Color photographic materials containing an antistain agent

An improvement in the prevention color-fog and staining in color-photographic materials is obtained by the inclusion of acylamino substituted hydroquinones derivatives. The compounds can easily be synthesized do not crystalize from their dispersions and are not oxidized to colored by-products during development.

This invention relates to an antistain agent for colour photographic 
recording materials and to a process for the stabilization of colour 
photographic materials by the addition of a suitable antistain agent which 
is capable of reducing the formation of colour fogs. 
Coloured images are known to be produced by developing exposed silver 
halide emulsions in the presence of the usual colour developers so that, 
in addition to the silver image, a coloured image is produced by reaction 
of the oxidized colour developer with colour couplers which are present at 
the same time. These colour couplers may be added in known manner either 
to the emulsion layers or to adjacent layers or to the developer solution. 
The colour developers normally used for the production of coloured images 
are, in particular, p-phenylene diamines, or their substituted 
derivatives. 
Coloured images produced by the usual processes frequently have colour fogs 
or discolourations. Formation of a colour fog is due to the fact that the 
developer compounds are to a certain extent oxidized by the atmosphere and 
that the oxidized developer couples with the colour coupler in those parts 
of the photographic recording material in which no silver image was 
originally produced. This unwanted oxidation of the developer may be due 
to the action of air or it may be due to the presence of additives in the 
emulsion, and it may occur equally in the different layers or it may be 
more pronounced in one or more layers so that the effect produced may be 
either a uniform colour fog or a discolouration of the photographic 
material. 
This effect is mainly observed in recording materials which contain 
couplers in the light-sensitive layers, and particularly if the developer 
solutions have not been sufficiently stabilized against oxidation. The 
colour fog or the discolouration cannot be prevented by the methods 
normally used for stabilizing the silver emulsions. 
In U.S. Pat. Nos. 2,403,721 and 2,701,197 and in German Offenlegungsschrift 
No. 2,110,521 it has been proposed to use alkyl and dialkyl hydroquinone 
derivatives as antistain agents for colour photographic materials. 
These compounds have, however, various disadvantages, including the fact 
that many of them can only be prepared by complicated processes comprising 
2 to 4 stages and the fact that some of them are not sufficiently 
resistant to diffusion so that when employed in multilayered colour 
photographic recording materials they are liable to migrate between the 
individual layers to give rise to undesirable side effects. Furthermore, 
they are liable to crystallise before or after their application or to 
have a deleterious effect on the physical or chemical properties of the 
layers, one particularly disadvantageous effect of some alkyl 
hydroquinones being that they give rise to coloured by-products by an 
oxidation reaction either during application of the layer containing them 
or during development. The discolouration of the photographic material 
produced by these by-products is particularly disturbing in colour 
photographic copying materials. 
It is also known that an improvement in colour reproduction can be achieved 
by arranging, between the light-sensitive silver halide emulsion layer and 
a layer containing the colour couplers, an intermediate layer of a 
composition such that it suppresses the diffusion of oxidation products of 
the developer into the layer which contains colour couplers. To achieve 
this effect, the substances incorporated in this intermediate layer 
include compounds which react with the developer oxidation products to 
form colourless compounds. These so-called white couplers only reduce the 
colour fog to an extent which is insufficient for practical purposes. 
It is therefore an object of the present invention to provide new antistain 
agents which do not have the disadvantages described above, which can 
easily be synthesised which do not crystallise from their dispersions in 
aqueous, hydrophilic colloid coating compounds either before or during or 
after their application and which are not oxidized to coloured by-products 
during development.

It has now been found that hydroquinone derivatives of the general formula 
##STR1## 
in which R.sub.1 and R.sub.2 which may be the same or different represent 
hydrogen, an alkyl chain preferably having up to 3 carbon atoms, halogen 
in particular chlorine or a sulpho or carboxyl group, 
R.sub.3 represents an acyl group which is derived from an aliphatic 
carboxylic acid for example from palmitic or stearic acid, but in 
particular from aroxy substituted, preferably phenoxy substituted, 
carboxylic acids, such as di-t-pentyl-phenoxy-acetic acid, 
4-chloro-2-tetradecylphenoxyacetic acid or dodecyloxyphenoxypropionic 
acid; an aliphatic or aromatic chlorocarbonic acid ester or a substituted 
or unsubstituted carbamic acid, 
clearly fulfil the stated requirements. 
Hydroquinone derivatives which carry an .alpha.-, .beta.- or .gamma.-aroxy 
substituted, in particular a phenoxy substituted, aliphatic acylamino 
group in the 2-position are particularly suitable. This phenoxy group may 
be substituted once or more than once, for example with alkyl or alkoxy 
groups, in particular those having up to 18 carbon atoms, with halogen, in 
particular chlorine, hydroxyl, cycloalkyl, in particular cyclopentyl or 
cyclohexyl, sulpho or carboxyl. Furthermore, the phenoxy group may contain 
a condensed carbocyclic ring which may be partially hydrogenated. 
The aliphatic acylamino group preferably contains up to 5 carbon atoms. 
The following compounds have proved to be particularly suitable: 
##STR2## 
The antistain agents used according to the invention may be prepared quite 
simply by reacting aminohydroquinone hydrochloride with fatty acid 
chlorides. Aminohydroquinone hydrochloride is synthesised in known manner 
from nitrohydroquinone, for example according to the method of Henrich, 
Ber. 54, 2506. 
Compound 3: .alpha.-2,4-Di-tert.-pentyl-phenoxybutyrylaminohydroquinone 
16.1 g (0.1 mol) of aminohydroquinone hydrochloride are dissolved in 
150 ml of acetonitrile and 
24.2 g (0.2 mol) of dimethylaniline. 
33.85 g (0.1 mol) of 2,4-di-t-pentyl-phenoxybutyryl chloride are added 
dropwise at room temperature. The reaction mixture is stirred for one hour 
and then poured on a mixture of ice water and hydrochloric acid and the 
product is extracted with ethyl acetate. After removal of the ethyl 
acetate by distillation, the residue is crystallised with ligroin. 
Recrystallisation from nitromethane. 
Melting point: 157.degree. to 159.degree. C. 
Yield: 33 g=76% of the theory. 
Compound 4: 2-Tetradecyl-4-chlorophenoxy-acetylaminohydroquinone: 
The compound of formula 4 is obtained from 
2-tetradecyl-4-chlorophenoxyacetyl chloride by a similar method to that of 
Example 1. 
Melting point: 118.degree. to 121.degree. C. 
The other compounds may be prepared in a similar manner. 
Another possible method of synthesis consists of starting with known cyan 
components such as 
2-.alpha.-di-tert.-pentylphenoxy-n-butyramino-4,6-dichloro-5-methylphenol 
and hydrogenating these to the corresponding hydroquinone derivatives via 
the benzoquinone stage according to German Offenlegungsschrift No. 
2,509,408. 
The compounds according to the invention are particularly suitable for 
reducing the formation of a colour fog or of discolouration in colour 
photographic materials. 
The compounds according to the invention may be used to advantage wherever 
it appears suitable to inactivate unwanted oxidation products of the 
colour developer. 
The antistain agents according to the invention convert the oxidzed form of 
any primary aromatic amine colour developer used for colour development, 
into the developer compound or into a form which will not couple with the 
colour coupler. 
The compounds according to the invention may be used in a layer of any 
multilayered colour photographic material. For example, they may be added 
to one or more of the light-sensitive layers and/or to protective layers 
or intermediate layers applied on or between light-sensitive layers. They 
may be used in colour photographic materials in which colour couplers are 
incorporated in the light-sensitive emulsion layer and they may also be 
used in multi-layered colour photographic materials which do not contain 
any colour coupler. The colour photographic materials may either be 
recording materials, copying materials or reversal materials. The 
compounds may also be incorporated in a diffusion resistant form in the 
separating layers of multilayered colour photographic materials, thereby 
contributing to better colour separation so that migration of oxidized 
colour developer from one layer to another is suppressed. 
When added as diffusion resistant compounds to colour couplers, the 
compounds according to the invention serve to control the gradation of the 
silver halide layers. When not resistant to diffusion, the compounds 
according to the invention may be used in light-sensitive layers and in 
adjacent layers or they may be added to photographic processing baths such 
as the short stop baths, fixing baths or hardener baths or they may be 
used as aqueous solutions on their own before or after the photographic 
process or between separate stages thereof to prevent the formation of 
colour fog. 
As already mentioned above, the compounds may be introduced into the 
photographic material at any time before chromogenic development of the 
silver image or they may be added to a bath after development, for example 
in order to suppress the formation of colour fog due to coupling of the 
colour couplers with residual colour developers which have not been 
removed. 
The compounds according to the invention may be used at various 
concentrations depending on the light-sensitive silver halide emulsion 
used in any individual case, the concentration of silver halide in the 
emulsion layers and the required concentration of the dye which is to be 
formed. When used in the photographic material, e.g. in the silver halide 
emulsion layers, these compounds are advantageously added in quantities of 
from 0.004 to 0.04, mol per mol of silver, preferably 0.008 mol per mol of 
silver. If the compounds are introduced into the colour photographic 
materials in the form of a solution, for example in a processing solution, 
they are suitably employed at concentrations of between about 100 mg and 5 
g per liter of solution, preferably between 500 mg and 2 g per liter of 
solution. The optimum concentration depends on the particular photographic 
recording material in which the antistain agent is to be used, and it can 
easily be determined by known methods. When the antistain agents are used 
in auxiliary and intermediate layers, they are preferably added in 
quantities of from 50 to 500 mg, more preferably from 150 to 200 mg per 
m.sup.2. 
The compounds according to the invention are preferably added as solutions 
to the auxiliary layers or to the light-sensitive layer. The solvent used 
may be water, a lower aliphatic alcohol, tetrahydrofuran, acetone, ethyl 
acetate, dimethylformamide or mixtures thereof. A preferred method of 
introducing the compounds according to the invention consists of 
dissolving them together with the colour coupler and then introducing the 
combined solution into the light-sensitive silver halide layer. 
Introduction of the compounds according to the invention into the 
light-sensitive emulsion is preferably carried out after chemical ripening 
or before the completely prepared emulsion is cast. 
The colour photographic materials used according to the present invention 
may be any of the usual silver halide emulsions. The silver halides 
contained in them may be silver chloride, silver bromide, or mixtures 
thereof, and may have a small silver iodide content of up to 10 mol 
percent. The binder used for the photographic layers is preferably 
gelatine but this may be partly or completely replaced by other natural or 
synthetic binders. Suitable natural binders include e.g. alginic acid and 
its derivatives such as its salts, esters or amides; cellulose derivatives 
such as carboxymethylcellulose, alkyl celluloses such as hydroxyethyl 
cellulose; starch or its derivatives such as ethers or esters, or 
carageenates. The following are suitable synthetic binders: Polyvinyl 
alcohol, partially saponified polyvinyl acetate and polyvinyl pyrrolidone. 
The emulsions may also be chemically sensitized, for example, by the 
addition of sulphur compounds such as allyl isothiocyanate, allyl thiourea 
and sodium thiosulphate during chemical ripening. Reducing agents such as 
the tin compounds described in Belgain Patent Specifications Nos. 493,464 
and 568,687; polyamines such as diethylene triamine and aminomethyl 
sulphinic acid derivatives such as those mentioned in Belgain Patent 
Specification No. 547,323 may also be used as chemical sensitizers. 
Noble metals such as gold, platinum, palladium, iridium, ruthenium or 
rhodium and compounds of these metals are also suitable as chemical 
sensitizers. This method of chemical sensitization has been described in 
the article by R. Koslowsky, Z. Wiss. Phot. 46, 65-72 (1951). 
The emulsions may also be sensitized with polyalkylene oxide derivatives, 
for example with a polyethylene oxide having a molecular weight of between 
1000 and 20,000 with condensation products of alkylene oxides and 
aliphatic alcohols, glycols, cyclic dehydration products of hexitols, 
alkyl substituted phenols, aliphatic carboxylic acids, aliphatic amines, 
aliphatic diamines and amides. The condensation products have a molecular 
weight of at least 700, preferably more than 1000. These sensitizers may, 
of course, be combined to produce special effects, as described in Belgian 
Patent Specification No. 537,278 and in British Patent Specification No. 
727,982. 
The emulsions may also be optically sensitized, for example with the usual 
polymethine dyes such as neutrocyanines, basic or acid carbocyanines, 
rhodacyanines, hemicyanines, styryl dyes and oxonoles. These sensitizers 
have been described in the work by F. M. Hamer, "The Cyanine Dyes and 
Related Compounds" (Interscience Publishers). 
The emulsions may contain the known stabilizers, e.g. homopolar compounds 
or salts of mercury containing aromatic or heterocyclic rings, such as 
mercapto tetrazoles, simple mercury salts, sulphonium mercury double salts 
and other mercury compounds. Azaindenes are also suitable stabilizers, 
particularly tetra- or penta-azaindenes and especially those which are 
substituted with hydroxyl or amino groups. These compounds have been 
described in the article by Birr, Z. wiss. Phot. 47, 2-58 (1952). Other 
suitable stabilizers include heterocyclic mercapto compounds such as 
phenyl mercapto tetrazole, quaternary benzothiazole derivatives and 
benzotriazole. 
The emulsions may be hardened in the usual manner, for example with 
formaldehyde or halogen substituted aldehydes which carry a carboxyl group 
such as mucobromic acid, diketones, methane sulphonic acid esters, 
dialdehydes, compounds containing vinyl sulphone groups, halogenated 
triazines such as monohydroxydichlorotriazine or the hardeners described 
in German Offenlegungsschriften Nos. 2,225,230; 2,317,677; 2,408,814; 
2,439,551 and 2,547,589. 
The emulsions may also contain compounds which increase the sensitivity, 
plasticizers and coating auxiliaries. 
As is well known, photographic materials consisting of a substrate on which 
light-sensitive silver halide emulsion layers sensitive to red, green and 
blue light are applied above one another are particularly suitable for 
producing coloured images. Silver images may be developed in these layers, 
and dyes can be produced imagewise in proportion to the developed silver 
images. The dyes produced are preferably cyan, magenta and yellow. It is 
preferred to produce dye images which are in a complementary relation to 
the region of the spectrum to which the silver halide emulsion layer has 
been sensitized. 
Photographic materials which may be used according to the invention 
include, for example, photographic materials for taking original 
photographs, copying materials, reversal materials, reprotechnical films 
and colour photographic materials such as those used, for example in the 
dye diffusion process. 
The substrates used for the colour photographic materials according to the 
invention may be any of the usual substrates such as foils of cellulose 
esters, polycarbonates, in particular those based on bis-hydroxyphenyl 
alkanes, polyesters, in particular polyethylene terephthalate, and paper, 
for example baryta paper supports or paper coated with polyolefines, e.g. 
with polyethylene or polypropylene, which have been exposed to corona 
treatment to improve adherence of the photographic layers to them. Glass 
may, of course, also be used as the substrate. Colour developers are used 
for producing the dye images in the photographic materials according to 
the invention, for example the usual aromatic compounds based on 
paraphenylenediamine containing at least one primary amino group. Suitable 
colour developers include, for example, N,N-dimethyl-p-phenylene diamine; 
N,N-diethyl-p-phenylenediamine; monomethyl-p-phenylenediamine; 
2-amino-5-diethylaminotoluene; N-butyl 
N-.omega.-sulphobutyl-p-phenylenediamine and 
2-amino-5-(N-ethyl-N-.beta.-methanesulphonamidoethylamino)-toluene. Other 
suitable colour developers have been described, for example, in J. Amer. 
Chem. Soc. 73, 3000 to 3025 (1951). 
The materials according to the invention may contain colour couplers, 
masking couplers and white couplers of various constitutions incorporated 
in a diffusion resistant form in hydrophilic layers of binder, that is to 
say they may, for example, be incorporated in a light-sensitive silver 
halide emulsion layer or they may be incorporated in a light-insensitive 
layer of binder adjacent thereto. If the colour couplers are 
water-soluble, they may be added as alkali metal salts in aqueous or 
aqueous alcoholic solution. Water-insoluble couplers may be dispersed in 
known manner, for example with the aid of ethyl acetate and a wetting 
agent, and incorporated with the emulsion in the form of a dispersion. In 
that case, if the coupler tends to recrystallise in the dispersion, an oil 
former such as dibutylphthalate may be added. Couplers which are not 
diffusion resistant may also be added. These may be incorporated in the 
hydrophilic layers with the aid of mordants or they may be incorporated 
with the aid of a colour developer solution by a classical method of the 
photographic reversal process, as described in U.S. Pat. No. 2,252,718. 
Compounds derived from phenol or .alpha.-naphthol are used as cyan 
couplers, compounds derived from 2-pyrazolinone-5 or indazolone as magenta 
couplers and compounds derived from .beta.-ketocarboxylic acid 
derivatives, for example benzoyl acetanilide, are used as yellow couplers. 
The couplers may be unsubstituted in the coupling position or they may 
carry in the coupling position a substituent which is split off in the 
reaction with the developer oxidation products, for example to release a 
development inhibitor. Suitable colour couplers have been described, for 
example, in the survey entitled "Farbkuppler" by W. Pelz in Mitteilungen 
aus den Forschungslaboratorien der Agfa-Leverkusen-Munchen, Vol. 3, pg. 
111. 
EXAMPLE 1 
The following dispersions or solutions are added to 1 kg of a red-sensitive 
photographic silver iodobromide emulsion which has been prepared from 145 
g of silver nitrate and contains a proportion of silver to gelatine of 
0.6: 
(a) 42 g of the cyan component 
1-hydroxy-N-[.delta.-(2'-cyclopentyl-4'-t-butylphenoxy)-n-butyl]naphthamid 
e dissolved in 130 ml of ethyl acetate and 20 g of tricresyl phosphate are 
dispersed in known manner in 170 ml of a 10% aqueous gelatine solution. 
(b) 4 g of the red azo mask 
1-hydroxy-4-(6'sulpho-2'-naphthylazo)-N-(2'-methyl-octadecylamino-5'-sulph 
ophenyl)-2-naphthamide are dissolved to form a 5% aqueous alkaline 
solution. 
(c) 2 g of the DIR coupler, 
1-hydroxy-4-(2'-phenyl-tetrazolemercapto)-N-(2'-tetradecyloxyphenyl)-2-nap 
hthamide are dispersed as described under (a) above. 
The emulsion containing the additives (a), (b) and (c) is then cast on a 
cellulose triacetate substrate to form a layer of about 4.5.mu. in 
thickness and dried. A strip of film was exposed through a step wedge and 
then subjected to colour negative development at 25.degree. C. in known 
manner, using a colour developer of the following composition: 
Developer D 
4 g of 2-amino-5-(N-ethyl-N-hydroxyethylamino)-toluene sulphate 
monohydrate, 
2.5 g of sodium hexametaphosphate, 
4 g of anhydrous sodium sulphite, 
2 g of hydroxylamine hydrochloride, 
100 g of potassium carbonate, 
1 g of potassium bromide, 
water up to 1000 ml. 
A second colour wedge is prepared by adding dispersion d to the reaction 
mixture indicated above. 
(d) 3 g of compound 3 are dissolved in 10 ml of ethyl acetate and 1.5 g of 
tricresyl phosphate and dispersed in known manner in 12 ml of a 10% 
aqueous gelatine solution. This emulsion is then cast as described above, 
dried, exposed and developed. The two cyan colour wedges obtained differ 
from each other in that the one first prepared has a colour fog of 0.3 
(optical density) while the one containing antioxidant according to the 
invention has a colour fog of only 0.2. 
EXAMPLE 2 
A multilayered material is prepared with the cyan casting emulsion 
described in Example 1. The red sensitive emulsion layer is first covered 
with a 1 to 2.mu. thick layer of gelatine containing 8 g/m.sup.2 of white 
coupler No. 4 described in German Auslegeschrift No. 1,123,913. A 
green-sensitive layer prepared as follows is then applied: 
The following dispersions are added to 1 kg of a silver iodobromide 
emulsion which has been prepared from 135 g of silver nitrate with a 
silver/gelatine ratio of 0.6: 
(a) 32 g of the magenta component 
1-(2',4',6'-trichlorophenyl)-3-(2",4"-dipentylphenoxybutyroyl-3'-aminophen 
yl)amino-pyrazolone in 100 ml of ethyl acetate and 30 g of tricresyl 
phosphate are dispersed in known manner in 250 ml of a 10% aqueous 
gelatine solution. 
(b) 2 g of the yellow masking dye, 
1-(1",1"-difluoro-2",2"-fluoro-chloroethyloxy-2-phenyl)-3-(4'-hexadecyl-su 
lphonylphenyl)-amino-4-(4'-phenoxy-ethoxyphenyl)-azo-pyrazolone-5 are 
dispersed either in a similar manner to (a) or together with the magenta 
component described under (a). 
(c) 3.5 g of the DIR coupler, 
1-(2"-.alpha.-methyltridecyl-4-chloro-phenoxyacetyl-4'-aminophenyl)-3-pyrr 
olidino-4-(2'-phenyl-tetraazolemercapto)-pyrazolone-5 are dispersed either 
in a similar manner to (a) or together with the magenta component 
described in (a). 
Over this layer is cast another green-sensitive layer which, however, has a 
higher sensitivity than the layer underneath it. This upper layer is 
prepared as follows: 
The following dispersions are added to 1 kg of a silver iodobromide 
emulsion which has been prepared from 155 g of silver nitrate in a ratio 
of silver to gelatine of 0.4: 
(d) 10 g of the magenta component under (a) is dissolved and dispersed as 
described therein. 
(e) 4 g of the masking dye under (b) is dispersed in the manner described 
therein. 
A Yellow filter layer according to Carey and Lee is cast above this last 
mentioned layer. 
On top of these layers is cast a blue-sensitive silver iodobromide emulsion 
layer which has been prepared from 80 g of silver nitrate in a 
silver/gelatine ratio of 1.4 and to which the following dispersions have 
been added: 
(f) 70 g of the yellow component, 
.alpha.-piraloyl-.alpha.-5'-carbomethoxytriazole-2-hexadecyloxy-5-methylsu 
lphonamido acetanilide are dissolved in 200 ml of ethyl acetate and 
dispersed in 280 ml of 10% aqueous gelatine solution. 
(g) 4 g of the white coupler, 
1-(4'-methylsulphonylphenyl)-3-(2"-.alpha.-methyltridecyl-4"-chloro-5"-met 
hylphenoxyethoxycarbonyl-amino)-4-methylpyrazolone-5 are dispersed either 
in a similar manner to (f) or together with the yellow coupler described 
under (f). 
To this multilayered casting is added a protective gelatine layer 1 to 
2.mu. in thickness. 
A strip of film of this multilayered material was exposed through a step 
wedge and developed with the colour development bath described in Example 
1. A second colour wedge is prepared by adding dispersion (h) described 
below to the above described green-sensitive layer which contains 
additives (a), (b) and (c): 
(h) 1 g of compound 3 is dissolved in 5 ml of ethyl acetate and 0.5 g of 
tricresyl phosphate and dispersed in known manner in 12 ml of a 10% 
aqueous gelatine solution. 
In addition, a dispersion prepared in the same way as described under (h) 
but containing 1.5 g of compound 3 is added to the other green-sensitive 
emulsion which contains additives (d) and (e). 
Furthermore, a dispersion prepared as described under (h) but containing 3 
g of compound 3 are added to the blue sensitive emulsion which contains 
additives (f) and (g). 
A multilayered casting prepared with these additives is exposed and 
developed in the same way as described above. Grey wedges having the 
following fog values are obtained in both cases: 
______________________________________ 
Added Compound 3 
Magenta fog Yellow fog 
______________________________________ 
Without 1.15 0.85 
With 1.01 0.66 
______________________________________ 
This demonstrates the effectiveness of the compound according to the 
invention. 
EXAMPLE 3 
A multilayered material prepared in the same way as described in Example 2 
but with the addition of compound 4 in place of compound 3 in the same 
layers as in Example 2 and in the same quantities is subjected to a series 
of development times: 
______________________________________ 
Development time in min. 
2 3 4 5 
______________________________________ 
Magenta fog without additive 
0.57 0.95 1.25 1.6 
Magenta fog with compound 4 
0.55 0.77 1.05 1.3 
Yellow fog without additive 
0.55 0.65 0.96 1.28 
Yellow fog with compound 4 
0.53 0.60 0.8 1.10 
______________________________________ 
It can be seen from the Table that the fog reducing effect sets in clearly 
after only 3 minutes and is maintained thereafter. 
EXAMPLE 4 
Compound 4 which is to be used according to the invention is added to the 
yellow filter layer of the multi-layered material of Example 2 in 
quantities of 4 g (4 g/liter of filter yellow) in the manner already 
described. A multilayered material containing no additives and a 
multilayered material containing, in the yellow filter layer, 4 g of 
2,5-dioctylhydroquinone, which is already known in the literature and has 
been described in U.S. Pat. No. 2,403,721, are used for comparison. The 
following fog values were obtained: 
______________________________________ 
Film sample Magenta fog Yellow fog 
______________________________________ 
without additive 0.74 0.90 
with compound 4 0.66 0.78 
with dioctylhydroquinone 
0.70 0.73 
______________________________________ 
The superior effect of the compound according to the invention in reducing 
fog is clear from a comparison of the above fog values. 
EXAMPLE 5 
Another multilayered material according to Example 2 containing no 
antistain agent is compared with a material which, like that of Example 4, 
contains 4 g of compound 1 per liter of filter yellow in the casting 
solution for yellow filter. A material as described in Example 4, 
containing 2,5-dioctylhydroquinone in the yellow filter layer, was 
developed in the same manner as comparison material. The following fog 
values were obtained: 
______________________________________ 
Film sample Magenta fog Yellow fog 
______________________________________ 
without additive 0.81 1.02 
with compound 1 0.68 0.80 
with dioctylhydroquinone 
0.75 0.88 
______________________________________ 
This shows clearly the fog reducing effect of the compound according to the 
invention.