Photographic elements comprising thiazolyl couplers capable of forming infrared-absorbing dyes for integral sound track

Color photographic motion picture elements adapted to form a multicolor photographic dye image and an integral, infrared-absorbing, dye sound track and comprising 1-hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide couplers that are capable of forming quinone imine dyes absorbing infrared radiation in the spectral range from about 600 to about 1000 nm by reaction with an oxidized aromatic primary amino developing agent, the thiazol-2- yl group of said naphthamide couplers bearing a 4-para-C.sub.1 -C.sub.4 alkoxyphenyl group or a 4-para-C.sub.1 -C.sub.4 alkylphenyl group, the hydrogen atoms of said C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 alkyl being unsubstituted or at least one of them having been substituted by a halogen atom.

The present invention relates to novel couplers capable of forming 
infrared-absorbing dyes, more particularly to couplers capable of forming 
integral, infrared-absorbing, dye sound tracks in colour photographic 
motion picture elements, to photographic colour elements comprising such 
couplers, and to materials comprising such infrared-absorbing dyes. 
The photographic image as well as the sound track image in black-and-white 
motion picture projection films are known to consist of silver usually, 
the sound information in the sound track being present in the form of 
periodical variations in density or of periodical variations in the ratio 
between areas that are completely dark and areas that are fully bright. 
This sound information can be read optically by a photocell detecting 
infrared radiation that has been modulated by passing through these 
variations in density or in area. The photocells customarily used for this 
purpose are i.a. the S-1 photocells, which have a maximum sensitivity in 
the infrared region of the spectrum, more particularly in the infrared 
region from about 750 to about 850 nm, in which region silver absorbs 
uniformly. 
Although in sound tracks of colour motion picture projection films silver 
has been used customarily, the application of silver therein requires 
special selective treatments including a separate development of the sound 
track portion. To avoid such special selective treatments attempts have 
been made to use dyes instead of silver for the sound tracks of colour 
motion picture projection films. This allows the formation of both a dye 
image and a dye sound track during the same and only colour development 
step. The dye that builds up the sound track is a quinone imine coupling 
product that should have peak absorption in the infrared region where the 
photocells, e.g. the S-1 photocells, are sensitive, namely from about 750 
to about 850 nm. 
Infrared-absorbing dyes that can be used at least partially in integral dye 
sound tracks have been disclosed in U.S. Pat. No. 2,266,452, U.S. Pat. No. 
2,373,821, JP PU 59,838, UK P 1,424,454, U.S. Pat. No. 3,458,315, U.S. 
Pat. No. 3,476,563, UK P 519,208, in Research Disclosure N.degree.13460 of 
June 1975, N.degree.15125 of November 1976, and N.degree.18732 of November 
1979. 
U.S. Pat. No. 4,178,183 teaches the use of 
1-hydroxy-2-N-(4-phenyl-5-ballasted-thiazol-2-yl)-naphthamide couplers for 
forming integral, infrared-absorbing, dye sound tracks in colour 
photographic motion picture elements. 
However, the absorption peaks of the infrared-absorbing dyes hitherto used 
for integral dye sound tracks are not broad enough and are insufficiently 
bathochromic. Their peak absorption usually lies between 800 and 820 nm. 
In these circumstances silver is still needed at least partially to 
guarantee sufficient absorption in the sensitivity range of the S-1 
photocells and to ensure sufficient density. Moreover, the use of these 
dyes gives rise to a loss in output of the sound track. 
It is therefore an object of the present invention to provide 2- or 
4-equivalent couplers that are capable of forming dyes that have enhanced 
infrared peak absorption, have a broadened more bathochromic absorption 
range that encompasses the sensitivity range of the S-1 photocells, and 
are not subject to loss in output of the sound track. 
It is another object of the present invention to provide colour 
photographic motion picture elements comprising such couplers that are 
capable of forming infrared-absorbing dyes for integral dye sound tracks 
without requiring special selective treatment as above referred to, and 
which have sufficient density in the absence of silver and show no 
significant loss in output of the sound track. 
It is a further object of the present invention to provide dyes that have a 
high infrared peak absorption and offer a broadened more bathochromic 
absorption range than the known infrared-absorbing dyes. 
Other objects of the present invention will become apparent from the 
disclosure herein. 
The above objects are accomplished by the use, in colour photographic 
motion picture elements, adapted to form a multicolour photographic dye 
image and an integral, infrared-absorbing, dye sound track, of at least 
one 1-hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide coupler that is 
capable of forming an infrared-absorbing quinone imine dye by reaction 
with an oxidized aromatic primary amino developing agent, the thiazol-2-yl 
group of said naphthamide couplers bearing a 4-paraphenyl group or a 
4-para-C.sub.1 -C.sub.4 alkylphenyl group, the hydrogen atoms of said 
C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 alkyl being unsubstituted or 
at least one of them having been substituted by a halogen atom. 
1-Hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide couplers, which can be 
prepared very simply and are very interesting from an economical 
standpoint, are those corresponding to the following general formula: 
##STR1## 
wherein represent: 
R--a C.sub.1 -C.sub.4 alkoxy group e.g. methoxy and ethoxy, a C.sub.1 
-C.sub.4 alkyl group e.g. methyl, or a C.sub.1 -C.sub.4 alkoxy group or 
C.sub.1 -C.sub.4 alkyl group wherein at least one of the hydrogen atoms 
has been replaced by a halogen atom such as fluorine e.g. difluoromethoxy; 
Y--an alkyl group having at least 8 carbon atoms e.g. tetradecyl, which 
renders the coupler fast to diffusion in hydrophilic colloid media; 
Z--hydrogen or a substituent, e.g. a chlorine atom, that splits off during 
the coupling reaction, thus conferring 2-equivalent character to the 
coupler. 
In addition to chlorine, other interesting substituents that may confer 
2-equivalent character to the naphthamide couplers of the present 
invention are e.g. an acyloxy group, an alkoxy group, an aryloxy group, a 
heterocycloxy group, an alkylthio group, an arylthio group e.g. phenylthio 
and carboxyphenylthio, an alkylsulphonyl group, an arylsulphonyl group, an 
alkylsulphinyl group, an arylsulphinyl group, an alkyl- or 
aryl-substituted carbonylmethoxy group, an alkoxy- or aryloxy-substituted 
carbonylmethoxy group, and a heterocyclic thio group such as a 
tetrazolylthio group. 
The present invention provides a photographic element comprising a support 
and a plurality of photosensitive silver halide emulsion layers for 
forming a multicolour photographic dye image and an integral, 
infrared-absorbing, dye sound track, one of said photosensitive silver 
halide emulsion layers or a non-photosensitive hydrophilic colloid layer 
in water-permeable relationship therewith, comprising at least one 
dispersed 1-hydroxy-2-N-(5-alkylthiazol-2-yl)- naphthamide coupler capable 
of forming an infrared-absorbing quinone imine dye by reaction with an 
oxidized aromatic primary amino developing agent characterized in that 
said naphthamide coupler bears on the thiazol-2-yl group a 4-paraC.sub.1 
-C.sub.4 alkoxyphenyl group or a 4-para-C.sub.1 -C.sub.4 alkylphenyl 
group, the hydrogen atoms of said C.sub.1 -C.sub.4 alkoxy or C.sub.1 
-C.sub.4 alkyl being unsubstituted or at least one of them having been 
substituted by a halogen atom. 
According to one embodiment of the present invention a photographic element 
is provided, which comprises: 
a support, 
an image-recording layer pack comprising in any desired sequence at least 
one image-recording blue-sensitive gelatin silver halide emulsion layer 
containing at least one yellow image dye-forming coupler, at least one 
image-recording red-sensitized gelatin silver halide emulsion layer 
containing at least one cyan image dye-forming coupler, at least one 
image-recording green-sensitized gelatin silver halide emulsion layer 
containing at least one magenta image dye-forming coupler, and one or more 
intermediate layers between said image-recording emulsion layers, 
a photosensitive sound-recording gelatin silver halide emulsion layer, and 
an antistress layer, 
said photosensitive sound-recording layer and/or a non-photosensitive 
hydrophilic colloid layer in water-permeable relationship therewith 
comprising said 1-hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide coupler. 
The present invention further also provides infrared-absorbing quinone 
imine dyes formed by a coupling reaction between an oxidized aromatic 
primary amino compound and the said 1-hydroxy-2-N-(5-alkylthiazol-2-yl)- 
naphthamide coupler. 
Representative examples of 1-hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide 
couplers that can be used in accordance with the present invention are 
listed in the following Table 1, the symbols used therein referring to the 
above general formula. 
TABLE 1 
______________________________________ 
Melting 
Coupler No. 
R Y Z point 
______________________________________ 
1 methoxy tetradecyl 
chloro 
138 
2 ethoxy tetradecyl 
chloro 
150 
3 difluoromethoxy 
tetradecyl 
chloro 
143 
4 methyl tetradecyl 
chloro 
136 
______________________________________ 
The novel couplers according to the present invention can be prepared by 
techniques well known to those skilled in the art e.g. according to the 
following general reaction scheme by first performing a cyclization 
reaction of appropriately substituted .alpha.-bromo-alkanoylbenzene 
derivatives with thiourea to form the corresponding 2-aminothiazoles and 
next to carry out a condensation of phenyl-1-hydroxynaphthoates, which may 
carry a coupling off substituent in the 4-position, with these 
2-aminothiazoles. In the following general reaction scheme, R has the 
significance as defined under the above general formula. 
##STR2## 
According this reaction scheme the 
1-hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide couplers corresponding to 
the above general formula can be prepared very simply and very 
economically. 
It was surprising to find that among the many substituents on the 
thiazol-2-yl group, which have been studied, only the above-specified 
alkoxyphenyl and alkylphenyl substituents of the couplers of the present 
invention made it possible to form quinone imine dyes having infrared 
absorption characteristics significantly better than those of the known 
couplers not containing the said specific substituents. The infrared 
absorption range of the quinone imine dyes formed in accordance with the 
present invention extends from the red region at about 600 nm to well into 
the infrared region at about 1000 nm. This absorption range consequently 
covers the entire sensitivity range of the S-1 photocells. Moreover, the 
broadening of the absorption peak with increasing colour density is 
considerable and progressive. The density values obtained with the quinone 
imine dyes formed in accordance with the present invention are much more 
favourable than those obtained with the known quinone imine dyes. In 
general, the maximum dye density of these quinone imine dyes produced 
throughout the spectral region of from 750 to 850 nm may exceed 1.5. The 
signal-to-noise ratio of the dye sound tracks made in accordance with the 
present invention is better than that of known dye sound tracks. Heat 
stability tests and dark-fading tests have proved that the heat and light 
stability of the infrared-absorbing sound track dyes obtained from the 
couplers used in accordance with the present invention are very good and 
that the loss in density of the dye tracks during ageing is very low. 
The couplers according to the present invention can thus be used 
advantageously in a hydrophilic colloid layer of colour photographic 
motion picture elements for forming infrared-absorbing dyes for integral 
dye sound tracks. The couplers of the present invention can be 
incorporated successfully into a hydrophilic colloid layer by dissolving 
them first in at least one water-immiscible, oil-type solvent or 
oil-former, adding the resulting solution to an aqueous phase containing 
gelatin and a dispersing agent, passing the mixture through a homogenizing 
apparatus so that a dispersion of the oily coupler solution in an aqueous 
medium is formed, mixing the dispersion with a hydrophilic colloid 
composition e.g. a gelatin silver halide emulsion, and coating the 
resulting composition in the usual manner to produce a system in which 
particles of coupler, surrounded by an oily membrane, are distributed 
throughout the gel matrix. The dissolution of the coupler in the 
oil-former may be facilitated by the use of an auxiliary low-boiling 
water-immiscible solvent, which is removed afterwards by evaporation. 
The couplers according to the present invention can be dispersed in 
hydrophilic colloid compositions with the aid of at least one known 
oil-formers such as an alkyl ester of phthalic acid, e.g. dimethyl 
phthalate, diethyl phthalate, di-n-butyl phthalate, di-i-amyl phthalate, 
dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl 
phthalate, didecyl phthalate, n-amyl phthalate, 
dibutylmonochlorophthalate, butylphthalylbutyl glycolate, 
2,4-di-n-amylphenol, 2,4-di-tert-amylphenol, a phosphoric acid acid ester 
e.g. diphenyl phosphate, triphenyl phosphate, tri-o, m-, or p-cresyl 
phosphate, o-cresyl diphenyl phosphate, dioctyl phosphate, di-octyl butyl 
phosphate, tri-n-octyl phosphate, tri-ndecyl phosphate, trixylenyl 
phosphate, tris-(isopropylphenyl)phosphate, tributyl phosphate, trihexyl 
phosphate, trinonyl phosphate, trioleyl phosphate, 
tris-(butoxyethyl)phosphate, a citric acid ester e.g. O-acetyltriethyl-(or 
butyl-, hexyl-, octyl-, nonyl-, or decyl)-citrate, a benzoic acid ester 
e.g. butyl (or hexyl-, heptyl-, octyl-, nonyl-, decyl-, undecyl-, 
dodecyl-, tridecyl-, tetradecyl-, hexadecyl-, octadecyl-, oleyl-, etc.) 
benzoate, n-butyl-2-methoxy benzoate, pentyl-o-methyl benzoate, 
decyl-pmethyl-benzoate, octyl-o-chlorobenzoate, lauryl-p-chlorobenzoate, 
propyl-2,4-dichlorobenzoate, octyl-2,4-dichlorobenzoate, 
stearyl-2,4-dichlorobenzoate, oleyl-2,4-dichlorobenzoate, 
octyl-p-methoxybenzoate, a fatty acid ester e.g. hexadecyl myristate, 
dibutoxyethyl succinate, dioctyl adipate, dioctyl azelate, 
decamethylene-1,10-diol diacetate, triacetin, tributyrin, benzyl caprate, 
pentaerythrite tetracapronate, isosorbide dicaprylate, an amide e.g. 
N,N-dimethyl lauramide, N,N-diethyl lauramide, N,N,di-n-butyl lauramide, 
N-butylbenzene sulphonamide, trioctyl trimellitate, a chlorinated 
paraffin, an aliphatic ester of glycerol and derivatives thereof e.g. 
glycerol triacetate, ethers e.g. allyl ether, or an oil-former as 
described in i.a. U.S. Pat. Nos. 2,304,940; 2,322,027; 2,353,262; 
2,533,514; 2,801,170; 2,801,171; 2,835,579; 2,852,383; 2,949,360; 
3,287,134; 3,554,755; 3,700,454; 3,748,141; 3,767,142; 3,779,765; 
3,788,857; 3,837,863; 3,936,303; 4,004,928; 4,075,022; 4,106,940; 
4,178,183; 4,233,389; 4,250,251; in UK P 958,441; 1,222,753; 1,272,561; 
1,424,454; 1,501,233; 2,027,130; in DE OS 2,432,041; 2,538,889; 2,613,504; 
2,629,842; 2,903,681; 2,909,402; 2,932,368; in DE P 1,152,610; in JA P 
23233/71; 29461/74; 28693/77; 15127/78; 1521/78, in JA Pat.Publications 
34715/77; 82078/75; 26037/76; 27921/76; in BE P 768,585 and 833,202, and 
in the Research Disclosures 18732 (Nov. 1979) p. 634-38 and 16745 (March 
1978) p. 58-59. 
The couplers according to the present invention can be dispersed easily in 
hydrophilic colloid compositions with the aid of at least one high-boiling 
substantially water-insoluble oilformer of the class of substituted 
2-propanols and carboxylic; phosphoric, and phosphonic acid esters thereof 
as disclosed in U.S. Pat. No. 4,430,422. Among these oil-formers, which 
can be used in combination with the couplers according to the present 
invention, the carboxylic acid acid esters and especially the 
2-ethylhexanoic acid ester of 1,3-di-n-octyloxy-2-propanol, the myristic 
acid ester of 1,3-di- methoxy-2-propanol, the 2-ethylhexanoic acid ester 
of 1-n-butoxy-3-(2'- ethyl)-n-hexyloxy-2-propanol, the myristic acid ester 
of 1-methoxy-2-pro- panol, and the 2-ethylhexanoic acid ester of 
1,3-di-n-hexyloxy-2-propanol offer the best results. The combination of 
the couplers according to the present invention with these especially 
identified oil-formers results in additional advantages in that an even 
higher bathochromic shift as well as a strong oppression of opalescence 
may be obtained. 
The couplers according to the present invention can also be dispersed in 
hydrophilic colloid compositions with the aid of a combination of at least 
one of the above-mentioned known oil-formers and at least one of the 
above-mentioned high-boiling substantially water-insoluble oil-formers of 
the class of substituted 2-propanols and carboxylic, phosphoric, and 
phosphonic acid esters thereof. 
For dispersing the couplers according to the present invention, the 
oil-formers, especially those of the class of substituted 2-propanols and 
carboxylic, phosphoric, and phosphonic acid esters thereof can be used in 
widely varying concentrations e.g. in amounts ranging from about 0.1 to 
about 10 parts by weight and preferably from 0.5 to 2 parts by weight 
relative to the amount of the couplers dispersed therewith. Excellent 
results were obtained with 0.5 part by weight of the oil-formers relative 
to 1 part of the couplers of the invention. For instance, very good 
results were obtained with a fine-grain silver halide sound-recording 
emulsion comprising per sq. m. an amount of silver that is equivalent with 
0.6 g of silver nitrate, 0.8 g of coupler according to the invention, and 
0.4 g of preferentially used oil-former. 
Inasmuch as the nature and the concentration of the oil-formers may have an 
influence on the absorption characteristics of the quinone imine dyes 
obtained from the couplers according to the invention, it may thus be 
possible to adjust the absorption spectrum of these dyes in a desired 
sense by establishing the optimum oil-former composition and adjusting the 
concentration of said preferentially used oil-formers. 
It may be useful to combine at least one of the above defined oil-formers 
with at least one auxiliary solvent that is insoluble or almost insoluble 
in water and has a boiling point of at most 150.degree. C., such as lower 
alkyl acetates e.g. methyl acetate, ethyl acetate, n-propyl acetate, 
isopropyl acetate, butyl acetate, ethyl formiate, methyl propionate, ethyl 
propionate, carbon tetrachloride, sym-dichloroethylene, trichloroethylene, 
1,2-dichloropropane, chloroform, amyl chloride, diethyl carbonate, diethyl 
ketone; methyl ethyl ketone, methyl-n-propylketone, diethyl ketone, 
diisopropyl ether, cyclohexane, methylcyclohexane, ligroin, benzene, 
toluene, xylene, nitromethane. The auxiliary solvent may also be a 
water-soluble organic solvent such as methanol, ethanol, isopropanol, 
dimethylsulphoxide, tetrahydrofuran, N-methylpyrrolidone, dioxan, acetone, 
butyrolactone, ethylene glycol, ethylene glycol monomethyl ether, ethylene 
glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol 
monoethyl ether, diethylene glycol monomethyl ether, glycerol, 
acetonitrile, formamide, dimethylformamide, tetrahydrothiophene dioxide, 
or dimethoxyethane. The auxiliary solvent may also be one described in 
i.a. U.S. Pat. Nos. 2,801,170; 2,801,171; 2,949,360; 2,835,579. 
For processing the colour photographic motion picture elements for forming 
the image dyes as well as the infrared-absorbing dyes for integral dye 
sound tracks any conventional colour developing agent can be employed. 
Inasmuch as the colour developing agent will react in oxidized form with 
i.a. the couplers used in accordance with the present invention, the 
nature of the particular colour developing agent will, of course, also 
determine the characteristics of the infrared-absorbing dyes obtained 
therewith. Colour developing agents that are very well suited for 
processing the colour photographic motion picture elements comprising the 
couplers of the present invention are e.g. 2-amino-5-diethylamino-toluene 
hydrochloride (CD-2), 
2-amino-5-[N-ethyl-N-(methylsulphonylamino)-ethyl]aminotoluene sulphate 
(CD-3), 4-amino-3-methyl-N-ethyl-N( -hydroxyethyl)aniline sulphate (CD-4), 
and N,N-diethyl-p-phenylene diamine sulphate (TSS). 
The colour photographic motion picture elements comprising the couplers of 
the present invention can be of the positive print film type or of the 
reversal film type. 
Further details on the formation of integral infrared-absorbing sound 
tracks in photographic elements and on the infrared-absorbing quinone 
imine dyes obtained therewith as coupling product in a separate layer of 
such photographic elements during the same processing step as the one 
wherein the colour image is formed, can be found in U.S. Pat. Nos. 
4,178,183; 4,233,389; 4,250,251 ; 4,430,422 and in the Research 
Disclosures 18 732 (Nov. 1979) p. 634-638; 15 125 (Nov. 1976) p. 24-25; 13 
460 (June 1975) p. 50. 
Such sound-recording layer(s) should have a spectral or general sensitivity 
such that an undesired image is not formed on image-wise exposure of the 
image-recording layers. 
The couplers of the present invention used for forming infrared-absorbing 
quinone imine dyes can be incorporated into a layer of the sound-recording 
layer unit making part of a colour photographic motion picture element. 
Such element may consist e.g. of a sound-recording layer unit comprising 
at least one sound-recording photosensitive gelatin silver halide emulsion 
layer coated on top of the image-recording layers. 
A common layer composition of a colour photographic motion picture element 
comprises in order of sequence : a film support, the blue-sensitive silver 
halide emulsion layer(s) containing yellow-forming colour coupler(s), 
optionally (an) intermediate layer(s), the red-sensitized silver halide 
emulsion layer(s) containing cyan-forming colour coupler(s), optionally 
(an) intermediate layer(s), and the green-sensitized silver halide 
emulsion layer(s) containing magenta-forming colour coupler(s). The 
sound-recording layer(s) can have different locations as specified 
hereinafter, e.g. they can be coated on top of the green-sensitized 
layer(s). 
Different sound-recording silver halide compositions are possible. For 
instance, the sound-recording silver halide emulsion is sensitive to 
ultraviolet radiation alone, or to infrared radiation, or to radiation of 
the spectral region between 470 and 500 nm. What is important is that 
during the image exposure of the colour element the sound-recording layer 
does not respond. In these cases the sound-recording layer can be coated 
directly on the uppermost green-sensitized layer. 
According to another alternative the sound-recording layer can be sensitive 
to the blue spectral region, but to a far less extent than the 
blue-sensitive layer(s) containing the yellow-forming couplers so that 
during the image exposure of the colour photographic motion picture 
element the sound-recording layer does not respond. The blue-sensitive 
sound-recording layer, which can e.g. be a fine-grain silver chlorobromide 
emulsion sensitive in the spectral range from 400 to 470 nm, may comprise 
a cyan-forming coupler in addition to the coupler forming an 
infrared-absorbing dye. When an additional cyan-forming coupler is used, 
the reaction with oxidized developer leads to the formation of a cyan dye 
in addition to the infrared-absorbing dye according to the invention. Cyan 
dyes are known to absorb also in the lower infrared region. The combined 
infrared absorption of both dyes thus increases the infrared absorption 
range and the density. 
Likewise according to a further alternative the sound-recording layer can 
be sensitive to the green spectral region, but to a far less extent than 
the green-sensitized layer so that during the image exposure of the colour 
photographic motion picture element the sound-recording layer does not 
respond. 
According to a further alternative the sound-recording layer can be 
sensitive to the red spectral region. 
The sound-recording layer can be sensitive to both the red and green 
spectral regions, but to a far less extent than the image-recording 
red-sensitized and green-sensitized layer(s) so that during the image 
exposure of the colour photographic motion picture element the 
sound-recording layer does not respond. 
According to all these above-mentioned embodiments the sound-recording 
layer contains one or more couplers for forming infrared-absorbing dye 
sound tracks. 
According to a further embodiment the colour photographic motion picture 
element comprises in order of sequence a film support, the blue-sensitive 
silver halide emulsion layer(s) containing yellow-forming colour 
coupler(s), optionally (an) intermediate layer(s), the red-sensitized 
silver halide emulsion layer(s) containing cyan-forming colour coupler(s), 
optionally (an) intermediate layer(s), the sound-recording silver halide 
emulsion layer(s) containing coupler(s) forming infrared-absorbing dye(s) 
in accordance with the invention, optionally (an) intermediate layer(s), 
the green-sensitized silver halide emulsion layer(s) containing 
magenta-forming colour couplers, and if desired (an) antistress layer(s). 
According to this embodiment the sound-recording silver halide emulsion 
layer(s) containing coupler(s) forming infrared-absorbing dye(s) in 
accordance with the invention is (are) sensitive in the blue spectral 
region from 400 to 470 nm, but is (are) far less sensitive than the 
blue-sensitive silver halide emulsion layer(s), and it (they) may contain 
in addition to the coupler(s) forming infrared-absorbing dye(s) (a) 
cyan-forming colour coupler(s) as already described above. The silver 
halide of this (these) sound-recording emulsion layer(s) may be silver 
chloride or chlorobromide, preferably fine-grain silver chloride 
comprising 0-40 mol % bromide and 0-5 mol % iodide. 
According to a different embodiment the colour photographic motion picture 
element does not encompass a separate sound-recording layer containing a 
coupler that is capable of forming infrared-absorbing dyes. Instead 
thereof the latter couplers can be incorporated e.g. together with 
magenta-forming coupler(s) into the green-sensitized layer(s). However, 
the coupling speed of the magenta-forming couplers should then 
substantially exceed the coupling speed of the couplers forming the sound 
track dyes, so that in case of a normal image-wise exposure, the latter 
couplers, which are slow-coupling, cannot be affected as a result of 
insufficient amounts of oxidized developer. During the intensive sound 
track exposure both kinds of couplers respond and form their respective 
dyes, but the S-1 photocells only react to the infrared density obtained. 
Alternatively, the couplers that are capable of forming infrared-absorbing 
dyes can be incorporated together with the cyan image-forming coupler(s) 
into the red-sensitized layer(s). During the intensive sound track 
exposure both kinds of couplers respond and form their respective dyes, 
but the S-1 photocells again only react to the infrared density obtained. 
In all above-mentioned embodiments the uppermost emulsion layer may, of 
course, be protected by (an) antistress layer(s). 
Further details on layer structures of colour photographic motion picture 
elements can be found in U.S. Pat. Nos. 3,705,799 - 3,705,801 - 3,737,312, 
and 4,208,210; in DE-OS 2,302,661; in UK-P 1,411,311 - 1,429,108, and in 
the Research Disclosure 18 732 (November 79) p. 634-38. 
Although in the making of dispersions of the couplers of the invention in 
hydrophilic colloid compositions gelatin is favoured as hydrophilic 
colloid, other water-soluble colloidal substances or mixtures of these can 
be used too e.g. colloidal albumin, starch, zein, alginic acid and 
derivatives thereof, such as salts, esters, and amides, casein, cellulose 
derivatives such as carboxymethyl cellulose, synthetic hydrophilic 
colloids such as polyvinyl alcohol, poly-N-vinyl pyrrolidone, anionic 
polyurethans, copolymers of acrylic esters, acrylonitrile, and 
acrylamides, etc. 
During the manufacture of the colour photographic silver halide motion 
picture element according to the invention, the couplers corresponding to 
the above general formula can be incorporated in the presence of at least 
one of the above defined oil-formers into the coating composition of the 
silver halide emulsion layer(s) or other colloid layer(s) in 
water-permeable relationship therewith according to any technique known by 
those skilled in the art of incorporating couplers, into colloid 
compositions. For more details about particularly suitable techniques that 
can be employed for dispersing the couplers of the invention into 
hydrophilic colloid compositions there can be referred to U.S. Pat. Nos. 
2,304,939; 2,304,940; 2,322,027; 2,801,170; 2,801,171; and 2,949,360. 
The couplers of the invention can be dispersed in the presence of a 
surface-active agent or dispersing aid. The surface-active agent used may 
be of the ionic, non-ionic or amphoteric type. Examples of suitable ionic 
surface-active agents are the sodium salt of oleylmethyltauride, sodium 
stearate, 2-heptadecyl-benzimidazole-5-sulphonic acid sodium salt, sodium 
sulphates of aliphatic alcohols containing more than 5 carbon atoms per 
molecule, e.g. 2-methylhexanol sodium sulphate; the sodium salt of 
di-isooctyl ester of sulphonated succinic acid, sodium dodecyl sulphate 
and p-dodecylbenzene sulphonic acid sodium salt. Examples of suitable 
non-ionic surface-active agents are saponine, condensation products of 
ethylene oxide and alkyl phenols, e.g. p-octylphenol and p-isononyl phenol 
and phenylethylene glycol oleate. Other examples of anionic and non-ionic 
surface-active agents can be found in UK P 1,460,894. 
A survey of surface-active agents, representatives of which can be used in 
dispersing the couplers of the present invention, was made by Gerhard 
Gawalek in "Wash- und Netzmittel" Akademieverlag, Berlin (1962). 
It is also possible to use mixtures of anionic and non-ionic surface-active 
agents as described e.g. in UK P 1,460,894. 
Other interesting surface-active agents that can be used in dispersing the 
couplers of the invention are the short-chain fluorine-containing 
surface-active agents disclosed in U.S. Pat. No. 4,292,402. 
The photosensitive silver halide emulsions used in the making of colour 
photographic motion picture elements according to the present invention 
can be sensitized chemically as well as optically. They can be sensitized 
chemically by carrying out the ripening in the presence of small amounts 
of sulphur-containing compounds such as allyl thiocyanate, allyl thiourea, 
or sodium thiosulphate. The emulsions can also be sensitized by means of 
reducing agents e.g. tin compounds as described in FR P 1,146,955 and in 
BE P 568,687, imino-aminomethane sulphinic acid compounds as described in 
UK P 789,823 and small amounts of noble metal compounds such as gold, 
platinum, palladium, iridium, ruthenium, and rhodium compounds. They can 
be sensitized optically by means of cyanine and merocyanine dyes. 
The emulsions can also comprise compounds that sensitize the emulsions by 
development acceleration e.g. compounds of the polyoxyalkylene type such 
as alkylene oxide condensation products as described i.a. in U.S. Pat. No. 
2,531,832 - 2,533,990, in UK P 920,637; 940,051; 945,340; 991,608 and 
1,091,705, onium derivatives of amino-N-oxides as described in UK P 
1,121,696, and thioethers as described in U.S. Pat. No. 4,292,400. 
Further, the emulsions may comprise stabilizers e.g. heterocyclic 
nitrogen-containing thioxo compounds such as benzothiazoline-2-thione and 
1-phenyl-2-tetrazoline-5-thione and compounds of the 
hydroxytriazolopyrimidine type. They can also be stabilized with an 
aromatic or heterocyclic mercapto compound as described in the UK PA 
39457/80 or with mercury compounds such as the mercury compounds described 
in BE P 524,121; 677,337, and in the UK P 1,173,609. 
The hydrophilic colloid layers, in particular the photosensitive emulsions 
layers, making part of the colour photographic motion picture elements of 
the present invention may be hardened, if desired, with the aid of known 
hardening agents. Particularly interesting hardening results were obtained 
with hardening agents corresponding to the following general formula: 
##STR3## 
wherein: 
each of R.sup.1 and R.sup.2 (same or different) represent hydrogen, a 
C.sup.1 -C.sup.3 alkyl group, an aryl group e.g. phenyl, an aryl group 
substituted with a lower alkyl group or with halogen e.g. phenyl 
substituted with methyl, ethyl, chloro, or bromo, an aralkyl group e.g. 
benzyl, an aralkyl group substituted with a lower alkyl group or with 
halogen, or 
R.sup.1 and R.sup.2 together represent the atoms necessary to complete a 
saturated heterocyclic group, preferably morpholino or piperidino, said 
saturated heterocyclic group optionally being substituted with a lower 
alkyl group or with halogen e.g. methyl, ethyl, chloro, or bromo, 
R.sup.3 hydrogen, methyl, or ethyl, and 
X a chemical bond or a C.sub.1 -C.sub.3 group e.g. methylene, ethylene, or 
propylene. 
The photosensitive emulsions containing the couplers of the invention may 
also comprise any other kind of ingredient such as those described for 
such emulsions in Research Disclosure no. 17,643 of December 1978. 
The emulsions can be coated on a wide variety of photographic emulsion 
supports. Typical supports include cellulose ester film, polyvinylacetal 
film, polystyrene film, polyethylene terephthalate film and related films 
or resinous materials. 
The infrared-absorbing dye sound tracks produced in the colour photographic 
motion picture elements of the present invention are equal in fidelity 
with known silver sound tracks. No higher gain is required to achieve 
comparable decibel output, since the dye sound tracks produced in 
accordance with the invention--unlike known dye sound tracks--have a 
maximum density that is of substantially the same value as that of silver 
sound tracks. 
The infrared-absorbing quinone imine dyes formed by a coupling reaction of 
1-hydroxy-2-N-(5-alkyl-thiazol-2-yl)-naphthamide couplers according to the 
present invention with an oxidized aromatic primary amino compound can be 
used also as filter dyes in non-photographic materials such as in glass or 
synthetic resin materials e.g. in window glass as commonly used in shop 
and office windows for filtering the sun rays. It is obvious that the 
infrared-absorbing dyes obtained in accordance with the invention may find 
other interesting applications.

The following examples illustrate the present invention. 
EXAMPLE 1 
Samples of colour photographic motion picture elements were made, all the 
samples being identical except for the composition of their 
sound-recording layer. The difference in the composition of the 
sound-recording layers only referred to the nature of the coupler and the 
oil-former used therein. The samples had the following layer sequence: 
black antihalation layer 
transparent film support 
subbing layer 
image-recording blue-sensitive gelatin silver halide emulsion layer 
containing a yellow image dye-forming coupler 
gelatin intermediate layer 
image-recording red-sensitized gelatin silver halide emulsion layer 
containing a cyan image dye-forming coupler 
sound-recording chlorobromide emulsion layer sensitive in the blue spectral 
region from 400 to 470 nm and comprising silver in an amount equivalent to 
0.6 g of silver nitrate per sq. m., 1.5 g/sq. m. of gelatin and 0.75 g/sq. 
m. of coupler, as defined in Table 2, dispersed with the aid of an equal 
weight of oil-former, also defined in Table 2 hereinafter 
image-recording green-sensitized gelatin silver halide emulsion layer 
containing a magenta image dye-forming coupler 
antistress layer. 
The couplers and oil-formers used in the sound-recording layer of the 
samples are identified in the following Table 2. The comparison A is 
1-hydroxy-2-N-(4-phenyl-5-thiazol-2-yl)-naphthamide, which is the 
4-equivalent coupler described in Example 1 of U.S. Pat. No. 4,178,183, 
and comparison B has the same structure as comparison A except that it is 
2-equivalent and as a consequence carries a coupling off group, which in 
the present case is a chloro substituent at the 4-position of the 
naphthamide ring system. Couplers 1, 2, and 4 are couplers according to 
the present invention, identified in Table 1. In the same table reference 
is made also to the accompanying FIGS. 1 to 8, which show a density versus 
wavelength (in nm) plot obtained from the measurement on the sound track 
quinone imine dye formed as described hereinafter. 
TABLE 2 
______________________________________ 
refer to 
Coupler Oil-former FIG. No. 
______________________________________ 
Comparison A 
dibutyl phthalate 1 
Comparison B 
dibutyl phthalate 2 
Coupler 1 dibutyl phthalate 3 
Coupler 1 1,3-dimethoxy-2-propanol 
4 
myristic ester 
Coupler 1 1,3-di-n-octyloxy-2-propanol 
5 
2-ethylhexanoic ester 
Coupler 1 1-n-butoxy-3-(2'-ethyl)-n-hexyloxy- 
6 
2-propanol 2-ethylhexanoic ester 
Coupler 2 1,3-di-n-octyloxy-2-propanol 
7 
2-ethylhexanoic ester 
Coupler 4 1,3-di-n-octyloxy-2-propanol 
8 
2-ethylhexanoic ester 
______________________________________ 
All samples were exposed similarly to white light having a colour 
temperature of 3200.degree. K., to be recorded in the image-recording 
layers and then exposed again in the sound track area to light so as to 
affect the sound-recording layer. 
The exposed samples were then processed as described hereinafter, no 
special selective treatment being given to the sound-recording layer. The 
processing was as follows: 
The samples were rinsed for 15 s in a prebath at 27.degree. C. having the 
following composition: 
______________________________________ 
water 800 ml 
borax 20 g 
anhydrous sodium sulphate 
100 g 
sodium hydroxide 1 g 
water to make 1000 ml 
(pH 9.25 at 27.degree. C.) 
______________________________________ 
The black antihalation layer was removed with water at 27.degree. C. Next, 
the samples were immersed for 3 min in a colour developing bath at 
36.7.degree. C. (.+-.0.1) having the following composition: 
______________________________________ 
water 800 ml 
calcium-sequestering agent 
1 ml 
anhydrous sodium sulphite 
4.35 g 
2-amino-5-diethylamino-toluene 
2.95 ml 
hydrochloride 
anhydrous sodium carbonate 
17.10 g 
anhydrous sodium bromide 
1.72 g 
7 N sulphuric acid 0.62 ml 
water to make 1000 ml 
(pH 10.53 at 27.degree. C.) 
______________________________________ 
The samples were then treated with the following stopbath for 40 s at 
27.degree. C.: 
______________________________________ 
water 900 ml 
7 N sulphuric acid 50 ml 
water to make 1000 ml 
(pH 0.9 at 27.degree. C.) 
______________________________________ 
The samples were then bleached in the following bath for 1 min at 
27.degree. C.: 
______________________________________ 
water 900 ml 
anhydrous potassium hexacyanoferrate (III) 
30 g 
anhydrous sodium bromide 
17 g 
water to make 1000 ml 
(pH 6.5 at 27.degree. C.) 
______________________________________ 
The bleached samples were rinsed in water for 40 s at 27.degree. C. and 
nest immersed in the following fixing bath for 40 s at 27.degree. C.: 
______________________________________ 
water 800 ml 
58% aqueous solution of ammonium 
100 ml 
thiosulphate 
anhydrous sodium sulphite 
2.50 g 
anhydrous sodium hydrogen sulphite 
10.30 g 
water to make 1000 ml 
(pH 5.8 at 27.degree. C.) 
______________________________________ 
Finally, the samples were rinsed for 1 min in water at 27.degree. C., 
immersed for 10 s in the following stabilizing bath at 27.degree. C., and 
allowed to dry: 
______________________________________ 
water 900 ml 
37.5% aqueous solution of formaldehyde 
15 ml 
stabilizer additive 0.14 ml 
water to make 1000 ml. 
______________________________________ 
In consequence of the high density values obtained in the sound tracks, the 
signal to noise ratio of the dye sound tracks made in accordance with the 
present invention exceeds that of known dye sound tracks. 
Comparable results were obtained with the other couplers of the present 
invention, which are identified in Table 1 hereinbefore given. 
As a consequence of these higher standards reached with the couplers of the 
present invention, it is possible to use an image- and sound-recording 
colour photographic motion picture element in which the sound record is 
processed simultaneously with the image record using the same baths, the 
sound record entirely consisting of an infrared-absorbing quinone imine 
dye as described above. 
Dark-fading tests of the quinone imine dyes obtained in accordance with the 
present invention proved that their heat and light stability was excellent 
and that the loss in density during ageing was very low. 
Alternatively, the samples, instead of being bleached with the above 
hexacyanoferrate (III) bleach bath, could be bleached also with 
persulphate-based baths by first treating them with the following 
accelerator bath: 
______________________________________ 
water 900 ml 
anhydrous sodium metabisulphite 
3.3 g 
glacial acetic acid 5.0 ml 
persulphate bleach accelerator 
3.3 g 
ethylene diamine tetraacetic acid 
0.5 g 
tetrasodium salt 
water to make 1000 ml 
(pH 4.0 at 27.degree. C.) 
______________________________________ 
and next with the following bleach bath: 
______________________________________ 
water 850 ml 
chlorine scavenger 0.35 g 
sodium persulphate 33 g 
sodium chloride 15 g 
anhydrous sodium dihydrogen phosphate 
7.0 g 
85% phosphoric acid 2.5 ml 
water to make 1000 ml 
(pH 2.3 at 27.degree. C.) 
______________________________________ 
In comparison with the known processing system for forming a silver-based 
sound track, the above described processing method comprising a bleaching 
step with the above-described persulphate bleach bath offers an important 
advantage in that it. does not include a second development and requires 
but one fixing step. 
An even further simplification of the above described processing can be 
realized by using a bleach-fixing (blix) bath. In that case the processing 
sequence can be reduced to a treatment with successively the prebath, the 
colour developing bath, the stopbath, all three as described above, then 
treatment with the blix-bath having the following composition, rinsing, 
and treatment with the above described stabilizing bath. 
Composition of the blix bath: 
______________________________________ 
water 700 ml 
sodium sulphite 10 g 
mercaptotriazole 2.5 g 
ethylene diamine tetraacetic acid 
13 g 
tetrasodium salt 
ethylene diamine tetraacetic acid 
50 g 
iron salt 
ammonium bromide 10 g 
ethylene diamine tetraacetic acid 
5 g 
ammonium thiosulphate 150 g 
water to make 1000 ml. 
(pH 6.3 at 27.degree. C.) 
______________________________________ 
In order to facilitate evaluation of the quinone imine dye sound tracks 
formed, samples were prepared of photographic elements as described 
hereinbefore with the difference that no image-recording layers were 
coated onto the subbed film support. The samples were exposed through a 
step wedge having a constant of 0.5, the density steps of which range from 
density 0.5 at step 1 to density 3 at step 6, to light so as to affect the 
sound-recording layers. The samples were then processed as described 
hereinbefore for the multilayer colour photographic motion picture 
elements containing image-recording layers also. 
In the accompanying FIGS. 1 to 8 a plot of density D versus wavelength (in 
nm) of the quinone imine dye images obtained is shown. The different 
curves of a plot refer to different consecutive steps of the step wedge, 
through which the sample was exposed. 
Comparison of the plots shows that the absorption peaks in FIGS. 1 and 2 
(comparison couplers A and B respectively dispersed with dibutyl 
phthalate) range between 740 for the lower curve and 800 nm for the upper 
curve, whereas the absorption peak in FIG. 3 (coupler 1 dispersed with 
dibutyl phthalate) ranges between 750 for the lower curve and 860 nm for 
the upper curve, which is well into the infrared region, and the 
absorption peaks in FIGS. 4 to 6 (coupler 1 dispersed with the oil-formers 
indicated in Table 2) and in FIG. 7 (coupler 2) are near 870 nm for both 
the lower curve and the upper curve, which is even farther into the 
infrared region. 
Further comparison of the plots shows that the absorption ranges of the 
dyes obtained from comparison couplers A and B in FIGS. 1 and 2 are 
narrower than those of couplers 1, 2, and 4 in FIGS. 3 to 8, which in the 
lower curves appear to have two absorption peaks resulting in one 
broadened composite peak that encompasses the whole sensitivity range of 
the S-1 photocells. 
Comparison of the infrared spectra of the dyes in FIGS. 1 to 8 clearly 
demonstrates that the values of infrared absorption above 850 nm obtained 
for the dyes derived from 1, 2, and 4 substantially exceed those of the 
dyes derived from the comparison couplers. For clarity a reference line 
has been drawn at wavelength 850 nm in each Figure. 
EXAMPLE 2 
As referred to in the above Example 1 samples were made of sound-recording 
layers coated on subbed film supports. The samples were identical, except 
for the composition of the sound-recording layer. The difference in the 
composition of the sound-recording layers only referred to the nature of 
the coupler and the oil-former used therein. These couplers and 
oil-formers are identified in the following Table 3. 
TABLE 3 
______________________________________ 
refer to 
Coupler Oil-former FIG. No. 
______________________________________ 
Compar- dibutyl phthalate 9 
ison A 
Coupler 1 
1,3-dimethoxy-2-propanol myristic ester 
10 
Coupler 2 
1,3-dimethoxy-2-propanol myristic ester 
11 
Coupler 4 
1,3-dimethoxy-2-propanol myristic ester 
12 
______________________________________ 
Comparison A is the known coupler identified in Example 1. 
All samples were exposed and processed in the same way as described in 
Example 1, except that instead of the CD-2 colour developing agent of 
Example 1, the CD-3 colour developing agent 
2-amino-5-[N-ethyl-N-(methylsulphonylamino)-]-aminotoluene sulphate was 
used now. It is to be noted that in CD-3 development a higher exposure 
dose is required to achieve the same density values as in CD-2 
development. 
In the accompanying FIGS. 9 to 12 plots of density D versus wavelength (in 
nm) of the quinone imine dye sound tracks obtained are shown. 
Comparison of these plots learns that the absorption peaks in FIGS. 10 to 
12 (couplers 1, 2 and 4 dispersed with the oil-former indicated in Table 
3) are closer to the infrared region than those obtained with the known 
coupler. 
Further comparison of the plots also shows that the couplers of the present 
invention give dyes, which show two absorption peaks resulting in one 
broadened composite peak that covers the sensitivity range of the S-1 
photocells in a better way than the peak obtained from the known dye. 
Comparison of the infrared spectra of the dyes in FIGS. 9 to 12 clearly 
demonstrates that the values of infrared absorption above 850 nm obtained 
for the dyes derived from couplers 1, 2, and 4 substantially exceed those 
of the dye derived from the comparison coupler A. For clarity a reference 
line has been drawn at wavelength 850 nm in each Figure. 
In consequence of the high density values obtained, the signal to noise 
ratio of the dye sound tracks made in accordance with the present 
invention exceeds that of the known dye sound track. 
Comparable results were obtained with the other couplers of the present 
invention.