CA1058942A - Photographic material - Google Patents

Abstract

PHOTOGRAPHIC MATERIAL
Abstract of the Disclosure A colour photographic material containing in a blue sensitive silver halide emulsion layer a diffusion-resistant 2-equivalent yellow coupler and an open-chain or ring-closed ketomethylene white coupler which is substituted by alkyl or aryl on the methylene group. The material shows a reduced basic fogging tendency and increased stability against the influence of heat and moist conditions.

Description

~5~3~4Z

Thi~ invention relates to a colour photographic matsrial which, in a blue-sen~itive silYer halide emulsion layer contains a dif~usion resi tant 2~equivalent yello~ coupler and an open-chain or ring-shaped ketomethylene white coupler whlch is substituted by alkyl or aryl on the methylene group. The colour photographic material according to the invention shows reduced basic fogging and increased stability in a heating cabinet having heat and moist conditions in the blue-sensitive layer.

It is known that colour photographic images can be obtained by developing the exposed silver halide oi a lightsensitive silver halide emul~ion layer with an aromatic developer sub~tance containing primary amino group~ in the presence o~ colour coupler~. The colour couplers react with ~5 the oxidisdd colour developer to ~orm the image dye depending upon the silver image pre~entO
~he light~ensitive photographic multilayer material i8 ;~: generally used in subtractive three-colour photography, containing separate red-,green~ and blue-sen~itive ~ilver .halide emulsion layers in which cyan~ magenta and yellow image dyeæ, respec~ively, are ~ormed during colour develop-ment in the pre~ence Or suitable col~ur coupler~.
The couple~s used for the cyan dyes are normally phenol3 or naphthols~ the cou~lers used for the magenta dyes are usu~lly pyra~olones and the couplers u~ed ior the yellow dye are usually compound~ containing a methylene group with two ~ ;
carbonyl group6 attached to it. ~he dyea iormed by coupling are azomethinea, indamines or indophenol~, depending upon ~he ~S8~4~

kind of the coupler and developer used. Conventional yellow couplers contain an active methylene group which reacts with the oxidised colour developer during colour development, four equivalen~ of developable sil~er halide being required ior the reaction. Accordingly, these couplers are known as 4-equivalent couplers. There are al~o couplers containing a methylene group in l~hich one hydrogen iB substituted by a group which can be split o~ during coupling. In this ca~e, only two equivalents o~ developable ~ilver halide are required ~or ~o~min~ the dye. Accordingly, these co,uplers are known as

2-equivalent couplers.
The following groups,have already baen proposed as splittable groups for yellow couplers:
1~ ~alogenl as described for example in French Patent 1~ Specifications No.991,45~ and 869,169, US Patent Speci~ication~ No.2,728,658 and 3,277,155 and German Offenlagungs~chriit No.2,114,577;
20 the group OR, where R iæ alkyl9 aryl or a heterocyclic ~radical or acyl radical, as described ~or example in Briti~b Patent Specification NO.1~O92~5O6J in French Patent Speci~ication~ No.1,411,385 and 1,385,696, and in US Patent Speci~ications No,3,447,928 and 3,408,194;

3. a group SR~ as de~cribed for example in Briti~h Patent Speci~ica$ion No.953,454 and US Patent Specification ,' No.3,2659506;

4. a group R1 / N~ ~ ~ R2 \ N~ l~' R3 A-G 1247 _ 3 _ ~':

, . . .. , : . .

105~ 4Z

as described in ~erman Offenlegungs~chrift No. 1,8a~,420;

5. the radicals SO3H and SCN, as described in British Patent Specification No. 638,039 and United States Pat~nt Specifi-cation No. 3,253,924;

6. a group ;
/ Co ~ / SO2~
-N Z or -N Z
\ CO ~ \ CO -~ ' as described in German Offenlegungsschrifts No. 2,163,812;
2,213,461 or 2,057,941; ;

7. certain pyridone and pyridazone groups, as described in German Offenlegungsschrift No. 2,318,807;

8. also the heterocyclic groups mentioned in German Offen-legungsschrift OS 2 329 587, British Patent No. 1,476,760 `~
and Canadian Application 201,911. `
, Accordingly, the splittable groups mentioned above under ,~
groups numbers 6 to 8 are essentially nitrogen-containing hetero-cyclic radicals corresponding to the ~ormula :
,.~ . r~ ~ .
:~ : --N Z

:~
in which Z represents the ring members required to complete a cyclic acid amide, a cyclic acid imide or a 5-membered or 6 membered unsaturated heterocyclic ring, such as for example a , pyridone, pyridazine, 3-hydroxy-6-pyridazinone, 2-pyridinone, 1,2,4- or 1,2,3-triaxinone, quinazolinonej benzotriazinone or benzoxalinone, pyrrole, indole, indoxyl, pyrazole, benzopyrazole, imidazole, benzimidazole, triazole, benztriazole, 2-benzthiazo-,, lone, 2-benzoxazolone or phthalimide ring.

.. .. . . . ..
~ ::,: , :~S~4~2 In principle, the advantage of 2-equivalent couplers over 4-equivalent couplers is already known:
The quantity of silver halide required to form a certaln quantity of dye is about half the quantity required in the case of 4-equivalent couplers, so that the quantity o~ ~ilver halide required ~or producing the lightsensitive pho-tographic material can be reduced. The result of this is that the emulsio~ layer can be thinner, which in turn has a favourable effect upon resolution and sharpness 0~ the photographic material.
~mong the conventio~al 2-aquivalent yellow couplers with the aforementioned splittablegroups, the 2-squivalent coupler :~
~ith halogen~ aroxy or the aforem0ntioned groups 6 to 8 h~ve proved to be particularly suitable in practice as splitta~le groups, because in the colour development o~ a photographic material the reactivity of the 2-equivalent yellow couplers ~:
must be iast eno~gh to ensure adequate colour densities, even with ~hort processing times.

However, one problem which has not yet been satisiaotorily -~
solved in practice is that the basic ~og level of 2-equivalent yellow couplers i8 generally higher than that o~ corresponding 4-equivalent yellow coupler~ and is more or le~s pronounced according to the type ~ splittable group~. This behaviour is~unaf~ected by the constitution o~ the corresponding yellow coupler.
In addition, the IOg s tability of 2-equivalent yellow couplers, especially when the expo~ed, unproce~sed photographi¢

A-G 1247 - 5 ~

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

. .

l~Sl~9~Z
material is stored at elevated temperature, remains unsatis- ;
factory despite numerous attempts to increase fog stability :
by using new, splittable heterocyclic groups, for example those mentioned above under groups numbers 6 to 8.
Accordingly, there i5 a need in practice to reduce the basic fog level of 2-equivalent yellow couplers of the kind used in light sensitive photographic materials by suitable measures, and to increase their fog stability.
It is an object of the present invention to provide a light sensitive material in which the disadvantages of known materials containing a 2-equivalent yellow coupler are reduced . ~; :
or substantially obviated.
It is known per se that white couplers of the above type can fie added to conventional colour photographic materials containing conventional 4-equivalent couplers in order to ~ ~.
obtain improved colour separation. In practice, however, it ;~ ~`
is recommended to use difusion-resistant white couplers in the intermediate layers of the respective silver halide ~emulsion layers of a multilayer material with incorporated colour couplers to ensure that the developer oxidation product ,.
- .

~.

(~ ~
... ; ,. . ... .. .
, . .. ..

~S~3~4Z

formed during devc10pment does not reduce the maximum density o~ the dye image formed through undesirable co-reaction of the white coupler to form colourless coupling products.
It has also been proposed to add white couplers to the silver halid~ emulsion layer in order to control the gradation and sensitivity of conventional 4-equivalent couplers.
According to German Offenlegungsschrift No.l,906,0lO, the gradation of slow-coupling 4-equivalent 5-pyrazolone couplers ~-substituted in the 3-position by alkyl, acylamino or sulphon-amido, can be slightly increased by diffusion-resistant white coupler compounds which contain an acid group and which, for this reason, can presumably act as a wetting agent and there is no hint in the disclosure of the speci~ication that the maxi-mum density produced by the colour coupler is not imparied by ~.-the addition o~ the white couplerO
.
Accordingly, it was surprising to find, in accordance with the invention, that the combination of diffusion-resistant, .~ hydrophilic or hydrophobic, more especially hydrophohic9 white couplers,.for example 5-pyrazolone couplers subs$ituted by alkyl or aryl in the coupling position, wi$h 2-equivalent yellow couplers in the blue-sensitive emulsion layer of a colour photographic material reduces the basic fog level substantially independently of the constitution of the yellow coupler orsplittable group and that the stability of the basic fog level during storage in warm a~r can be considerably improved.
It has surprisingly been found that an addition of up to A-G 1247 _ j -5~3194z 40 mol ~, preferably from 5 to 30 mol % and more especially from 10 to 20 mol ~, of white couplers to the layer, based on the quantity of 2-equivalent yellow couplers used, has subs-tant-ially no deleterious effect either upon the sensitivity or upon the maximum density of 2-equivalent yellow couplers whose Split~_ able radicals are halogen, aroxy or one of the heterocyclic radi-cals mentioned above in groups number~ 6 to 8. This effect is surprising insofar as the coupling rate o~ the pyrazolone white couplers, ~or example, is faster than that o~ the relatively quick~reacting 2-equivalent yellow couplers with the releasable groups halogen, aroxy or groups numbers 6 to 8 as defined aboYe.
Even with a more slowly reacting white coupler, the skil-led worker would have expected an exposed an~ developed step wedge to have reduced the density o~ the dye produced by the colour c~up-ler on chromogenic development through co-coupling of the whlte coupler in the range o~ short exposure times, thus giving r}s~e to a reduction in the sensitivity of the blue-sensitive layer, and maximum colour density to have been reduced by compet~tive coup-ling in the range of long e~posure times.
It has been ~ound that, even in the case of photographic materials in which the molar ratio of silver to colour coupler in the blue-sensitive layer is relatively low, amounting to .' approximately 2:1, the combination according to the invention of 2-equivalent yellow couplers and white couplers has hardly any effect either upon colour density or upon sensitivity. ~In general, the molar ratio of silver to colour coupler in the blue -sensitive layer is more than 2:1 and preferably more than 3:1.
Accordingly, the invention relates to a photosensitive colour photographic material with at least one silver halide emulsion layer which, in a blue-sensitive silver halide emulsion layer, contains a di~usion-resistant, preferably hydrophob1c 2-equivalent yellow coupler and up to 40 mol ~, preierably 1~5~
from 10 ~o 30 mol ~, more especially from 10 to 20 mol ~, based on the quantity of yellow coupler used, of a diffusion-resistant white coupler~ more especially a white coupler based on 5-pyrazolone.
Examples of 2-equivalent yellow couplers ~itable for use in accordance with the invention are open-chain ketomethylene yellow couplers such as acylacetonitrile or acyl acetyl yellow couplers, more especially acylacetamide yellow couplers, in which one hydrogen of the methylene group is substi-tuted by a splittable group X, X representing halogen, preferably chlorine,~
aro~y, for example phenoxy, or the group -N Z
~ ~ .
in which Z represents the ring members required to complete a cyclic acid amide, a cyclic aci~d imide or a 5- or 6-membered unsaturated heterocyclic ring, such as for example a pyridone9 pyridazine, 3-hydroxy-6-pyridazinone, 2-pyridinone7 1,2,4- or 1,2,3-triazinone, quinazolinone, benzotriazinone or benzoxa--~. .
linone, pyrrole, indole, indoxyl, pyrazole, benzopyrazole, imidazole, benzimidazole, triazole, benztriazole, 2-benzthiazo-lone, 2-benzoxazolone or phthalimide ring.
In general3 the choice of the 2-equivalent yellow coupler radical which may be used ~n accordance with the invention is not critical. It is generally preferred to use those which ~how the required photographic properties through suitable choice of the substituents. Suitable 2-equivalent yellow coupler radicals, are for example, ketomethylene yellow coupler radicals corresponding to the formula o I B - C - CH - B~
in which B represents a straight or branched chain alkyl radical ,' .~ , ' .. ., ,; :.. , ' ,. . , : :

31 6~5~ Z

with preferably 1 to 32 carbon atoms, more pre~erably 1 to 18 carbon atoms, the secondary or tertiary carbon atom in a secondary or tertiary alkyl radical pre~erably being directly a-ttached -to the carbonyl radical; an alkoxy alkyl radical, a dicycloalkyl radical, a heterocyclic radical or an aryl radical which may optionally be substituted by alkyl with preferably 1 to 18 carbon atoms9 alkoxy with preferably 1 to 18 carbon atoms, halogen, ~or example fluorine or bromine, acyl, acylamino, acyloxy, carbamyl, sulphamyl, sulphonamido or carboxy;
B' represents cyano or the group R
-C-N

15. R5 represents hydrogen or an alkyl radical preferably with ~-1 to 5 carbon atoms, for example a methyl or ethyl radical;
R6 represents an alkyl radical pre~erably with 1 to 18 carbon atoms~or pre~erably an aryl radical, for example a phenyl radical which may be substituted by alkyl with preferably 1 to 18 carbon atoms, alkoxy with preferably 1 to 18 car bon atoms, halogen, for example fluorine or bromine, acy~, acyloxy, acylamino, carbamyl, sulphamyl, sulphonamido or carboxy.
In order to obtain su~iciently high resistance to di~fusion, the substituents Rl, R2j B or B', preferably the-substituents B and B', are provided with radicals which make them resistant to di~fusion9 ~or example straight or branched chain alkyl radi.cals with lO to ~ carbon atoms. Alternatively, they may bé substituted by alkyl-substituted phenoxy radicals which are attached to the opti.onally aromatic radicals B~ B', : , . :, , , . , . . . : . , : , - : . : . - ; , .:: , .

9d~Z

R1 or R2 aither directly or indirectly, for example through -0-, -S-, -CONH-, -NHGO-, -SO2NH-; -NHSO2-, or other intermediate membersO ~ere alkali ~olubility is re~uîred 7 a-t least one of the radicals B, B', Rl or R2 can contain alkali-solubilising --groups, preferably sulpho groups. ;
The 2-equivalent yellow couplers which may be used in accordance with the invention are known ~ se and are obtained by known methods. These 2-equivalent yellow couplers with the a~orementioned heterocyclic releasable groups9 are generally obtained by reacting the corresponding 2-equivalent yellow couplers containing halogen as the splittablegroup with the required heterocyclic compound in an aprotic solvent, such as ..
acetonitrile, dimethylformamide or hexamethyl phosphoric acid ~`
triamide, in the presence o~ a base, as described ~or example 15 in the literature references mentioned above under groups ;~
numbers 6 to 8.
White couplers suitable for use in accordance with the invention are di~fusion--resistant, hydrophilic or preferably hydropho~ic 5-pyrazolone compounds, in which one hydrogen on the methylene group is replaced by an aliphatic, cycloaliphatic, aromatic or mixed aromatic-aliphatic radical, for example -alkyl with 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms, more especially cyanoethyl, ethyl, methyl, benzyl or phenyl.
To obtain adequately high resistance to diffusion, the 5-pyrazolone compounds substituted in the 4-po~ition which may be used in accordance with the inven$ion additionally contain directly or indirectly through optionally aromatic radical~ :~
in the l- or 3-position radicals which make them resistant A-G 1247 -.11 -.,.. , .,~ .. ..

.. . . " . : . . ~ . .

~6~5894Z

to diffusion, ~or example linear or branched a:Lkyl radicals containing from 10 to 18 carbon atoms; alkyl-substituted phenoxy radicals, such as a t-butyl-cyclopentyl phenoxy radical, or alternatively they may be at-tached to a polymeric latex, as described for example in German Of~enlegungsschrif~
OS 24 07 569 and OS 23 04 319 or OS 2,044,992.
Preferred white couplers are monomeric or polymeric 5-pyrazolone compo~nds which are substi-tuted in the 4-position by alkyl and in the 3-position by alkyl with .from I to 20 carbon atoms, or acylamino, ~or example carbonamido or sulphonamido, the a~orementioned acyl group being derived from aliphatic, araliphatic or aromatic carboxylic acids or sulphonic acids.
The white couplers suitable for use in accordance with the invention are known ~ se and ean be obtaine~ in known manner by condensing the corresponding a-substituted benzoyl ~;
acetic esters with phenyl hydrazines, as described for example in German Patent No.1,155,675 and German Of~englegungsschri~t No.1,909,067. To make them soluble in alkalis, the white couplers may contain acid groups. It is preferred to use hydrophobic white couplers which can be introduced into the layer in dispersed form or which are actually prepared in disp~rsed ~orm in aqueous phase, ~or example by latex poly-merisation.
~he production of latices o~ this kind is described9 ~or example, in Belgian Patent Specification No.669,971 and in British Patent No.1,130,581. In general, 2-pyrazoline-5 one white couplers which are e.~hylenically unsatur~ted in.the 3-position are polymerised with one or ~ore monomers contain-.. .. .. . . . .

,-,, . ~ . . .. . .

1(3 ~8~4Z
:
ing at least oneethylenic group.
Examples o~ yellow co~plers suitable for use in accordance with the invention are set out in Table I below:

Table I
O O
B-C-CH_C-R
,~

B . X I Fp ( C) _ _ _ ____ ~

~1 ~ C14H~9 ~ OCH3 ~ ~ ~ ~C-H 92 ::

: ' ~ ~ ;' : SO N~ ~H N I
~ In ~ J ~

._ ~ 37~ ;

4 ~14E~29 NH--~ N2~1 se A-G 1247 - 13 - ;

~51~39~4;2 I_ ~ ~

~5 ~ ~ ~1 4H29 -NH~ Co~ lcH3No2 L ~ 1 03 t -- -1 6 t-Butyl ~S02NHCH3 N 1 00 14H29 _~ N~z ~11 `

I ~C14H29 OCH ~ HOOC~ ' 127 ., HOOC J

~_ ~ . _ ~.___~_~ _~
~ , :

g I ~jC1 4H29 ~ H300C~ I 55 _~ CU300 N

~. :,...

A-G 1247 - ~4 -, , . . ,.
.. . .

~058~4;2 B R X Fp ( C ) ._ _~ _ _ t-Butyl C16H33 CH300C ~N ~1 . . __ __ ~ S02N ~CH3 11 ~, OCH3 ~ ) CH300C ~ 107 ,,......... . . .~ . , NC N
12 ~9- -NH--~3 ~3 ~ 176 . . ; 1' `
_ ~ -_ . ~ ~

¦ 13 ¦ t-13u 1 ~ C_COOCH3 72 ~ ;

502NHCH3 I I ~
___ ____ _, ~ ~ -NH~ ~2~ CH3 119 _ , ',", ~Ll)S1399LZ

_. __ _ ~ R X Fp (C) _ __ ~

1 15 ~~ -N~ ~ N 89; ¦

,_ Cl _ - ~ t- --NH- ~3NH C O o~N

16 ¦ t-ButylC5H1 1 , 180 C~ H11 ~- CH2 . I

~r7 b-But rl~ 0C1 6H3 ~ ¦ o~N I 130 502NHCH3 ¦ , I. . . ~ ~ t~

~~ -NH--~3 ~ 102 . : I COOCH
~ I , : ':
__ A-G 1247 - 16 - .

.

4~

~ __ ___ Fp ( C `
_____~_ _ _ ' .' 19 I t-Butyl ~ OC1 6H33 ~ 0~,~

, _ _~ .. . .

20 , t-Butyl ~ ~6 33 ~ 7N ¦ 110 l S02NHCH3 Cl _ _ ! _ ~_ . .

21 ¦ ~ OC1 6H33 S02NHCH3 Cl 1~ ~--H I tt 22 ~ t-E~uty ~ ~6 CH3 N~ ~ oLly I . S02NHCH3 _~ -~ ~ . .
~2NHCH3 ~ o=~

: 23 t-Butyl /N ¦ 54 1 . :
¦CH3 C1 8H37 I I .
..

~OS~99L2 ~ _~ , _ . _, . .
B~ R X !Fp ( c) _ __~ _ . . +_ _ , Z4 t-Butyl ~6H33 =f~3 91 _ __ ~ . ~ ~

~ 25 ~ t-Butyl ~ PC16H33 8=
! S02NHCH3 1 .. _ _., ...

C14H29 I CH~ 0~ .
26 ~ ~NH~) ~
i, ~ ' i I i.
' ~S02N~ICH3 27 It-I3utyl ~ 3 CH3~0 ~ 70 C ~ 6H33 ¦ 3 OC16H33¦ ~3 ¢~o A-G 1247 . - 18 -.,'~

.... . . .... . ...
.. . .
- ~." , , ; ' , :, l~S8C1~4~

=~:~ il ~ l _ _ ___ OCH3 O

~1 4H29 ~

_~ _ . , . ... , O
_~C 1~ 33 ~H3 ~) ~ -NH ~ COOH 106 OOH3 O ¦

31 ~ 4H29 ~ ~ 132 ~302~ 2 CO~C~3 ~-_ _ _ ~, O ~ '.~-32 C~ 4U~ 9 Z;~' COOCH3 _ __ _ .~ __ ~'' ' . ; 14H~g .
~3 ~ ~ 3CH3 Cl ! 95 . ~. ~ '.~
__ _ " ., ., A G 1247 ' - 19 -.. .. . . . .

~s~g42 - - ~ - ~ - - - -B R X F~ (C) , , ~ ~ . . ~ . __ . 34 ~ - NH ~g F 56 . ~ __ ~ , OC ~ 4H29 S02N~ICH~5 ; ~5 ~ ~ ~ ~ Cl 4 ~ ~ ~ _ IC14H29 ~ ~

1 ~6 ¦ ~ l - H ~ -S02cH3¦ Cl ¦ 4 ¦~A .

., _.~_ ~ ~
: 37 ~ CC1~ ~ 3 ~ Cl 96 , ~:
' According to the invention, couplers l to 32 are ~ -.
preferably used with hydrophobic white couplers, whil~t couplers 33 to 379 with halogen as the splittable group, may be used with hydrophilic and hydrophobic white couplers in the blue-se~sitive layer according to the invention~ AS
shown in the following.
Examples of white couplers suitable ior uqe in accordance with the invention are set out in ~able II below Table~II

' ; . . : . . .
- ~

~6~5~94Z

Tab H
C1 5H31 -GO-~-C--C-CH3 N /C-O
Cl~,Cl Cl CH

II C~o_cH2_cH2_o-c~-NH-c _ C-CH3 C14H29 N\ / =O

S02(~H3 ~30-Co-NH-C~--C-CH
III ~l t 3 C1 5H3/ N C=O

I

~Cl . ~:

IV Cl ~O CH~-CXz-O-C~O-NH-C--CH-CH3 C1 4H29 : N ~=0 ~Cl .

,~

, .. ,, ....... . , . - , ... .. ... . ... .. . . .

~L~s~ z V Cl ~--O~C~-CH2-O-CO-NH-C ~ CH~CH3 C14H29 \ N /
Cl- ~ -Cl ~ . .
CH3 Cl VI _ -CH2-C - - f O=C-NHll J CH3 O=C OC4Hg by wei Bt ~ ~ Y = 24.2 ~
¢~ J ~ , byweiBt VII C17H35 ~ CH3 ~ ; ;
~=0 . ,~
Cl~

Cl _ _ ~ CH - - CH- - CH CH - _ ~III l . ¦ 2 O,C--NH ~ CH~ COOH

rl I~ 3,4-dimethyl 2~ octadecylene ~uccinamidop~enyl)-5~pyrazolone 3-phenyl-4~methyl-1(3~-octadecylene ~uccinamidophenyl)-5-pyrazolone 1~5~2 XI CH ~ CH3 ~, J--W~ CO-CH-C16H3 The colour photographic material~ according to the in~ention which, in the blue sensiti~e æilver halide emulsion layer, contain a combinati~ o~ the a~orementioned 2 equlvalent yellow couplers and white couplers, are di~tinguished by the following advantagss:
As already mentioned, the basic ~og level of the blue-~en~itive emul3ion layer is reduced in comparison with colour photographic materials containing the aforemen~ioned 2~

equivalent couplers~ whilst the ~og ~tability of the colour .
photographic materials according to the in~ention i9 considerably increased wi.thout any really adverse efiect upon sensitivity or grada~ion. The 2-equivalent yellow couplers used in accordance with the invention show out~tanding coupling -activity which ix in no way in~luenced by the simultaneou~ use o~ the white couplers, 90 that the aiorementioned adv&ntages of the 2~equivalent couplers c~n be fully utili~ed, In the productio~ o~ the lightse~sitive colour material accordi~g to the inrention9 the dif~u~ion-re~i~tant yellow ooupler~ can be introduced into the silver halide emulsion layers by a~y oi the known technique~. For e~mple) the water-insoluble or in~dequately water~oluble colour couplers oan be di~o~ved in ~uitable water-im~i~cible or water-mi~cible~ high-boiline ~olvent~ ~uch a~ ~or e~ample~ dibutyl A-G 1247 ~ - 23 -' ' :
': .' . , :: ' ' ' ' ' ' ' ,. : , : ~

:10~ 4;~

phthalate or tricre~yl phosphate, or low-boiling organio ~ol~ents ~uch as ethylacet~te, methylene o~loride9 chloroform or diethyl o~rbonate, or mlxturs~ thereof. The resulting solution i8 then disper~ed, optionAlly in the pre~ence o~ a wettirlg agent or di3persant, into the hydrophilic colloid composition which repre~ent3 all or only part of the binder o~ the colloid layer. Tha low-boiling solvent may then be di~tilled o~
In addition, the hydrophilic colloid composition may of cour~e contain other ~tandard ingr~dient~.
The solution oi the colour coupler doe~ not have to be directly di~persed or dis~olved in the ca~ting compo3ition o~
the ~ilver halide emulsion layer or any other weter permeable layer. Thie solution may ~ith advantage be initially disper~ed or dissol~ed in an aqueous, non~tight sen~itive solution o~ a hydrophilic colloid~, a~ter which the mixture obtained, following removal o~ the organic solvent u~ed, ii any, i~
thoroughly mixed ~u~t before application with this ca~tilag composition o~ the light~ensitive silver halide emulsion layer or the other water-perme~ble layerO More iniormation on particularly suitable technique~ ~or i~corpor~ting colour couplers into hydrophilic colloid layere o~ & photographic material can be found in published Dutch Patent Applications No.65 16 42~; 65 16 424; 66 00 098; 66 00 099 and 66 00 628;
in Belgian P~tent Spe~ication~ No.722~026 and 750,889; in US Patent Speci~ tion~ No.2,304,940; 2,269~158; 2,284,887;
2, 304, 939; 2, 304, 940 and 2 9 322, 027; in Briti ~h Patent Speci-1~099~16;
~i~ation~ No.791,219; 1,098,594; 1,099,414; 1,099,415;/l,Og9, 417; 1~218~190, 1~272~561; 1~297~347; and 19297,94q; i~ ~-A-G 1247 ~ - 24 - ~

,, . , , , ~ , , l~S~g3~2 ~, French Patent Specification No. 1,555,663 and in German Patent Specification No. 1,127,714. These Dutch Applications were filed and published assigned to Gevaert-Agfa N.V. as follows: -No. Filed Published 65 16 423 Dacember 16, 1965 February 25, 1966 .
65 16 424 December 16, 1965 February 25, 1966 66 00 098 January 5, 1966 March 25, 1966 ~ .
66 03 099 January 5, 1966 March 25, 1966 ` :
66 00 628 January 18, 1966 March 25, 1966 :
,, , -', , : ~'`' ' ':" `
:, ~
` -' ;` ; ' ~ , ~' ;'`~';

-, ...

~ ¦ -24a-" ., " , . . . .. . . .

,f''`'` ~058~
, The white couplers used in ~ccordance ~ith the inyention may be similarly incorporated. However, the colour couplers ~ ~
and the white couplers do not have to be separately incorporated ~ ~ -in the casting composition of the silver halide emulsion layer.
Instead, they may ev~n be directly dissolved together in a solvent, dispersed and added to the silver halide emulsion.
The dispersions or emulsions according to the invention - -may be used in various kinds of photographic coloux materials, i.e. in negative, positive and also rever~al materials. The colour photographic multilayer ma~erials usually contain at least one blue-sensitive silver halide emulsion layer with a ` -`~
yello~ coupler, at least one green-sensitised silver halide emulsion layer ~ith a magenta coupler and at least one red- ~
sensitised silver halide emulsion layer with a cyan coupler. ~ ~;
These colour materials may further comprise one or more `
intermediate layers, ~ilter layers and surface protection layers.
Suitable supports include paper, glass, cellulose ester ~;
film, polyvinylacetate film, polystyrene film, polyeth~lene ~
: .
terephthalate film and other such filmc; of resin-like materials.
Ho~ever, it i5 also possible to use papers coated with ~-olefin polymers, for example papers lined with polyethylene, polypr~pylene, and ethylene-butylene copolymers. ~;~
; ~ To prepare photographic colour images according to the invention, an exposed silver halide emulsion layer is developed ~ ~
.:
~.

''' ' ~

': ' "..':;'. ~:

.: ., - . . , ...... .. , " :

89~

with an aroinatic primary amine developer in the presence o~ a colour coupler according to the invention. Suitable developer substances include any colour developer substances which are able to form azomethine dyes. Suitable developer substances are aromatic co~pounds such as p-phenylene diamine and derivatives thereof, for example N,N-dialkyl-~-phenylene diamines such as N,N-diethyl-~-phenylene diamineJ N,N-diethyl-3-methyl-~-phenylene diamine, 4-amino-3-methyl-N-ethyl-N-methane sulphonamido ethyl aniline, N-ethyl-N-~-hydroxyethyl- ~ -~-methyl-~-phenylene diamine, N-butyl-N- ~-sulphobutyl-p-phenylene diamine and N-ethyl-N-~-hydroxyethyl-~-phenylene diamine.
Other suitable colour developers are described~ for example, in J.Amer.Chem.Soc. 73, 3100 - 3125 (1951).
Suitable lightsensitive emulsions are emulsions of silver halides such as silver chloride, silver bromide or mixtures thereof~ which may have a small silver iodide content of up to 10 mol ~, in any of the hydrophilic binders normally used. Gelatin is preferably used as binder for the photo-graphic layers. However, it may be completely or partly re-placed by other natural or synthetic binders. Examples ofnatural binders include alginic acid and derivatives thereof, .
such as salts9 esters or amides, cellulose derivatives such as carboxy methyl cellulose, alkyl cellulose such as hydroxy ethyl cellulose, starch or derivatives thereo~, such as ethers or esters, or carragenates. Suitable synthetic binders A-G 1247 - 26 ~

.. ~ . . . . . .... .

: . . . .

--- 1 [3S~ 4;Z
include polyvinyl alcohol, part.ially hydrolysed polyvinyl aceta-te, and polyvinyl pyrrolidonel The emulsions may also be chem:ically sensiti~ed, Yor example by the addition of sulphur-contain:ing compounds during chcmical ripening, for e~ample allyl isothiocyanate, allyl thiourea, sodium thiosulphate and the like~ Other suitable chemical sensitisers include reducing agents, for example the tin compounds described in ~elgia~ Patent Speci-fications No.493,464 or 568,687, also polyamine~ such as diethylene triamine, or aminomethane sulphinic acid deriva-tives, for example according to Belgian Patent Specification No.547,323. ;
Other suitable chemical sensitisers include noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium. This method o~ chemical sensiti~ation is described in the article by R. KOSLOWSKY
in Z.Wiss Phot. 46, 65 - 72 (1951). It is also possible -to sensitise the emulsions with polyalkylene oxide derivatives, ~or example with polyethylene o~ide having a molecular weight in the range from 1000 to 20,000, and with condensation products of alkylene o~ides and aliphatic alcohols, g~ycols cyclic dehydration produ¢ts of hexitols, with alkyl-substituted phenols, aliphatic carbo~ylic acid~, aliphatic amines, aliphatic diamines and amides.The condensation products have a molecular weight of at least 700, preferably more than 1000. To obtain special effects, the~e ~ensitisers may of course be used in co~binationj as described in Belgian Patent Specification No.537,278 and in British Patent Speci-fication No.7277982.
The emulsions must show adequate sensitivity in the blue spectral region. .In general~ non-~ensitised emulsions who~e ~n~itivity i~ ba~ed on the natural 3ensitivity of the silver .. , ... ... . , . ~
~ . . ..

,. . . : . . .

~85~
halides employed are used for this purpose. HoweYer, it i9 ~lso possible spectrally to sensitise the silver halide emulsions in the blue region, for example by sensitisers of the kind described in British Patent Speci~ication No.1,285,078 The emulslons may contain the usual stabilisers, for example ho~opolar or salt-like compounds o~ mercury with aromatic or heterocyclic rings, such as mercapto tria~oles, simple mercury salts, sulphonium mercury double salts and other mercury compounds. Other suitable stabilisers includs azaindenes~ preferably tetra- or penta-azaindenes, especially those substituted by hydroxyl or amino groups. Compounds o~
~, this kind are described in the article by BIRR, Z~Wisso Phot.
47, 2-58, (1952). Other suitable stabilisers include heters-cyclic mercapto compounds, ~or example phenyl mereapto tetrazole, quaternary benzthiazole derivatives, and benztria-zole.
To promote coating unifo~nity, to reduce the formation of repellant spots and/or to increase the coating speed, the hydrophilic colloid layers, for example silver halide layers~
2Q intermediate layers and surface layers~ may contain ooating aids such as~ ~or example, saponin~ salts of dialkyl sulpho-succinic acid, such as sodium diisooc~l sulphosuocinate, 2-alkyl sulphoben~imidazoles, for example the ~odium 3alt o~
2~heptadecyl ben~imidazole disulphonic acid, alkaryl polyeth~r sulphuric acids, al~aryl polyether sulphonic acid, carboxy alkylated polyethylene glycol ethers or esters, o~ the type described in French Patent Speci~ication No.1~537,417, such as ~or example iSo-c~Hl7-c6~ 0CM2CH2)~0C~2C _, sulphates, sulphonates and carbo~ylakes~ ~or example sodium isotetradecyl sulphate, more especially fluorinated surfaoe active agents of the kind described, ~or example, in Belgian Patent Speci~ication NoO742~680 and in German O~enlegungs , , ~1394;~

schrifts 1,950,121 and 1,942,665, and also the following compounds:

SO~Na C8F1 7S02N ( C2H5 ) (CH2CH20 ) 4 ~ ., H(CF2)nCOO(CH2CH20~16CH3 mit n H(cF2)6coo(cH2cH2o)23~co(cF2)6 H(CF2)nCOO~C~I2CH~0);~54CO(CF2)nH mit n = 8 oder 10, FClHC CF2-0 ( CH2CH20 ) 13 CF2 F;3C - ( CF2 ) 6CONH ( CH2~H2 ) 1 7H

COO-~CH2CH20)1;5-co ~ 3 OCF2-CFClH OCF2-CFClX

~ he emulsions may be hardened in the usual way before or after coating~ for example the photographic layers may be hardened with ~ormaldehyde or halogen-substituted aldehydes containing a carboxyl group, such as mucobro~ic acid~ di-ketones, ~ethane sulphonic acid esters, and dialdehydes.
;~
The photographic layers may also be hardened with ..... .
hardeners of the epoxy type, of the heterocyclic ethyleneimine or acryloyl type. Examples of hardeners ~uch as these are described, for example,in German Of~enlegungsschrift No. -~
2,263,602 or British Patent Specification Nol~266,655. It is also possible to harden the layers by the process deecribed in German Offenlegengsschrfft No.2~218,009 in order to obtain ;~
colour photographic materials which are suitable $or high-temperature processing ..... , .. . . . ,, , , , . .... , ...... .. ,. " , , .. . . .. . ~ . . . . .

~L~5~2 It is also possible to harden the photographic l~yers and the colour pho-tographic multilayer materials with har~rs based on diazine, triazine or 1,2-dihydroquinoline/the type described in British Patent Specifications No.1,193,290;
1,251,091; 1,306,544; 1,266,655; French Patent Speoi~ication No.7,102,716 or in Germano~enlegungsschrift OS 23 32 317.
Examples of hardeners such as these include diazine derivatives containing alkyl or aryl sulpho~yl groups, derivatives of hydrogenated diazines or triazines such as, for example 1,3,5-hexahydrotriazine, flu~rine-~ubstituted diazine derivatives such as, for example, fluoropyrimidines, esters of 2-substituted 1,2-dihydroquinoline- or 1,2-dihydro-isoquinonline-N-carboxylic acids. Other suitable hardeners include vinyl sulphonic acid esters, carbodiimide or carbamoyl hardeners of the type described, for example, in German Offenlegungsschrif ~ No.2,263,692; 2,225,230 and 1,808,685, French Patent Specification No.1,491,807; German Patent Specification No.872,153 and in East German Patent Specification No.7218. Other suitable hardeners are described, for example, in British Patent Specification No.1,268,550.

The advantageou~ use o~ 2-equivalent yellow couplers end whit~ couplers according to the invention is described in the following Examples:

.... .. ... . . . . .. . ... .
'''' ~

~S89~2 Preparation of emulsion 1. 35 g o f yellow coupler No.9 together with 35 g of tricresylphosphate were dissolved in 70 ml of ethylacetate, and the resulting solution emulsiIied at 55C into 350 ml of a 5~ gelatin solution containing 3.5 g of the sodium salt o~
p-dodecyl benzene sulphonic acid. Following evaporation of the e-thylacetate in a thin-layer evaporator, the emulsified product was added to 1 kg of bromoiodide emuslion whose silver content had been adjusted by the addition of more gelatin solution to 0.2 mol per kg for a gelatin con~ent of 80 g per kg.
2. An emulsion was prepared in the same way as emulsion 1, except that 10 g oi white coupler II were additionally in~
corporated in the emulsion, whilst the gelatin content of the emulsion was adjusted to 70 g pler kg in order to maintain the total solids concentration in t;he mixture ready for casti~g.
3. An emulsion was prepared in the same way as emulsion 1, except that 100 ml o~ latex coupler VI (solids content 10~) were additlonally incorporated in the emulsion9 and the gelatin concentration adJusted in the same way as in emulsion 2.
4. An emulsion was prepared in the same way as emulsion 3, ~-e~cept that 100 ml of a 10% solution of the alkali-soluble latex coupler VIII were used instead of latex coupler VI.
Emulsions 1 to 4 thus prepared were cast onto a tri-acetate film coated with a 15 mm thick gelatin adhesion layer, the silver halide coating amounting to 9 millimols per square metre.
The photographic materials 1 to 4 thus prepared were hardened by pouring over them a solution of 20 g of l-ethyl- ;
3-dimethylaminopropyl carbodiimide hydrochloride ahd 10 g of , ", , . , . ,., ,, ,, . , , ., : .

~s~9~z gelatin in 1000 ml ol` water. The photographic material 1 to 4 were then cut into several strips, one strip being stored at room temperature whilst the others were stored for 3 days at 57C/35~ relative humidity. The strips were then exposed behind a grey step wedge in a conventional sensitometer and colour developed for 3 minutes 15 seconds at 38C with a standard colour developer containing N-ethyl-N-3-hydroxye-thyl-3-methyl-p-phenylene diamine as developer subs-tance~ The sensitometric evaluation of the result thus obtained is shown in Table III below, Sl representing the basic fog level after storage at room temperature and S2 the basic ~og level after storage at 57C/35~ relative humidity, and ~he final colour densities (DmaX) obtained being quoted in relative values.
Table III
~ ~ _ . .~ . . _ .
Emulsion Sl S2 Dmax a E
- ~
1 0.18 0.24 2.25 _ 2 0.13 0.11~ 2.25 0 3 0.12 0~15 2.20 - 1 DIN
4 0.16 0.22 2.30 0 ~ . . ~ .
Emulsion 1 is a comparison emulsion which does not ~ ~
contain any emulsifiable white coupler according to the invsntion.
As the results show, the combination according to the invention of 2-equivalent coupler and emulsiflable hydrophobic white couplers produces a considerable reduotion in basic ~og level and an increase i,n the fog stability of the colour coupler when stored under humid conditions without any adverse effect either upon the final colour density obtained or upon sensitivity as `
a result of co-coupling of the white couplerO
Table III also shows that the reduction in basic fog A-G 1247 - 32 - , i8~
level and the in~rease in fog stability are better obtained by a hydrophobic white coupler than by a soluble w~ite coupler.
EXA~IPLE 2 _ 5. 35 g of yellow coup:Ler No.13, together with 17.5 g of dibutyl phthala-te and 3.5 g o-f sulphosuccinic acid-bis-(2-ethyl)-hexylester were dissolved in 85 ml of ethylacetate at 55C, and the resulting solution emulsified into 350 ml of a 5~0 gelatin solution. The emulsified product was then added to 1 kg of the silver halide emulsion mentioned in Example lS emulsion 1.
6. An emulsion was prepared in the same wayt except that 7 g of white coupler II were additionally incorporated in the emulsion. The gelatin content of the silver halide emulsion is then adjusted to 73 g of gelatin per k~. Emulsions 1$ 5 and 6 thus obtained were cast in the same way as described in Example l and subjected to the photographic test described in Example 1. The sensitometric evaluation o~ the results obtained in this way is shown in Table IV below:
~ab ~ ;
Emulsion Sl S2 Dmax ~E
,,, ,, ., .. ~, _ ~_ ,. . . , 5 0.13 0.30 2.50 _ 6 0.~9 0.10 2.50 0 Comparison of emulsion No.6 according -to the invention with comparison emulsion ~o.5 shows that the basic fog level (Sl) and heating-cabinet fogging (S2~ are reduced wi-thout any loss of sensitivity or maximum density.

__ This Example shows that basic ~og level and hea-ting cabinet fogging of the blue-sensitivelayer of multilayer colour photographic materials can be reduced with advantage in accordance with the invention:
A-G 1247 ~ 33 ~

g'~

Preparation of the bl~le-sensitive emul~ion:
7. 30 g of yellow coupler No.30 were dissolved in 90 ml of ethylace-tate and the resulting solution emulsified at 55C
into 300 ml of a 5~ gelatin solution in which 3 g of the sodium salt of dodecylbenzene sulphonic acid were dissolved.
Theethylacetate is then removed in a thin-layer evaporator and the emulsified product added to the silver halide emulsion described in Example 1, emulsion 1.
8. A similar emulsion was prepared, except that 4.5 g of white coupler II were incorporated in~he emuslion.

9. A similar emulsion was prepared, except that 9 g of white coupler II were incorporated in the emulsion.
Emulsions 7 to 9 th;ls prepared were each east onto a colour photographic semifinished product, and hardened by ~-pouring over them a solution of 20 g of 1-ethyl-3-dimethyl-aminopropyl carbodiimide hydrochloride and 10 g of gelatin in 1000 ml of water.
The colour photographic semifinished product consisted ;
of a transparent substrate which in its bottom layer con.tained a red-sensitised iodide bromide emulsion with a silver content of 0.03 mol of Ag/m2 and 1.2 g/m2 of a cyan coupler of the ~-formula ~ C-N-(CH2)4-0 ~ C~H~1 (t) emulsified in dibutylp~h~ate,in its middle layer a green-sensitised iodide bromide emulsion with a silver content of 0.03 mol of Ag/m2 and o.g g/m2 of the magenta coupler ~ NH-~O ~ NH_C~_CH2_ ~ 5H11-(t) 0~ ~ (t)-C5H1 1 Cl ~ Cl ~ .
. ci ::

~S3~42 emulsified with tricresylphosphate and, above this layer, .is provided with a yel].ow filter layer with a colour density of 0.7.
The photographic materials prepared in this way were exposed as described in Example 1 an~ developed for 3 minutes 15 seconds in the same colour developer, and then stored at room temperature and in a heating cabinet in the same way as described in Example 1.
The fog levels and maximum colour densities and sensi-tivities of the individual samples are then measurea behind a blue filter. The results obtained are set out in Table V -below:
Table V

5 ~ 1 I sæ ¦ Dmax ~ ¦

7 0.45 0.52 3.5 _ 8 o.36 0.38 3.5 0 :

0.29 0.30 3.4 - 1 DIN ~:
AB the results show, it was also possible in this case (~amples 8 and 9 according to the invention) to obtain a considerable improvement in basic fog level after storage at room temperature and after storage under humid conditions without any appreciable loss o~ colour density or sensitivity.
The eensitometric properties of the cyan layer and magenta layer were not a~fected in any way by the white couplers incorporated in the yellow layer.

EX~MPLE 4 The procedure is the same as in Example 3~ except that emulsion 7 was replaced by emulsion 1 ~rom Example 1, whilst .

~.: ,. .

emulsions 8 and g were rep`Laced by emuLsion 2 ~rom Example 1, wi-th -the difference th~t, only 7 g, rather than 10 g of white coupler II were used, whilst no tricresylphosphate was used as the oil former in the coupler~containing emulsions. The results obtained are set out in Table VI below:
Table VI
_ . _ . _ _ ~_ . ~ _ ,_ Emulsion Sl S2 Dmax ~ E
_ _ . __.

0.25 o.29 2.2 _ 11 0.17 0.18 2.2 EX~MPLE 5 12. 12 g o~ yellow coupler No.31 together with 12 g of dibutyl phthalate and 1.2 g o~ sulphosuccinic acid-bis-t2~ethyl)-hexyl ester were dissolved in 60 ml of a 1 : 1 mixture of ethylacetate and 1,2--dichloroethane, and the resulting solut:ion emulsified at 55C into 240 ml of a 10 gelatin solution. The a~xiliary solvent was subsequently removed in the ~sual way, and the emulsified product added to 1 kg of a gelatin-diluted silver chlorobromide emulsion con-taining 0.135 mol of silver halide per kg.
13. An emulsion was prepared in the same way as emulsion 12, except that 36 g of white coupler II were additionally incorpora-ted in the emulsion. The gelatine content of the silver halide emulsion was lower by the white coupler content.
1~. An emulsion is prepared in the same way as emulsion 13, except that white coupler VI was used instead of white coupler II.
15. An emulsion was prepared in the same way as emulsion 12 except that yellow coupler 10 was used instead of yellow i:,, . , . . ~ . , , coupler 31.
]6. An emulsion was prepared in the same way as emulsion 15, except ~hat 3.6 g oi` white coupler VII were additionally incorporated in the emulsion.
Emulsions 12 to 16 thus prepared were cast onto a transparent triacetate film with a silver coating of 1.6 g of silver nitrate per square metre. The layers were hardened with triacrylformal. The photographic materials thus prepared were cut into several strips, one of which was stored ~or 8 days at room temperature and the others for 8 days at 57C/35 relative humidity. The strips were then exposed behind a grey step wedge in a conventional sensitometer and de~eloped for 8 minutes at 20C in a standard colour developer containing N,N-diethyl-p-phenylene diamine developer substance. The samples were evaluated sensitometricallylin the same way as descrlbed in Example 1, the results being set out in Table VII below~
Table VII
. .. . _ _ . ....
~mulsion $1 S2 Dmax ~ E
~L - _____. .. ~ _ . . . . _, 12 0.0~ 0.17 3.0 _ 13 0-05 0.12 2.9 0 14 0.05 0.13 2.95 - 1.5 DIN
0.07 0.20 2.5 0 16 0.05 0.08 2.l~ 0 , _ ~ - ~ ,-Emulsions 12 and 15 are conventional emulsions, whilst emulsions I3, 14 and 16 clearly show that the basic fog level Sl and heating~cabinet fogging S2 can be distinctly reduced by the combination according to the invention.

~.~3C~4z ~XAMPLE 6 , Preparation of the emuls:ion:
17. An emulsion was prepared in the same way as emulsion 12, except that equimolar quantities of yellow coupler 37 were used instead of yellow coupler ~1.
18. An emulsion was prepared in -the same way as emulsion 17, except tha-t white coupler II was addi-tionally added in a quantity of 20 mol ~, based on the content of yellow coupler 37.
19. An emulsion -was prepared in the same way as emulsion 17j.
except that 40 mol ~ of white coupler II, basod on the content of yellow coupler 37, were used.
Emulsions 17 to 19 thus prepared were cast onto a trans-parent substrate, hardened and cut into several strips in the same way as in Example 5. Some o~ the strips were stored for 6 days at room temperature, and the rest for 6 days at 57C/35 rela-tive humidity. The strips were then developed for 16 minutes in a standard colour developer containing N,N-diethyl- :
3-methyl-~-phenylene diamine as the colour developer substanoeO
Sensitometric evaluation of the samples was carried out in the same way as in Example 1.
Comparison of samples 18 and 19 according to the invention with conventional sample 17 showed that the basic fog level (Sl) in emulsions 18 and 19 amounts to 0.18 and 0.179 respectively, whilst the conventional sample has a basic fog level of 0.21. In addition, the basic fog level o~ samples 18 and 19 according to the invention a~ter heating cabinet storage amounted to 0.26 and 0.25, respectively and in the case of the conventional sample to 0.32.
Similar results were obtained when white coupler VII or VIII is u~ed instead of white coupler II.
However, it was found that sensitivity and maximum density ; '. ~ ,,, ,, , , . . , ., . " ., ~i894Z

decreased slightly with increasing white coupler content.
Comparison of the results show that a particularly advantageous combination according to the invention is obtained when hydrophobic white couplers with 2-equivalent couplers~ whose releasable groups are aroxy and heterocyclic, nitrogen-con-taining radical as defined above, are present in emulsified form in the blue-sensitive silver halide emulsion layer of a . .
colour photographic material.
'`'. ' :

A-G 1247 ~- 39 ~

Claims (5)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A light sensitive colour photographic material with at least one silver halide emulsion layer, which material contains a blue sensitive silver halide emulsion layer and in said blue sensitive emulsion layer a diffusion resistant 2-equivalent open chain ketomethylene yellow coupler which is an acylacetamide yellow coupler in which one hydrogen of the methylene group is substituted by a splittable group selected from the group consisting of halogen, aroxy or the group wherein Z represents the ring members required to complete a cyclic acid amide, cyclic acid imide or a 5- or 6-membered unsaturated heterocyclic ring wherein the improvement comprises the blue sensitive emulsion layer contains in addition, up to 40 mol % based on the quantity of yellow coupler used, of a diffusion resistant pyrazolone-5 white coupler compound in which one hydrogen atom on the methylene group of the pyrazolone-5 compound is substituted by an aliphatic, cycloaliphatic, aromatic or araliphatic group.

2. A light sensitive material as claimed in claim 2 wherein the acylacetamide yellow coupler is hydrophobic.

3. A lightsensitive material as claimed in claim 1 wherein the 2-equivalent yellow coupler is a hydrophobic ketomethylene acetamide yellow coupler one hydrogen of the methylene group being substituted by halogen and as white coupler from 5 to 30 mol % based on the yellow coupler content of a hydrophobic or hydrophilic pyrazolone-5 white coupler which is sub-stituted in the 4-position by a substituent selected from the group consist-ing of aliphatic, cycloaliphatic, aromatic and araliphatic groups.

4. A lightsensitive material as claimed in claim 1 wherein the molar ratio of silver to 2-equivalent yellow coupler in the blue-sensitive silver halide emulsion layer is more than 2 : 1.

5. A lightsensitive material as claimed in claim 1 wherein the pyrazolone-5 white coupler compound is substituted by alkyl in the 4-position and by a group selected from alkyl of 1 to 20 carbon atoms and acylamino groups in the 3-position which may be derived from aliphatic, araliphatic, aromatic carboxylic acids or sulfonic acids.