CA1329039C - Light-sensitive silver halide photographic material feasible for rapid processing - Google Patents

Abstract

ABSTRACT

The light-sensitive silver halide photo-graphic material comprises a support and, provided thereon, at least one light-sensitive silver halide emulsion layer which contains silver halide grains having silver chloride content of 90 mole % or more and containing a gold compounds. A dye-forming coupler is dispersed therein by the use of a high boiling-point organic solvent having a dielectric constant of not more than 6Ø The photographic material also includes a compound represented by General Formula (S):

(S)

Description

.
, ~ LIGHT-SRN5ITIV~ SILVRR HALID~ PHOTOGRAPHIC MATRRIAL

;............................ F~ASIBL~ FOR RAPID PROC~SSING
', FIL~D O~ THR INV~NTION
The present invention relates to a light-~en~itlve silver halide photographic material, and more ~ particularly, to a light-~en~itive ~ilver hallde j photographlc material ~easlble for rapid processing and ~ also capable of aahieving excell~nt preservation of a dy?e ., : image formed by the reaction of an oxidized product o~ a aolor d~veloæing agent with a dye-for~in~ coupler having béen conta~ned in the light-sensitive material.

/~ :
BACKGROUND OF TH~ INV~NTION
: A dye ~mage is formed by exposing a light-sensitive silver~halide photographia m~terial, followed by color .~ .
:develop~ng, and ~he dy~ lmage obtained is desired to have ~3 high fa~tne~s to light, heat and humidity. The ~astnes~
o~ a dye imaye is af~ected by variou~ factors, and is ~`,~ ,~

--,' ' ~

1 32903q known to yreatly depend on the properties of a dye-forming coupler which ~orms a dye by reactiny wlth a color developing agent, and of a h$gh boilin~ organic solvent used ~or di~solving the dye-formin0 coupler. Hvwever, when the dye-forming coupler is ~elected, not only it i~
important ~or a dye to have the fa~tness, but also it is essential for the dye to have a de~ired absorption characteri~tlc for the purpo~e of color reproduction, and moreover it i~ desired to have good color development ef~iciency and good ~tability in a _olvent. Thu~, the scope of the ~election can not be limitless. For this rea~on, there is a limit in improving the ~a~tness by ~electing the dye-formin~ coupler. On the other` hand, the hlgh boiling ~olv~nt u~ed for di~soivlng the coupler may have important lnfluence to the fastness of a dye, and Japanese Patent Publ~cation Open to Public In~pection (herelnafter referred to as Japanese Patent O.P.I.
Publication) No. 205447/1985 di~clo3eQ that the fa~tne~
can be improved by u~ing a high boiling solvent having a ~iven dielectric con~tant.
However, it was revealed that although the fa~tne~s o~ a dye to be formed may be improved by usi~g the high boiling organic solvent di~closed in the above publicatlon, the color development performance o~ the dye-~orming coupler dissolved therein tend3 to be lowered.

~ .

"

.
,.,~

1 ~2'~0~9 -- 3 ~
On the other hand, recent years, in the present photographic fi~ld, what have been ~ought after are light-~en~itive silver halide photographic materials that can practice rapid processing, may have high image quallty and yet ~uperior processing stabili~y, and can be of low co~t.
Partlcularly sought after are light-~en~itive silver halide photographic material~ that can be proces~ed rap~dly.
Namely, it i~ practiced to continuou~ly process light-sen~itive silver halide photographic materials usually in an automatic processing machine installed in every photofini hing laboratory. However, as a part of lmprovement in ~ervices to u~er~, it is de~ired to ~ini~h proces~ing and return produ¢ts to u~sr~ in the day the development orders were received, and, nowaday3, it i9 ~urther desired even to return products in ~everal hour3 a~ter receipt of orders, whereby there is increasin~
nece 3ity for the rapid processing. Development of the rapid pro4essing ig als~ ha tened becau~e a ~hortened prc,c~s~in~ time may bring about increa~e in the production ef~icienoy and a cost deorease may be thereby made pos~ible .
To achieve the rapid proces~ing, there have been made approaches from tow aspects, i.e., a light-sensitive ~aterial and a proces~in~ solution. In respeot of the .; .

.
', 1 32qO3q color developing processing, it has been attempted to make hi~her the temperature, p~ and concentration of a color developing agent, and lt is also knowrl to add additives such as development accelerator~. The above development accelera-tors may include l-phenyl-3-pyrazolidone d1sclosed ln British Patent No. 811,185, N-methyl-p-amin~phenol disclosed in U.S. Patent No. 2,417,514, N,N,N',N'-tetramethyl-p-phenyle~ediamine disclosed in Japane~e Patent Publication Open to Public Inspection ~her0inafter referred to as Japanese Patent O.P.I. Publication) No.
16654/1975, etc. The method u~in~ the~e, however, can achleve no ~ufficient rapidne~s, and may be often accompanied with deterioration of performance such as increa~e in fog.
On the other hand, the shape, size and composition of ~ilv~r halide grains of a silver halide emulsion used in the light-sens1tlve material are known to greatly af~ect the develop~ent speed and ~o forth. In particular, it i9 found that the haloyen composition may greatly a~fect the same and a very remarkably high development ~peed can be shown when a chloride-rich silver halide is u~ed.
When, in general, the light-sensitive sllver halide photographic materials are processed in a photofini~hing laboratory over a long period of tise while repleDIsh1n~

1 32903q a replenishing solution, ther~ i al~ a proble~ that the variation of photographic characteri~tic~ (in particular, the gradation variation) may be broug~t about by the change in the compositlon of a proces~ing ~olution. This problem is beaoming large with an increasing tendency of the low replenishing of the processing ~olution.
Bspecially, it $5 nearly impossible to perfectly prevent a bleach-fixlng solution from unintentionally mixing in a developlng solution, even $f the rate of replenishing the reple~ishing solution is strictly ~et, the evaporation i~
prevented, and nothing is made to be eluted ~rom a light-sen~itive material. Particularly in a roller canveyance type automatic processing machine, the state of thin~s i8 ~uch that there i~ caused a remarkable differenae in the amount of uninte~tional mixing of the bleach-fixi~g ~olution into the developing solution, depending on the quantity o~ processing and the ~anner of the squeeg~ing, and, in the event that the rate of replenishing the replenishing solution i5 lowered, the rotation ~peed of the replenishing solutio~ lowered to ~au3e the further di~ference in the rate o~ the unintentional mixing.

~, The variation of photographic performance~ ~in mo~t ca~e~, fog increase and gradatlon variation) cau~ed by such unlntentional mixing o~ a bleach-fixing solution may ~.
i~ be a great obstacle to stablQ and good color reproduction ., ,...
., ~

., ., ., 1 ~2~039 and grada-tioll reproduction. Since, for the reasons mentioned above, lt is very diffi~ult to prevent the unintentional mixing itself of the bleach-fixing solution preferred i~ that the variation of photographic per~ormance~ is small even i~ the bleach-fixing solution i~ unintentionally mixed, in other word~, that the so-called BF contamination re~istance i~ good.
Al~o, the pH value of a color developing solution may vary because of exces~iveness or insufficiency of the amount ~or the repleni~hment o~ a replenishing solut ion .
In general, the pH of a color developing solution i~
~o clo~ely related with ~he color development actlvity that the photographic performances (sensitivity, gradation and ~og) may vary with the pH variation o~ the color development ~olution to impair the ~tability of the photographic per~ormancee. There~ore, preferred i~ that the varlation of photographic performances i5 small against the p~ change al~o, in other word~, that the so-oalled pH variation resistance i9 good.
In order to newly produce a light-sen~ltiv~ 3-i lver halide photographic material that may have a good rapid proce~ing performance and proce~sing stability and al80 ~ay achieve excellent dye-image pre ervation, it wa~ tried to u~e the high boiling solvent disclo3ed in Japane~e Patent O.P. I. Publioat ion No. 20544~/1955 and the above .

.

1 32'~G39 chloride-rich ~ilver halide emulsion in ~imple co~bination, but lt wa~ found that although excellent preservatioII of a dye-image can be achieved, there are di~advantage~ ~uch that the color development perfor~ance is unexpectedly poor, fog is too high, and the processing ~tabillty is short.
Accordingly, since in the prior arts, none of the techniques is ~ufficlent for newly producing the light-sensitive s:ilver halide pho-tographic material that may have good rapid proc0ssin~ performance and proces~ng ~tability and al30 may achieve excellent dye-ima~e preservation, a new technique that can solve the above problems has ~een sought after.
In view of the foregoing, the present inventors, as a result of inten~ive studie~, have used a gold compound and an organic ao~pound havlng particular ~tructure in ; combinativn in the above system comprislng the combination o~ the partlcular high bolliny ~olvent and the chloride-rich silver halide emulsion, whereby it wa~ possible to obtain the ef~ct that could not be expected from any prior art~, and, as a result, they have found a technique to newly produce a light-sen~itive silver halide photo~raphic material excellent in the dye image preservation, rapid processing performance and proce~$ng stabllity, that has been impos~ible to obtain in any prior ~, 1 32903~

arts. The presellt invention has thus been accompli~hed.

SUMMARY OF THE INVENTION
A firYt object of the pre~ent invention i~ to provide a light~sensltive 3ilver halide photographic material that can achieve excellent preservation of a dye image to be ~ormed, and also i~ Peasible ~or the rapid proce~ing. A second object o~ the presellt invention i9 to provide a light-~ensitive ~ilver halide photographic material having ~uperior BF contamination resi~tance and pH variation re~i~tance, in other word~, ~uffering 1ess variation o~ photographic per~or~ances even with the variation o~ color developing conditions, The above object~ o~ the prlssent lnvention can be achieved hy a light-sen~itive sllver halide photographic ~aterial having support and provided thereon with at least one silver hallde emul3ion layer containing a dye-forming coupler, wherein the light-~en3itive ~ilver halide ~photographic material i5 characteri~ed in that at lea3t one of said silver halide emulsion layer contains i) 3ald dye-~orming coupler di~per~ed therein with u8e 0~ a high boiling organic solvent having dielectric constant of 6.0 or les~, ii) silver halide grains containing a gold compound and havixlg ~ilver chlorid~ content of 90 mole %
or more, and iii~ a compound represented by Ge~eral .

`.-1 32qO3q _ 9 _ Formula (S) shown below.General Formula (S):

~Q ~ ~
~;C - S M
' N

wherein Q is a group of at~ms necessary to complete a 5- or 6-membered heterocyclic ring or a 5- or 6-membered ring fused with a benzene ring and M is a hydrogen atom, an alkali meta:L or an ammonium group.

D~TAILED D~SCRIPTION OF T}IE INV~NTIUN
The present invention will be described below speclfiaally.
Dye-forming coupler~ are used in the emulsion layers Gf the light-sen~itive material according to the present i nvent i on .
These dye-forming coupler~ may preferably have ~ntramolecularly a group, called a balla~t group, having 8 or ~ore of carbon atom~, capable of making the coupler~
non-di f fu3ible .
Yellow dye-forming couplers that can be preferably u~ed may include acylacetoanilide type couplers. Of 1 ~29039 these, advantageous are benzoylacet~anilid~ type and pivaloylacetonitrlle type compounds. Preferably, they include the compounds repre~ented by ~eneral Formula (Y) shown below:
General Formula (Y):

CI-I3 Rlr C H3~ C -C O C ~ C O N ~ ~/ ~ R2r I I \~
C H3 Zlr R3~

In the formula, R1~ represents a halogen atom or an alkoxy group. R2y repre~ent~ a hydrog~n atom, a halogen atom, or an alkoxy ~roup. R3y represents an acylamino ~roup, alkoxy carbonyl group, alkyl~ulfamoyl group, arylsul~amoyl group, arylsul~onamide group, alkylureido group, arylureido ~roup, succinimide ~roup, alkoxy ~roup or aryloxy group. ZlY repre~ent3 a group eliminable through the coupling reaction with an oxldized product of a color developing ayent.
Speci~lc examples of u~able yellow coupler~ are tho~e disclosed in British Patent No. 1,0~7,B74, Japanese Patent Examined Publlcatlon No. 407~7/1970, Japane~e Patent O.P.I. Publications No.1031/19~2, No. 26133/1972, No. 94432/1973, No. 87650/1975, No. 3631/1976, No.
115219/1977, No. 99433/1979, No. 133329/1979 and No.

1 3?9039 30127/1981, U.S. Patent~ No. 2,875,057, No. 3,253,924, No.
3,26~,506, No. 3,408,194, No. 3,551,155, No. 3,511,156, No. 3,664,841, No. 3,725,0~2, No. 3,730,~22, No.
3,~91,445, No. 3,900,483, No. 3,929,484, No. 3,933,500, No. 3,973,968, No.3,9gO,896, No. 4,012,269, No. 4,022,620, No. 4,029,508, No. 4,057,432, No. 4,106,942, No.
4,133,g58, No. 4,269,936, No. 4,286,053, No. 4,304,845, No. 4,314,023, No. 4,336,327, No. 4,356,258, No. 4,386,155 and No. 4,401,752, etc.
Magenta couplers that can be preferably used may inc1ude 5-pyrazolone type coupler~, pyrazoloazole type coupler~, etc. More preferably, they ~nclude the couplers r~pre~ented by General Formula (P) or (aI) shown below.
General Formula ~P):

Rpl Y--CH--C--W~, ~C~N,N (Rp2) rn ,,~ I .
~r ., ' , In the formula, Ar represent~ an aryl group; Rp repre~ent~ a hydrogen atom or a substitu~nt; and Rp2 repre~ent a ~ubstituent. Y repres~nt~ a group ellminable through the reaction with an oxidlzed product of a color d~velopin~ agent; W represents -NH~, -NHCO- ~where the ., .
.. .

',"' ~ 329039 nitrogen atom i3 attached to a carbon atom in the pyrazolone ring) or -NHCONH-; and m i~ an in~eger of 1 or 2.
~eneral Formula (aI):

Ra N--N

ln th~ for~ula, Za r~present a group of non-metallic ato~s necessary ~or the for~ation o~ a nitrogen-containlng heterocyclic rlng, and the ring to be formed by the Za may have a ~ubstituent.
represent~ a hydrogen ato~ or a substituent ~ inable through the reaction with an oxidized product of a color developin~ agent.
repre~ent~ a hydrogen atom or a ~ubstitue~t.
The ~ub~tituent repres~nted by the above Ra may include, for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyalic group, an acyl group, a sulfonyl group, a ~ulfinyl group, a phosphonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, a ~piro compound residual group, an organic 1 32903C) hydrocabon compound residual group, an alkoxy group, an aryloxy group, a heterocyclic oxy ~roup, a ~iloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an aoylamino group, a ~ulfonamide group, an imide group, an ureido group, a ~ulfamoylamino group, an al~oxycarbonylamino group, an aryloxycarbonylamino group, an alkoxy carbony1 group, an aryloxycarbonyl group, an alkylthio group, an arylthio group and a heterocyclic thio group.
The~e are dlsclosed, for example, in U.S. Paten-ts No. 2,600,788, No. 3,061,432, No. 3,062,653, No.

3,127,269, No. 3,311,47~, No. 3,152,896, No. 3,419,391, No. 3,619,429, No. 3,555,318, No. 3,684,514, No.
3,888,6ao, No. 3,907,571, No. 3,928,044, No. 3,930,861, No. 3,930,866 and No. 3,933,500, Japane~e Patent O.P.I.
Publication~ No. 29639/1974, No. :111631/19~4, No.
: 129538/1974, No. 13041/1975, No. 58922/1977, No.
62454/1980, No. 1.18034/1980, No. 38043/1981, N~.
35858/19B2 and No. 23855/1985, British Patent No.
1,247,493, Belgian Patents No. ~69,116 and 792,525, West ~erman Patent No. 21 56 111, Japane~ Patent Examined Publication ~o. ~0479/1971, Japanese Patent O.P.I.
Publication~ No. 125~32/1984, No. 228252/1984, No.
162548/1984, No. 171.956/1984, No. 33552/1985 and No.
43659/1985, West German Patent No. 10 70 030, U.S. Patent ~,~

; ,,. . : , .

No. 3,725,05~, etc.
Cyan dye-formin~ couplers to be u~ed may include phenol type and naphthol type cyan dye-~orming coupler~.
of these, preferably u~ed are the coupler~ repre~nted by General Formula (~ or ~F) ~hown below.
General Formula (~):

~ ' 0~ .
~3~NHCOR
R 2 E~CONH~
. Zl~

In the Pormula, Rl~ repre ents an aryl group, a cycloalkyl group or a hoterocyalic group. R~ represent~
an alkyl group or a phenyl group. R3~ represents a hydrogen ato~, a halo~en ato~, an alkyl group or an alkoxy group. Zl~ represerlt~ a hydrogen atom, a halogen atom or ~: a ~roup eliminable through the reaction with an ~xidized product of an aromatlc primary amine type color dev~lopin~
agent.
General Formula (~):
OH

R6 ~ NHCOR4F

~ ~5~ ~
.~ ~F
., , ~, . .

.. . .

1 3?903q In the ~ormula, R4F repre~ents an alkyl yroup ~or example, a methyl group, an ethyl group, a propyl group, a butyl group, a nonyl ~roup, etc.). R5F repre~ent~ an al~yl group, (~or exa~ple, a methyl ~roup, an ethyl group, etc.). R6F represen~ a hydrogen a~o~, a halogen at~m (for example, fluorine, chlorlne, bromine, etc.~ or an alkyl group (for example, a methyl group, an e~hyl group, etc.). Z2F represents a hydrogen atom, a halogen atom or a group eliminable through the r~action with an oxidized product o~ an aromatic primary amine type color developing agent.
: These cyan dye forming couplers are di~clv3ed in U.S. Patent~ No. 2,306,410, No. 2,356,4~5, No. 2,362,598, No. 2,367,531, No. 2,369,929, No. 2,423,730, No.
2,4?4,293, NoO 2,4~6,008, No. 2,45~8,466 No. 2,545,68~, No.
2,72B,660, No. 2,~72,162, No. 2,395,826, No. 2,976,14fi, No. 3,002,836, N~. 3,419,390, No. 3,446,62Z, No.
3,4~6,563, No. 3,73~,316, No. 3,758,308, and No.
3,839,044, Britlsh Patents No. 478,991, No. 945,542, No.1,084,480, No. 1,3~7,237, No. 1,388,024 and No.
1,543,040, Japanese Patent O.P.I. Publication~ No.
37425/1972, No. 10135/1975, No. 25228/1975, No.
112038/19~5, No. 117422/19~5, No. 130441/1975, No.
6551/1976, No. 37647/19l6, No. 52828/1976, No.
108841/1976, No.109630/1978, No. 48237/1979, No.

.
.`' , 1 ~29039 -- 1~
66129/19~9, No. 131931/19~, No. 32071/1980, No.
1~6050/1984, No. 31953/1~84 and No. 117249/1985, etc.
The dy~-image forming coupler~ u~ed in the present inveIItion may be used in the re~pective silver halide e~ul~ion layers usually in the range of 1 x 10 3 mole to 1 mole, preferably 1 x 10 2 mole to 8 x 10 1 mole, per mole of silver halide.
Usually, the above dye-forming couplers may be added by dissolving the couplers ln a hlgh boillng organic solvent having a boiling point of 150C or more optionally together with a low bolling and/or water soluble organic ~olvent, and carrying eut emulsification disper~ion in a hydrophilic binder such a~ an aqueous ~elatin solution by u~ of a ~ur~ace active ~gent, followed by addiny the disper~ion to an intended hydroph:Llic colloid layer.
There may be insarted a ~tep of re~moving the dl~per~ing ~olution or, at the same ti~e of the di~persion, the low boiling organlc ~olvent.
In the present invention, the ratio of the hi~h boilin~ organic olvent of the pre~ent invention to the low boiling organic solvent may preferably be 1 : 0.1 to 1 ;, . : 50, more preferably 1 : 1 to 1 : 20.

~ The hiyh boiling organic ~olvent according to the .. pre~ent invent ion may b~ any of the compounds having :

j dielectric constant of 6.0 or le~. There i~ no .',~ .
~ .

~' ,: - . , particular limitation in the minimum, but preferably the dielectric con~tant may be 1.9 or more, As the high boiling or~anic solvent that can be used in combination, there may be included ester3 ~uch as phthala~e~ and phosphates, organic amides, ~etones, hydrocarbon compound~, etc. having the dielectric con~tant of 6.0 or le~s. More preferred are phthalate3 or phosphates.
Preferred i~ a high boilin0 organia ~ol~ent havlng the vapor pressure o~ 0.5 mmHg at 100C. ~he sr~anic ~olvent may be a mixture of tow or more type~, provided that thi~ mixture may have the dielectric constant of 6.0 or le~s. The high boiling organic ~olvent that can be used in combination may include, for example, dibutyl phthalate, dimethyl phthalate, tricresyl pho3phate, tributyl pho~phate, eta. The dielectric con~tant mentioned in thi~ invention refers to the dielectric co~stant at 30C.
The phthalate~ may include the compound represented by Gen~ral Formula (HA~ shown below:
~eneral Formula (HA) COORH ~

RH1 and R~2 each represent an alkyl group, an 1 3!~qn3s - lB -alkenyl group or an aryl group, provided, however, that the sum of carbon atom numbers of the group~ repre~ented by RHl and RH~ i~ 9 to 32. More preferably, the ~um of the carbon atom number~ is 16 to 24.
The alkyl group represented by RHl and RH2 in the above General Formula (HA) may be ~traight chain or branched one, including, for example, a butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, a heptadeayl group, an octadecyl group, etc. The ary group represented by RH1 and RH2 may include, for example, a phenyl group, a naphthyl group, etc.; the alkenyl group may include, ~or exa~ple, a hexenyl group, a heptenyl group, an octadecenyl group. The~e alkyl group, alkenyl group and aryl group may have a single or plural number of substituent(s). In the above, RHl and RH2 may preferably be an alkyl group, including, for example, a 2-ethylhexyl group, a 3,5,5-trimethylhexyl ~roup, a n-octyl roup, a n-nonyl group, etc.
The phosphates may include those represented by General For~ula ~HB) shown below:
General Formula (HB) :
:

.:

.

.~ .

1 ~2qO39 -- lg --R
RH50 1 OR~3 R~3, R~I4 and RB5 ~ach repre~ent an alkyl group, an alkenyl group or an aryl group, provided, however, that the sum of the carbon atom numbers of the group~
represented by RH3, RH4 and R~ 24 to 54.
The alkyl group represented by R~3, RH4 and RH5 in General Formula (HB~ may include, for example, a butyl group, a pentyl group, a hexyl group, an oc~yl group, a nonyl group, a dodecyl group, a pentadecyl group, a hexadecyl ~roup, an octadecyl group, a nonadecyl group, et¢.
These alkyl ~roup, alkenyl ~roup and aryl ~roup may have a sin~le or plural number of substituent(~).
Preferably, RH3, RH4 and R~5 each reresent an alkyl ~roup, lncluding, ~or example, a 2-ethylhexyl group, a n-octyl group, a 3,~,5-trimethylhexyl group, a n-nonyl group, a n-dscyl group, a sec-decyl group, a sec-dodecyl ~roup, a t-octyl group, etc.
Typical exaDIples of the organic solvents are shown below, but this invention is by no means limited to the~e.

;,~
'^~ .
,'.
~ ~ .
' . .
, . . .
.

G~3neral Formula (HA):

,,~C O O F~ H I
W~
C O O E~H 2 . _ .
Comp. No. RHI R ~2 H--1 --C6H,3(n) --C6H,3(n) __ . ... .... __ H--2 IC2Hs --CH2 ICH(CH2)3CH3 --C H 2 C H ( C H 2 ) 3 C H 3 C 2 H s . _ _ __ _ . , H--3 --C8H~7(n) --Cl,H~7(n) ~_ _ _._ - . . . _ .
H--4 ~CgHIg(i) --C~H,g~i) . . ._ . _ ~
H - ~ ~CgH~g(n) --CgH~y(n) ._ _ ~_ _. _ . . ~

H--6 --CH2CH2CHCH2C--CH~ --CH2CH2CHCH2C--CH~

_ _ _, H--7 --C,~H2,(i) --C,oH2J(i~
~. . _ _ . ._ ..
. H--~ --C,OH2~(n) --C,OH2,(n) . . . . _ _ ..
~ H~ 9 --C"H23(i) --C"H23(i) . ...
- H--1 û C 12 H 25( n ) --C 12 H 25( n ) . _ ~ . .. _._.. _ H--1 1 --C , 2 H 2 s ( i ) --C , ~ H 2 S ( i ) ~ ~__ . _ ,.~

.~

General Formula ( HB ):
o Il R~ P--O R~3 O RH~

.
_ _ compR~3 i Rl l~t R 1 . ,. ~ ~. _ H--1 2i 2 H s --CH2 I H(CH2hCff3 --CH2CI HtCH2)~CH3 . --CH2CH(CH2)3CH3 C 2 H s C 2 H s ~ .. . ___ .
H--1 3 --C g H I g ( i ) ~ C g H I g ( i ) ~ C g H I g ( i ) , .
H--1 4 --CgH,g(n) --CgHIg(n) --CsHIs(ll) H--1 5 --C~oH21(i) --C~oH21(i) --C~oH21~i) . _ H--1 6 --C~OHz~(n) --CJ0H2l(n) --C~OH2~(n) H~1 7 --C~H2~(i) --C~H2~(i) --C~lH2~(i) ., . .. ~
i H--1 8 --C~2H2s(i) _--C~2H2s(i~ --Cl2H2s(i) . j H~ 1 9 , .
H--2 () r~ ~
~ ~COOC~H~7 ';1:

~.$i ~

,.,~
~' .
:
., .

., .

-~ 21~ ~2 9 0 39 i ,CH2~,CH2~
fH2 I H Cl H2 ~C H 2~ ~ C H 2 (~ C , 2 H 2 5 ,~ ~

'.`~:

1 32qo3~

The hiyh boiling organic 301vent according to the present invention can be used in the range of 0.01 mole to : 10 moles, preferably 0.05 mole to 5 moles, per mole of silver halide.
The silver halide grains of the present invention have ~ilver chloride content o~ 90 mole % or more, and ~ilver bromide content of preferably 10 mole % or le~, and ~ilver iodide content of 0.5 mole % or le~s. More preferably, the grains may compr~se silver chlorobromide having ~ilver bromide content of 0.05 to 5 mole %.
The silver halide grains may be used alone or a3 a mix with other silver halide grains ha~-ing diffarent composition. They may be also u~ed as a ~ix with silver halide grains havlng silver chloride content o~ 10 mole %
or les~.

, .
:~ In the ~ilver halide emulsion layer containing ~he : silver halide grains of the pre~ent invention, havin~ the ~ilver chloride cuntent of 90 mole ~ or more, the ~ilver halide grains having the silver chloride conten-t of 90 mole % or more may be held in the whole ~ilver halide ` grains contained in said emulsion layer, in the proportion .~ of 60 % by weight or more, preferably 80 % by weight or . more.
The compo~ition of the silver halide grains of the present invention may be homogeneous from inside to ''.``~
., .

~, , ,~

outside of a grain, or may be different between the in~ide and outside of a grain. In the case -the composition is di~erent be~ween the inside and outside of a grain, the composition may vary continuously or di~continuou~ly.
There iY no particular limitation in the grain ~ize o~ the silver halide grain~ of the present lnvention, but i-t may preferably range between 0.2 and 1.6 ~m, more preferably 0.25 and 1.2 ~m. The above grain size can be mea~ured according to variou~ method~ generaliy u~ed in the present technical field. A typical me~hod is disclo~ed in Rabland, "Grain Slze Analytical Method"
IA.S.T.M. Symposium on Light Microscopy, pp.94-122, 1955~
or "The Theory of The Photographic Proce~s" (by Meath and Jam~s, Third Editlon, published by Macmillan Publishing Co., Inc., see 5econd Para~raph).
This grains size can be measure~l by u~e o~ a pro~eation area or diametric approximate value of a graln.
In the case the grain~ are substantially of uniform shape, the grain size distribution can be considerably precisely expres~ed as the diameter or the projecti~n area.
The distribution o~ grain size of the silver halide ~rains of the present invention may be either polydisperse or monodisperse. Tile ~ilver halide gralns may preferably monodisper~e silver halide grains having the variation coef~ioient in the grain size di~tribution of the ~ilver /

, 1 32qo3s halide grains, of 0.22 or less, more preferably 0.15 or less. Here, the variation coefficient i~ the coefficient showing the width of grain 9ize dlstribution, and de~ined by the following equation:

Standard deviation of ariation coefficient (S/r~ = ~rain ~ize distribution Average grain size Standard deviatlon (S) of = ¦ ~(r - ri)2ni grain size distribution \¦ ~ ni Average grain size ~r) = ~niri ~ ni Here, ri represent~ the grain size o~ the respective yrains, and n~ represents the number thereof. The grain slze herein mentioned re~ers to it~l diameter in the ca~e of a spherical ilver halide grain, and, in the case of a cube or a grain having the ~hape other than a ~phere, th~
diameter obtained by calculating its projected image to a circular image having the corre3ponding area.
The silver halide grains used in the emul~lon of the present invention may be obtained by any of an acidic method, a neutral method and an ammoniacal method. The grains may be allowed to grow at one time, or ~row af~er ~eed grains have been ~ormed. The manner to prepare th~
~eed gralns and the manner to grow them may be sa~e or different.
The manner to react a soluble ~ r ~alt with a ~oluble halogen ~alt ~ay be any o~ a regular mixlng ~ethod, a reverse mlxing method and a simultaneous mixing method, or a combination o~ any of the~e, but preferred are grains forme~ by the simultaneous mixing me~hod. A~ a type of the simultaneous mixing method, there can be u~ed ths pAg-controlled double ~et method di~closed in Japane~e Patent O.P.I. Publication No. 48521/1979.
I~ neces~ary, there may be further used a silver halid~ ~olvent ~uch a~ thioether.
The ~ilver halidQ grains according to the present invention that can be used may have any shape. A
pre~erable example i~ a cube hav1n!~ ~ 100~ face a~ a crystal sur~ace. Al~o, grains having the shape o octahedrons, tetradecahedron~, dode~ahedron~, etc. may be prepared according to the procedure3 di~clo~ed in the ~peci~ications o~ U.S. Patent~ No. 4,183,756 and No.

4,225,666, Japane~ Patent O.P.I. Publication No.
265~9/19~0, Japane~e Patent Publication No. 42~S~/lgaO, etc., and the publications ~uch as The Journal o~
.
Photo3raphlc Science, 21, 39 (1973), and these ~rains can be al~o used. There may be further used grains having a twin cry~tal ~ace.
The silver halide grains according to the present c: ~ , . .

- I 3 2 9 0 3 r~

~ 26 -invention that can be u~ed may be grains compris~ng a sin~le ~hape, or may be a mixture o~ grains having various ~3hapes, In the course of ~ormation and/or growth of the silver halide grains used in the emul~ion o~ the present invantion, metal ion3 may be added to the grain~ by use of at lea~t on~ of a cadmium salt, a zlnc salt, a lead salt, a thallium salt, an iridium salt or a complex ~alt thereo~, a rhodium salt or a complex salt thereof, and an iron salt or a complex salt thereof to incorpora~e any of these metal elements into the in3ide o~ the grain~ and/or the ~urPace of the gràins, and also a reduction s~n~itizing nuclei can be imparted to th~ in~ide o~ the grain3 and/or the sur~ace of the grain~ by placlng the grain~ in a ~uitable reductive atmosphere.
The emul~ion containlng the silver halide grains of th~ pre~ent in~ention (herelna~ter "the emulsion o~ the pres~nt inventio~") may be either one from which unne~ea~ary soluble ~alts have been removed after completlon of the growth of silver halide grains, or one from which they remain unremoved. When the salts are removed, they can be removed according to the method di~clo~ed in Research Disclosure No. 1~643.
The silver halide grains u~ed in the emulsion of the present invsntion may be grains such that a latent image 1 32qO39 is chiefly f~r~ed on the ~ur~ace, or grain~ such th~t lt i~ formed chiefly in the inside of a grain. Preferred are the grain~ ln which a latent image i8 chiefly formed on the ~urface.
The emulsion of the present invention can be chemically sensitized according to aonventional method~.
Namely, a ~ulfur ~en~itization ~ethod using a compound containing ~ulfur'capable of re~cting with ~ilver ion3, and active gelatlIl, a selenium sensitization method u~ing a ~el~nium compound, a reduction ~ensitization method u~ing a reducing ~ub~tance, and a noble metal aensitization method u~ing noble metal compound~ ~uch as gold and 90 ~orth can be u3ed alone or in co~bination.
In the pre~ent inv~ntion, a chalcogen ~en~itizer oan be used a~ a chemical ~ensitizer~ The chalgo~en ~ensitizer i5 a general term ~or a ~ul~ur ~en~itizer, a s~lenium ~ensitizer and a telluriu~ sensitizer. For photo~raphic u~e, preferr~d ar~ the ~ulfur ~en~ltizer and the ~elenium ~en~itiæ~r. The sulfur sensitizer may include, for example, thio~ul~ate, allythiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluene thiosulfonate and rhodanine. Be~ldes the~e, thçre can be al~o used the ~ulfur ~en~itizers disclosed in U.S. Patent~
No. 1,5~4,944, 5,410,~9, No. 2,2~8,947, No. 2,728,668, No. 3,501,313 and No. 3,656,955, German La~d-open Application (OLS) No. 14 ~2 866, Japanese Patent O.P.I.
Publications No. 24937/1981 and No. 45ol6/ls8o~ etc. The ~ulfur sensitizer may be added in an amount that may vary in a con~iderable range dependi ng on t he var i ous condi~ion~ such as pH, temperature, ~ize of llver halide grains, but, a~ a 3tandard, pre~erably in an amount o~
10 ~ to 10 1 mole per mole of ~ilver halide.
The ~eleniu~ sansitlzer can be used in place of the ~ulfur Ren~itizer, which 4elenium ~nsitizer ~ay include lsoselenocyanate~ such as allyi~o~elenocyanate, ~elenoureas, selenoketone~, selenoamides, ~alt~ and e3ters of ~elenocarbonic acid, selenopho~phates, and ~elenide~
~uch as diethyl ~elenide and dlethyl diselenide. ~xamples o~ these are di~clo~ed in U.S. Patent~ No. 1,574,944, No.
1,602,592 and No. 1,623,499.
Reduction ~ensitization can be further u9ed in .
combination. There ~ no particular limitation in a reducing agent, and lt may include ~tannous chloride, ~ thiourea dioxide, hydrazine, polyamine, etc.
; Noble met~l compound~ oth~r than gold, for example, ~ palladium compounds or the like can be used in ~ combination.
. The silver halide grains according to the present invention contains a gold compound. The gold compound of ~: the pre~ent invention may any of gold having the oxidation ~.' :'.

- 29 ~ ~ 3 ~ 9 3 9 number of valence tl or ~3, and variou3 gold compound~ may be used. Typical examples thereof may include chloroaurate, pctassium chloroaurate, auric trichloride, pota~sium auric thiocyanate, pota~ium iodoaurate, t~tracyanoauric a~ide, ammonlum aurothiocyanate, pyridyl trichlsrogold, gold ~ul~ide, gold ~elenide, etc.
The gold co~pound~ may be used in such a manner that it may ~ensitize the ~ilver halide grain~ or may be u~ed in ~uch a manner that it may not ~ub~tantially contribute to the sensitization.
The gold compound may be added in an a~ount that may vary depending on varlou~ conditions, but, a3 a 3tandard, in an amount of 10 ~ to 10 1 mole, preferably 10 ~ to 10 2 mole. The compound may be added at any time, i.e., at the time of the ~ormation of ~ilver ha:Lide grain-~, at the tlme of physical ripening, at the ti~e of chemical ripening, or after completion of the chemical ripening.

(to be continued) 1 32903'~
- 29' -Gold compounds are added preferably during the period of chemical ripening. As a chemical sensitizer to be used in thi~ case, aforesaid gold compound may be used either independently or in comblnation with aforesaid chemical sensitizer (e.g. sulfur sensitizer, selenium ~ensitizer, reducing agent and others). In the present invention, it is especially pre~erable to use a gold compound independently as a sensitizing agent (so-called a gold sensitization) or to u~e a gold compound in combination with a sulfur sensitizer tso-called gold-sulfur sensitization). When the gold-sulfur sensitization is carried out, a gold compound and sulfur sensitiz~r may be added simultaneously or separately. When a gold compound and a sulfur sensitizer are added separately, either one of them may be added firsl:.
The e~ul~ion of the pre~ent invention can be ~pectrally sen~itized to a de~ired wavelength reglon with ; use of a dye known in the photographic f ield a3 a sensitizing dye. The sensitizing dye may be used alone, but may be used ~n combination of two or ~ore ones.
Together with the sensitiæing dye, the emulsion may contaln a ~upersen~itizing agent which i~ a dye having itself no action of spoctral een~itlzatlon or ~ co~pound ~ 329039 ~ub~tantlally abaorbing no visible ligh~, and that can ~trengthen the 3en~itizing action of the 3en~itizing dye.
The light-~ensitive ~11ver hallde photographic material contains the co~pound represented by ~eneral For~ula (5).
General Formula (S):

Q ~ ~
~C - S M
N

. . .
wherein Q is a group of atoms necessary to complete a 5- or 6-membered heterocycli.c ring or a 5- or 6-membered ring fused with a benzene ring and M is a hydrogen atom, an alkali metal or an ammonium group.

The 5-m~mbered heterocyclic ring represented by Q
may include an imidazole ring, a tetrazole ring, a thiazole rlng, an oxazole ring, a ~elenazole rlng, a benzimidazole ring, a naphthoimidazole ring, a benzothiazole rlng, a naphthothiazole rlng, a benzo~el2r;azole ring, a naphthoselenazole ring, a benzoxazole ring, etc., and the 6-membered heterocyclic ring may include a pyridine ring, a pyrimidine ring, a quinoline rin~, etc. The~e 5- or 6-membered heterocyclio ring may include those having a substituent. The alkali metal atom represented by M may include a sodium atom, a pota~slum atom, etc.
0~ the compound represen~ed by General E'ormula (5), particularly preferable compound ~ay include the compound~
repre~ent~d respectively by ~eneral Formula (SA), General Formula ~SB) and General Formula (SD) Rhown below.
General Formula ~SA):

I~l S ~ R.,~

N ~-N

~A1 Z represent~ -N-, an oxygen atom, ~r a 3ulfur atom.
RA represents a hydrogen atom, an ;alkyl sroup, an aryl group , an alkenyl yroup, a cycloalkyl group, -SR~1, -N \ , -NHCOR~4, -NHS02R~5, or a heterooycllc ring, wherein RA1 represents a hydrogen ato~, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a A4 2RA5; RA2 and RA3 each repre~ent a hydrogen atom, an alkyl group or an aryl group; and R~4 and R~5 ~ach represent~ an alkyl group or an aryl group. M
repre~ent~ a hydrogen atom, an alkali metal atom or an ammonium group.

~ 3~-9~3q The alkyl group repre~ented by R~l, RA2, RA3, RA4 and RA5 in General Formula (SA) may include, for axample, a methyl group, a benzyl group, an ethyl group, a propyl group, etc.; and the aryl group may include a phenyl group, a naphthyl ~roup, etc.
The alkenyl group repre~ented by RA and RAl may include, ~or example, a propenyl group, etc., and the cycloal~yl group, may include, for example, a cyclohexyl group, etc. The hetervcyclic group represented by RA may include, for exa~pl~, a furyl group, a pyridinyl group, etc.
; The above alkyl group and aryl group represented by RAl, RA2, RA3, RA~ and RA5 and the alkenyl group and cycloalkyl group repre~ented by RA and RAl may al50 include those ~urther havin~ a sub~tituent.
The alkali metal atom represented by M may include a potasslum atom, a ~odium atom, etc.
General FGrmula (SB):
~ M S~b k~ RA
~<N
R.~2 RA and M have the same meaning as RA and M in General Formula (5A) respectiv~ly. RBl and RB2 have also ,.

.

,~ , ~ 329039 the ~ame meaning a~ RA1 and RA~ in General Formula (SA) re~pectively.
The alkyl group represented by RA and RB in General Formulas (SA) and ~SB~ may include, for e~ample, a methyl group, an ethyl group, a butyl group, etc.; the alkoxy group may include, for example, a methoxy group, an ethoxy group, etc.; ~nd the ~alt of the carboxyl group or sulfo group may include, for example, a sodium salt, an ammonium salt, etc.
In General Formula (SA), the aryl group repre~anted by RA may include, for example, a phenol group, a naphthyl group, etc.; and the halogen atom may include, for example, a chlorine atom, a bromine atom, etc.
: General Formula (SD~:
Ar N - N

N

In the formula, Ar represent~ a group of;

` (ID~n ; ~ RD)n ' ~ or {~ ~
: RD

1 3~9039 R~ represent~ an alkyl group, an alkoxy group, a carboxyl group or a salt t~ereof, a ~ulfo group or a salt thereof, a hydroxyl group, an amino group, an acylamino group, a carbamoyl group, or a sulfonamide.
n repre~ent~ an integer of O to 2.
M has the same meaning with M in General Formula (S) .
In General Formula (SD), the alkyl grvup represented by RD may include, for example, a methyl group, an ethyl group, a butyl group, etc.; the alkoxy group may include, for example, a methoxy group, an ~thoxy group, etc.; and the salt of the carboxyl group or sulfo group may inelude, for example, a sodium salt, an ammonium ~alt, etc; the acyl~mino yroup repre~ented by RD may include, for example, a methylcarbonylamino yroup, a benzoylamino group, ~tc~; the carbamo~l group ~ay inolude, for exa~ple, an ethylcarbamoyl group, a phenylcarbamoyl group, etc.;
and the sulfonamide group may include, for example, a m~thyl~ulfonamide group, a phenyl~ulfonamide, etc.
The above a1kyl group, alkoxy group, aryl group, amino yroup, acylamino group, carbamoyl group, sulfonamide group, etc. may al~o contain those further having a ~ub~tituellt.
Typical examples o~ the compound represented by ~ner~1 For~ula ~5) are ~hown below.

.
.

1 3~-q o3c3 MS 0~ R~
~ 11 N--N
~~3xemplary ~ _ .
compc)und a . . _ _ .
S -- 1 --C2 Hs _ H._ . . .
S -- 2 --CH2--CH= CIl2 --H
...
S -- 3 --CH--CH--Cl-l2--CH3 --H
_ .
S -- ~ --C7H~i --H
,, ._ S -- 5 --C9HI9 --Na . ____ . _ _ A . _._ ____ . ._ . __ _.____ S -- 6 . ~ _ --I l ~ S ~ 7 --C4 H~(t) --H
.~ .
~S -- 8 ~NHC H 3 _ H
.~ . . , S- 9 ~ -~[' . .. _ ~ .
S -- 1 0 1~3 --H
, .... _ .
S -- ll --NH~) _~

~ .
- :
, , " , 1 32qO39 . ................ , ~_._ . ___ ~xemplary Ra M
compound _ __ . . ~ __ S -- 12 --N H ~ CH3 ~NH~
_ ~ S -- ] 3 --NITI C O CHs --H
. ,.
S -- 14 --NH S 02~ --H

S -- ] 5 --N ( CH~ )2 --H
,, .
S -- 16 ~NIlCH2~ --H

S -- 1 7 --C H 2 ~ _ I~
.1 . I
'~ S -- 18 --S--CHs --H
. _ ..
S -- l 9 --S ~ --~T
.. .. ... _ S -- 2 0 _~

' '.
,, ;, ,. ,. .: .,~

1 32903q ' ~ S~SY R A
, 11 11 N--N
_ .
13xemp l~ry R,,~, ?~
; compound S -- 21 _ ~ . H
,.
.~ S -- 22 --C2H5 _~1 ,,. ~ _ S -- 23 --C~H~(t) --H
, , S -- 2 ~ --C ~ H ,~ --H

' S-25 ~ . _1.1 S - ~ 6 ~ N 0 2 _ ~
,. ~ .. ... _ . _.......................... _ .
S -- ~7 ~N ( CH3 )2 ~ -~`: _. _ S -- 2 8 M--~ --H
~ ~ ~ _ S -- 29 --NE~ --H
',; ~ : _ ~ S -- 30 --N ( CH9 )2 --I-I
. ~.... __ `;~ . .S -- 3 1 --C H2 C H = C I12 --H
, , .

.~
--..

... .
"

.~ ' ' .

13xe~plary _ M
compound S ~ 32 S H --H
... __ .....
S -- 3 3 --N H C O C 2 H ~ --H

i`~ ::

, ,~ - .

: ' :~
' '.' ' ' ` ; " ,' ~S~ ,RA
Il 11 N--N
. . . . .
~xemp lary R A R A 1 M
compound . .
~ _ ~, -- I
S -- 34 --C2H5 _H --H
_ I

....
S -- 3G --~H3 ~ H
. . _ .
S -- 37NI1COCH9 --CHa --11 ._ . . _ _ S -- 38--NH C O~ --CO~ _ 11 ... ..... _ ..
S -- 39 NHCOCH3 --COC~I3 --11 . ~
S -- 40--NH C O CH3 --CH~ --H
.~ ~.. . .. . _ S -- 4l --NH C O C2H5 ~CN --N~
. . ._ ._ S -- 42 --NHC O~ {~ --~ I
.`,: . ..
S -- 43 --NH S 2 CH3 _ H --H
.. _ ._. I
~ S ~ 1 ~ --~ HCO~OC~13 - C113 ¦ --N3 .., ~ .

.

. ~emplary . .......... RA 1 compound . _ S -- 45 --NflCO~3 --CH2 CH--CH2 --H
_ .
S -- 4 6 --NHCO~. . --CH2CH~.O~ _ 11 .
,~

, ~
,,~ :
"

,~ :
,, .

...
.,,~, , .

1 3~903q MS~ R~

R~R~l compound R~ R ~1 R B 2 M
. . __ S -- 4 7 --C 2 H5 --CH 3 --C~I3 --H
_ ___._ _ __ S -- ~8 ~3 --Cll~ --CH3 --H

S -- 4 9 ~ N H2 --H ~ --H

S -- 5 0 --NII~ CB --II --C~ HD --I1;
.... _ _ S 5 1 --~HCOCI~I3 --CH3 --CH3 _ . ..
Y 5~ --NHCO~ --CH~ -CH9 _ 11 --NH--~
_ --C l~l 3 C ~ j l --H

,' ~

~ ' . , .
.

1 32903~

.A r N N~
¦¦ ~'~ SM

Exemp lary A r M
compound _ S--5 5 ~3 ~ _ --H

S--56 ~NH S 2 CH~ --H
- -- -I
S--57 ~OCH9 --Na S -- 5 8 ~ C O O H --H
_ _ S--59 ~NHCO --H

,S -- 6 0 ~; NHCOCH3 --H
. .
S--61 ~> --Na , . _ _ _ _ _ .
S--62 4~CH, --H

S--63 ~CONHCHs . --H
_ C O O H
_ ~ _ --H

-., -- J~3 --_ . .
Lxemplary A M
compound _ S -- 6 ~ ~ - NH4 ~ j ~CO~

S -- 6 8 ~_ SO, l!la --H

,~

:

.
: .

1 ~29û39 The compound represented by General Formula ~S) may include the compound~ disclo~ed, for example, in Chemical and Pharmaceutical Bulletln, Tokyo, Vol. 26, 314 (1978), Japanese Pat~nt O.P.I. Publlcation nO. ~9436/1980, Berichte der Deutschen Chemi~chem Gesell~dra~t, ~2, 121 (1948), U.S. patent~ No. Z,843,491 and No. 3,107,270, Briti~h Patent No. 940,169, Japanese Patent O.P.I.

Publication No. ld2639/l9~6, Journal of Americam Chemical Society, 44, 1~02-1510, Japanese Patent O.P.I. Publication No. 59~63/19~0, etc., which can be ~yntheslzed accordin~
to the procedure~ al~o disclo~ed in the~e publication3.
To incorporate the compou~d represented by General Formula (S) accordlng tn thi~ invention (herelnafter "Compound (5)") irlto thc ~ilver halide emul~ion layer of the present invention, it may be di3~01ved in water or in a reely water~ml~clble organic ~olvent (for exa~ple, methanol, ethanol, etc.~, and then added. The compound (S~ may be used alone or in combination wlth other compounds represented by General Formula (S) or any ~tabilizer or fog r~trainer oth~r than the compound represented by General Formula (S).
The compound (S) ~ay be added at any time b~fore formation of ~ilver halide gralns, during formation of ~llver halide grai~, aft~r co~pletion o the formation of ~ilver halide yrains and before initiation of chemical 9 0 3 q ripening, during chemical ripening, a~ the time of ~ompletion of chemlcal ripening, or after completion of chemical ripening and before coating. Preferably, it may be added during chemical ripening, at the time of completion of chemical ripening, or after completion of chemical ripaning and before coating. The addition may be oarried out by adding the whole amount in one tim~, or by divlding it into ~everal times.
As to the place for the addition, the compound may be added directly to a silver halide emul~ion or a coating solution of the ~ilver halide emulsion, or may be added to a coatlng solution for an ad~acent non-light-~en~itive hydrophilic aolloid layer ~o that the compound may be oantalned in the silv0r halide emulsion layer of the present invention by the action o~' diffuslon at the time of multi-layer coating.
There is no partlcular limitation in the amount for ths addition, but the compound may be added uYually in the range of 1 x 10 6 mole to 1 x 10 1, preferably 1 x 10 5 to 1 x 10 ~.
Some of Co~pound (S) of the present invention are compounds known in the pre~ent indu~trial field a~
stabilizer~ or antifoggant~. For example, they are diRclosed in Briti~h Patent No. 1,2~3,030, Japane3e Patent Pilblication No. 9936/1993, Jepanese Patent Publlcation No.

.~

1 .

1 32C,~039 27010/19~5, Japanese Patent Q.P.I. Publication No.
102639/1976, Japa~ese Patent O.P.I. Publication No.
22416/1978, Japanese Patent O.P.I. Publi~ation No.
59463/lg80, Japanese Patent O.P.I. Publication No.
Ygg36/19aO and Japan0se Patent O.P.I. Publication No.
232342/1984, etc. However, in the above known publications, though having the descrip~ions relating to the restraint o~ fog or stabilization of emulsion~, the effect obtainable by the present invention, i.e., the e~ect achieved when the gra~n~ having the high ~ilver chloride content and containing the gold compound is sub~ected to the color developlng, ha3 not been known at all. In general, Compound (S) i5 known a~ compounds that can ~how the fog restraint action and ~o forth while being accompanied with de~ensitization and development restraint (a~ di~clo~ed, for ex~mple, in "Funda~ental~ o~
Photographic Indu~trie~, Silver Scllt Edition", Korona~ha Co., p.195, 1979). It was quite unexpected effect that these compound~ can improve the rapid processing performance when applled in the system of the pr~sent invention.
Moreover, in respect of the processin~ ~tability in the ~y~tem of the present inventlon, there was al~o obtained quite unexpected efect such that the light-sensitive ~atorial can have good and atable ~ 47 ~ t ~ a 3 '3 reproducibility again~t the photographic variation, for example, the gradation variation, due ~o the lnclu~ion of a bleach-fixing ~olution into a color developing ~olution and the pH variation o~ the color developing ~olution, in other word~, it can be excellent in the ~o-called BF
conta~lnation resi~tance and pH vari~tlon re-Qi~tance.
~eviewing more ~pecifically, the compound included in the compound of General For~ula (SA), wherein Z represents -N-R, the 3ame compound wherein Z repre.~ent~ an oxygen atom, and the compound repre~ented by General Formula (SD) ~hows great e~ect in the 8F contamination re~i~tance, and the compound of General Formula (SB) show~ great effect in the pH variation re~i~tanoe.

The above con~ideration i~ ba~ed on nothing ~ore than 3uppositlon, and the Pact i~ ~till unclear.
In the pre~ent invention, to harden the ~ilver halide emul~ion layer, it i5 pre~erable to u~e a hardening agent of a chlorotriazine type, represented by ~eneral For~ula (HDA) or (HDB) shown below.
General Formula (HDA):

Rd 2~"N ~C

N~,N

R d I

., 1 32903~

In the formula, Rdl represent~ a chlorine atom, a hydroxyl group, an al~yl group, an alkoxy group, an alkylthio group, an -OM group (wherein M 1~ a ~o~oval~nt ~etal ato~, an -NR'R" yroup (wherein R' and R" ~ach repre~ent a hydrogen atom, an alkyl group or A~ aryl ~roup), or an ~NHCOR"' (wherein R"' represent~ a hydrogen atom, an alkyl group or an aryl group); and Rd~ repre~ent~
a group having the-~ame meaning a~ the abov~ Rdl, excluding a chlorin0 atom.
~eneral For~ula ~HD~):

Rd ~ N~y( Q ) P--L--( Q ) q ~,N ~, Rd 4 N ~; N N~ N
C~ C

In the for~ula, Rd3 and Rd4 e~ch represent a chlorine atom, a hydroxyl group, an alkyl group, an alkoxy group or an -OM group (wherein M i8 a monovalent ~etal atom). Q and Q' each repre~ent a linklng group ~howing -O~, -S- or -NH-; ~ represents an alkylene group or an arylene group; and p and q each represent O or 1.
Typical examples of the pre~erred hardening agent repr~ented by the abova General Formula~ (HDA) and (HDB) are de~cribed below.

~ 3~qO39 ~9 t3sneral Formula ( HDA ):

Rd 2~ N ~T,C Q
N~,N
Rd~

Comp . No . Rd I Rd 2 _ __ . __ __ -- -~
H D--1 --O H --O Na ~ _ _ - ~ r HD--2 --CQ --ONa .
HD--3 ~OCH3 ~~ONa ._ :~ HD--4 ~C~ --OC2Hs . .
HD~ 5 --CQ ~ O K
~ . ....................... . '''----I
HD~ 6 ~OH ~ OK
H~D _ 7 _ CQ - N H2 H D--8 --C ~ - N H C O C H 3 _ H D 9 --O H --N H C 2 H s , ~ ;~ ~ , : ::

:

..
\::

., ,, .

~ . . -'~, , .' .

~ 329Q3'~

9eneral Formula ( HDB ):

~d ~ N~( Q )P ~ L--( Q )q ~ N ~Rd N ~ N N ~ N
CQ CQ

-~ r- -- -- -~
Comp. No. Rd 3 Rd ~ Q P Q ' q . L
. , .. ~. _ ,. _ ........... ~

H D--1 0 --CQ --C~ r 1 O 1 ~ ~

Hl:)--1 1 --ONn --ON~ O 1 O 1 --CH2CH~--. _ ~_ ... _ llD--1 2 ON~ --ONa _ O _ O --CH2CH2--~ .. __ _ _ HD--1 3 ~OCH~ --OCH~ S 1 S 1 --CH2CH2--_ _ H __ _ _ HD--1 4 --ONn --ONa --N--1 --N--1 --CH2C~z--.: . _ _ _ HD--1 5 --ONa --ON~ H 1 O 1 --CH2CH2--To add the hardening agent represented by General Formula (HDA~ or (HDB) to silver halicle emul~ion layer3 ~nd other con~tituent layer!3, it may be di~3~01ved in water or a wat~r-ml~alble solvent ~or example, methanol, ethanol, etc::. ), and then the ~olution may be added to ~oating 301ution ~or the above aonstitl~ent layer~. The addi tlon may be carried out aocordlng to any of tne batch .

, .

1 32903q ~ystem and the in-llne ~ystem. There i~ no particular limitation ln the time of the additio~, but it may be preferably added immediately before coating.
The3e hardening agents may be added in an amount of 0.5 to 100 mg, preferably 2.0 to 50 ~g, ba~ed on 1 g of gelatin to be coated.
An image-~tahilixing agent to prevent the deterioration of a: dye image can be used in the light-~ensiti~e silver h~lide photographic material o~ the present invention.
Hydrophilic colloid layers such a~ protective layer~
and intermediate layer~ o~ the light-~en~itivs material o~
the present invention may contain an ultraviolet ab~orbent.
The ultravlolet ab~orbent may pre~erably include benzotriazole compounds ~ubqtituted wlth a~ aryl group (~or example, those di~closed in Japanese Patent , Publications No. 10466/1961, No. 1687/1966, No.
~ 26147/1967, No. 29620fl969 and No. 41572/1973, Japanese - Patent O.P.I. Publications No. 95233/19~9 and No.
142975/1982, U.S. Patents No. 3,253,921, No. 3,533,~94, No. 3,754,919, ~o. 3,794,493, No. 4,009,033, No. 4,220,~11 and No. 4,323,fi33, and Research Di~closure No. 22519).
The light-sensitive ~ilver halide photographic aterl:~l of this Invention can be exposed by u~e of electromagnetic wave having the spectral region to which the emul~ion layers constituting the liyht-sen~itive material of the present invention have the sensitivity.
As a li~ht source, there can be used any known light source~ including na-tural light (sunliyht), a tung~ten lamp, a fluore~sent lamp, a mexcury lamp, a xenon arc lamp, a carbon arc lamp, a xenon fla3h lamp, a cathode ray tube flying spot,'every kind of la~er beams, light from a light-emitting diode, light emitted from a fluorescent ~ub~tance energized by electron rays, X-rays, gamma-ray~, alpha-ray~, etc.
A~ for the exposure time, it i~ possible to make expo ure, not to speak of expo~ure of 1 millisecond to 1 ~econd usually used in oamera~, o~ not more than 1 microsecond, for example, 100 micro~econd~ to 1 microsecond by use of a cathode raly tube or a xenon arc lamp, and it i~ also possible to ~a~e exposure longer than 1 second. Such expo~ure may be carried out continuou~ly or may be carrled out intermittently.
The color developing agent used in the color developing ~olutlon in the pre~ent invention include~
known ones widely used in the various color photographic proce~es. The~e developing agentQ include aminophenol type and p-phenylened~amine type derivatives. The~e ~"
, cc~pound~, whlch are more stable than iD a ~ree state, are ) 1 3~9039 used generally in the ~orm of a ~alt, ~or example, ln the form of a hydrochloride or a sulfate. Also, th~se compounds are u~ed generally in concentration of about 0.1 to 30 g per 1 liter o~ a color developing solutlon, pre~erably in concentratlon o~ abou~ 1 ~o 15 g per 1 liter o~ a color develo~ing solution.
The aminophenol type developing agent may include, for example, o-aminophenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, etc.
Most u~eful primary aromatic amine type c~alor developing agent include~ N,N'-di~lkyl-p-phenylen~diamine compound, wherein the alkyl group and the phenyl group ~ay be ~ubstituted with any ~ub~tituent. 0~ the3e, exampl--~ of particularly U9e~Ul aompound~ may include N-N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-dimethyl-p-ph~nylenediamine ~Iydrochloride, 2 amino-5-(M-~thyl-N-dodecylamino)-tolu~ne, N-ethyl-N-,~-methane~ulfonamidoethyl-3-~ethyl-4-aminoaniline sulfate, N-ethyl-N-~-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N'-diethylaniline, 4-amino-N-(2-methc.xyethyl)-N-ethyl-3-methylaniline-p-toluene sulfonate, etc.
In addition to the above primary aromatic amine type eolor developing agent, the color developing agent u~ed in . .

1 32qo3s the processing of the light-~ensitive silver halide photographic material according to the present invent~on may also contain known compound~ for developing solution components. For example, there may be optionally contained alkali ag~nts such as qodlum hydroxide, ~odium carbonate and potassiu~ carbonate, alkali ~etal thiocyanate~, benzyl alcohol, water softenlng ag~nt3, thickening agents,; etc.
Thi3 color developing solution may have usually the pH of ~ or ~ore, most u~ually about 10 to 13.
The color development temperature may be usually l~C or more, and generally in ~he range of 20C to 50C.
For th~ rapid proces~ing, the developing may be preferably carried out at 30C or more. The color development time may ~e preferably in the range of 20 ~econds to 60 : second~, more preferably in the range of 30 second~ to ~0 ~econds.
The light-sensitive ~ilver halide photographio , `~ ~aterial according to the pre~ent invention may contain the above color deYelopin~ agent in hydrophilic colloid layers a~ a color developing agent itself or as a ~ precursor thereof, and may be processed by use o~ an '. alkaline activated bath. The precursor of color , ; developing agent is a compound capable of forming a color ; .
` developing agent u~der the alkallne condition, and ~ay :

1 ~29039 include precursors o~ the type of a Schi~f base with an aromatic aldehyde derivatlve, polyvalent metallic ion complex precursors, phthalic acid imide derivative precursors, phosphoric acid amlde derivative precur~ors, su~ar amine reaction product precursors, and urethane type precur30rs. These precursors of the aromatic primary amine color dev01Oping agents are di~clo~ed, for example, in U.S. Patent3 No. 3,342,599, No. 2,50~,114, No.
2,695,234 and No. 3,l19,492, British Patent No. 803,~83, Japanese Pa-tent O.P.I. Publications No. 18562B/1978 and No. 79035/1979, and Research Disclosures No. 15159, No.
12146 and No. 13924.
The~a aromatic primary amine color developin~ agents or the pre~ursors thereof are re~uired to be added ln such an amount that a ~ufficient co~or development can be achieved only with the amount. This amount may considerably ranQe depending on the type of light-~en~itive materials, but, approximately, they may be u~ed in the range of 0.1 mole to 5 mole~l preferably 0.5 mole ~o 3 mole~, per ~ole of silv~r halide. These color i developing ayents or the precursors thereof may be used alone or ln combination. In order to incorporate them into a light-sensitive material, they can be added by dis~olvlng them ln a suitable ~olvent such a~ water, Ltthanol, ethanol and acetone, can be added as an .:

, , , 1 3~903'3 emul~ification disper~ion formed by using a high boil1ng organic ~olvent ~uch a~ dibutyl phthalate, dioctyl phthalate and tricrezyl phosphats, or can be added by impregnating a latex polymer with them a3 disclo~ed in Re earch Disclosur~ No. 14850.
The llght-~ensitlYe silver halide photographic material of the present invention is subjected to bleaching and fixing after color develvpiny. The bleaching may be carried out at the same time with thP
~ixing. As a bleaching agent, there may be used various compounds, among which compounds of polyvalent m~tals ~uch a~ iron (III), aobalt (III) and copper ~ , particularly, complex salts o~ cations of these polyvalent metals with organic aclds, for example, metal complex salts of aminopolycarboxylic acid ~uch a~
ethylenQdiaminetetraacetia aoid, n;1trylotrlaaetic ~cid and N-hydroxyethyl ethylenediaminediacetic acid, malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, ~tc., or ferricyanates, bichromate, etc~ may be uaed alone or in comblnation.
~ 5 a fixlng agent, there may be used a ~oluble complexing ag~nt capablc of ~olubili~ing a silver halide as a cvmplex ~alt. This soluble complexing agent ~ay include, for ~xample, sodium thiosulfate, ammonlum thio~ulfate, potassiu~ thiocyanate, thiourea, thioether, 1 32'~039 0~c .
After the fixing, washing with water is usu~lly carried out. In place of the wa~3hing wlth water, ~tabilizing ~ay be carried out, or both of them may be carried out in combination. A ~tabllizing solution used in the stabilizing ~ay contain pH ~djuster~, chelating agents, mildewproofing agent~, etc. Specific condition~
for the~e are available ky makin~ reference to Japane~e Patent O.P.I. Publication No. 134636/1983, etc.
~ he present inveIItion can achieve excellent light place pre~ervation of the dye image obtained, i8 fea~ible for the rapid proce~ing as the gradation of the ~ame level as in ordinary processing c~n be attained in the rapid processing, and, al90 in re~pect of the variation of developin~ conditions, can be epoah-making as having superior BF contamlnat~on resi~tance and pH variatioll resistanee. Also, it can not be expected from any prior ar~s that the cooperat~ve effect of the gold compound and Co~pound (S) of the present invention can greatly contribute the above effect.

, ~XAMPL~S
~ xamples of the present invention will be described helow in detail, but the embodiment~ of the pre~ent invention are by no means limited to these.

.

.
~: ;
.

~xample 1 Preparation of sllver halide emulsions:
~M-l>
An aqueous solution o~ ~llver nitrate and an aqueou~
~o~ution of ~odium chloride were added and mixed with ~tirring in an aqueous solution of inert gelatin according to a double ~t method. Hera, condltions ware controlled to keep the tempe~ature of 60C and the pH of 3 . O and pA~
of 7.8. Sub~equently, desalting wa~ carried out according to a conventional method to obtain ~M-1. The ~M-1 was a monodisperse emulsion comprising cubic ~ilver chloride grains having an average grain slze of 0.5 ~m.
<~M-2 An aqueous solution o~ ~ilver nitrate and an aqueou~
~olution compri~ing potas~ium bromide and sodium chloride were added a~d mixed Wi th stirring in an aqueous solution of inert gelatin according to a double jet method. H~re, conditions were controlled to keep the temp~rature o~ 60C
a~d the pH of 3.0 and p~g of 7.d followin~ the procedure~
disclo~ed in Japanese PatQnt O.P.I. Publication No.
4543~/1984. Subsequently, desaltillg was carried out accordlng to a conventional method to obtain ~M-2.
The 13M-2 was a monodisparse emul~3ion comprising cubic silver chlorobromide grains çontalning 1.~ mole % of ~ilver bromide a~ the silver h2~1ide composition arld having an average grain size of 0.5 ~m.
<EM-3>
In the same manner a~ for EM-2, prepared was ~M-3 whl~h was a monodisper~e e~ulsion comprislng tetrahedral silver chlorobromide grains containing 90 mole % of 9i lver bromide a-~ th~ silver halide compo~itlon and having an average grain size o~ 0.5 ~m.
Subsequentl~, using ~M-l to ~M-3, chemical ripenln~
was carried out according to the procedures shown below to prepare ~M-4 to ~M-23.
Sodium thlosulfate in an amount of 2 mg per mole of silver halide, and the gold compound and Compound (S) as shown in Table 1 were added at 60C. The gold compound, however, wa~ added 60 minute~ a~te!r the ad~ition of sodium thiosulfate, and Cvmpound (S), 10 minutes a~ter the addition o~ the gold compound. Compound (S) wa~ added in an amount o~ 2 x 10 3 mole per mo].e of silver halide.
Next, using the high boiling organic ~olvent a~
shown in Table 2a, and also using the coupler di~persion prepared accordin~ to the procedures shown below and the above EM-4 to EM-23, respectively, the emulsion wa~ coated on a polyethylene-coated paper to have a coated ~ilver amount of 0.4 gtm~ in terms of metallic silver, a coupler a~ount of 0.9 g/m2 and a gelatin amount of ~.0 g/m2.
Gelatin was further coated thereon as a protective layer .
. .
. .
'~"
'',:

1 ~2~3q in an a~ount o~ 3.0 g/m2.
~Method of di3persing coupler~
In a mixed solvent comprising 10 ml of the high boiling or~anic solvent and ethyl acetate, 40 g of coupler (YC-1) were di3solved, and ~he ~olut~on obtained wa~ added in an aqueous gelatin solution containing ~odium dodecylbenzenesulfonate, followed by dispersion by uae o~
an ultrasonic homogenizer.
YC-l: CQ

,---( CH3 )3 CCOCHCONH~ C s H I, ( t ) ~ NHCO(CH2) 30~3Cs H ~I(t ..
C H 2 ~

On S~mple 1-1 to Sample 1-30 thus obtained, rapid : proces~in~ pcr~ormance test~, B~ contamination resist~nce tests, pH v~riation r sistance test~ and light place pre~ervation test~ were carried out according to the procedures ~hown below.
tRapid proce~ing performance test]
Using a ~ensitometer I~S-7 type; available from ~onishiroku Photo Indu~try Co., LtD.), optical wedge expo~ure wa~ carried out by white light, followed by -~ ~2903q processing of the following proce~ing ~tep (A) and processing step (B).
Here, processing step (A) i~ an ordinary proce~sing, and processing step (B) i~ a rap~d processing.
[Proce-~sing ~tep (A~]
Processin~ timeTemperature Color developing: 3.5 min 33C
Bleach-~ixing: ; 1.5 mln 33 C
Washing: 3 min 33~7C
Dryin0: - ~OC
[Composition of color developing solution (A)]
Pure water ~OO ml Benzyl alrohol 15 ml Diethylene glycol 15 ml Hydroxylamine ~ulfate 2 g N-ethyl-N-~-methane~ulfonam~doethyl-3-methyl-4-a~inoaniline ~ulfate 4.5 Pota~ium carbonate 30 g Pota~ium bromide 0.4 g Pota~ium chloride 0.5 g Pota~ium ~ulfite 2 g Made up to 1 lit by adding pure water (pH = 10.2~
[Composition of bleach-fixing ~olution (A)]
3thylenediaminetetraacetic acid ~erric ammonium 61 g ~thylenedia~inetetraacetic acid dia~monium 3 g 1 32903q Ammonium thio~ulfate 125 g Sodium metabi~ulfite 13 ~
Sodium sulfite 2.~ g : Made up to 1 lit by adding water (pH = 7.2) [Proce~sing ~tep tB)~
Temperature Time -Color developing 34.7 ~ 0.3C 45 ~ec Beach-fixiny ' 34.7 + 0.6~C 45 ~ec Stabllizing 30 to 34C 90 ~ec Dryin~ 60 to 80C 60 ~ec ~olor developing ~olution ~B)]
Pure water ~00 ml ~thylene ~lycol 15 ml N,N-diethylhydroxylamine 10 g Pota~sium chloride 2 g N-ethyl-N-~-methane~ulPonamidoethyl-3-methyl-4-aminoaniline sulfate 6 g Sodiu~ tetrapolypho~phate 2 ~
Pota~sium carbonate 30 g Brightenlng a~ent (a 4,4'-diamino~tylbene-disulfonic acid derivative) 1 g Made up to 1 lit a~ a whole by adding water, and ad~u~ted to pR 10.0~.
.~ ~Bleach-fixin~ ~olution ~B)]
.

.
'''' , . .

thylenediamlnetetraacetic acld f~rric ammonium dlhydrate ~thylenediaminetetraacetic acid 3 g A~monium thiosulfate (a 70 % solution) 100 ml ~m~onium sulfite ~a 40 % 301ution) 27.5 ml Adjusted to p~a 7.1 with use of potassium carbonate Gr glacial acetiG acid, and made up to 1 lit as a whole by addin~ water.
~ Stabilizing ~olution (B)~

5-Chloro-Z-methyl-4-isothiazolin-3-on l l-Hydroxyethylidene-l,l-dipho~phonic acid 2 g Made up to 1 lit by adding water, and ad~usted to pH ~.0 with use of ~ulPuric ~cid or potas~iu~ hydroxide.
On the sampleq obtained, reflectiorl density was :mea~ured with U~2 of a densitometer (PDA-65; available from Konishiroku Photo Industry, Co., Ltd.) to find y in re~pect of processing steps (A) and (B). Result~ are shown in Table 2b. Here, the y repre~ents the inclination of a ~traight line connecting the density 0.5 and 1.5 in the charaeteristic curve. In Table 2b, the smaller the differencR between the value of y 1n processing step ~B) and the value of y in processing step ~A) i~, the better tha rapid processing performance is judged to have been ach.ieved.
~ BF contamination resistance te-qt]

1 ~290~t - 64 ~

Prepared was a color developing solution to which 1.0 ml o~ the above bleach-fixing solution ~B) wa~ added to 1 11t. of the above color developiny solution (B).
U8ing this color developing ~olution, proc~ssing wa~
carriad out accordin~ to the above processirlg 9tep (B), and the density was measured. Re~ult~ are Qhown in Table 2b. In the table, Q y i~3 a value showing the var~ation width observed when processed with the develop$ng solu~ion in which the bleach-fixing solutit~n wa~ mixed, on the ba~i~ o~ the gradation ~) observed when proces~ed with a developin~ ~olution in which no bleach-~ixing ~olutlon was ~ixed. The smaller thi~ value i~, the better the BF
contamination resistance ls.
Here, the ~ representing the gradation ha~ the same meaning as in the ca~e o~ the above rapid proce~sing performance test.
[pH variation resistance test]
With the sa~e compo~itio~ a3 the ab~ve col~r developing solution (B), prepared ~ere color developing 801ution~ adjustsd to pH = 9.8 and 10.6, respectively.
Using these colox developing solutions, processing was carrl~d out according to color developing ~tep (B), and the d~n~ity was measured.
Re~ult~ are shown in Table 2b. In the table,~ y i8 a value sh~wing the varlatlon wldth observed when ' .... .

processed with the developing solution of pH = 10.6, on the basi~ of the gradation (~) observed when proce~ed with the developing ~olution of pH = 9.8. The smaller this value i9, the better the pH variation resistance i~.
; Here, the y representiny the gradation has the same meaning as in the case o~ the above rapid proce~sing performance test.
rLight place preservation te~t]
The value was expressed in terms of the retention of the inltial density Do = 1.0 o~ a color image when irradiated with sunlight for 20 day~ using an under glass ~: weath2ring ~tand.
Retention = (D/Do) x 100 (D - den~lty after co~or fading) Result~ are shown in Table ~b.

~., .:

~.~

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-1 32903~

Table 1 Che~l- Chemi-cally cally silver ~en~i un~ensi- chlo- Com-tized tized ride ~old compound pound mul~ion emul~ion content (mol~molAgX) (S) ~M-fl EM-l , 100 - SC-l EM-5 ~M-l 100 - S-6 ~M-6 ~M~l 100 - S-49 ~M-7 ~M-l 100 - S 60 ~M-8 ~M-l 100 Chloroaurate (5~10 5) SC-l ~M-9 EM-l 100 Ghloroaurate (5xlO 5) SC-6 ~M-10 EM-l 100 Chloroaurate (5xlO 5) S-49 ~M-Il ~M-l 100 Chloroaurat~ (5~10 6) S-60 ~M-12 ~M-2 ga.6 - SC-l ~M-13 ~M-2 98.5 - C-6 ~M-14 EM-2 98.5 - C-49 eM-15 eM-~ 98.5 - c-6a ~M-16 EM-2 98.5 Chloroaurate (5xlO 5~ SC-l ~M~17 EM-2 98.5 Chloroaurate (5xlO ~ S-6 BM-18 ~M-2 98.5 Chloroaurate (5xlO 5) S-49 EM-l9 EM-2 98.5 Chloroaurate (5xlO 5) 5-60 1 32~039 ; Tabl~ 1 (Cont'd) Chemi- Cheml-cally cally silver ~ensi- u~sen~i- chlo- Com-tized tlzed rlde Gold compound pound e~ul~ion emul~ion content ~mol/molA~X) ~5) ~M-20 ~M-3 , 10 Chloroaurate ~5xlO 5~ SC-1 ~; ~M-21 ~M-3 10 Chloroaurate (5xlO 5) S-6 EM-22 ~M-3 10 Chloroaurate ~5x10 5) S-49 ~M-23 ~M-3 10 Chloroaurate ~5xlO 5) S-60 . ~ _ , .
Co~parative compound (SC-1):
., .
. . .
..i ~!~ O H

H 3 C~lN N ~3>
~., .. i ,j ,~i ,~, .~
., .

;, .

. .
~., .
,.......................................................... .

1 ~29039 Table 2a .. . .
Silv~r Silver Hi~h boilin~
hal1de chlc~- Chloro- o~anic ~olvent emul- r~de aurat~ Com- Diel~c-Sample ~lon content ~olJ pound Comp. trio (mole 9~ molAgX) ~S) Ns~. aon~tarlt 1-1 ` (X~ BM-4 100 - SC-1 ~-6 4 . 6 1--2 (X) ~3~i-4 100 --SC--1 }1--12 5. 1 1--3 (~) E3M--4 100 --SC--1 DBP 6 . 4 1-4 (X) EM-4 100 - SC-i'I'CP 6 . 9 lU0 - S-~ ~-6 ~.6 1-6 (X) E~M~6 100 - S-6 ~1-12 6.1 1--7 (X) 8M-fi 100 --S-49 ~-6 4 . 6 l-û (X) 15M-6 100 -- 5-49H--1 2 5 .1 1--9 (X) BM Y lO0 --S~60 H--6 4 . 6 1--lO(X) l~tg-7 lG0 _ S--60 ~1--12 5.1 : ~ I
X3 ~M-~ 109 6 x 10 5 SC-1 H-6 4 . 6 `~ ~1--12(X) 13M-~ 100 6 x 10 6 SC--1 H--12 5.1 .
1-13 (Y) I~M-9 100 6 x 10 5 S-6 H--6 4 . 6 ; ~ . .
1-14(Y) ~ g 100 6 x 10 ~ S-6 ~{-12 6. 1 1-IG~Y) EM-10 100 5 x 10 5 5_49H-6 4.6 1--16(Y) EM-10 100 5 x 10 5 S--49 ~I--12 5.1 ~:~ 1-17(Y) EM-11 100 5 x 10 5 S-60 H-6 4.6 a (Y) EM 11 100 5 x 10 6 S-60 H-12 5 .1 .,~ ' .

~ ' , .

, .

~ 329039 Table 2a (Co~t'd) .... .. .
Silver Silv~r Hi~h boillng hallde chlo- Chloro- or~anic sol~ant e~ul ride aurate Com- Dielec-Sa~ple 910~ content (mole/ pound Comp. tric (mol~ %) mole A~ L__ No, oon~tant 1-19(X) ~M-1298.5 _ SC-l H-6 4.6 1~20(X) ~M~1398.5 _ S-6 H-6 4.6 1-21tX) EM 1498.5 _ S-4g H-6 4.6 1-22(X) ~-15 98.5 ~ S-60 ~-6 4.6 1-23~X) ~M 1698.5 5xlO 5 SC-l H-6 4.6 1-24~Y) ~M-1798.5 5xlO 5 S-6 H-6 4.6 1-25(Y) ~M~1898.5 5xlO 5 S-49 H-6 4.6 1-26~) EM-l998.5 5xlO 5 S-60 H-6 4.6 1-27~X) EM-20 10 5xlO 5 SC-l H-6 4.6 1-28(X) EM-21 10 5xlO 5 S-60 H-6 4.6 1-29(X~ EM-22 lO 5xlO 5 S-49 H-6 4.6 1~30(~ ~M-23 10 5xlO 5 s-60 H-6 4.6 .~ .
X: Co~parative example * DBP: Dibutylphthalate ~: Present inventlon ** ~CP: Tricresyl pho~phete i .

. .

,, .

~ 70 - 1 32q 0 39 Table 2b Rapid proce~sing BF inclu- pH var- Light f~asibillty sion re- iation place Sam- Process- Process~ tance r~lstance preser-ple ing step ing ~tep __~9y~ Y1___ vation (A) (B) 1-1 3.20 2.53 0.95 0.61 ~6 1-2 3.~5;2.62 0.98 0.58 ~7 1-3 3.1~ 3.15 0.~5 0.~1 ~3 1-4 3.22 3.20 ~.72 0.4~ 51 1-5 3.16 2.61 0.~0 0.49 78 6 3.18 2.65 0.69 0.55 76 :
. 1-~ 3.23 2.85 0.~9 0.41 76 ; 1-8 3.20 2.~7 0.~2 0.39 75 1-9 3.19 2.~0 0.67 0.3~ 77 1-10 ~.20 ~.16 0.63 0.2~ 77 :
11 3.1~ 2.50 0.85 0.48 ~8 12 3.08 2.55 0.~3 0.62 76 13 3.20 3.18 0.23 0.25 ~7 ,:
3.23 3.2~ ~.2~ 0.22 ~
, 1-15 3.18 3.09 0.37 0.19 ~5 3.15 3.1~ 0.33 0.1~ 76 1-17 3.1~ 3.15 0.23 0.18 78 1-13 3.20 3.16 0.25 0.16 76 -, ~, .~ .

1 32qO3q Table 2b (Cont'd) ; Rapid proces~ing BF inclu- pH var- Light fea~ibility sion re- iation place Sa~- Process- Proces~- sistance resistance pre~er-~le_ ing s~ep ing ~tep (~) 5~y) vation (A) (B) 1-19 3.~3 2.63 0.92 0.~5 77 1-~0 3.21 ;2.70 0.68 0.53 7~
1-21 3.18 2.75 0.~7 0.38 78 1~2Z3.21 2~77 0.72 0.35 75 1-23 3.20 2.65 0.85 0.45 77 1-2~ 3.2~ 3.20 0.15 0.22 76 1-25 3.23 3.1~ 0.25 0.13 76 1-26 3.20 3.~1 0.22 0.12 ~9 1-27 3.20 2.13 1.10 0.73 78 1-2~ 3.23 1.~5 0.85 O.S5 7 1-2g 3.23 1.9~ 0.~5 0.48 ~
1-30 3.24 1.91 0.93 0.52 ~9 *: For 20 day~ under ~unlight .

1 ~29039 It i~ seen rom Table~ 2a and 2b that;
1) Samples 1-3 and 1-4 employing high boillng ~olvent~
having the dielectric con~tant o~ more than 6 can achieve only very poor light place preservation, 2) Sample~ 1-2~ to 1-30 e~ploying emuls~on~ containing ~ilver halide grains having low silver chloride content aan not achieve sufficient gr~.datlon undar the rapid processing c~ndition as used in the present ~xample, and oan not ~how good processing stability; and 3) the ~amples showing ~uperior rapid proces~ing performance while achieving excellent image preservation, and al~o ~howing good processirlg stability for BF
contamination resi~tance and pH variation resistance are obtained only by the combination of all of the high boiling organic solvent, silver hialide emul~ion having high ~ilver chloride content and ]prepared by usinçl the gold compound, and Co~pound (s) according to the pre~ent invent i on .

Making review in greater detail, it is ~een that Sampl~s 1-24 to 1~26 cont ining a trace amount of ~ilver bromide show particularly improved rapid proce3sing per~ormance and proc~ing stability.
Accordingly, it i~ understood that the effect of the present invention i9 unique effect that can be obtained only by the consti-tution of the present invention, whereby - !

1 329~39 both the image preservation and rapld processing feasib~lity ~including processing ~tabllity) can be achi eved.
~xamp 1 e 2 ~Preparation o~ EM-24 to EM-57~
Chemical ripening wa~ carried out on EM-1 prepared xample 1 in thç ~ame manner as in ~xample 1, provided that chloroaurate,. Compound (S3 and co~parative compound 5C-2 were used as shown in Table 3a.
[Preparation of cyan coupler dispersion]
A cyan coupler di~persion was prepared in the ~ame manner as in the ca~e of the yellow coupler disper~ion in ~xample 1, exsept that CC-1 was u3ed a~ a cy~n dye-forming coupler and H-2 was used as the high boiling organic solvent.
C~

OH Csl~r~l(t) CQ~NHCOCHO~=~CsHIl(t) C H ~ C 2 H s C~ -Subsequently, u~ing the above ~M-24 to ~M-5Y and cyan coupler dispersion, Samples 2-1 to 2-34 were produced in the ~ame procedure~ as in ~xample 1, provided that the .

.

. .

-1 32903~

coupler coating amount was altered to 4.8 g~m2.
The rapid processing performance and processing stabllity (BF contamlnation resl3tance and pH varlation resistance) were tested on 5ample~ 2-1 to 2-34 thus obtained in the same manner as in Example 1. Re~ult~ are shown in Table 3b , ~ :

~. ~
,:
;':

`~ ~
'.

,, , , .
.

:. .

: _ 75 _ 1 3~ 9 0 3 .
Table 3a .
Silver Silver High boiling halide chlo- Chloro-~ emul- rld~ aurate Co~~ Di~lec-i~ Sample sion content (mol/ pound Comp. tric ~mole %1 olAgX) ~S) No. constant 2 - 1 (X)~M-24 98.~ - SC-2 .H-2 5.3 2-2 ~X) RM-25 i93-5 3 X 10 5 5C-2 H-2 5.3 2-3 (X) ~M-26 98.5 - S-l H-2 5.3 ~ 2-4 (Y) RM-27 98.5 3 x 10 5 S-l H-2 5.3 .~ 2-6 (Y) ~M-28 9B.5 3 x 10 5 S-2 H-2 5.3 2-6 ~Y) ~M-29 9~.5 3 X 10 5 S-9 H-2 5.3 ;~ 2-7 (Y) ~M-30 98.5 3 X 10 5 S-10 H-2 5.3 2-B ~Y) ~M-31 9B.5 3 x 10 ~ S~12 H-2 5.3 ; 2 9 (Y) ~M-32 98.5 3 X 1~ 5 S-13 H-2 5.3 2-lO(Y) EM-33 98.5 3 X 10 6 S-15 H-2 5.3 :~ 2-ll(Y) ~M-34 98.5 3 X 10 5 S-19 ~-2 5.3 . Z-lZ(Y~ ~M-35 9B-5 3 x 10 5 5-21 H-2 5.3 ~ 2-13~Y~ ~M-36 98.6 3 X 10 5 S-29 H-2 5.3 '`~ 2-14(Y~ RM-37 98.5 3 x 10 5 S-33 H-2 6.3 r~ 2 - 15 (Y)EM-3~ 98.5 -5 H-2 ~.3 , 2-16~Y) ~M-39 98.5 3 x 10 5 S-41 H-2 5.3 : 2-17(Y) ~M-40 98.5 3 X 10 6 S-42 H-2 5.3 ; Z-18~Y) BM-41 98.5 3 x 10 5 S-43 H-2 5.3 2-l9(Y) ~M-42 98.5 3 x 10 5 5-47 H-2 5.3 2-20(Y) ~M-43 98.5 3 x 10 5 S-4~ H 2 5.3 i 2-21(Y) ~M-44 9B.5 3 X 10 5 S-49 H-2 5.3 ~i~ 2-22(Y) RM-45 98.5 3 X 10 5 S-51 H-2 6.3 . 2-23(Y) ~M-4~ 98.5 3 x 10 5 S-52 H-Z 5.3 .. 2-24(Y) ~M 47 9~.6 3 x 10 5 S-54 H-2 5.3 r ~, : ' :`~
.

' , Table 3a (Cont'd) Silver Silver H~gh bolling halide chlo- Chloro- 9:_~h~ Olv~n~
emul- ride aurate Com- Dielea-Sample ~ion content ~mole/ pound Comp. tric ~mole ~) mole Ag) (S) No. constant 2-25(Y) EM-4898.5 3 ~ 10 5 5-55 H-2 5.3 2-26(Y) ~M-49;g8.5 3 x 10 6 S-56 H-2 5.3 2-27~Y~ EM-5098.5 3 x 10 5 S-58 H-2 5.3 2 28(Y) ~M - 51 98 . 5 3 x 10 5 S-59 H-2 5.3 2-29(Y) EM-5298.5 3 x 10 5 S-61 H-2 5.3 2-30(Y) ~M-5393 . 5 3 x 10 5 S-64 H-2 5.3 2-31(Y) ~M-5498,5 3 x 10 6 S-65 H-2 5.3 2-32(Y~ P.M-5598.5 3 x 10 5 S-67 H-2 5.3 2-33(Y) ~M-5698.5 3 x 10 5 S-68 H-2 5.3 2-34(Y) EM-5798.5 3 x 10 5 5-1/ H-2 5.3 ..
` Y: Comparatlve example X: Pre~ent inve~tion SC-2:
<~ N ~,N Z o : ~ ~ H
*: S-l: 1 x 10 3 mole/mole AgX
5-49: 1 x 10 3 mole/~ole AgX

,~ .

, 1 3~9039 It is seen from Table~ 3a and 3b that Samples 2-4 to 2~34 ln which the gold compound and compound (S~ were used in the emulsion o~ the present invention having high ~ilver chloride content are all excellent in the rapid processing performance and processing stability ~or BF
contamination re~istance and pH variation re~i~tance.
Making review in detail on Compound (S), it is ~een that the compound incl~ded in the co~pound of General Formula (SA1, wherei~ Z repre~ent~ -N-~A1 or an oxygen atom, and the co~pound represented by General Formula (SB3 show particularly good BF contamination resi~tance, and the compound of General Formula (5B) ~how~ particularly good pH variation resi~tance. As for the light place preservation, although not contained in the data, there can ~e achieved excellent preservation ~ince the hlgh boiling organic solvent according to thQ pre~ent invention i~ used.
' !:~
On EM-2 prepared in ~xample 1, chemical ripening ~including spectral ~ensitiz~tion) was carried out at 60C
by u9ing 1 . ~ m~ o~ sodium thiosulfate per mole of silver halide, ~ensitizing dye~, chloroaurate, and Compound (S~
or comparative compound ~SC-1) as ~hown in Table 4 to prepare EM-58 to EM-69.
Next, couplers YC-1, MC-I ard CC-I were respectlvely ;

I -32~ 03C1 dis~olved in EI-6 or DBP to have the content a~ ~hown in I'able 5, to prepare 6 kinds of coupler dispersion~.

Table 4 Sen~itizlng dye Chloroaurate Compound tS) E=u1slon mgJmolA~7X (mol/~olAgX) ImolJmolAgX) 13M--~8 D--1; 120 -- SC--1 (2 x10 ~M-59 D-1 120 - S-6 (2 sc 103) RM-60 U-1 120 1 x 105 S-6 ( 2 x 103) EM-61 D-l 120 1 x 105 S-6 (5 x 104) ~M-62 n-2 150 - SC-2 (2 x 103) RM-63 D-2 150 - S-6 ( 2 x 103) RM-64 D-2 150 6 x 10 S-6 (2 x 103) RM-65 D-2 150 6 x 105 S-G t5 x 104) RM--66 D--340 -- SC--1 ( 2 x 10 3) E;M-6~ 3:)-340 - S-6 5 2 x 103) ESM-68 D-3 40 3 x 10 S-6 5 2 x 10 ~M-69 D-3 40 - S-6 (5 x 104) , .

';, ~, .

;
,, -D-l:

tE~ ~C H=~

C 3 1~ b S 0 3 l~la C3H6S O ~

D- 2 :

~CH -CH=<

~0~ ~(4 D-3 :
CH--CH =CH- C H=CH~

C~, H~ S~;~' , C~
~: MC-l:
`~ . CQ
N H~
N~
G ~,C ~ NHCOC,~2s(h) `, ~
CQ

.

1 ')2qo39 Next, the above emulslons and coupler di~persions were used in the combination as shown in Table 6a to produce Samples 3-1 to 3-9 having the con~titution a~
Rhown in Tabl0 5.
A~ to the hardening agent, bl~(vinylsulfonylmethyl) ether wa~ used in respect o~ Sample~ 3-1 and 3-4, and exemplary hardening agent HD-2, in respect of 5amples 3-6 to 3-9. In re~pect of Sample 3-9, it was added to the second layer and the fourth layer in the amount that may give a coating amount o~ 1.5 x 10-~ mole/m2, respectively.

Table 5 .
Laver Con~t:itution ~ ----- 2 5~venth lay~r Gelatin ~1.0 g/m ) ~ _________________________________________________________ Sixth layer Ultravlolet ab~orbent (UV-l, 0.3 g/m2 Ge lat i n (0.7 g/m ) .
__________________________________ __________ ___________ Fifth layer Red-sen~ltive silver chlorobromide emul~ion (coated silver amount O . 25 g/m ) Cyan coupler (CC-l, 0.3 g/m2) High boiling organic solvent (0.2 g/m~) Gelatin (1.0 g/m2) f ----_--__________ f ;`
~`

''' 1 3~9~)39 Table S (Cont'd~

Fourth layer Ultraviolet ab~orbent (UV-l, 0.~ g/m2) Gelatin (1.3 g/m ) __________________________ _____________________ _ ______ Third layer Green-~ensitive silver chlorobromide emul~ion (coated ~ilver amount, 0.13 ;,g/m2 ) Mage~ta coupler ~MC-l, 0.4 g~m ) High boiling organic ~olvent (0.2 g/m2) Gelatin (1.5 g/m2) -- ___________________ Second layer: Gelatin (1.0 g/m2) ____________~________________~ __ _______________________ Fir~t layer: Blue-sensitive silver chlorobromide emul~iQn (coated ~ilver amount, 0.40 ~2) Yellow coupler (YC-l, 0.9 g/m2) High boiling organic ~olvent (0.03 g/m2) . Gelatin (2.0 g/m ~ .
______________________,__________________________________ ~ Support: Polyethylene ~oated pap~r 1 32sn3q UV~

O H
3~ C s H " ( t ) CsH f I (L) On Sample~ 3-1 to 3-~ thu~ obtained, test~ for rapid proce~sing performance, proaes~ing ~tability and light place preservation were carried out in the ~ame manner as ln ~xample :1. Re~ult~ are shown in Tables 6b and 6c, wherein the rapid processing performance was ~hown a~
dif~erence ~y) ln the y between the pro~es~ing step~ (A) and (B). The larger the~ y i~, the poorer the rapld proce~sing per~ormance is judged to be.

,. .
,`'~

.:

~, , ;.
,~

1 32qo3s Table 6a . ~
Sllv~r halide High boling organic emulslon___ _ solvent __ _ Hard-Sampl~ l~t 3rd 5th Yellow Magenta Cyan ening layer l~yer ~ cou~ler agent 3-1(X) ~M - sa ~M 62 ~M-66 DBP DBP DBP CHD
,~ , ' *
3-2(X~ RM-5B ~M-62 ~M-66 H-6 H-6 H-6 CHD

3-3~X) RM-59 ~M-63 EM 67 H-6 H-6 H-6 CHD

3-4tY) ~M-60 ~M-64 EM-68 H-6 H-6 H-6 CHD
,:~
3-5(X) ~M-58 EM-62 EM-69 DBP DBP VBP HD-2 3-6~X) EM-58 ~M-62 EM-69 H-6 H-6 H-6 HV-2 ~ ~-7~X) ~M-69 RM-63 ~M-67 DBP DBP DBP HD-2 : 3-~(Y) EM-60 ~M-64 ~M-6A H-6 H-6 H-6 HD-2 ~ ~ 3-9~Y) ~M-61 EM-65 ~M-69 H-6 H-6 H-6 HD-2 . . .
X: Comparative exampl~
Y: Present ~nvention *CHD: Comparative hardening agent:
bis~vJnylsulfonyl) ether , .

Table 6b ... _ _.
Rapid processing BF contamination performance ~y) _ re i~tance (~Y?
Sample M C Y M

3-1 0.10 0.08 0.09 0.2~ 0.33 0.31 3-2 0.~5 0.38 0.4~ 0.75 0.9~ 0.92 . , .
3-3 0.56 0.32 0.39 0.62 0.80 0.78 3-4 0.18 0.07 0.12 0.22 0.2B 0.25 ':
S~5 0.21 ~.10 0.1~ 0.61 0.90 0.~8 .
3-6 ~.~3 0.35 0.45 0.~5 0.30 0.32 3-~ 0.55 0.30 0.33 0.53 0.~7 0.~5 "
3-8 0.05 0.03 0.05 0.14 0.12 0.14 3-9 0.0~ 0.04 0.06 0.15 0.13 0.16 ~: - . . . _.__ .
,~ ~
~, :

' ~

.

~. , ,' ' .
,'.~' ' .

Table 6c ~ _ ,_ .. . .. _ pH variation Light pla~e pre~erva-resi~tance ~y)_ tion (Reten~ion (% ) ) Sample Y M C Y M C
. . .

3 1 O.Zl 0.23 0.27 ~3 65 ~1 3-2 0 . 35 0 . 38 0 . 42 78 ~2 77 3-3 0 . 32 0 . 31 0 . 33 ~ 84 75 3-4 0. 20 0. 19 0 . 25 78 ~3 7 3-~ 0 . 19 0 . 23 0 . 22 55 ~3 61 3-6 a. 32 0.36 0.37 75 82 7B

3-7 0 . 2~ 0 . 28 0 ~ 32 78 83 ~7 ~: 3-8 0. 12 0. 10 0. 11 ~9 83 78 --9 0 .12 0 . 09 a . l2 7B 84 ~8 .~ ~

~: :

~' ' ' ' .: ' `: ' .
. ' .

;`, ' :
r' ' , 1 32qO39 It is seen from Table 6 that, even in the multi-layer sy~tem as $n the pre~ent Example, a light-s~n~itive material excellent in the rapid proce~sing perfor~ance, proce~ion stability for BF contamination resistanc~ and pH variation re~i~tancel and dye image pre~ervation can be obtained only in the constitution of the present invention in the same manner a3 ln ~xamples 1 and 2, It is also ~een that the tridhlorotriazine type co~pound represented by General For~ula ~HDA) or (HDB) i~ preferably used as a hardening agent, and that Co~pound (S) can exhibit si~ilar effect even when added to a photographic layer contiguou~
to an emul~ion layer.

(to be continued) Example-4 [Preparation of EM-701 Aqueous silver nitrate solution and aqueous halide solution containing both potassium bromide and sodium chloride were stirred in an inert gelatin aqueous solution by means of a double-jet method and thereby were mixed. In this case, the conditions;.for aforesaid mixing were under control according to the method described in Japanese Patent Publi~ation Open to Public Inspection No. 45437/1984 to keep the temperature o~ 50 C, pH of 5.5 and pAg of 7.5. Then the mixture was desalted through an ordinary method and washed, thus EM-70 was obtained.
This EM-70 is a monodispersed emulsion having an averag~ grain size of 0.4 ~m and a silver halide composition consisting of cubic silver chlorobro:mide grains containing 0.3 mol % of silver bromideO
CPreparation of EM-71 through EM-781 EM-70 was subjected to the chemical ripening at a ~emperature of 60 ~C by the use of sodium thiosulfate .(1 mg per 1 mol of silver halide), sensitizing dye ~D-3] (50 mg per l mol of silver halide) and chloroauric acid (3 x 10 5 mol per 1 mol oE silver halide~ as shown in Table - 7 and upon completion of the chemical ripening, S-57 (1 x 10Y-3H mol per 1 mol o~ silver halide) was added to prepare red-sensitive emulsions EM-71 ~hrough EM-77. EM-78 was further prepared by ., . . .

- 88 - 132~03~

changing the time for adding chloroauric acid by 30 minutes compared with that for S-57.

Table-7 Emulsion Time of addinq chloroauric acid EM-71 not added EM-72 30 min. before sodium thiosulfate EM-73 3 min. before sodium thiosul~ate EM-74 concurrently with sodium thiosulfate EM-75 1 min after sodium thiosulfate EM-76 30 min after sodium thiosulfate EM-77 90 min after sodium thiosulfate EM-78 30 min later compared with S-57 , Each of aforesaid EM-71 through EM-78 was used as a r~d-sensitive emulsion and Samples 4 -1 through 4 - 8 having an arrangement in Table - 8 were prepared. As a red-sensitive emulsion, Sample 4 - 9 was prepared by ~he use of EM-71 in the same way as that in Sample 4 - 1 except that chloroauric acid was added during the preparation of emulsion coating for the 5th layer so that the coating density of 5.6 x lO 8 mol/m2 was obtained.
Samples 4 - 1 through 4 - 9 thus obtained were subjected to the evaluation for the rapid processing suitability and ~he stability for processing in the same method as that in ., .
,. . .

1 32903q - s9 -Example-3. In the present Example, however, the density for : red light only was measured for the density measurement because the observation was focused on the behavior of the emulsion layer of the 5th layer. The results are shown on Table-9.

., .
.: :

,, .

, . . .

1 32903'~

Table-8 ~y~ Composition : 7th layer Gelatin (1.0 g/m2), HD-2 (0.1 g/m2) 6th layer UV absorbing agent (UV 1 0.3 g/m2) Gelatin (0.7 g/m23 5th layer Red-sensitive silver chlorobromide emulsion ; (silv'er coating density 0.20 g/m2) Cyan coupler (C-2 o.3 g/m2) High-boiling organic solvent H 12 (0.2 g/m2) Gela~in (1.0 g/m2) 4th layer UV absorbing agent tUV-1 0.7 g/ma) Gelatin (1.3 g/ma3 3rd layer Green-sensi~ive silver chlorobromide emulsion EM-65 (silver coating denæity 0.30 g/m2) Magenta coupler tMC-1 0~4 g~m2) :~ High-boiling organic solvent H-12 (0.2 s/m2) ,. Gelatin tl.~ gJm2) 2nd layer Gelatin (1.0 g/m2) 1st layer Blue-sensitive silver chlorobromide emulsion EM-61 ~silver coating density 0.35 g/m~) Yellow coupler (YC-l 0.9 g/m23 High-boiling organic solvent H-12 tO.03 g/m2) Gelatin (2.0 g/m2) i ~; Support Polyethylene resin-coa~ed paper F F

(t~HllCS~OCHCONH
CH (CH3 ) 2 '~

': .
,; ' .
`:

.

,~ ' ' ' ' ' ~" .

~ 32903~

Table 9 Sample Red- When chloroauric Rapid BF pH
sensi- acid is to be processing inclusion variation tive added fe~sibility resistance resistance emul- (~ r) (~r) sion 4-1 EM-71 not added 0.43 0.87 0.41 ~Compa-rative examr ple) 4-2 EM-72 30 min. before 0.15 0.31 0.23 (m is sodium thio-inven- sulfate tion) 4-3 EM-73 5 min. before 0.08 0.21 O.lg ( " ~ sodium thio-sulfate 4-4 EM-74 Concurrently 0.07 o.26 0.1 ( " ) with thio-sul:Eate 4-5 1 min, after O.lo 0.27 0~17 ( '' ) sodium thio-sulfate .~
4-6 30 m m. after 0.07 0.22 Ool9 ( " ~ sodium thio-.` sulfate 4-7 90 min. after 0.09 0.26 0.20 ) sodiwm thio-sulfate 4-8 30 min. later 0.31 0.6s 0.33 compared to S-57 ., .
4-9 During prepara- 0.3s 0.69 0.34 ( '' ) tion of emulsion coating solution ., ~ ~2~039 Table-9 shows that gold compounds related to the present invention offer their effects when they are added at various timing as shown in Table-9 and further shows that the greater effects are obtained when they are added during the period from the start to the end of chemical ripening.

Claims (14)

1. A light-sensitive silver halide photographic material comprising a support and, provided thereon, at least one light-sensitive silver halide emulsion layer which contains silver halide grains having silver chloride content of 90 mole % or more and containing a gold compounds, a dye-forming coupler dispersed therein by the use of a high boiling-point organic solvent having a dielectric constant of not more than 6.0 and a compound represented by General Formula [S];

[S]
wherein Q is a group of atoms necessary to complete a 5- or 6-membered heterocyclic ring or a 5- or 6-membered ring fused with a benzene ring and M is a hydrogen atom, an alkali metal or an ammonium group.

2. The light-sensitive silver halide photographic material of claim 1, wherein said dye forming coupler is an acyl acetoanilide yellow dye-forming coupler.

3. The light-sensitive silver halide photographic material of claim 1, wherein said dye forming coupler is a 5-pyrazolone-type or a pyrazoloazole-type magenta dye-forming coupler.

4. The light-sensitive silver halide photographic material of claim 1, wherein said dye forming coupler is a phenole-type or a naphthole type cyan dye-forming coupler.

5. The light-sensitive silver halide photographic material of claim 1, wherein said high boiling-point organic solvent has a vapor pressure of 0.5 mmHg or less at 100°C.

6. The light-sensitive silver halide photographic material of claim 1, wherein said high boiling-point organic solvent has a dielectric constant of 1.9 to 6Ø

7. The light-sensitive silver halide photographic material of claim 1, wherein said high-boiling point organic solvent is selected from the group consisting of a phthalic acid ester, a phosphoric acid ester, an organic amine, a ketone, and a hydrocarbon compound.

8. The light-sensitive silver halide photographic material of claim 1, wherein said high-boiling point organic solvent is selected from the group consisting of a phthalic acid ester represented by general formula [HA];
[HA]
wherein RH1, and RH2 are independently selected from the group consisting of an alkyl group, an alkenyl group and an aryl group provided that the total number of carbon atoms contained in RH1 and RH2 is 9 to 32; and a phosphoric acid ester represented by general formula [HB]
[HB]

wherein RH3, RH4 and RH5 are independently selected from the group consisting of an alkyl group an alkenyl group and an aryl group provided that the total number of carbon atoms contained in RH3, RH4 and RH5 is 24 to 54.

9, The light-sensitive silver halide photographic material of claim 8, wherein said total number of carbon atoms contained in RH1 and RH2 is 16 to 24.

10. The light-sensitive silver halide photographic material of claim 1, wherein said silver halide is a silver chlorobromide containing silver bromide at a proportion of not more than 10 mole %.

11. The light-sensitive silver halide photographic material of claim 1, wherein said silver halide contains silver bromide at a proportion of 0.05 to 5 mole %.

12. The light-sensitive silver halide photographic material of claim 1, wherein said 5- or 6-membered heterocyclic ring or said 5- or 6-membered ring fused with a benzene ring is one selected from the group consisting of an imidazole ring, a tetrazole ring, a thiazole ring an oxazole ring, a selenezole ring, a benzimidazole ring, a naphthoimidazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a benzoxazole ring, a pyridine and a pyrimidine.

13. The light-sensitive silver halide photographic material of claim 1, wherein said gold compound is selected from the group consisting of auric chloride, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, tetracyanoauric azide, ammonium aurothiocyanate, pyridyltrichlorogold, gold sulfide, and gold selenide.

14. The light-sensitive silver halide photographic material of claim 1, wherein said compound represented by general formula [S] is selected from a compound represented by general formulae [SA], [SB] and [SD];
[SA]

wherein Z is selected from a group, oxygen atom or sulfur atom, RA is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, a - SRA1 group, a group, - NHCORA4 group, a - NHSO2R5 group and a heterocyclic ring, RA1 is selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a - CORA4 group and a -SO2RA5 group, RA2 and RA3 are independently selected from a group consisting of a hydrogen atom, an alkyl group and an aryl group, RA4 and RA5 are independently selected from the group consisting of an alkyl group and an aryl group and M
is a hydrogen atom, an alkali metal or an ammonium group;.
[SB]

wherein RA is selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, a - SRA1 group, a group, - NHCORA4 group, a - NHSO2RA5 group and a heterocyclic ring, RA1 is selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a - CORA4 group and a -SO2RA5 group, RA2 and RA3 are independently selected from a group consisting of a hydrogen atom, an alkyl group and an aryl group, RA4 and RA5 are independently selected from the group consisting of an alkyl group and an aryl group and M
is a hydrogen atom, an alkali metal or an ammonium group, RB1 is selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a - CORA4 group and a - SO2RA5 group, RB2 is selected from a group consisting of a hydrogen atom, an alkyl group and an aryl group;
and [SD]
wherein Ar is selected from the group consisting of a group , a group and a group, in which RD is selected from the grroup consisting of an alkyl group, an alkoxy group, a carboxy group or a salt thereof, a sulfo group or a salt thereof, a hydroxy group, an amino group, an acylamino group, a carbamoyl group and a sulfonamide group, n is an integer of 0, 1 and 2, and M is a hydrogen atom, an alkali metal or an ammonium group.