,737, etc.), amine compounds (for example, JP-A-Sho!≠-1007/7, etc.), etc.).

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

In addition, examples of internal latent image type emulsions used in the present invention include those described in US Pat. ! Octopus, λ10. 3゜206, Jr.
3. Same as 3. Guda 7. ri 27, same 3゜7 Otsu/, core 4. And the same! , 93! Examples include conversion type emulsions, core/shell type emulsions, and emulsions incorporating different metals, as described in , 0/Hiro et al.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, H Freezer (
(HoFrieser)
agender Photography
Prozesse mit Silver-halo
Geniden) J (Akademische Verlagsgesell)
schaft.

/ri6? Annual) t7! The method described on pages 73 to 73 can be used.

Namely, sulfur sensitization using compounds* containing sulfur that can react with activated gelatin and bales (e.g., thiosulfates, thiourine 25, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts); , Az7s, hydrazine derivatives, formamidine sulfinic acid, silane compounds): Reduction sensitization using gold compounds (e.g., gold@salts,
pt%Rh.

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.

Specific examples of these include US patents/
, ! 714, 94tl/-1 2. ulo, trW
.

λ, -71, WIA7, J, 7Jr, Jjr.

Same J, AIt, Y! J et al., U.S. Patent J, 9r! for reduction sensitization methods. , 60? , same J, tl/P, 5'7μ
, sameμ, orhiro, ajr, etc., regarding the noble metal sensitization method, U.S. patent λ, 3tata, 01! , same λ, da4tt, oto,
Nine patents are listed in each of the British patents TIT, OTI, etc.

More specific chemical sensitizers include sulfur sensitizers such as allylthiocarbamide, thiourea, thallium thiosulfate and cystine; It may contain a metal sensitizer such as botanical chloroparadate; a reduction sensitizer such as tin chloride, phenylhydrazine or reductone, and the like. Sensitizers such as polyoxyethylene compounds, polyoxypropylene compounds, and compounds with high-grade ammonium groups may also be included.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. In other words, azole analogs include benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, and benzimidazoles (
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptotetrazoles (especially /-phenyl-y-mercaptotetrazole), mercaptopyrimidines (particularly nitro- or halogen-substituted); 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 l-hydroquine + R[(/, j, ja, 7) Many compounds known as antifoggants or stabilizers can be added, such as tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acids; and the like.

The silver halide emulsion of the present invention is disclosed in U.S. Patent No. 3.4A//
,? /Ha same 3. ≠//, 9/2, same 3. /lAu,t
ji Do 3,321,216, Do! , j hiro7. A! 0. Special public official Akihiro? -! Polymer latexes made of homo- or copolymers of alkyl acrylates, alkyl methacrylates, acrylic acids, glycidyl acrylates, etc. described in 33/ etc. can be used for purposes such as improving the dimensional stability of photographic materials and improving film properties. It can be contained in

When the silver halide emulsion of the present invention is used as a photosensitive material for lithographic printing, a polyalkylene oxide compound can be used to enhance the infectious development effect. For example, US patent co, ≠00, ! , 3, same 3rd. Old>44
, 137, same No. 3. Kotaμ.

j+ o EJAm book, French patent i/, 4tY/,
10! , same No. 1. ! ri1. , t7J Ming Shusho, Machiko Akihiro O
5-23μ6 on the bright i side” Ul JP-A-Sho to-i, tta
Ko3, same j4t-71726. same! Bu-/! Compounds such as those described in 33 Mei A 1 can be used. Preferred series are alkylene oxides with carbon numbers -~μ,
Preferably, a polyalkyne oxide consisting of at least 70 ethylene-sized cyto units such as ethylene oxide, propylene-/, 2-oxide, butylene-/, 2-oxide, water, aliphatic alcohol, aromatic alcohol, fatty acid, organic amine, etc. , a condensate with a compound having at least/one active hydrogen atom such as a hequintole derivative, or a protocopolymer of two or more polyalkylene oxides. That is, as a polyalkylene oxide compound, specifically (polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol alkylaryls, polyalkylene glycol esters, ho+)alkylene chloride)-fatty acid amides , polyalkylene glycol amines, polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, and the like can be used. The polyalkylene oxide compound that can be used has a molecular weight of 300 to lj, ooo, preferably too-r, ooo. The amount of these polyalkylene oxide compounds added is 1 mole of silver halide, 1:11! f to 3f is preferred. The addition time can be selected at any time during the manufacturing process.

The silver halide photographic emulsion of the present invention can contain color pigments such as cyan coupler, magenta coupler, yellow coupler, etc.
It can include a coupler and a compound that disperses the coupler.

That is, it may contain a compound that can develop a color by oxidative coupling with an aromatic/grade atom developing material (for example, a phenylenediamine derivative, an aminophenol derivative, etc.) in a color development process.

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

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

The silver halide photographic emulsion of the present invention may contain water-soluble dyes (eg, oxonol dyes, hemioxonol dyes and merocyanine dyes) as filter dyes or for various purposes such as preventing irradiation.

The photographic emulsion of the present invention may contain various surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, enhancing color density, increasing contrast, and sensitizing). May include.

For example, nonionic surfactants such as saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol alkyl ethers, glycidol derivatives, fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates) , amphoteric surfactants such as alkyl sulfonates, alkylbenzene sulfonates, and alkyl sulfate esters; amphoteric surfactants such as alkyl amine salts, aliphatic or aromatic ammonium salts, and heterocyclic surfactants such as pyridinium and imidazolium. Cationic surfactants such as grade ammonium salts can be used.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of Jffi or more. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenol L p-oxicutenol derivatives, and bisphenols.

The photographic emulsion of the present invention may contain an inorganic or organic hardening agent. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), activated vinyl compounds (
/, J, j-) lyacryloyl-hexahydro-5-1
Reazin, /.

3-vinylsulfonyl-11furonoξnor-1, etc.),
Active halogen compounds (co-, dichloro-6-hydroxy?'-3-)riazine, etc.) can be used alone or in combination.

The photosensitive material produced using the present invention contains hydroquinone derivatives, aminephenol derivatives,
It may also contain gallic acid derivatives, ascorbic acid derivatives, etc.

In the silver halide photographic emulsion used in the present invention, in addition to gelatin, protective colloids include acylated gelatin such as heptadated gelatin and malonated gelatin, cellulose compounds such as hydroxyethyl cellulose and carboxymethylcellulose; Soluble starches such as polyvinyl alcohol, polyvinylpyrrolidone, hydrophilic polymers such as polyacrylamide and polystyrene sulfonic acid, plasticizers for dimensional stabilization, latex polymers and matting agents may be added. Completed (eye n1sh
ed) The emulsion is coated onto a suitable support, such as baryta paper, resin-coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates.

Exposure to obtain photographs may be carried out using conventional methods. i.e. natural light (sunlight), tungsten electric light,
Any of a wide variety of known light sources can be used, such as fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, and cathode ray tube flying spots. The exposure time is 771,000 seconds, which is normally used in cameras.
Exposure times of seconds, as well as exposures shorter than 771,000 seconds, such as using a xenon flash lamp //1o'~///
Exposures of 0" 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 with color filters. Laser light can be used for exposure. (For example, Na-He laser light). Also, electron beams, X-rays, r-rays, α
It may be exposed to light emitted from a phosphor excited by a line or the like.

The spectral sensitizing dye of the present invention is used for sensitizing silver halide photographic emulsions for various color and black and white sensitive materials. Emulsions used include, for example, color positive emulsions, color beneau emulsions, color negative emulsions, color reversal emulsions (which may or may not contain couplers), and photosensitive materials for plate making (for example, lithographic film, etc.). ), emulsions used in photosensitive materials for cathode ray tubes, colloids and
Transfer process (Colloid tran
sferprocess@s) (e.g. US Patent 2,7/l
,,0! The emulsion used in the silver salt diffusion transfer plate a*, x, (8i1ver 5altdi
fusiontransrer process)
Emulsions used in color diffusion transfer processes, emulsions used in color diffusion transfer processes, imbit transfer processes
i.

tranqter process) (U.S. patent
Emulsions used in silver dye bleaching methods (described in U.S. Pat. Emulsions used in photo-developable print-out (Direct Pr1nt image) photosensitive materials (for example, as described in U.S. Pat. No. 3,033.tr2, etc.), emulsions used in heat-developable photosensitive materials , ・Photosensitive materials for optical development, emulsions used in the family (for example, described in the British patent Octopus 0.277), etc.

made using the present invention. For example, Research Disclosure (Research Disclosure) is used for photographic processing of light-sensitive materials.
Any of the known methods and known treatment liquids as described in Disclosure)/76, pages 21-30 (R, D-/'7bu≠3) 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. The processing temperature is usually chosen between lr 0c and to''c, but may also be below /r oc or above r oc .

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

Example-1 70 moles of silver chloride, 29. J Morch's silver bromide, and O
0! A sulfur-sensitized silver halide emulsion consisting of molar silver iodide was prepared. The average diameter of the silver halide grains contained in this emulsion was o, sj microns. This emulsion 1k
g contained 7.03 moles of silver halide.

Each emulsion was weighed into a pot, and the sensitizing dye and sulfinic acid compound according to the present invention were sequentially added as shown in Tables 1 to z, and mixed and stirred at ≠06C. Further μm hydroxy-6-methyl-/,! , 3a, 7-chitrazaindene at 0°-? /emulsion/dirt, /-hydroxy-
J, j-dichlorotriazine soda O, /f/emulsion/
9, further sodium dodecylbenzenesulfonate 0,
/f/milking/A9 was added once, and then coated on a polyethylene terephthalate film base to obtain a photographic material. Similarly, a comparative coating sample containing a sensitizing dye and a sulfinic acid compound was also obtained.

For each of these samples, a yellow filter manufactured by Fuji Photo Film Co., Ltd., an SC-≠≦ (filter that transmits light with a wavelength longer than μAOnm), and a blue filter (35>Onm) were used.
The sample was exposed to tungsten light (Jr Yu!'K) for 1 second through a pantonomic filter that transmits light from ≠Hiroshi Onm.

After exposure, it was developed for 2 minutes at 2o''C using a developer with the following composition.The density of these was measured using a densitometer manufactured by Fuji Photo Film Co., Ltd., and the yellow filter sensitivity (8y) and the blue filter sensitivity (8B ) and fog were obtained.The optical !1 degree reference point for determining the sensitivity was the point of [fog + i, z].

Composition of developer When using, add 2 volumes of water to prepare a working solution. The obtained results are shown in Tables 1 to 7 as relative values.

Further, as a result of evaluating the residual coloration (stain) of the dye in the unexposed area of the sample after development processing, there was no sensitizing dye whose stain increased due to the combined use of the sulfinic acid compound represented by the general formula (III).

Sensitizing dyes used for comparison Looking at Table 1 of the compounds used for comparison, the sensitizing dyes (I-λ) are 1. jXlo
The maximum sensitivity (ay) is reached at 'mol/milk agent. When compound (DI-J) is used in combination with this, dye desensitization (8B)
It can be seen that the spectral sensitivity (Sy) is improved. Also, the amount of sensitizing dye (■-22) used is 2
times/7×10-5 mol/# The emulsion has higher sensitivity. That is, the combination of the sensitizing dye and the sulfinic acid compound of the present invention improves single-dye desensitization and also increases fractional sensitization. As a result, a larger amount of sensitizing dye can be used (
In other words, it can be seen that an increase in dye density is associated with an increase in the amount of light captured. Similarly, it can be seen from Tables 2, 3, 3, and 3 that the combination of the sensitizing dye of the present invention and the sulfuric acid/acid compound is useful for increasing sensitivity. On the other hand, as is clear from Tests &/-/j to l-/7 in Table 1, sulfonic acid compounds have no effect at all. Furthermore, as is clear from Table λ Test Asako//~Co/3 and Table 1 Test Aj-IS-1-7, the above-mentioned effect is extremely low even in the case of sulfinic acid compound '4m, with a compound having a structure different from that of the present invention. Weak or not present at all. Even among sensitizing dyes, tricarbocyanine, which consists of seven methine groups, has no effect as shown in Table 1.

Example 2 A sulfur-sensitized silver halide emulsion consisting of 23 moles of silver bromide and 7 moles of silver iodide was prepared. The average diameter of the silver halide grains contained in this emulsion was 0.7 microns. This emulsion/Jc9 contained 00 j-moles of silver halide.

Weigh out 9 of this emulsion in each pot and see Tables 7 to 11.
As shown in the table, the sensitizing dye of the present invention and the sulfinic acid compound were sequentially added, and the mixture was mixed and stirred until μo'C was reached. Further, a sensitizing dye and a sulfinic acid compound for comparison were added in the same manner and stirred. Furthermore, ≠-Hydroxy-t-methyl-/,! , 3a.

7-tetrazaindene as θ, 0/? /emulsion/l-hydroxy-3,! - 0 dichlorotriazine/soda,
/f/emulsion/9 was further added with 0 part of sodium dodecylbenzenesulfonate, and /r/emulsion/base was sequentially evaporated and coated on a polyethylene terephthalate film base to obtain a photographic light-sensitive material.

These samples were each fitted with a yellow filter manufactured by Fuji Photo Film Co., Ltd., a filter that transmits light with a wavelength longer than 5czo<toonm), a blue filter manufactured by Eastman Kodak Co., Ltd., and a band with transmittance maximum at ≠JOnm. With tungsten light (2rj≠'K) through a pass filter)! Exposure for seconds. After cod exposure, development was carried out at 2°C for 7 minutes using a developer having the following composition. The densities of these were measured using a densitometer manufactured by Fuji Photo Film Co., Ltd., and yellow filter sensitivity (Sy), blue filter sensitivity (813), and fog were obtained. The optical density reference point at which the sensitivity was determined was the point [Cub IJ + o, 2).

The composition of the developer solution (addition of water to /l) The results obtained are shown in Tables r to 17 as relative values.

Sensitizing dye used for comparison (I-8) (I-C) (ID) No. ? As is clear from Tables to Table 17, the combination of the sensitizing dye and sulfinic acid compound according to the present invention improves dye desensitization,
It can be seen that this method is useful for increasing the degree of spectral amplification. 17th
The combination of sensitizing dye and sulfinic acid compound used for comparison in the table is disclosed in JP-A-10-10r and t3t as a combination that prevents the increase in fog and the decrease in sensitivity over time. It can be seen that there is no sensory effect at all.

Example-3 A photographic light-sensitive material was obtained in exactly the same manner as in Example-/. These samples were exposed in the following manner.

A gray contact screen for negatives (Inu Nippon Screen Goku'J, /JOL/inch) was completely attached to the sample, and a neon/helium laser oscillation device (NEC Exposure was carried out for 10-5 seconds using a GA8 LASE+% GLG203 (manufactured by Shishiki Co., Ltd.). After exposure, development was carried out for 100 seconds using automatic development 9 at =700 using a developer having the composition shown below.

The relative sensitivity was compared based on the sensitivity that varies from the blackened area to zero. In addition, residual coloring of the dye (
ST/) from A (excellent) to F (poor)! The evaluation was divided into stages.

The results are shown in Table 11.

The combination of sensitizing dye (E) and compound (F) used to compare the composition of the developer is a lithium-ion type that uses a neon/helium laser as a light source to form a halftone image by one-way scanner exposure. As a useful sensitizing method for sensitizing materials, JP-A-4
It is specifically described in the specification of '-/1724. The method disclosed in the above specification is an excellent method with substantially sufficient sensitivity, but the combination of a sensitizing dye and a sulfinic acid compound according to the present invention provides even higher sensitivity and superior silver halide photography. We can provide photosensitive materials. Another excellent feature is that there is no increase in staining when used in combination.

The above-mentioned photosensitive material according to the present invention has a one-point quality with a developing time of 10
The blackened area at 0 seconds is 10.60, and the halftone dot of deochi is 70.
When observed under a 0x magnification, it was equivalent to the combination of the comparative dye and the comparative compound.

(Effects of the Invention) According to the present invention, a method has been discovered for reducing the aforementioned increase in dye desensitization caused by an increase in the amount of spectral sensitizer added in a silver halide emulsion. As a result, we succeeded in obtaining the desired desired performance. Dye desensitization is attributed to a reduction in latent image formation rather than a reduction in photo-induced electron generation. As a result of the present invention, it was possible to improve the reduction in latent image formation, and as a result, high spectral sensitivity could be obtained.

Furthermore, when the amount of spectral sensitizer added is increased, the high-light sensitivity tends to decrease due to the aforementioned factors that generally cause dye desensitization. It is also important to increase the high-light sensitivity when spectral sensitization is performed.For example, JP-A-Sho! o-xr, r2t, JP-A-1
41-73. /37, West German Open Patent (OLS) J, OA
Various studies have been made as described in J, A42, etc. However, in the present invention, in the spectral sensitization method of silver halide grains, this high illuminance sensitivity is also combined,
I was able to make it higher.

In recent years, with the advancement of electronics, the exposure methods for photographic materials have become increasingly diverse, but
In line with the demand for shortening the time required for transmission, high-intensity, short-time exposure methods are increasing, and the need to develop photosensitive materials with high sensitivity to high-intensity is increasing. Examples of photographic systems that require particularly high illumination suitability include facsimile systems for electronically transmitting manuscripts between FTs, high-speed phototypesetting systems for speedy printing typesetting, and scanner systems for speedy printing plate making. There are cathode ray tube display systems that display and record output information from a computer or computer using a cathode ray tube. Furthermore, even in general photographic photosensitive materials, high illuminance short-time exposure such as a-bo photography is carried out, and high illuminance sensitivity is required only for special photosensitive materials.

These light sources include, for example, xenon flash light,
Cathode ray tube phosphor flying spot, laser light,
There are a wide variety of sources, including xenon arc light, a combination of a high-pressure mercury lamp and a high-speed shutter, light-emitting diodes, and glow discharge tubes.

Furthermore, according to the present invention, it was possible to obtain a silver halide photographic emulsion with less staining due to dyes remaining after development.

Preferred embodiments of the present invention are listed below.

The silver halide photographic emulsion according to claim 1, wherein the amount of the compound represented by formula (III) used is /x10 mol to 1 mol per mol of silver halide.

2. If m in general formula (1) is 2 within the scope of the claims.

3. In the claims, when r in general formula (It) is 2 or 3.

4< In the claims, when r in the general formula (II) is / and the case is used in a silver iodobromide emulsion.

In Embodiment-2, Zl and Z2 of general formula (1)
is a benzimidazole nucleus & Embodiments -/
In the case where m in the general formula (I) is 2 and it is used in a silver chlorobromide emulsion or a silver chloroiodobromide emulsion.

7 Embodiment -/In the general formula (II), r is 2
3, and when used in a silver chlorobromide emulsion and a silver chloroiodobromide emulsion.

t, In Embodiment B, zl, z of general formula (1)
When 2 is a benzimidazole nucleus.

In Embodiment-t, the prepared silver halide photographic emulsion uses a neon/helium laser as a light source.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (1)

[Scope of Claims] At least one sensitizing dye represented by the following general formula (I) and/or at least one sensitizing dye represented by the general formula (II); A silver halide photographic emulsion containing at least one compound represented by III) in combination. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z_1 and Z_2 may be the same or different and each represents an atomic group necessary to form a heterocycle. However, m
When is 1, only thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, and quinoline nucleus are represented. R_1 and R_2 may be the same or different and each represents an alkyl group, an aryl group, an alkenyl group, or an aralkyl group. R_3 represents a hydrogen atom, and R_4 and R_5 may be the same or different and each represents a hydrogen atom, an alkyl group having 4 or less carbon atoms, a phenethyl group, or a phenyl group. R_3, R_4, R
_5 may be connected to each other to form an alkylene bridge. m represents 1 or 2. p, q, and n may be the same or different and each represents 0 or 1. X^■ represents an acid residue. ) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z_3 represents the atomic group necessary to form a heterocycle.Q represents the rhodanine nucleus, 2-thiohydantoin nucleus, 2-thio Represents a selenazolidine-2,4-dione nucleus or a 2-thioxazolidine-2,4-dione nucleus. R_6 and R_7 may be the same or different and each represents an alkyl group, an aryl group, an alkenyl group, or an aralkyl group. R_8 and R_9 may be the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and R_8 and R_9, R_8 and R_8 (r≧2
(in the case of r≧2), or R_9 and R_9 (in the case of r≧2) may each form a ring. l represents 0 or 1. r represents 1, 2, or 3. ) General formula (III) R_1_0-SO_2M (In the formula, R_1_0 represents a phenyl group or a naphthyl group. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an organic base.)