CA2010252A1 - Silver halide photographic light-sensitive material - Google Patents

Abstract

Abstract A photographic material which comprises a light-sensitive silver halide emulsion layer and a non-light sensitive hydrophilic colloid layer provided outside of the light-sensitive silver halide emulsion layer to the supportis disclosed. Total content of gelatin of the layers at a side of the silver halide emulsion layer is 2.0 to 2.8 g/m2 and the non-light-sensitive hydrophilic colloid layer contains a polymer latex. The material provides a high contrast image and is suitable for the use of lithography.

Description

(~ ~7~ ~

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SILVER ~ALIDE P~OTOGRAP~IC LIGHT-SENSITIVE MATERIAL

FIELD OF TnE INVENTION

The present invention relates to a silver halide photo-graphic light-sensitive material for graphic arts use, and more particularly to a silver halide photographic light-sensi-tive material for graphic arts use which is excellent in the ultra-high-speed processability as well as in the coatability.

BACRGROUND OF T~E INVENTION

In the printing and graphic arts industry, there has been a growing demand for more speedup of processing and more im-proved image quality; for example. there has been desired a graphic arts silver halide photographic light-sensitive mate-rial which can be subjec-ted to a ultra-high-speed processing in a dry-to-dry processing time of only 60 seconds to provide a contrasty image with a gamma value of 6.0 or more in a density of 0.3 to 3Ø
One method for achieving such a ultra-high-speed process-ing as in the 60-second dry-to-dry time is to perform develop-iny and fixing at raised temperatures, but the method is unac-ceptable because of affecting the preservability of processing solutions and increasing the vapor therefrom into the process-ing room. It is therefore desirable to manage to perform such the ultra-high-speed processing at a low temperature (not hicJher than 380C). Also, reducing the amount of silver is ef-fective in a high-speed processing. However, there is a cor-rection work called 'reduction' in a plate-making process, so that it is necessary to provide therefor a high silver-content silver halide photographic light-sensitive material which con-tains not less than 3.5g/m~ of silver and vet adaptable to ultra-high-speed processing. A very useful means for process-ing at a low temperature such the high silver-content silver halide photographic light-sensitive material is -to reduce the amount of the binder, particularly gelatin, contained therein.
However, reducing the amount of gelatin invites deterioration of the coatability to cause an uneven and nonuniform coating or a rainbow-colored gloss on the coated surface due to changes in the thickness - so-called rainbow mottle, -thus resulting in a drop of the light-sensitive material's produc-tivity.
Another notable problem caused by reducing the amount of gelatin is the appearance of a lot of pinholes attributable to the matting agent contained usually in the outermost layer.

Ill a dry-to-dry ultra-high-speed processing for not longer than 60 seconds, the drying time is preEerably within l5 seconds. In order to shorten the drying time, to the dry-ing system oE ordinary automatic processors ~dry-to-dry ~0 to 150 seconds) are taken various measures such as increasing the dryiny air quantity, reducing the drying air humidity, raising the drying temperature, and using a far-infrared heater, ultra-sonic oscillator or microwave dryer. The difference between such drying systems largely affects the change in the dimen-sions oE a light-sensitive material before and after the pro-cessing thereof. Therefore, it is necessary to provide a light-sensitive material capable of showiny the same dimen-sional change even when treated in different drying condi-tions.
SVMMARY OF THE INVENTION
It is an object of the present invention to provide a silver halide photographic light-sensitive material which is capable of keeping its high productivity with very little coat-ing unevenness or rainbow mottle despite its gelatin content being as small as 2.0 to 2.8g/m~.
It is another object of the present invention to provide a silver halide photographic liyht-sensitive material capable of forming a contrasty image of which the gamma value in a density of 0.3 to 3.0 is not lower than 6.
It is a further object of the present invention to pro-vide a silver halide light-sensitive material capable of always giving an almost constant change in its dimensions before and after processing regardless of the drying time and drying system used.
A silver halide photographic light-sensitive material of the invention comprises a support having thereon at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer provided on the outside of said silver halide emulsion layer to the support, in which the total gelatin content of said layers containing said light-sensitive silver halide emulsion layer is 2.0 to 2.8g/m7 and at least one of said non-light-sensitive hydrophil-ic colloid layers contains a polymer latex.

DETI~ILED DESCRIPTION OY TIIE INVENTION
In order to make the above light-sensitive material highly contrastyJ it is necessary to incorporate into at least one oE the hydrophilic colloid layers thereof a tetrazolium compound or a hydrazine compound.
The polymer latex to be contained in the photographic light-sensitive material of the invention includes tho~e hydr-ates of vinyl polymers with the acrylates, methacrylates, and styrenes described in U.S. Patent Nos. 2,772,166, 3,32s,286, 3,~11,911, 3,311,912 and 3,s2s,620; and Research Disclosure No. 19551 (195) (July, 1980).
Useful examples of the polymer latex for the invention - 5 - ~ 2 inelude homopolymers oE metha-alkyl acrylates sueh as methyl methaerylate or ethyl methaerylate; copolymers of a metha-allcyl acrylate or styrene with aerylie aeid, N-methylol-acryl amide or glyeidol methaerylate; homopolymers of alkyl aeryl-ates sueh as methyl acrylate, ethyl aerylate or butyl acryl-ate, or eopolymers oE an alkyl acrylate with acrylie aeid or N-methylol-aerylamide (acrylie aeid eomponent of the eopolymer is preferably up to 30% by weight); homopolymers of butadiene or eopolymers of butadiene with one or more of styrene, butoxy-methylaerylamide and aerylie aeid; and vinylidene ehloride-methyl acrylate-aerylic acid tri-eopolymers.
The following are partieular examples of the polymer latex suitably usable in the invention.

Exempl if ied latex compounds:

CQ
~CII--C~12)~C ( C--Cllz-~ y (x/y= 50/50) COOC ~ 11 9 CQ

~CII--Cllz3~Cll--Cl12-~y (~/Y= 50/50) COOC; 1l 9 OCOCII 3 ~CH--Cllz3~CH--CH2~y (x/y= 95.6/4.4) COOII

~CII--Cllz)x ( Cll--Cllz-)y ( ICII--Cllz-~
C=O
-C~lz-C~ z O
(x/y/z = ~0/20/40) )2~

--~ICll--C112-3x ( ~ C112~y (x/y=50/50) COOC2115 C= O
O--Cll2--(`~ Cll2 ~ 111 Cll2)X ( CII~C112)y ( I H--Cl-1 CO O C ,. II D ~ COO~`~

(x/y/z= 39.a~/5~/1.6 ~C112--~t B:--Cl13, C2Hs, C~H3 C=O
OR

~C~12--Cll~
-.

- ~- 2~25 CH 3 Cll 3 ~C112--IC -)X . ~ I 112--C--~; (X/Y= 93/7) C=O C=O

C!l 3 Cll 3 ilZ--I--)x ( C112--l~ (X/y=93/7) C=O CO O

OCII 3 OCII 2 Cll 2 OC

C~1 3 Cll 3 C~l 3 ~C112~ ~C~lz--l--)~ (X/y = 93/7) C=O C=O

~I L -- 12 ~CH2--C )X - ( CH2--ICH~ (X/Y= ~3/7) c=o c=o OCH 3 0}1 .

~C112--C--~X ( Cl12CII--~CI12CII--)~
C=O C=O C=O
OCH~ 011 Nll--CIIzOH
(X/Y/z= 93/3/~) ~CI12--C~C~z--Cll--)~ (X/y= 93/7) C=O C=O
OCI13 Nll--C112011 Cll 3 c~l 3 C}l 3 --~CHz--C--)X ~ Cl12--l~C~12--I--)~
C=O C=O C=O O

OC~I:, 011 OCI12CI120C
( C--CH2) Cll 3 (X/y/z = 93/3/~) ~CI12--Cll~ 1~:--Clll, --C211s, --C~llg C=O
OR

~CI12--CH--3,~ ( CHz--C--)y ( Cll2--Cil--)~
C=O C=O C-O
OC2H 6 OH OCil2CII--CH 2 O

(X/Y/z = 93/3/~) Cll 3 --~C112--Cll~ C112--C--)y (X/Y~ 93/7) C= O COOII
OC2~15 ~C112--Cll--)~CH2--CH= CH--Cl12)y ~ CH2--7H--)~
- COOH
(x/y/z= 59/39/2) C~
~C112--IC ~X ( C112--ICll )y ( C112--lCIl~

(x/y/z= 85/13/2) -~C~12--CII~CI12--Cll= Cll--Cl12~CI12--C~
CO~ltlCH~OC~I-Ig ~x/y/z= ~/33/3) ~CIIz~Cll~CI12~CII=Cll~Cllz)~Cllz~CH~cH2_7ll )~
f~l~ I COOII
CONHCII 2 OC; 119 (w/x/y/z= 63/32/3/2 ~CI12--CII~C112 -Cll= CII~C~12-3~

(X/Y= G7/33) L --24 lCll3 ~CH 2--CH--3 w ( -CH--CH 2 ) x ( C--CH 2 ) y--( CH--CH
~D cooc~ ~l9 COOC~19 COOII

~w/x/y/2 = ~5/43/8/~) The polymer latex used in the invention has an average particle size of preEerably 0.005 to l~m, more preferably 0.02 to ~ m, and most preferably not more than O.l~m.
The polymer latex used in the invention may be contained on either one side or both sides of the support. When contain~
ed on both sides, the kind and/or amount of the polymer latex contained on each side may be either the same or difEerent.
As long as the polymer latex is added to at least one of the non-light-sensitive hydrophilic colloid layers provided on the outside of the silver halide emulsion layer to the sup-port, the polymer latex may be added also to any layers other than the non-light-sensitive hydrophilic colloid layer. Where contained on the side including the light-sensitive emulsion layer, the polymer latex may be contained in the emulsion layer and also in the topmost non-light-sensitive colloid layer as a protective layer, not to mention other layers such as a subbing layer and an intermediate layer, if any, between the silver halide emulsion layer and the topmost layer. Fur-ther, the polymer latex, if present on the multilayer side of the support, may be contained in any single layer.
In the invention, the amount of the polymer latex with a particle size of not more than l~m dispersedly contained in at least one of the non-light-sensitive hydrophilic colloid layers provided outside the emulsion layer on the emulsion side of the su~port is preferably not less than 0.18g/m~, and the total amount of the polymer latex contained in the whole non-light-sensitive hydrophilic colloid layers outside the emul-sion layer is preferably not less than 0.2g/m~.
The polymer latex content of at least one of the non-light-sensitive hydrophilic colloid layers on the outside of the silver halide emulsion layer to the support is preferably 0.01g/m2 to 1.og/m2, and more preferably 0.02g/m~ to 0.6g/m2.
The gelatin content of the hydrophilic colloid layer to which the polymer latex is added is preferably 0. lg/mZ to l.Sg/m2, and more preferably 0.3g/m2 to 1.2g/m2. Also, in the inven-tion, the polymer latex is contained preferably in an amount of not less than O.OSg/m~ in at least one emulsion layer and not less than O.lg/m2 in the whole emulsion layers. The gela-tin content of the emulsion layers is preferably 0.3 to 2.2g/m2, and more preferably O.S to 2.2g/m2.
The tetrazolium compound used in the invention is a com-pound represented by the following Formula I:
Formula I
~ l~z Rl ~N--N X~
N = N ~- R 3 In Formula I, R1, R2 and R3 each represents an alkyl group such as methyl, ethyl, cyclopropyl, propyl, isopropyl, J ~

,y~ l ol)lll.y l., I~ t;y l., L~ h~ )c~nt~:l or eyc~ l.olli?xyl; an amono (,Ir~.lL); an ~ yl.~ C~ ~1r:0~.IL1 ~IIIS'h ~ aCIC3tyl.~ llC); ~t tlyCiCOX~,L
,); arl ~ cOxy ~;JCCIl.~ llCh nfI I(I~thOXy, att~(3xy, )rOr)OXy, but~~
oxy or ~3~nl-.oxy; (In ~ y:L(:3xy clrou3~ ~iueh a,f-3 2IC'el~y.'i.O~Sy; a halo~Jc~n f~ itSi ~'I.-ll)i.l.t~ r~ t ~3r l.)rc~ t~; d c'(.lr.t3LllI~c3yl (Irc3u~,3;
clll tle,y:l~l t~ ~ll? Si~lfC¦I ~1'l clC~3l'.y~ 0; ~1l1 Il.l~OXy(:LtLbOllyl. C~jrOllp C~Il aS3 (3lh0xyt.~al:t-lonyl; a e~lrbt)~sy.l (~lrollu; atl cleyl (JrouL~ f.3uehasi ae~31~,~.l.; fl C~yclnc3 ~ C)u~ Ll n.Ll.Lo CJLO~lp, a m(~reLtr?i:o ~.~rc3up, a r~ l. I o ~i y fJ 1 0l~l,) O r. 1~ n ~n n 1. r ~ o Sil~.] f oxy ~1 r. ou~ ~
.
X ,lo (lIl f~nl~aIl, ~ l IIcI I O~ICll LoIl'-~ 1llC~I) aS) a ('I)lOr:L<If~
I C)[~ OllI~ :I.t~ o/~ 3~ IC' .I.~I rcl~l :lea l ,lJ ~3 ~ o rc :i t~ ~Iq l CI ~i ~Illa l~ t ~ 1, f~ e ~.~ L .~ .1 (l L3l1~1 p~ rc~l Lo r i.c~
tl~l<l; ac~l.d rrl<l:l.c:cll.sl ol ot~l~ln:Le aC'l<l'l ~3IIC~tl fl3 sluL~ol-lL~ aeiLd ~.lnd u~rh~a3i~y:1,l.c~ ~la:l,cl; ~n.lcàtll.c: ac~l :lv~ltc)r~; .i.nc~:l.l.lcl.LIlq :I.ower alkyLbc~
3~1U l l~QI~ C~ ,lC~ .l4)lll3 ~f3~1C. ~ M ~ .O I, ~It311~1Ll l. ~ C~ C ~ .3.CI ~rl.lon;
h~ lCylb~311Y;~3tIC?SILIll4all:LC' ac~lcl (-InlOrlf.`) SJ~ICh ~1'3 p~:lcaclc,~eylben~
3,fiLI~ tlc~.l,cl ~Il.L~ :llcyl (3ll:1.ec~rl~ 4? al~ an~3 su~h .lldy~ 3ll~ Q ~ 3~c~.Lcl illll~311.-; Llll(;~ll fl~ ?t~raph4?n~1--3~ e<3 ~3LIC.~ lt~ ll.LOI~ 3~1C~Il Llfl CI.L-~ f.?t~llyltl~Xyl--.C~ ~3ll~ 3 tll'l~ 311; ~3<~ ac~ .1cotlc3:1. 3l~L~c~t.(~ nll.Lcall3 '~ h ~3 ~3~ y~t~ilc~ y at3t:y.l 1.1.aC)llCa~ Lilt~ ll,LOI1; h:~:JIlC?r al.~lp~ t ic al13 '3~1lcl3 ~.3l ~ar;L~ E~O~ On; i~ncl ttlorl~? pol,yn~er8 prov1clecl c~l~i r~lc:l.l.a~ ah 1~ calycl~ry;L lc ac~l~-l cln.iC3ll~3 .
l~,x~lnL.).l,~l ol:! tll~ ~omlaoul~ rt?~3~ntecl la~ L~ormu].a :L uc3aLale .L~ lt? .l~ 3~ l a~ r~b~ 1, Ll~ ? :LIlvelll~.

not limited by the examples.

Table 1 Compound No. R1 R2 R3 xe I - 1 11 11 11 cQe I - 2 1I p-C113 p-C113 CQe I -- 3 11 nl-CI13 m-CI13 CQQ
I--D~ H o-CI13 o-CI13 CQ~
I --5p-CI13 p-CI13 p-C113 CQe I - 6 }1 p-OC113 p~OClla CQe I--7 11 m-OCl13 n~-OCH3 CQe I --8 H o-OCH3 o-OCH3 CQe I --9p-OC}13p-OCI13 p-OCI13 cQe I--10 H p-C2115 p-C2115 CQe 1--11 11 m-C21l5 m-Cz115 CQe I --12 11 p-C3H7 p-C3117 CQQ
I --13 H p-OC2115 p-OCzH5 CQe I--14 H P-OCI13 p-OCI13 CQe I ~ 15 tl p-OCll~ p-OC~Hs CQe I --16 11 p-OC511" p-OCI13 cQe I--1711 p-OC311l 7-n p-OC8H, 7-n CQe I--18 H p-CI 2H2 5-np-C, 2~125-n CQe I--1911 p-N(CI13)2 p-N(C113)2 CQe I--2011 p-N}12 p-N}12 CQe I -21 11 P-O11 p-O11 CQe I --22 11 nl-OII m-OII CQe I --23 11 p-CQ p-CQ cQe I --24 1-1 In-CQ m-CQ cQe I --25 p-CN p-C113 p-C113 CQe I --26 p-SII p-OC113 p-OCI13 cQe I -2711 p-OCI13 p-OCH3 n-C12H25 ~ SO3e - 16 - 2~

These tetrazolium compounds of the invention can be easi-ly synthesized in accordance with those methods described in the Chemical Reviews, vol.55, pp.335 to 483.
The tetrazolium compound having Formula I of the inven-tion may be used in the amount range of about 1 mg to about lOg, and preferably about lo mg to about 2g per mole of silver halide.
The tetrazolium compound having Formula I of the inven-tion may be used alone or in combination of two or more kinds thereof in an arbitrary ratio. Further, the tetrazolium com-pound of the invention may be used in combination in an arbi-trary ratio with other tetrazolium compound outside the inven-tion.
In the invention, when an anion capable of combining with the tetrazolium compound of the invention to lower the hydro-philicity thereof is used in combination therewith, particu-larly good results can be obtained. Examples of the anion include acid radicals of inorganic acids such as perchloric acid; acid radicals of organic acids such as sulfonic acid and carboxylic acid; anionic activators including lower alkylben-zenesulfonic acid anions such as p-toluenesulfonic acid anions, p-dodecylbenzenesulfonic acid anions, alkylnaphthalene-sulfonic acid anions, lauryl sulfate anions. tetraphenyl-borons, dialkylsulfo succinate anions such as di-2-ethylhexyl-sulfo succinate anions, polyether-alcohol sulfate anions such 5~

as polyethenoxy cetyl alcohol sulfate anions, stearic acid anions, and polyacrylic acid anions.
Such the anion may. after being mixed with a tetrazolium compound of the invention, be added to a hydrophilic colloid layer or may be added alone to a silver halide emulsion layer containing or not containing a tetrazolium compound of the invention or to a hydrophilic colloid layer.
The hydrazine compound used in the invention is prefer-ably a compound represented by the following Formula II:
Formula II
Ql ~2 X, l l 11 R'--N --N -C- R2 wherein R1 is a monovalent organic residue; R2 is a hydrogen atom or a monovalent organic residue: Q~ and Q~ each repre-sents a hydrogen atom, an alkylsulfonyl group including one having a substituent, or an arylsulfonyl group including one having a substituent; and X1 is an oxygen atom or a sulfur atom. Preferred among those compounds represented by Formula II is one in which X1 is an oxygen atom and R2 is a hydrogen atom.
The monovalent organic residue represented by the above Rl or R~ includes an aromatic residue, a heterocyclic residue and an aliphatic residue.
The aromatic residue includes a phenyl group, a naphthyl i2 group and the same groups having a substituent such as an alkyl group, an alkoxy group~ an acylhydrazino group, a dialkyl-amino group, an alkoxycarbonyl group, a cyano group, a carboxy group, nitro yroup, an allcylthio group, a hydroxy group, a sul-fonyl group, a carbamoyl group, a halogen atom, an acylamino group, a sul~onamido group, or a thiourea group. Examples of the phenyl group having such substituents include a 4-methyl-phenyl group, a 4-ethylphenyl group, a 4-oxyethylphenyl group, a 4-dodecylphenyl group, a ~-carboxyphenyl group, a 4-diethyl-aminophenyl group, 4-octylaminophenyl group, a 4-benzylamino-phenyl group, 4-acetamido-2-methylphenyl group, a 4-(3-ethyl-thioureido)phenyl group, a 4-[2-(2,4-di-tert-butylphenoxy)but-ylamido]phenyl group, and a ~-[2-(2,4-di-tert-butylphenoxy)-butylamido]phenyl group.
The heterocyclic residue is a 5- or 6-member single ring or condensed ring which has at least one atom selected from the group consisting of oxygen, nitrogen, sulfur and selenium atoms and which may have a substituent. Examples of the residue ring include a pyrroline ring, a pyridine ring, a quino-line ring, an indole ring, an oxazole ring, a benzoxazole ring, a naphthoxazole ring, an imidazole ring, a benzimidazole ring, a thiazoline ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a selenazole ring, a benzoselen-azole ring, and a naphthoselenazole ring.
These heterocyclic rings may be substituted by an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group, an alkoxy group having 1 to 4 earbon atoms sueh as a methoxy group or an ethoxy group, an aryl group having 6 to 18 earbon atoms such as a phenyl groupJ a haloyen atom sueh as ehlorine or bromine, an alkoxycarbonyl group, a cyano group or an amino group.
~ he aliphatic residu~ includes a straight-chain or branehed-chain alkyl group, a cycloalkyl group, the same groups having a substituent, an alkenyl group and an alkinyl group.
The straight-ehain or branehed-ehain.alkyl group is an alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 earbon atoms, sueh as a methyl group, an ethyl group, an iso-butyl group and a 1-oetyl group.
The cyeloalkyl group is one having 3 to 1o carbon atoms, such as a cyelopropyl group, a cyelohexyl group and an adamant-yl group.
A substituent to the abo~Je alkyl group or eyeloalkyl group ineludes an alkoxy group sueh as methoxy, ethoxy, prop-oxy or butoxy; an allcoxyearbonyl group; a earbamoyl group; a hydroxy group; an alkylthio group; an amido group; an aeyloxy group; a eyano group; a sulfonyl group; a halogen atom sueh as ehlorine, bromine, fluorine or iodine; and an aryl group sueh as phenyl, halogen-substituted phenyl, alkyl-substituted phenyl. Examples of the group substituted inelude a 3-methoxy-2~ 2~

propyl group, an ethoxycarbonylmethyl group, a 4-chlorocyclo-hexyl group, a benzyl group, a p~methylbenzyl group, and a p-chlorobenzyl group. The above alkenyl group includes an allyl group, and the alkinyl group includes a propargyl group.
The Eollowing are preferred examples of the hydrazine com-pound of the invention.
II-1 1-formyl-2-~4-[2-(2,4-di-tert-butylphenoxy)butylamido]-phenyl}hydrazine.
II-2 1-formyl-2-(4-diethylaminophenyl)hydrazine.
II-3 1-formyl-2-(p-tolyl)hydrazine.
II-4 1-formyl-2-(4-ethylphenyl)hydrazine.
II-5 1-formyl-2-(4-acetamido-2-methylphenyl)hydrazine.
II-6 1-formyl-2-(4-oxyethylphenyl)hydrazine.
II-7 1-formyl-2-(4-N,N-dihydroxyethylaminophenyl)hydr-azine.
II-8 1-formyl-2-t4-(3-ethylthioureido)phenyl]hydrazine.
II-9 1-thioformyl-2-{4-[2-(2,4-di-tert-butylphenoxy)butyl-amido]phenyl}hydrazine.
II-lo 1-formyl-2-(4-benzylaminophenyl)hydrazine.
II~11 1-formyl-2-(4-octylaminophenyl)hydrazine.
; II-12 1-formyl-2-(4-dodecylphenyl)hydrazine.
II-13 1-acetyl-2-{4-[2-(2,4-di-tert-butylphenoxy)butylamido]-phenyl}hydrazine.
II-14 4-carboxyphenylhydrazine.
II-1~ 1-acetyl-1-(4-methylphenylsulfonyl)-2-phenylhydrazine.

- 2l - ~ 2 IX-16 1-ethoxycarbonyl-1-(4-methylphenylsulfonyl)-2-phenyl-hydra2ille .
II-17 1-formyl-2-(4-hydroxyphenyl)-2-(4-methylphenylsulfon-yl)hydrazine.
II-18 1-(4-acetoxyphenyl)-2-formyl-1-(4-methylphenylsulEon-yl)hydrazine.
II-19 1-formyl-2-(4-hexanoxyphenyl)-2-(4-methylphenylsulfon-yl)hydrazine.
II-20 1-formyl-2-~4-(tetrahydro-2H-pyran-2-yloxy)phenyl]-2-(4-methylphenylsulEonyl)hydrazine.
II-21 1-Eormyl-2-[4-(3-hexylureidophenyl)]-2-(4-methylphenyl-sulfonyl)hydrazine.
II-22 1-formyl-2-(4-methylphenylsulfonyl)~2-[4-(phenoxythio-carbonylamino)phenyl]hydrazine~
II-23 1-(4-ethoxythiocarbonylaminophenyl)-2-formyl-1-~4-meth-ylphenylsulfonyl)hydrazine.
II-24 1-formyl-2-t4-methylphenylsulfonyl)-2-[4-(3-methyl-3-phenyl-2-thioureido)phenyl]hydrazine.
II-25 1-{{4-{3-[4-(2,4-bis-t-amylphenoxy)butyl]ureido}phen-yl}}-2-formyl-1-(4-methylphenylsulfonyl)hydrazine.

~ NIINIICII0 - 2 2 ~ 52 (lI - 27) ~ NllNllCOOC211s Br ( 11 - 28) N~ NtlNllCOCII 3 NllCOCI120~Csll~ ~(t) Csll~ l(t) ( ~1 - 29) ~NIICNH~NIINHCI10 ( 11 - 30) ~NIICNII~NIINIIS02N<CH3 OC~ ~llZ 9 ( J[ ~ 3 1 ) (t)Cslll I ~OCHCONII~NHNIICHO
(t)C5~1 "

.

- ~3 - 2~ )25;~

( Il - 32) CH 3~- NIINIIS0 2 CH 3 NIIC0~ N--N
\~ I ~SII
N= N~

3 3 ) CH3~ NIINIICII0 CH3 NHCOCIIO$~C511l ,(t) CsHI l(t) ( 1l - 34 ) .

Cl ~1~2 60~So2NH~NHNHC~10 ( 11 - 35) N~--NIINHC0(CH2)30~--C5HI l(t) ` .
C51~ 1 1 (t) , .

- 2 4 - ~ 5 ( 11 - 36) Cll 3 N~9--Nl-INIICIIO
CH3 CONll(CI12)~0~Csll~ l~t) Cslll l(t) ( 11 - 3 7 ) C, ~H2 gO~NllCO ~NIINIIIClCH3 ( 11 - 38) O~--N~ NIINHCO ICIIO ~ C s H I I ( t ) C2Hs Cblll l(t) ( 11 -- 39) ~\ NIINIICIIO

1 0 ) ~, ~ ~ \NllNllCOCH20~CsH~I(t) Cs~

- 2 5 - ~3 ( ~ - 'Il) NIINIICIIO

2 ) CONII ( CI12 ) ~ 0 4/~ C s ll Cslll ,(t) ~ N~\ N~lNllcllo ( Il - 43) ~ NHNIICIIO

( 11 - '1 ~1 ) NIINIICO ICI-IO ~ C 511, 1 ( t ) C~HD C 11 (t) , ~
5 ) ~ Cll ~NIIN~ICON \

- 2 6 - 2 ID~ ~5~

6 ) ~ NIINIISO 2 ~ OC ~ 2112 5 7 ) C 5 1l 1 1 ( t ) (t)C511- 1--~O~CI12)3NIICON~I~NIINIICOCON<

8 ) Cslll ,(t) (t)Cslll r~ O(CI12)3NIICONII~ NIINIICOCON<
Cll = Cll 2 4 9 ) (t)C511, 1 ~O(CI12)1NIICONII~NIIN~ICOCO
Cll2011 ( 11 - 5 0 ) C5~'1, 1 (~) (t)Cslll I ~O(CI12),NIICONII~NIlNllcoco--C~12$~
l12011 ~i2 5 1 ) (t)Cslll I ~O(CI12)2NIICONII~NI-INIICOCON/
Cll 20 ( 11 - 52) C~ll, 7NIICNII~NIINIICOCON /

( 1~ - 5 3 ) C5~11 ,(t) (t)C 8111 1 ~ O(CII2) ~ NIINIICONII~ NIINIICOCII 2 OCII~

( 11 - 5~) 11--C I o ll z 1 O--~ Cll = N ~ NIII`,VllCOCII 2 OCII 3 ' ~ ~
( 11 - 5 5 ) ` `

U - C, 0112 10 ~ Cl] 2 Nll ~ NIINIICOCII 2 OC~I 3 - 2 ~ aa~2 5 6 ) Il--C 811 l 7 ~ CONI3 ~ Nl3NI3COC~I 2 0C~I 3 ( 31 57) CN Nl-3CONII ~ Nl3NI3COCII20CII3 ( 11 - 5~) NNIICONI3~ Nl3NilCOC}I20CH3 Cll 3 ( 1~ - 59) C~33 tcs~ ~cs~ ~ NI-INIICOCONI3~NIcc~l3 Cll 3 .

.. . . .. . . . . . . .. .. . ... . . . ... . . . . . . ... . .

- 29 - 2~

The place into which is incorporated a hydrazine compound represented by Formula II is a silver halide emulsion layer and/or a non-light-sensitive layer located on the silver halide emulsion layer side oE the support, and preferably the silver halide emulsion layer and/or a layer thereunderneath.
The adding amount of the hydrazine compound is preferably lo S
to lo 1 mole, and more preferably lo 4 to lo 2 mole per mole of silver.
The silver halide of the silver halide emulsion used in the light-sensitive material of the invention may be any arbi-trary one Eor conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide or silver chloroiodobromide, and preferably a silver chlorobromide containing more than ~0 moleq~ silver chlo-ride for a negative-type silver halide emulsion. The silver halide grain may be one that is obtained by any of an acid method, a neutral method and an ammoniacal method. The silver halide emulsion used in the invention may be either of a single composition or of a plurality of grains different in the composition, which may be contained together in a single layer or separately in a plurality of layers.
Configuration of the silver halide grain of the invention is not restricted, but one preferred example is a cubic grain having a {loo} face as a crystal surface. The grain may also be oE an octahedral, tetradecahedral or dodecahedral configura-tion, which may be prepared in accordance with those methods described in U.S. Patent Nos. 4,183,756 and 4,2~5,666; Japan-ese Patent O.P.I. Publication No. 26~89/1980, and Japanese Patent Examined Publication No. 42737/1980; and the Journal of Photographic Science, 21. 39 (1973). Further, the grain may also be a crystal having a twin plane.
The si~ver ha1ide grains of the invention may be either ~rains oE unlfied form or mixed grains oE varied forms.
The silver halide yrains may be of any grain size distri-bution; the emulsion used may be an emulsion of a wide grain size distribution (referred to as a polydisperse emulsion), a single emulsion or a mixture of diEferent emulsions having a narrow grain size distribution (referred to as monodisperse emulsions), or a mixture oE a polydisperse emulsion and a mono-disperse emulsion.
The silver halide emulsion may be a mixture of separately prepared two or more difEerent emulsions.
In the invention, the monodisperse emulsion is preferred.
The monodisperse silver halide grains in the monodisperse emul-sion are such that the weight of the silver halide grains included within the grain size range of 20% -~ average grain size r account for not less than 60%, more preferably not less than 70%, and most preferably not less than 80$ of the weight of the whole silver halide grains.
The average grain size r herein is defined as the grain - 31 - ~ 25~

diameter ri obtained when -the product ni x ri3 oE the frequency ni of a grain having a grain diameter ri and ri3 becomes maxi-mum (calculated and rounded to three places of decimals).
The grain diameter, in the case of a spherical silver halide grain. is its diameter and. in the case oE a non-spheri-cal grain, is the diameter of a circular image eq~ivalent in the area to its projection image.
The grain diameter can be ob~ained by measuring the dia-meter oE a grain image on a photographed print or the area of a projected image obtained by magnifying the grain 10,000 to so,ooo times by an electron microscope. provided that the number of grains to be measured is loOO or more selected at random.
The particularly preferred high monodisperse emulsion of the invention is one in which the grain size distribution width defined by Grain sizes standard devlatiOn x loo = distribution width (%) Average grain size is 20~o or less, and more preferably 15% or less.
~ erein, the average grain size and the grain size stand-ard deviation are to be found from the previously defined ri.
The monodisperse emulsion can be prepared by making refer-ence to Japanese Patent O.P.I. Publication Nos. 4~521/1979, 49~38/19~3 and 122935/lg850 The light-sensitive silver halide emulsion, although _ 32 -allowed to be used remaining unchemically-sensitized, i.e., in a primitive emulsion, is usually subjected to chemical sensiti-zation. The chemical sensitization may be carried out in ac-cordance with appropriate ones of those methods described in the publications by Gla~kides and Zelikman, and the 'Die Grund-lagen der Photographischen Prozesse mit Silberhalogeniden', ~ka-demische Verlagsgesellschaft, 1968, compiled by H. Frieser.
Namely, a sulfur sensitization method which uses an ac-tive gelatin or a compound containing sulfur capable of react-ing with silver ions; a reduction sensitization method which uses a reducing substancc; and a noble-metal sensitization method which uses a gold compound or other noble metal com-pounds may be used alone or in combination. As the sulfur sen-sitizer, a thiosulfate, a thiourea, a thiazole, a rhodanine and other compound may be used, examples of which are describ-ed in U.S. Patent Nos. 1,574,94~, 2,410,689, 2,278,947, 2,728,668 and 3,656,9ss. As the reduction sensitizer, a stan-nous salt, an amine, a hydrazine derivative, formamizinesulfin-ic acid, and a silane compound may be used, examples of which are described in U.S. Patent Nos. 2,478,8s0, 2,419,974, 2,sl8,6s~, 2,983,609, 2,983,610 and 2,694,637. For the noble metal sensitization, a complex salt of a metal such as plati-num, iridium or palladium, belonging to Group VII of the period-ic table, can be used, examples oE which are described in U.S.
Patent Nos. 2,399,083 and 2,448,060, and British Patent No.

618,061.
The conditions of pH, pAg and temperature Eor the chemi-cal sensit:ization are not particularly restricted; pH is pre-ferably 4 to 9, particularly 5 to 8; pAg is preferably 5 to 11, particularly 8 to lo; and temperature is preferably 40 to 90C, particularly 45 to 75~C.
The photographic emulsion used in the invention may be chemically sensitized by combined use of the above-mentioned sulfur sensitization, gold-sulfur sensitization, reduction sen-sitization and noble-metal sensitization.
As for the light-sensitive emulsion, the foregoing emul-sion may be used alone or in a mixture of two or more ~inds thereof.
In practicing the invention, for the emulsion, after com-pletion of the above chemical sensitization, may be used ~-hydr-oxy-6-methyl-~,3,3a,7-tetrazaindene, S-mercapto-1-phenyltetr-azole, 2-mercaptobenzothiazole, and various other stabilizers.
Further, if necessary, a silver halide solvent such as thio-ether, a mercapto group-containing compound, and a crystal habit control agent such as a sensitizing dye may be used.
The silver halide grain for the emulsion of the invention may contain in the inside thereof and/or on the surface thereof metallic ions by adding thereto in the grain forming and/or growing process a cadmium salt, a zinc salt, a lead salt, a thalium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or an iron salt or a comple~ salt ~hereof.
The emulsion of the invention may have its useless solu-ble salt either removed therefrom after completion of the growth of the silver halide grain or remain contained therein.
The removal o~ the salt can be carried out in accordance with the method described in Research Disclosure 17643.
In the silver halide photographic light-sensitive mate-rial oE the invention, the emulsion may be spectrally sensitiz-ed to relatively longer wavelength-having blue, green and red lights or infrared light by using sensitizing dyes. The dyes to be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. The particularly useful ones are cyanine dyes, merocyanine dyes and complex merocyanine dyes. The basic heterocyclic nucleus of these dyes may be any one of those nuclei usually applied to cyanine dyes, which includes a pyrroline nucleus, an oxazol-ine nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxa-zole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus; a nucleus formed by the fusion of an alicyclic hydrocarbon ring with one of these nuclei; and a nucleus formed by the fusion of an aromatic hydrocarbon ring with one of these nuclei, such as an indolenine nucleus, a benzindolenine nucleus, an indole - 3s ~ 0~S~

nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus~ a benzoselen-azole nucleus, a benzimidazole nucleus, and a quinoline nucleus. Any of these nuclei may have a substituent on a carbon atom thereof.
The ketomethylene structure-having nucleus of the mero-cyanine dye or complex merocyanine dye may be a 5- or ~-member heterocyclic nucleus such as a pyrazolin-S-one nucleus, a thio-hydantoin nucleus, a 2-thiooxazlidin-2,4-dione nucleus, a thia-zolidin-2,4-dione nucleus, rhodanine nucleus, a thiobarbituric acid nucleus.
The sensitizing dye for use in the invention is used in the same concentration as used in conventional negative-type sllver halide emulsions. Particularly, it is advantageous to use the sensitizing dye in a concentration range substantially not to deteriorate the inherent sensitivity of the silver halide emulsion; preferably about l.OxlO S to SxlO 4 mole of the sensitizing dye per mole of silver halide, and particu-larly preferably about 4xlO 5 to 2xlo ~ mole per mole of silver halide.
The sensitizing dye of the invention may be used alone or in combination of two or more kinds thereof. Useful examples oE the sensitizing dye of the invention are as follows:
The sensitizing dyes for the blue-sensitive silver halide emulsion include those described in West German Patent No.

- 36 ~

929,080 U.S. Patent Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,g12,329, 3,656,95S, 3,~72,897, 3,694,217, 4,02s,349 and 4,046,572; British Patent No. 1,242,5B8; Japan-ese Patent Examined Publication Nos. 14030/1969 and 24844/-1977; and Japanese Patent O.P.I. Publication Nos. 73137/1973 and 172140/1986. The sensitizing dyes for the green-sensitive silver halide emulsion include those cyanine dyes, merocyanine dyes, and complex cyanine dyes described in U.S. Patent Nos.
1,939,201, 2,072,908, 2,739,149 and 2,945,763; British Patent No. 505,g79; and Japanese Patent Examined Publication No.
42172/1973. And, the sensitizing dyes for the red-sensitive emulsion and infrared-sensitive emulsion inc].ude those cyanine dyes, merocyanine dyes and complex cyanine d~es described in U.S. Patent Nos. 2,269,234, 2,270,378, 2,442,710, 2,454,629 and 2,776,280; Japanese Patent Examined Publication No. 17725/-1974; and Japanese Patent O.P.I. Publication Nos. 62425/1975, 29836/1986 and 80841/198S.
These sensitizing dyes may be used alone or in combina-tion. Combination of such sensitizing dyes is often used for the purpose of supersensitization. Typical examples of the combination are described in U.S. Patent Nos. 2,688,s4s, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862 and 4,026,707; British Patent Nos. 1,344,281 and 1,507,803; Japanese Patent Examined Publica-tion Nos. 4936/196~ and 1237stl978; and ~apanese Patent O.P.I.
Publication Nos. 11061st1s77 an~ 10992~/1977.
The silver halide photographic light-sensitive material o~ the invention may contain in the hydrophilic colloid layers thereof a wateL soluble dye as a filter dye or ~or the anti-irradiation, antihalation and some other purposes. Examples of ~uch the dye include oxonol dyes, hemioxonol dyes, styr~l dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, the oxonole dyes, hemioxonol dyes and merocyanine dyes are particularly use~ul.
In the silver halide photographic light-sensitive mate-rial of the invention, where the hydrophilic colloid layers thereof contain a dye or a ultraviolet absorbing agent, the dye or the agent may be mordanted by a cationic polymer.
To the emulsion of the light-sensitive material, in order to prevent its sensitivity deterioration or fogging during the course of the manu~acture, storage or processing thereo~, may be added various compounds; e.g., those compounds known as stabilizers, which include azoles such as a benzothiazolium salt, a nitroindazole, a triazole, a benzotriazole, a benzimid-azole ~particularly nitro- or halogen-substituted one). a heterocyclic mercapto compound such as a mercaptothiazole, a mercaptorbenzothiazole, a mercaptobenzimidazole, a mercapto-thiadiazole, a mercaptotetrazole ~particularly 1-phenyl-5-mer-captotetrazole); mercaptopyridines; heterocyclic mercapto com-, pounds, similar to the above, having a water-soluble group such as a carboxyl group or sulfone group; thioketo compounds such as oxazolinethione; azaindenes such as a tetrazaindene (particularly a 4-hydroxy-substitutecl (1,3,3a,7)-tetrazaind-ene); benzenethiosulfonic acids and benzenesulfinic acids.
Some examples oE the compound usable in the invention are detailed in K. Mees, The Theory of the Photographic Process, 3rd ed., 1966~
More detailed examples and the use of such compounds can be found in U.S. Patent Nos. 3,954,474, 3,982,947 and 4,021,248; and Japanese Patent Examined Publi~cation No. 28660/-1977.
The silver halide photographic light-sensitive material of the invention may contain the following various additives:
Those materials as viscosity increasing agents or plasticizers such as a styrene-sodium maleate copolymer and dextran sulfate as described in U.S. Patent Nos. 2,960,404 and 3,767,410;
Japanese Patent Examined Publication Nos. 4939/lg68 and 15462/-1970; West German DAS Patent No. 1,904,604; Japanese Patent O.P.I. Publication No. 63715/1973; and selgian Patent Nos.
762,833 and 558,1~3; hardeners such as aldehyde-type, epoxy-type, ethyleneimine-type, active halogen-type, vinylsulfone-type, isocyanate-type, sulfonate-type, carbodiimide-type, muco-chloric acid-type and acyloyl-type compounds; ultraviolet absorbing agents including those compounds as described in U.S. Patent No. 3,253,921 and British Patent No. 1,309,349, such as 2-(2;-hydroxy-S-tert-butylphenyl)benzotriazole, 2-(2~-hydroxy-3',S'-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3'-tert-butyl-5'-butylphenyl)-s-chlorobenzotriazole, and2-(2~-hydroxy-3',5'-di-tert-butylphe~l)-5-chlorobenzotriazolei and surfactants useful as coating aids, emulsification agents, agents for improving the permeability into processing solu-tions, deforming agents or for controlling various physical properties of the light-sensitive material. which include those anionic, cationic, nonionic and amphoteric compounds as described in British Patent Nos. 548,s32 and 1,216,389; U.S.
Patent Nos. 2,026,202 and 3,514,293; Japanese Patent Examined Publication Nos. 26580/1969, 17922/1968, 17926/1968, 13166/-196S and 20785/1973; French Patent No. 202,588; Belgian Patent No. 773,459; and Japanese Patent O.P.I. Publication No.
101118/1973. Preferred among these surfactants are sulfone group-having anionic surfactants such as sulfonated succin-ates, sulfonated alkylnaphthalenes, and sulfonated alkylben-zenes.
In the manufacturing process of the invention, the pH
range of the coating liquid is preferably 5.3 to 7.S. In the case of multilayer coating, a mixture of the respective layers' coating liquids mixed in proportion of their coating amounts is preEerred to have a pH oE s.3 to 7.5. If the pH is 5.3 or lower, the hardening makes slow progress, while if the p~l exceeds 7.5, it badly aE:Eects the photographic character-istics.
The component layers of the light-sensitive material of the invention may also contain a lubricant, examples of which include those higher alcohol esters of higher fatty acids described in U.S. Patent Nos. 2,588,756 and 3,1~1,060; the casein described in U.S. Patent No. 3,29~,979; those higher fatty acid's calcium salts described in British Patent No.
1,~63,722; and those silicon compounds described in British Patent No. 1,313,384, U.S. Patent Nos. 3,042,~22 and 3,489,567. Liquid paraffin-dispersed products may also be used Eor this purpose.
The light-sensitive material may also contain.a brighten-ing agent, exaTnples oE which include stilbene-type, triazine-type, pyrazoline-type, cumarine-type and acetylene-type com-pounds.
These compounds may be either water-soluble ones or insol-uble ones to be used in the form o:f dispersion.
The foregoing anionic surfactant is preferably one con-taining an acid group such as a carboxy group, a sulfo group, a phospho group, a sulfate group or a phosphate group, exam-ples of which surfactant include alkylcarboxylic acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulEonic acid salts, alkylsulfuric acid esters, alkylphosphoric acid esters, N-acyl-alkyltaurines, sul-~osuccinic acid esters, sulfoalkylpolyoxyethylenealkylphenyl ethers, and polyoxyethylenealkylphosphoric acid esters.
PreEerred compounds as the amphoteric surfactant include amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric or phosphoric estersJ alkylbetaines. and amine oxides.
Pre~erred compounds as the cationic surfactant include alkylamines, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridium and imidazolium, and aliphatic or heterocyclic ring-containing phosphoniurn or sulfonium salts.
Useful examples of the nonionic surfactant include sapo-nin (steroid type); alkylene oxide derivatives such as poly-ethylene glycol. polyethylene glycol/polypropylene glycol con-densate, polyethylene glycol-alkyl ethers or polyethylene gl~col-alkylaryl ethers, polyethylene glycol esters, polyethyl-ene glycol sorbitan esters, polyalkylene glycol alkylamines or -amides and silicone-polyethylene oxide adducts; glycidol deri-vatives such as alkenylsuccinic acid polyglycerides, alkyl-phenol polyglycerides; polyhydric alcohol's fatty acid esters;
and suyar's alkylesters.
As the matting agent, there may be suitably used any o~
those organic matting agents described in British Patent No.
1,055,713; U.S. Patent Nos. 1,939,213, 2,221,873, 2,268.662, 2,332,037, 2,376,005, 2,391,181, 2,701,24~, 2,992.101, 3,079,257, 3,262,782, 3,516,832. 3,539,344, 3,591,379, 3,7s4,924 and 3,767,448, and those inorganic matting agents described in West German Patent No. ~,592,321; British Patent Nos. 760,775 and 1,260,772; and U.S. Patent Nos. 1,201,905, 2,192,~41, 3,053,662, 3,06~,649, 3,257,206, 3,322,5s5, 3,3s3,9s8, 3,370,951, 3,~11,907, 3,437,~84, 3,523,~22, 3,615,554, 3,635,714, 3,769,020, 4,021,245 and 4,029,504.
Suitably usable as the antistatic agent are khose com-pounds described in British Patent No. 1,466,600:Research Dis-closure 15840, 1625g and 16630; U.S. Patent Nos. 2,327,828, 2,861,056, 3,206,312, 3,24s,~33, 3,428,451, 3,775,126, 3,963,498, 4,02s,342, 4,02s,463, 4,025,691 and 4,02s,704.
The particularly preferred embodiment of the invention is to use a tetrazolium compound, a polyethylene oxide deriva-tive, a quaternary phosphate compound or a hydrazine compound as a tone control agent for increasing contrast as described in Japanese Patent O.P.I. Publication Nos. 210458/1987 and 13~546/1987.
Also, there may be used a technique for improving dimen-sional stability by incorporating a polymer latex into the silver halide emulsion layer or backing layer. Examples of such the technique are disclosed in Japanese Patent Examined Publication Nos. 4272/1964, 17702/1964 and 13482/1968; U.S.
Patent Nos. 2,376,00s, 2,763,625, 2,772,166, 2,8~2,386, 2,8s3,~s7 and 3,397,9~8.
As a binder for the light-sensitive material o the inven-tion, gelatin is normally used. The binder may be composed of gelatin in combination with other hydrophilic colloid mate-rials including gelatin derivatives.
The gelatin usable includes lime-treated gelatin, acid-treated gelatin, the oxygen-treated gelatin described in Bull.
Soc. Sci. Phot. Japan No.16, p.30 (1966), hydrolyzed gelatin and enzyme-decomposed gelatin.
The gelatin derivative includes those obtained by the reaction of gelatin with various compounds such as an acid halide, an acid anhydride, an isocyanate, bromoacetic acid, an alkane~ultone, a vinylsulfonamide, a maleic imide compound, a polyalkylene oxide, and epoxy compound. Examples of the gela-tin derivative are described in ~.S. Patent Nos. 2,614,928, 3,132,94S, 3,186,846 and 3,312,553; British Patent Nos.
861,414, 1,033,189 and 1,005,784; and Japanese Patent Examined Publication No. 26~45/1967.
The light-sensitive material oE the invention may further contain various additives according to purposes. These addi-tives are detailed in Research Disclosure vol.176, Item 17643 tDec. 1978) and vol.l87, Item 18716 (Nov. 1979). The relevant pages and columns in the publications are listed in the follow-ing table.

- 44 ~

Addit.ives ~ 176~3 RD 18~116 1. Chemical sensitizersp.23 p.648, right col.
2. Sensitivity increasing ,, agents 3. Spectral sensitizers, p.648, right col.
supersensitizersp.23 to 24to p.649, right col.
4. Brighteniny agents p.24 5. Antifoggants andp.24 to 2s p.649. right col.

6. Light-absorbing agents filter dyes, W absorb- p.25 to 26 p 649, r1ght col ;.ng agents 7. Antistain agentsp.2s, right col.p 650, left col.
8. Dye image stabilizer p. 25 9. Hardeners p.26 p.651, left col.

10. Binders p.26 '~

11. Plasticizers, lubricants p.27 p.650, right col.

12. Coating aids, surfactants p.26 to 2 13. Antistatic agents p.27 ~

The sùpport used for the light-sensitive material of the invention includes an elastic reflection support such as a paper laminated with an a-olefin polymer such as polyethylene, polypropylene, ethylene/butene copolymer, or a synthetic paper; a film support composed of a semisynthetic or synthetic high molecular material such as cellulose acetate, cellulose ~ 5 2~Lo~

nitrate, polystyrene, polyvinyl chloride, polyethylene tere-phthalate, polycarbonate or polyamide; an elastic support obtained by providing a reflection layer on the above film;
and a metallic support. The most preferred among these sup-ports is a polyethylene terephthalate support.
A subbing layer usable in the invention includes those of the organic solvent type including polyhydroxybenzenes describ-ed in Japanese Patent O.P.I. Publication No. 3972/1974, and those aqueous latex subbing layers described in Japanese Patent O.P.I. Publication Nos. 11118/1974, 104913/1977, 19941/-198~, 19940/1984, 189~5/1984, 112326/1976, 117617/1976, 5~469/-1976, 114120/1976, 121323/1976, 123139/1976, 1141~1/1976, 139320/1977, 65422/1977, 109923/1977, 119919/1977, 65949/1980, 128332/1982 and 1~941/1984.
The subbing layer may have its surface usually subjected to chemical or physical treatment for surface activation, such as treatment with chemicals, mechanical treatment, corona dis-charge treatment, flame treatment, ultraviolet ray treatment, high-frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone-oxidation treatment.
The subbing layer is distinguished from the provided layers for the invention in that no restrictions be put on its coating point of time and conditions.
In the invention, dyes may be used as filter dyes and for - 46 - 2~

antihalation and various other purposes. The dyes for such purposes include triallyl dyes, oxanol dyes, hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes and azo dyes.
Especially, the oxanol dyes, hemloxanol dyes and merocyanine dyes are useful. Usable examples of such dyes include those described in West German Patent No. 616,007; British Patent Nos. ~84,609 and 1,177,429; Japanese Pa-tent Examined Publica-tion Nos. 7777/lssl~ 22069/1964 and 3B129/1979; Japanese Patent O.P.I. Publication Nos. 85130/1973, 99620/1974, 114420/-1974, 129S37/1974, 28827/1975, 10811S/1977, 185038/1982 and 2484s/ls8~; V.S. Patent Nos. 1,878,961, 1,884,03S, 1,912,797, 2,098,891, 2,1So,69S, 2,274,782, 2,298,731, 2,409,612, 2,461,484, 2,~27,S83, 2,S33,472, 2,~6s,7s2, 2,9~6,879, 3,094,418, 3,125,448, 3,148,187, 3,177,078, 3,247,127, 3,260,601, 3,282,699, 3,409,433, 3,~40,887, 3,s7s,704, 3J653J905, 3,718,472, 3,865,817, 4,070,3S2 and 4,071,312; P~
Report 7417S; and Photo. Abstr. 1 28 ('21).
Particularly, these dyes may be suitably used for room-light reversing light-sensitive materials; ~t is particularly preferable to use such dyes so as to make the sensitivity to 400nm light more than 30 times as high as that to 360nm light~
Further, in practicing the invention, there may also be used an organic desensitizer as described in Japanese Patent O.P.I. Publication No. 26041/1986, whose sum of the anode poten-tial and the cathode potential in a polarographic analysis is positive.
The light-sensitive material of the invention can be ex-posed to an electromagnetic wave light in the spectral region to which the component emulsion layer thereof is sensitive.
~xposure of the light-sensitive material can be carried out by using any one of known light sources including natural light ~sunlight), tungsten lamp light, fluorescent lamp light, iodine quartz light, mercury vapor lamp light, microwave-emit-ting UV light, ~enon arc light, carbon arc light, xenon flash light, cathod ray tube flying spot, various laser lights, light-emitting diode light. and those lights released from a phosphor excited by electron beam, X-rays, ~-rays and a-rays.
Good results can be obtained also when exposing the light-sensitive material to light from the UV light sourse disclosed in Japanese Patent O.P.I. Publication No. 210458/1~7 to which is attached a filter absorbing the 370nm and shorter wave-length regions or from a UV light source in the wavelength regions of from 370 to 420nm.
The exposure time may be not only a shorter time than 1 millisecond to 1 second which are used in usual camera expo-sure but also a much shorter time than 1 microsecond such as from 100 nanosecond to 1 microsecond by a cathode ray tube or xenon flash tube. And it is also possible to use a longer exposure time than 1 second. The exposure may be made either continuously or intermittently.

I !.r - 48 - ~ 2~

The invention can be applied to various li~ht-sensitive materials such as graphic-arts. X-rayJ general negative-type, general reversal-type, general positive-type and direct posi-tive-type light-sensitive materials, but can exhibit remark-able effects particularly when applied to a graphic-arts light-sensitive material which requires a very high dimensional sta-bility.
The light-sensitive material of the invention may be sub~
jected to known black-and-white, color or reversal processing, but is particularly effective when subjected to a high-con-trast processing for graphic arts light-sensitive materials.
A fixer solution for use in the processing of the light-sensitive material of the invention may contain a thiosulfate, a sulfite, various acids, salts, a fixing accelerator, a wet-ting agent, a surfactant, a chelating agent and a hardener;
for example, the thiosulfate and sulfite include potassium, sodium and ammonium sulfates and sulfites; the acids include sulfuric acid, hydrochloric acid, nitric acid, boric acid, formic acid, acetic acid, propionic acid, oxalic acid, tar-taric acid, citric acid, malic acid and phthalic acid; and the salts include potassium salts. sodium salts and ammonium salts of these acids. The fixlng accelerator includes those thio urea derivatives and intramolecular triple bond-having alco-hols as described in Japanese Patent Examined Publication No.
3$754/1970, Japanese Patent O.P.I. Publication Nos. 122535/-2~

~,9 1983 and 122536/1983; those thioethers described in U.S.Patent No. 4,1~6,459, anion-liberating cyclodextran ethers, crown ethers, diazabicycloundecene and di-~hydroxyethyl)but-amine. The wetting agent includes alkanolamines and alkylene glycols. The chelating agent includes nitrilotriacetic acid and amino acids such as EDTA. The hardener includes chrome alum, potassium alum and other aluminum compounds.
The fixer solution in the invention, in order to increase the hardening of the light-sensitive material, contains prePer-ably an aluminum compound. The aluminum compound content of the fixer solution is preferably 0.1 to 3g/liter in aluminum equivalent.
The sulfite content of the fixer solution is preferably 0.03 to 0.4 mole/liter, and more preferably 0~04 to 0.3 mole/-liter.
The fixer solution has a pH of preferably 3.9 to 6.~.
The pH range of the fixer solution not only provides satisfac-tory photographic characteristics but has remarkable effects upon packaging materials of the invention. The most preferred pH of the solution is 4.2 to 5.3.
The light-sensitive material of the invention is devel-oped at a temperature of preferably not higher than 500C, and more preferably 250C to 400C, for a period of normally within two minutes; particularly s to 2s seconds high spped process-ing also gives a good photographic image. Those processes - sn -other than the developing and ~ixing process, such as washing, stopping, stabilizing and prehardening or neutraliæing pro-cesses may be excluded.
The present invention exhibits its merits largely even when the light-sensitive material of the invention is subject-ed to a ultra-high-speed processing, whose processing time is as short as 20 to 60 seconds.
The 'ultra-high-speed processing' herein means a process-ing by an antomatic processor in which the quotient obtained when the overall period of time from the insertion of the lead-ing end of a light-sensitive material traveling through the developer bath, crossover section, fixer bath, crossover sec-tion, washing bath and drying section until the ejection of the leading end therefrom, i.e., the overall length of the processing line, is divided by the line transport speed is 20 seconds to 60 seconds. ~he reason why the crossover sections are included, although well-known to those skilled in the art, is that even in the crossover sections, the solution in the preceding process remains in a transported light-sensitive material to have its processing effect substantially make pro-gress.
EXAMPLES
The present invention is illustrated in detail by the fol-lowing examples.
EX~PLE 1 2~

Negative-type silver halide light-sensitive material samples as roomlight reversing light-sensitive materials were prepared in the following manner:
Preparation of emulsions Silver chlorobromide emulsions, containing 2 mole~ si]ver bromide and So mole% silver chloride, were prepared in the following manner:
A silver nltrate aqueous solution and an aqueous solution containing potassium pentabromorhodium in an amount of 23.9mg per 60g of silver nitrate, sodium chloride and potassium bromide were simultaneously mixed into a gelatin aqueous solu-tion with stirring in 2s minutes at 400C, whereby silver chloro-bromide emulsions each having an average grain si~e of 0.20~m were prepared.
These emulsions. after adding 200mg of a stabilizer 6-methyl-4-hydroxy~1,3,3a,7-tetrazaindene thereto, were washed and desalted.
The emulsions, after adding thereto further 20mg of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene, were subjected to sulfur sensitization. After the sulfur sensitization, respec-tively necessary amounts of gelatin and a stabilizer 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene were added, and then water was added to each of the emulsions to make its quantity 260ml.
Preparation_of latex (L) to be added to the emulsions A mixture liquid of 4.51kg of n-butyl acrylate, s.4skg of - S2 ~ 5~

styrene and O.lkg of acrylic acid was added spending an hour to, with stirring at 81C under a nitrogen atmosphere, a solu~
tion of 0.25kg of KMDS (dextran sodium sulfate) produced by Meito Industry Co. and Oooskg of ammonium persulfate dissolved into 40 liters of water, and then O.OOskg of ammonium persul-fate was added. After that, the liquid was stirred for 1.5 hours, cooled and then adjusted to pH 6 with ammonia water.
The obtained latex liquid was filtered through a GF/D
filter manufactured by Whotman Co.. and the quantity of the filtrate was made 50.5kg by adding water thereto, whereby a monodisperse latex L-6 having an average partlcle size of 0.25~ was prepared.
To the foregoing emulsions were added the following addi-tives, and silver halide emulsion coating liquids were prepar-ed in the following manner.
Preparation of emulsion coating liquids Each of the emulsions, after adding thereto 9mg of phenol as a fungicide, was adjusted to pM fi.s with a 0.5N sodium hydr-oxide solution, to which were then added in sequence 360mg of the following compound ~, Sml of a 20% saponin so]ution per mole of silver halide, 180mg of sodium dodecylbenzenesulfon-ate, 80mg of 5-methylbenzenetriazole, 43ml of the above latex liquid L-6, 60mg of the following compound M and 280mg of an aqueous styrene-maleic acid copolymer, and added water to malce the whole quantity 475ml, whereby emulsion coating liquids - ~3 ~ 52 were prepared.
Next, a protective layer coating liquid was prepared in the following manner.
Preparation of a protective layer coatinq liquid Pure water was added to gelatin in various amounts. The gelatin, after swelling, was dissolved at 400C, and then to this were added in sequence a 1~ solution of the following com-pound Z as a coating aid, the following compound N as a filter dye, an amorphous silica as a matting agent, the following com-pound B, and pH of the mixture was adjusted to 6.0 with citric acid. and then further added the latex L-6 in the amounts shown in Table 1, and added water to make the whole a given quantity, whereby a protective layer coating liquid was prepared.
Compound T

113C/~N~ ~ ~113 ~J Cll~3 - 34 - 2~

Compound Z

C~12 0 - Cll~(CII 2 ) ~ Cl13 NaO3S ~ 1 f -CH2CI-12CH~CH3)2 Compound M
Cil3X~--0II
~l~o~l Compound N

C~33 ~ ~ Cl~= C~ C~ 133 C N
N

SO3Na - ss -Compound A Compound B

.. 011 ~ tl ~ 11 Cl13 S~ ~113 ~
C02C3l-ls Subsequently, a backing layer coating liquid was prepared in the following manner.
PreParation of backinq_layer coating liquid B-1 Thirty-six grams of gelatin were swelled with water and dissolved by heating, and to this were added 1.6g of the follow-ing compound C-1, 310mg of compound C 2 and l.9g of compound C-3 as dyes. 2.9g of the above compound N in khe form of an aqueous solution, llml of a 20~ saponin aqueous solution. 5g of the following compound C-4 as a physical property adjusting agent, and 63mg of the following compound C-5 in the form of a methanol solution. This liquid, after adding thereto 800g of an aqueous styrene-maleic acid copolymer for viscosity adjust-ment, was adjusted to pH 5.4 with citric acid. Finally, 144mg of glyoxal were added, and then water added to make the whole quantity 960ml, whereby a BC coating liquid B-1 was prepared.

;

- s6 - 2~

Compound C-l .~ (Cl13)2 ~ \C ~ (C113)~

CH2S031i Compound.C-2 Ch > ~ ~I=CH-CII ~ 02H
N/

¢~
S03N~

Compound C-3 CH3 - ~ i ~li - s7 ~ 5~

Compound C-4 Copolymer latex of CQ
-~CII2-CH~- and -~CH
C02Cslls CQ wherein m:n = 1:~

Compound C-S

--CH= C~

CQ C7~1s C}l N Cl13 C711s A protective layer coating liquid B-2 for protection of the backing layer was prepared in the following manner.
Preparation of protective layer coating liquid B-2 Fifty grams of gelatin were swelled with water and dis-solved by heating, and to this were added 340mg of sodium 2-sulfona~e-succinic acid-bis (2-ethylhexyl)ester, 1.7g of poly-methyl methacrylate having an average particle size of 0.4~ as a matting agent, 3.4g of sodium chloride, l.lg of glyoxal and 540mg of mucochloric acid, and then added water to make the whole quantity lOOOml, whereby a protective layer coating liquid B-2 was prepared.

2~%
- ~8 -Preparat_on oE sample _for evaluation The above coating liquids were coat.ed on the both-side subbed surface~ oE a IOO~m-thiclc polyethylene terephthalate film described in Japanese Patent O.P.I. Publication No. 09941t-19~4, whereby the samp~es ~or evaluation li~ted in Table 1 were prepared.
In this instance, on une side oE the subbed support was coated the backing layer coating liquid B-1 so as to make the dry gelatin weight ~g/m~, and at the same time on the backing layer was coated the protective layer coating liquid B-2 so as to make tlle dry gelatin weight lg/m2. Subsequently, on the other side of the subbed support was coated an emulsion layer so as to make the dry gelatin weight as yiven in Table 1 and the weight of silver 4.3g/m~, and at the same time on the emul-sion layer was coated the protective layer coating liquid for protection of the emulsion layer, with addition thereto of formalin as a hardening agent, so as to make the gelatin dry weight and late~ weight as ~iven in Table 1, whereby evalua-tion samples ~-1 to A-10 were prepared.
Each of the above coating liquids was coated so as to have a wet layer thickness adjusted to 64~m by a slide hopper method at a line speed of '70m/min. Exposure of each of these samples was made with its emulsion side contacted with an original placed in a roomlight printer P~627FM, manufactured by Dai-~ippon Screen Co., provided l,~ith an anelectric dis-_ 59 _ charge tube light source, manufactured by FUSION Inc. of U.S.
Each sample was processed in the following processing sol-utions under the following conditions. The amount of silver was analyzed by an X-ray fluorescence analyzer. The amount of silver after the processing was expressed in terms of the amount of silver in an area that gives the maximum density.
As for the coating unevenness, evaluation was made by examin-ing each sample's whole area overall exposed and processed so as to givs a density of 1.3 by using the above-mentioned printer. And for the rainbow mottle, evaluation was made by examining how rainbow mottles appear on the coated side of each sample exposed and processed so as to give a density of 4.0 or more.
Developer Composition A:
Pure water (ion-exchanged water) lSO ml Disodium ethylenediaminetetraacetate 2 g Diethylene glycol 50 g Potassium sulfite (55~ W/V aqueous solution) lO0 ml Potassium carbonate 50 g Hydroquinone 15 g S-Methylbenzotriazole 200 mg l-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide, an amount necessary to adjust pH to 10.9 Potassium bromide 4.5 g Composition B:
Pure water (ion-exchanged water) 3 ml Diethylene glycol 50 g Disodium ethylenediaminetetraacetate2s mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole llo mg 1-Phenyl-3-pyrazolidone 500 mg Before use, the above compositions were dissolved in the order of A and B into 500ml of water, and water was added to make the whole quantity 1 liter.
Fixer bath Composition A:
Ammonium thiosulfate (72.s~ W/V aqueous solution) 230 ml Sodium sulfite 9~5 g Sodium acetate, trihydrated 15.9 g Boric acid 6.7 9 Sodium citrate, dihydrated 2 g Acetic acid ~90% W/W aqueous solution) 8.1 ml Composition B:
Pure water (ion-exchanged water) 17 ml Sulfuric acid (50% W/W aqueous solution) s.8 g Aluminum sulfate ~aqueous solution, : Al2O3 equivalent content 8.1% W/W) 26.5 g Before use, the above compositions were dissolved in the order of A and B into 500 ml of water, and water was added to make the whole quantity 1 liter. pH of the fixer wa`s about ~.3.
Rapid processing conditions StepsTemperature Time Tank capac_ty Developing 35C lS seconds 20 liters Fixin~ 350C 15 seconds 20 liters Washin~ 18C lo seconds 15 liters Drying 40C lo seconds The time of each step includes the transport time in the crossover section prior to the following step. Dry-to-dry time is 50 seconds.
The results are shown in Table 1.

... ~ ~ o t ~ 7 o ~ D .
~3 u ~ '''I ~ ~ '~ '~ ~ ~ "' '~ ~ ~ ~ ~
~ ' ~ '` - ~ 50 ,, o ~ ~
~ ~ O ~ ~ ~

~ l a) ~ c~
~;~1 ~
e rO ~ a~ ' æ.~o~ ~ ~
t~

~ ~ ~
O O ~ ~ ~'a ?~ 00 o~ O o~ o O o~ O ~D ~ .
E~ o '' ,, a~ ~e X ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ n~
~~ oooooooooooo ~
~ ol ~ O ~ O ~ O O ~ ~
~ 0~ ~i o o o _i o ~i o ~
~ ~ o o o o oo co oo oo o o o o ~ ~ 8 ~`3 ~ t i ~ ~1 ~1 ~1 ~1 ~1 ~1 ~ 1:`1 ~ ~ L~

a~ H H ~ ~ fi ,~ ~ H ~ ~ 1~
~ _~ _ _~ _ _ _ _ ~ _ ~
~ ~ ,~ ~`1 ~

- 63 ~ 2~

~XA~PLE 2 The following hydrazine compound HD was used as a contrast increasing agent in place of the tetrazolium compound T in Example 1.
Consequently, the same results as in Example 1 were obtained.

Compound ~D

(t)Cslll I O
(t)C5H" ~ (Cll2)3NIICNI ~ NIICOCHO

Experiments were made in the same manner as in Example 1 except that the following sensitizing dye C was added at the time of chemical sensitization for preparation of samples in : Example 1, and exposure was made through the same glass wedge to a tungsten lamp, and consequently, quite the same results as in Example 1 were obtained.

Sensitizing dye C
C1~2C~12CN

~' ,~S
C211~SO3Na EX~MPLE 4 Experiments were made in the same manner as in Example l except that the polymer latex L-6 added a~ter the emulsion coating in Example l was replaced by polymer latex L-3 and the polymer latex L-6 added to the protective layer coating liquid was replaced by polymer latex L-7 (provided R: -CH33. In this instance, 2.sq/m2 of polymer latex L-3 was added as a latex component to the emulsion layer, which was coated so as to have a wet thickness of 80~m, and to the protective layer was added latex L-7 as specified in Table 2, whereby samples B-l to B-12 were prepared. The results are shown in Table 2.

; :~

.

~1 q ~ oo r o c~ o ~n ~
O ~ JJ ~ .~ + + _1. + + + ~ + + + +
~ ~vl !~
~ ~ :~,o oo ~ ~ o~ a~ o oo ~ O ~1 ~ ~`
.,, ~ o ,1 ~ ~ ,1 ,1 C`l ~ C~ ~ ~ ~ ,1 ~ ~ ,~.+.~.~+*++++*
,~

.,~ ~ a~

I ~~ ~, ~ o J~ ~ ~ O ~ ~ ~ ~
~j 0 ~; ~ t ~1 .~ l ~o~

~ ~ D ~ ~ ~ ~
~ o o~ o ~ b~ ~, E~ ~ , ~ ~0 ~o ~ ~ ~ 8 ~ ~"
~o ~ o o o o o o o o ~ ~ o ~o ~ ~
11~ ~0 ~) Ll ~ 0 ~ O ~ 00 1~ 0 ~ O ~ ~:1 h ~_i O O ~i O ~i ~i 0 0 _i O ~I
~ o o oo oo o o o o oo 50 0 ~ ~ 0-~
.~ _ ~ ~ ..
~-1 ~ H H -- --~ -- ~
~ ~ 0 d~ ~ m m ~ m Table 2 shows that the invention can provide a light-sen-sitive material which is capable of forming a high-~ and high-density image excellent in the dimensional stability even in either a super-high-speed processing or a conventional process-ing, and which is free of pinholes and coating defects.

Claims (14)

1. A photographic material comprising a support having thereon a light-sensitive silver halide emulsion layer and a non light-sensitive hydrophilic colloid layer provided outside of the light-sensitive silver halide emulsion layer to the support, in which total content of gelatin of layers at a side of the silver halide emulsion layer is 2.0 to 2.8 g/m2 and the non-light-sensitive hydrophilic colloid layer contains a polymer latex having an average particle size of 0.005 to 1 µm.

2. A photographic material as claimed in claim 1, wherein a tetrazolium compound is contained in one of the layer.

3. A photographic material as claimed in claim 1, wherein a hydrazine compound is contained in one of the layer.

4. A photographic material as claimed in claim 3, wherein an average particle size of the polymer latex is 0.02 to 0.5 µm.

5. A photographic material as claimed in claim 4, wherein an average particle size of the polymer latex is 0.02 to 0.1 µm.

6. A photographic material as claimed in claim 1, wherein the polymer latex is contained in the hydropylic colloid layer outside of the emulsion layer to the support.

7. A photographic material as claimed in claim 6, wherein the content of the polymer latex in the hydrophlic colloid layer is 0.01 to 1.0 g/m2.

8. A photographic material as claimed in claim 7, wherein the content of the polymer latex in the hydrophlic colloid layer is 0.02 to 0.6 g/m2.

9. A photographic material as claimed in claim 6, wherein con-tent of gelatin in the hydropylic colloid layer is 0.1 to 1.5 g/m2.

10. A photographic material as claimed in claim 9, wherein content of gelatin in the hydropylic colloid layer is 0.3 to 1.2 g/m2.

11. A photographic material as claimed in claim 2, wherein content of the tetrazolium compound is 1 mg to 10 g per mole of silver halide in the photographic material.

12. A photographic material as claimed in claim 11, wherein content of the tetrazolium compound is 10 mg to 2 g per mole of silver halide in the photographic material.

13. A photographic material as claimed in claim 3, wherein content of the hydrazine compound is 10- 5 to 10-' mole per mole of silver halide in the photographic material.

14. A photographic material as claimed in claim 12, wherein content of the hydrazine compound is 10-4 to 10-2 mole per mole of silver halide in -the photographic material.