[0001] This invention relates to a light-sensitive silver halide colour photographic materials
for registration of objects in visible and infra-red area of a spectrum.
[0002] It is known the colour photographic material consisting from triacetate support coated
thereon silver halide emulsion layers sensitive to various zones of a spectrum (TU
6-17-688-85 "Aerial photographic film, type SN-6M, NPO "Svema").
[0003] The indicated photographic material has a low resolving power R
k=1,0 = 58 mm
-1.
[0004] It is known also a false colour silver halide photographic material consisting from
a nitrate cellulose sublayered support having coated thereon on the one side a green
anti-halo backing and on other side sequentially the first silver halide emulsion
layer comprised silver bromide-iodide emulsion with the grain average size d=1,2µm
and the contents of AgJ of 3 Mole %, containing 5-methyl-7-oxy-1,3,4-triazoindolizine
(F-1) as a stabilizer, pyrocatechin, 3,3,9-triethyl-5,5'-diphenyloxacarbocyanine nitrate
and 3,3'-diethyl-5-phenyl-5,6,9-trimethyloxathiacarbocyanine perchlorate as sensitizers,
a yellow colour coupler (Zh-4) [4-stearoylaminobenzoyl acetic acid 2'-(3',5'-dicarboxyphenoxy)-5'-carboxyanylide,
sodium salt of di-2-ethylhexyl ether of sulfosuccinic acid as a surfactant; the second
silver halide layer prepared from same emulsion as the first layer and containing
the same stabilizer F-1, pyrocatechin, sensitizer trietylamine salt of 3-ethyl-3'-γ-sulfopropyl-4-keto-4',5'-diphenyl-5-(3"-y-sulfopropyl-4",5"-diphenylthiazolidene-2"-ethylidene)
thiazolinothiazolcyanine betaine and 3,3'1,9-triethyl-4,5,4',5'-dibenzothiacarbocyanine
bromide as a sensitizer, as well as magenta colour coupler 1'-(4'-diphenoxy-3'-sulfophenyl)-3-heptadecylpyrazole-5-one,
dipotassium salt of diether of a mixture of polyglycerides of alkenyl succinic acids
as a surfactant; the third silver halide emulsion layer prepared from ammoniac silver
bromide-iodide photographic emulsion with 3 Mole % of AgI and with the grain average
size d = 1,0 µm containing stabilizer F-1, pyrocatechin, 3,3'-diethyl-10-methyl-5,5'-dimethoxy-6,6'-di-(methylmercapto)
thiadicarbocyanine-n-tolusulfonate as a sensitizer, a cyan colour coupler 2'-methylotadecylamino-5'-sulfoanylide
of 1-oxy-2-naphtoic acid (G-2), dipotassium salt of diether of mixture of polyglycerides
of alkenyl succinic acids as a surfactant; protective layer containing gelatin, emulgate
of 2,5-ditret-amylhydrochinone, phenol, surfactant (A. N. Iordanski "New false colour
negative films", Journal of a Scientific and Applied Photography and Cinematography,
volume 9, page 210-211, 1964). This material has a sensitivity S
0,85 = 50 GOST, contrast coefficient 1.7-2.4, D
max > 2,5 for all layers, D
o = 0,11, resolving power R
c=1,0 = 68 mm
-1 (GOST 9160-59).
[0005] It should be refer to defects of this material an insufficient level of a resolving
power and photographic sensitivity not allowing to decode reliably small objects on
photographies shot from large altitudes and from space, as well as a possibility of
processing only at low temperatures.
[0006] An object of this invention is to provide an extension of a range of high sensitive
false colour photographic materials with a sufficient level of a resolving power.
Detailed description of the invention
[0007] The object of the present inventions accomplished with the false colour silver halide
photographic material which comprises a polymeric support having coated thereon on
the one side antihalo backing layer, on the other side at least two light-sensitive
layers prepared from silver halide photographic emulsion, containing colour couplers
and infrared, orthochromatic and/or panchromatic sensitizing dyes; auxiliary and protective
gelatin layers; all sensitive layers are prepared from the silver bromide-iodide emulsion
with octahedral or flattened microcrystals with a grain average size 0,5-1,5 microns,
or from their mixture; one of the sensitive layers contains as infrachromatic sensitizing
dye one or more one compounds represented by the general formula (I)

wherein A represents H; A
1 represents OCH
2CH
2CH
2SO
3 ; O=lower alkyl; A and A
1 together represent CH
2C(CH
3)
2CH
2 ; A
2 represents H, lower alkyl; B represents H, 5,5'-di-OCH
3, 6,6'-di-SCH
3; R represents lower alkyl, (CH
2)
3SO
3- ; n = 0,1; X represents CH
3SO
3C
6H
4SO
3-, J, CH
3SO
3 -, the alkaline metal or is absent; other light-sensitive layer contains as an orthochromatic
sensitizing dye more than one compounds of the formula (II)

wherein Y represents 0, N; A represents lower alkyl or is absent; A
1 represents H, lower alkyl; B represents 5,5'-COOC
2H
5, 5,5 '-C
6H
5 ; R, R
1represent lower alkyl, (CH
2)
3SO
3-; [K]
+ represents NHC
5H
5 or is absent, and/or the third light-sensitive layer contains as a panchromatic sensitizing
dye one or more compounds of the formula (III)

wherein A represents lower alkyl; B represents 4,5-benzo, 4,5-tieno; B
1 represents 5-OCH
3, 5-C
6H
5, 4,'5' -benzo, 5-CH
3, 5-Cl; R, R
1 represent lower alkyl, (CH
2)
3 SO
3- ; [K]
+ represents HN(C
2H
5)
3, HN(C
4H
9)
3, C
5H
5-NH, the alkaline metal, 3,3'-diethylthiazolinocarbocyanine or is absent, and between
light-sensitive layers auxiliary gelatin layers including hardener are coated.
[0008] In addition the light-sensitive layers can contain 3,3'-[1",2"bis(ethoxy)-ethyl]-bis-(1-ethylbenzimidazolium)
diperchlorate, or disodium salt of 4,4'-bis(4",6-diphenoxy-1,3,5-triazynil-2-amino)stilbene-2,2'-disulfonic
acid or monosodium salt of 2-mercaptobenzoxazole-5-sulfonic acid as an activator of
the spectral sensitization.
[0009] As a hardener it is desirable to apply derivatives of triazine-1,3,5, namely: 1,3,5-triacryloylhexahydrotriazine
or sodium salt of 2,4-dichloro-6-oxytriazine-1,3,5.
[0010] It is desirable to introduce in the light-sensitive layers mixtures of silver bromide-iodide
emulsion with octahedral microcrystals and silver bromide-iodide emulsion with flattened
microcrystals in the ratio 1:9-9:1.
[0011] As magenta colour couplers preferably derivatives of pyrazolone-5 and/or aminobenzenesulfamino-1,2-xylene
are used: 1-(4-phenoxy-3-sulfophenyl)-3-stearoylamino-pyrazolone-5 (P-6), 3,5-di(2-methyl-5-octadecenyl-succinoylaminobenzenesulfamino)-1,2-xylene
[P-8], 1-(2,4,6-trichlorophenyl)-3 [2,4-di-tret-amyl-phenoxy-acetylamido)-benzamido]-pyrazolone-5
(ZP-24), 1-(4'-phenoxy-3'-sulfophenyl) -3 -heptadecylpyrazolone-5 (P-1), 1-(2',4',6'-trichlorophenyl)-3[2"chloro-5"-octadecylsuccinoyliminophenyl]aminopyrazolone
(N-651).
[0012] As cyan colour couplers preferably derivatives of 1-oxy-2-naphtoyl acid are used.
Among such compounds are the following: 2-methyl-octadecylamino-5-sulfanilide of 1-oxy-2-naphtoyl
acid (G-2), (2,4-di-tret-amylphenoxy)-bulylamide of 1-oxy-2-naphtoyl acid (ZG-97),
octadecylamide of 1-oxy-4-sulfo-2-naphtoyl acid (G-3).
[0013] As yellow colour couplers preferably anylides of acylacetic, pivaylacetic or benzoic
acids are used: 3,5-dicarboxyanylide of n-stearoylaminobenzoylacetic acid (Zh-2),
2-chloro-5 [γ-2,4-di-tret-anilid(phenoxy)-butyroylamino)-anilide]-α-n-carboxyphenyloxypivaylacetic
acid (N-596), 2-chloro-5 [γ-2,4-di-tret-amyl(phenoxy)-butyroylamino)-anilide] of α-n-carbomethoxyphenoxypivaylacetic
acid (N-574), 2'-methyloctadecylamino-5'-sulfanilide of benzoylacetic acid (Zh-8),
2'-chloro-5' (3", 5"-dicarboxyphenylsulfamydo)anilide of 2-octadecyloxybenzoylacetic
acid (N-353), 2-chloro-5[(γ-2',4'-di-tret-amylphenoxy) (butyroylamino)anilide of α-benzylhydantoylpivaylacetic
acid (Y-488), 2"-chloro-5" (3", 5"'-dicarbmethoxyphenylsulfamido)anilide of α-(3',
5'-dicarbmethoxyphenoxy)2-octadecyloxybenzoylacetic acid (N-609).
[0014] The false colour photographic material according to this invention expands essentially
a range of high sensitive (S
0,85 = GOST 200-700) materials with adequately high level of a resolving power (R = 100-145
mm
-1).
[0015] The following examples illustrate this invention, but do not limit it.
Example 1 (the prototype).
[0016] False colour silver halide photographic material is prepared by coating on the undercoated
nitrate cellulose base an emulsion and auxiliary layers of a following structure:
- Green antihalo sublayer from a mixture of isobutanol, propanol, novamal, BRO-721 dye
and dimethylphtalate;
- Gelatin sublayer containing per 1 L of desalinated water 40 g of gelatin, 30 ml of
the 4% solution of sodium salt of di-2-ethylhexyl ether of sulfosuccinic acid as a
surfactant;
- The first silver halide emulsion layer containing silver bromide-iodide emulsion with
an average grain size of 1,2 µm and AgJ content 3,08 %. The emulsion contains per
1 kg 40 ml of the 1% solution of F-1 5-methyl-7-oxy-1,3,4-triazoindolyzine as a stabilizer;
6 ml of the 1% solution of pyrocatechin, 40 ml of the 0,05% alcohol solution of 3,3',
9-triethyl-5,5'-diphenyloxacarbocyanine nitrate and 25 ml of the 0,05% alcohol solution
of perchlorate 3,3'-diethyl-5-phenyl-5',6,9-trimethyloxathiacarbocyanine; 30 ml of
the 5% solution of a yellow coupler (Zh-4) (2-(3,'5-dicarboxy-phenoxy-5'-carboxyanilide
of 4-stearoylaminobenzoylacetic acid), 6 ml of the 4% solution of surfactant, dipotassium
salt of diether of a mixture of polyglycerides of alcenylsuccinic acids;
- The second silver halide emulsion layer from the same emulsion as the first layer
but containing per 1 kg of emulsion 40 ml of 0,05% alcohol solution triethylamine
salt of 3-ethyl-3'-γ-sulfopropyl-4-keto-4',5'-diphenyl-5 (3"-γ-sulfopropyl-4",5"-diphenylthiazolynylydene-2"-ethylydene)thiazolinothiazolocyanine
betaine and 30 ml of 0,1% alcohol solution of 3,3",9-triethyl-4,5,4",5'-dibenzothiacarbocyanine
bromide as the spectral sensitizers and 200 ml of the 5% water solution of (P-1) 1-(4'-phenoxy-3"-sulfophenyl)-3-heptadezylpyrazolone-5
as a magenta coupler and 6 ml of the 4% solution dipotassium salt of a mixture of
polyglycerides of alkenylsuccinic acids as surfactant;
- The third silver halide emulsion layer from silver bromide-iodide emulsion with an
average grain size d=1,0 µm and contents of AgJ of 3 Mol. %, containing 40 ml of the
1% solution of a stabilizer F-1, 6 ml of the 1% solution of pyrocatechin, but including
per 1 kg of emulsion 30 ml of 0,01% alcohol solution of 3,3'-diethyl-10-methyl-5,5'-dimethoxy-6,6-di-(methylmercapto-
thiadicarbocyanine-para-tolusulfonate as a spectral sensitizer, 500 ml of the 3% solution of 2'-methyl-octadecylamino-5'-sulfoanilide
of 1-oxy-2-naphthoic acid (G-2) as a a cyan coupler, 6 ml of the 4% solution of dipotassium
salt of diether of a mixture of polyglycerides of alkenylsuccinic acids as a surfactant;
- a protective layer from the following composition: per 1 L of desalinated water 20
g of a gelatin, 20 g of 2,5-di-tret-amylhydrochinone, 8 ml of 4% solution of sodium
salt of di-2-ethylhexyl ether of sulfosuccinic acid as a surfactant.
[0017] A film is exposed according to GOST 9160-91 at colour temperatures 3200 K and 5500K
behind the filter ZhS-18, and processed according to TU 6-17-1372-89.
| Mode of processing |
| No. |
Processing stage |
Duration time, min |
Solution temperature, °C |
| 1 |
Colour development |
5-10 |
25±3 |
| 2 |
Bleaching-fixing |
10 |
23±1.0 |
| 3 |
Washing |
5 |
25±1.0 |
| 4 |
Drying |
- |
no less than 60 at the speed 100 m/h |
| Colour developer, g/L: |
| Trilon B |
2,0 |
| Hydroxylamine hydrochloride (sulfate) |
2,0 |
| Ethyloxyethyl-paraphenylene diamine |
4,5 |
| K2CO3 |
75 |
| Na2SO3 anhydrous |
2,0 |
| KBr |
2,0 |
| Benzotriazole |
0,02 |
| Water |
up to 1 L. |
| pH |
10,7±0,1 |
| Bleaching-fixing solution |
| Trilon B |
10,0 |
| Na2SO3 anhydrous |
30,0 |
| KH2PO4 |
5,8 |
| NaHPO4 |
4,3 |
| Na2CO3 anhydrous |
6,0 |
| Trilon B, iron salt |
60,0 |
| Thiosemicarbazide sulfate |
10,0 |
| Water |
- up to 1 L. |
[0018] Photographic sensitivity is determined on a criterion S
0,85 over a fog density on the formula S = K/H with a factor K = 20; a resolving power
is determined according to GOST 2819-84.
[0019] The results of tests of this and all following examples are indicated in the table.
Example 2 (comparative)
[0020] False colour photographic material is prepared by coating on two-side subcoated polyethylene
terephtalate support of emulsion and auxiliary layers of the following structure:
- blue antihalo sublayer consisting from suspension of colloid silver, containing per
kg 13.5 g of metal silver; 133 g of gelatin; 140 g of 2,5-ditret-octylhydrochinone;
150 ml of 4% solution of a mixture of sodium salt of diisobutylnaphtaline sulfonic
acid and 30 ml of 4% water solution of disodium salt of diethyl ether of N-γ-dodecyloxypropyl(sulfosuccinoyl)aspartic
acid as surfactants; 60 ml of the 3% solution of sodium salt of 2,4-dichloro-6-oxytriazine-1,3,5
as a hardener;
- gelatin sublayer containing per 1 L of desalinated water 40 g of and 30 ml of the
4% solution of sodium salt of di-2-ethylhaxyl ether of sulfosuccinic acid as a surfactant;
- the first silver halide emulsion layer prepared from polydispersional silver bromide-iodide
emulsion (average grain size 0,5 µm, variation factor, Cγ = 35 %, metal silver 54
g/kg, AgJ 3 mole %, gelatin 7 %). It is added per 1 kg of emulsion: 40 ml of the 1%
solution of F-1 5-methyl-7-oxy-1,3,4-triazoindolyzine as a stabilizer, 6 ml of the
1% solution of pyrocatechin, 60 ml of 0,1% alcohol solution of a spectral sensitizer
of the formula (II) (Y = N, A = C2H5, A1 = H, B = 5,5 '-COOC2 H5, R-= (CH)2SO3, R1 = C2H5, [K]+ - is absent); spectral sensitizer of the formula (II) (Y = O, A1 = C2H5, B = 5,5'-C6H5, R, R1 = (CH2)3SO3, [K]+ = NHC5H5) in an amount of 30 ml of 0,1% alcohol solution; then it is added 160 ml of the 5%
solution of 2'-methyloctadecylamino-5'-sulfoanilide of benzoylacetic acid (Zh-8) and
250 ml of 3% solution of 2'-chloro-5'-(3",5"-dicarboxyphenylsulfamido)anilide of 2-octadecyl-oxybenzoylacetic
acid (N-353) as yellow couplers (ratio Zh8:N-353 = 1:1) and 10 ml of diluted nitric
acid (1:30). Then it is added 40 ml of the 4% solution of sodium salt of di-2-ethylhexyl
ether of sulfosuccinic acid and 10 ml of 0,1% solution of dipotassium salt of diether
of a mixture of polyglycerides of alkenylsuccinic acids as surfactants and 20 ml of
3% solution of sodium salt of 2,4-dichloro-6-oxy-triazine-1,3,5 a hardener.
[0021] Gelatin sublayer has a following composition: per 1 L of desalinated water 40 g of
gelatin, 120 ml of the 3% solution of a yellow coupler N-353, 20 ml of the 4% solution
of sodium salt of di-2-ethylhexyl ether of sulfosuccinic acid and 10 ml of 0,1 M solution
of dipotassium salt of diether of a mixture of polyglycerides of alkenylsuccinic acids
as surfactants and 10 ml of the 3% solution of sodium salt of 2,4-dichloro-6-oxy-triazine-1,3,5
(DU-679) as a hardener.
[0022] The second silver halide emulsion layer is prepared from same emulsion, as a first
layer. It is added peri kg of emulsion 40 ml of the 1% solution of a stabilizer F-1,
6 ml of 1% pyrocatechin, 30 ml of the 0,2% solution of diperchorate 3,3-[1",2"-bis(ethoxy)-ethyl]-bis-(1-ethylbenzimidazolium)
as an activator of spectral sensitization, 80ml of 0,05% alcohol solution of spectral
sensitizer of the formula III (A = C
2H
5, B = 4,5-benzo, B
1 = 5-OCH
3, R = (CH
2)
3SO
3-, R
1 =C
2H
5, [K
+] is absent), 600 ml of the 3% solution of 2-methyloctadecylamino-5-sulfoanilide-1-oxy-2-naphtoic
acid (G-2) as a cyan coupler, 40 ml of the 4% solution of a sodium salt of di-2-ethyloxyl
ether of a mixture of polyglycerides of alkenylsuccinic acids as a surfactant, 18
ml of the 3% solution of sodium salt of 2,4-dichloro-6-oxy-triazine-1,3,5 as a hardener.
Gelatin interlayer is coated containing per 1 L of desalinated water 40 g of the 2%
gelatin solution, 50 ml of the 4% solution of sodium salt of di-2-ethylhexyl ether
of sulfosuccinic acid and 15 ml of 0,1 Mole solution of dipotassium salt of diether
of a mixture of polyglycerides of alkenylsuccinic acids as surfactants and 10 ml of
the 3% solution of sodium salt of 2,4 dichloro-6-oxytriazine-1,3,5 as a hardener.
[0023] The third silver halide emulsion layer is prepared from the same emulsion, as the
other layers, but it is added per 1 kg of emulsion 40 ml of the 1% stabilizer F-1,
6 ml of 1% pyrocatechin, 75% of 1% alcohol solution of disodium salt of 4,4'-bis(5,6-diphenoxy-1,3,5-triazinile-2-aminostilbene-2,2'-disulfonic
acid as an activator of sensitization; 45 ml of 0,02% alcohol solution of sensitizing
dye of the formula I (A, A
1 together -CH
2C(CH
3)
2CH
2, A
2 = CH
3, B = 5,5'-di-OCH
3, 6,6'-di-SCH
3, R = C
2H
5, X = CH
3C
6H
4SO
3-, n = 0); 15 ml of 0,03% alcohol solution of sensitizing dye of the formula I (A,
A
2 = H, A
1 = OCH
2CH
2CH
2CH
2SO
3-, B = H, R = C
2H
5, n = 1, X - is absent), 5 ml 0,5% solution of 2-heptyl-5-methyl-7-oxy-1,3,4-triazine
indazine, mixture of [1-(4-phenoxy-3-sulfophenyl)-3-stearoylaminopyrazolone-5] (P-6)
and 3,5-di-(2-methyl)-5-octadecenylsuczinoylaminobenzenesulfamino)-1,2-xylene (P-8)
as magenta couplers in the ratio of P-6:P-8 = 4:1, in amount of 350 ml of the 5% solution,
40 ml of 4% solution of sodium salt of di-2-ethylhexyl ether of sulfosuccinic acid
and 10 ml of 0,1 Mole solution of dipotassium salt of diether of a mixture of monoglycerides
of alkenylsuccinic acids as surfactants, 20 ml of the 3% solution of sodium salt of
2,4-dichloro-6-oxytriazine-1,3,5 as a hardener.
[0024] A protective layer is coated with the following composition: per 1 L of desalinated
water it is added 40 g of gelatin, 20 ml of the 4% solution of sodium salt of di-2-ethylhexyl
ether of sulfosuccinic acid and 10 ml of 0,1 Mole solution of dipotassium salt of
diether of a mixture of polyglycerides of alkenylsuccinic acids as surfactants, 50
ml of 5 % solution of a mixture of magenta couplers P-6 and P-8 in the ratio P-6:P-8
= 4:1, 20 ml of the 3% solution of sodium salt of 2,4-dichloro-6-oxytriazine-1,3,5
as a hardener.
[0025] A film is exposed and processed as in an example 1. The properties are represented
in the table.
Example 3.
[0026] False colour photographic material is prepared and processed similarly to the example
2, but all light-sensitive silver halide emulsions contain a mixture of two emulsions:
silver bromide-iodide emulsion with octahedral microcrystals with average grain size
0,7 µm and silver bromide-iodide emulsion with flattened microcrystals (aspect ratio
1:5) with average grain size 1,2 µm; in protective and auxiliary gelatin layers the
colour couplers are not added.
Example 4.
[0027] False colour photographic material is prepared and processed similarly to the example
2, but an interlayer is coated only on the first light sensitive silver halide emulsion
layer; into the second layer 700 ml of the 3% solution of a cyan coupler G-2 and 25
ml of the 3 solution of sodium salt of 2,4-dichloro-6-oxytriazine-1,3,5 as the hardener
are added; in the third light-sensitive layer 80 ml of 0,02% alcohol solution of a
sensitizing dye of the formula I (A, A
1 together - CH
2C (CH
3)
2CH
2, A
2 = CH
3, B = 5,5'-di-OCH
3, 6,6'-di-SCH
3, R = C
2H
5, X
- = CH
3C
6H
4SO
3-, n = 0), is added.
Example 5 (comparative)
[0028] False colour silver halide photographic material is prepared by coating on two-side
sublayered polyethylene terephtalate support of the emulsion and auxiliary layers
of the following structure:
- blue antihalo backing layer from a colloid silver suspension containing per kG of
emulsion 13,5 g of metal silver, 133 g of gelatin, 140 g of 2,5-di-tret-octylhydrochinone,
150 ml of the 4% solution mixture of sodium salts of diisobutylnaphtalene sulfonic
acid and 30 ml of the 4% solution of disodium salt of diethyl ether of N-γ-dodecyloxypropyl-(sulfosuccinoyl)-asparagine
acid as surfactants, 45 ml of the 3% solution of 1,3,5-triacryloylhexahydrotriazine
as a hardener, desalinated water up to 1 L;
- gelatin sublayer containing per 1 L of desalinated water 40 g of gelatin, 30 ml of
4% solution of sodium salt of di-2-ethylhexyl ether of sulfosuccinic acid as a surfactant;
- the first light-sensitive silver halide emulsion layer is prepared from polydispersional
silver bromide-iodide emulsion (average size of microcrystals d = 0,7 µm, Cv = 30 %, contents of AgJ 3 Mole %) containing per 1 kg emulsion 40 ml of the 1% solution
of 5-methyl-7-οκc

-1,3,4-triazoindolizine, 6 ml of the 1% solution of pyrocatechin, 100 ml of 0,05%
alcohol solution of 3,9-diethyl-3-γ-sulfopropyl-5-methoxy-4,5-benzothiacarbocyaninebetaine
as a spectral sensitizing dye, 600 ml of the 3% solution of 2-methyloctadecylamino-5-sulfoanilide-1-oxy-2-naphtoic
acid (G-2) as a cyan coupler, 150 ml of the 3% solution of 3,5-dicarboxyanilide-n-stearoylaminjbenzoylacetic
acid(Zh-2) as a yellow coupler (G-2:Zh-2 ratio = 4:1); 10 ml of 5% solution of cyan
dye - product of oxidation of 1,2-naphtyldiamine-5,7-disulfonic acid with a chloric
iron; 10 ml of the diluted nitric acid (1:30); 40 ml of 4% solution of the sodium
salt of di-2-ethylhexyl ether of sulfosuccinic acid and 10 ml of 0,1 M solution of
the dipotassium salt of diether of a mixture of polyglycerides of alkenylsuccinic
acids as surfactants;
- gelatin interlayer containing per 1 L of desalinated of water 40 g of gelatin, 120
ml of the 5% solution of octadecylamide of 1-oxy-4-sulfo-2-naphtoic acid(G-3) as a
cyan coupler, 30 ml of the 4% solution of the sodium salt of di-2-ethylhexyl ether
of sulfosuccinic acid and 10 ml of 0,1 Mole solution of the sodium salt of di-2-ethylhexyltetraethylenglycol
ether of sulfosuccinic acid as surfactants; and 15 ml of the 3% solution of 1,3,5-triacryloulhexahydrotriazine
as the hardener.
[0029] The second light-sensitive silver halide emulsion layer is prepared from the same
emulsion as the first layer, but it is added per 1 kg emulsion 110 ml of the 1% solution
of disodium salt of 4,4'-bis-(4,6-diphenoxy-1,3,5-triazynil-2-amino)stilbene-2,2'-disulfonic
acid as supersensitizer; 60 ml of 3,3'-diethyl-10-methyl-5,5'-dimethoxy-6,6'-di(methylmercapto)thiadicarbocyanine-n-tolusulfonate
as a spectral sensitizer; mixture of magenta couplers P-6 and P-8 in a mass ratio
2:1 in an amount of 375 ml of the 5% solution; 20 ml of 4% solution of sodium salt
of di-2-ethylhexyl ether of sulfosuccinic acid and 10 ml of 0,1 M solution of dipotassium
salt of diether of a mixture of polyglycerides of alkenylsuccinic acids as surfactants.
[0030] The protective layer is coated from the next composition: per1 l of desalinated water
40 g of gelatin; 15ml of 4% solution of sodium salt of di-2-ethylhexyl ether of sulfosuccinic
acid as the surfactant and 20 ml of the 3% solution of 1,3,5-triacroylhexahydrotriazine
as the hardener.
[0031] The material is exposed and processed as in an example 1. The properties are indicated
in the table.
Example 6.
[0032] False colour photographic material is prepared similarly to the example 5, but in
one of the light-sensitive emulsion layers it is added 20 ml of the 0,2% solution
of diperchlorate of 3,3'-[1",2"-bis(ethoxy)-ethyl]-bis-(1-ethylbenzimidazolium) as
the activator of the spectral sensitization and 8 ml of the 0,05% solution of sensitizing
dye of the formula III (A = C
2H
5, B = 4,5-benzo, B
1 = 5-OCH
3, R = (CH
2)
3SO
3-, R
1 = (CH
2H
5, [K]
+ is absent), and 30 ml of the 3% solution of sodium salt of 2,4-dichloro-6-oxytriazine-1,3,5
as the hardener; in the gelatin interlayer a cyan coupler is not added.
[0033] In the other light-sensitive silver halide emulsion a layer it is added as a sensitizing
dye a compound of the formula I (A, A
1 together = CH
2C(CH
3)
2CH
2, A
2 = CH
3, B = 5;5'-di-OCH
3, 6,6'-di-SCH
3, R = C
2H
5, X
- = CH
3C
6H
4SO
3-, n = 0) in an amount of 80 ml of 0,02% alcohol solution, 75 ml of the 1% solution
of disodium salt of 4,4'-bis-(4,6-diphenoxy-1,3,5-triazinile-2-amino)stilbene2,2'-disulfonic
acid as the supersensitizer and 6 ml of the 0,5% solution of 2-heptyl-5-methyl-7-oxy-1,3,5-triazaindolizine;
then 350 ml of the 5% solution of a mixture of magenta couplers P-6 and P-8 in a mass
ratio 4:1; 40 ml of the 4 % solution of the sodium salt of di-2-ethylhexyl ether of
sulfosuccinic acid and 10 ml of 0,1 M of a solution of dipotassium salt of diether
of a mixture of polyglycerides of alkenylsuccinic acids as surfactants and 15 ml of
the 3% solution of sodium salt of 2,4-dichloro-6-oxytriazine-1,3,5 as the hardener.
In the protective layer magenta couplers are not added.
[0034] A material is exposed and processed as in an example 1. The properties are represented
in the table.
Example 7.
[0035] False colour photographic material is prepared similarly to example 6, but all light-sensitive
silver halide layers is prepared from a mixture of silver bromide-iodide emulsion
with octahedral microcrystals with an average grain size 0,7 µm and silver bromide-iodide
emulsion with flattened microcrystals with an average grain size 0,15 µm and aspect
ratio 1:5 at emulsions ratio 9:1.
Example 8.
[0036] False colour photographic material is prepared similarly to example 6, but in one
light-sensitive layer it is added sensitizing dye of the formula II (A - C
2H
5, B - 4,5-benzo, B
1 = 5-OCH
3, R = (CH
2)
3SO
3-, R
1= C
2H
5, [K]
+ - is absent) in an amount of 120 ml of the 0,05% solution, then 800 ml of the 3%
solution of G-2 cyan coupler, 200 ml of the 3% solution of Zh-2yellow coupler; 60
ml of the 4% solution of sodium salt of di-2-ethylhexyl ether of sulfosuccinic acid
and 20 ml of 0,1 M of a solution of dipotassium salt of diether of a mixture of polyglycerides
of alkenylsuccinic acids as surfactants.
[0037] In the other light-sensitive layers it is added as sensitizing dye a compound of
the formula (I) (A, A
1 together = CH
2C(CH
3)
2CH
2, A
2 = CH
3, B = 5,5'-di-OCH
3, 6,6'-di-SCH
3, R = C
2H
5, X
- = CH
3C
6H
4SO
3-, n = 0) in an amount of 100 ml 0,02% of alcohol solution and 8 ml of the 0,5% solution
of 2-heptyl-5-methyl-7-oxy-1,3,4-triazaindolizine. A mixture of P-6 and P-8 magenta
couplers (in a mass ratio 4:1) is added in an amount of 400 ml of the 5% solution.
Example 9.
[0038] False colour photographic material is prepared similarly to example 5, but in one
light-sensitive silver halide emulsion layer a sensitizing dye of the formula III
(A = C
2H
5, B = 4,5-benzo, B
1 = 4',5'-benzo, R = R
1-(CH
2)
3SO
3-, [K]
+ = C
5H
5N
+H), in an amount 100 ml of 0,05% alcohol solution are introduced.
[0039] In the other light-sensitive silver halide layer as a sensitizing dye a compound
of the formula I (A, A
2 = H, A
1 = OCH
2CH
2CH
2SO
3-, B = H, R = C
2H
5, n = 1, X is absent), in an amount of 30 ml of 0,03% alcohol solution and a compound
of the formula I (A, A
2 together = CH
2C(CH3)
2CH
2, A
2 = CH
3, B = 5,5'-di-OCH
3, 6,6'-di-SCH
3, R = C
2H
5, X
- = CH
3C
6H
4SO
3-, n = 0) in an amount of 20 ml of 0,02% alcohol solution are introduced.
Example 10.
[0040] False colour silver halide photographic material is prepared similarly to example
9, but all light-sensitive emulsion layers is prepared from silver bromide-iodide
emulsion with flattened microcrystals with an average grain size 0,9 µm at the aspect
ratio 1:5.
Example 11.
[0041] False colour silver halide photographic material is prepared similarly to example
6, but as colour couplers a dispersion of cyan hydrophobic coupler (ZG-97) 2,4-(di-tret-amylphenoxy)-butylamide-1-oxy-2-naphtoic
acid is introduced. A dispersion of a ZG-97 coupler is prepared in high pressure homogenizer
according to the following prescription: ZG-97- 10 parts by weight, dibutylphtalate
- 8 parts by weight, ethylacetate - 16 parts by weight, water solution of gelatin
with a mass concentration 100 g/L - 65 parts by weight. An emulgator is used a water
solution of sodium salt of dodecylbenzenesulfonic acid, 12 parts by weight and 0,3
parts by weight of oil-soluble surfactant;
a dispersion of a magenta coupler (ZP-24) 1-(2',4',6'-trichlorophenyl)-3-[(2",4"-di-tret-amylphenoxyacetamydo)-benzamido]-pyrazolone-5
is prepared on the next prescription: ZP-24 - 6 parts by weight, dibutylphtalate -
8 parts by weight, ethylacetate - 24 parts by weight, water solution of gelatin with
mass concentration 60 g/L - 50 parts by weight, emulgator - 28 parts by weight;
yellow couplers N-596 (2-chloro-5-[(γ-2,4-di-tret-amylphenoxy)-butyroylamino)-anilide]
of α-n-carboxyphenoxypyvaloylacetic acid) and N-574 (2-chloro-5 [(γ-2,4-di-tret-amylphenoxy)-butiroylamino)-anilide]
of α-n-carbmethoxyphenoxypyvaloylacetic acid) is used as a joint dispersion, prepared
in high pressure homogenizer on the following prescription: N-596 - 4 parts by weight,
N-574 - 2 parts by weight, dibutylphtalate - 8 parts by weight, ethylacetate - 23
parts by weight, water solution of gelatin with mass concentration 80 g/L - 80 parts
by weight, emulgator - 200 parts by weight;
[0042] In emulsion of one layer (per 1 kg of emulsion) is introduced 600 g of a dispersion
of a coupler ZG-97 and 160 g of a joint dispersion of couplers N-596 and N-574(2:1).
[0043] In gelatin interlayer and protective layer a dispersion of a colour couplers is not
added.
[0044] A material is exposed as in an example 1, but processed on the process of C-41 type,
namely:
| Mode of processing |
| Processing stage |
Processing stage duration, min |
Temperature of solutions and washing water, °C |
| Development |
5-7 |
30.0±0.03 |
| Bleaching-fixing |
6-7 |
30±1 |
| Washing |
3 |
30±2 |
| Drying |
|
40-60 |
Example 12.
[0045] False colour silver is prepared from a mixture in the ratio 7:3of silver bromide-iodide
emulsion with octahedral microcrystals, d = 0,7, and silver bromide-iodide emulsion
with flattened microcrystals with aspect ratio 1:5.
Example 13.
[0046] False colour silver halide photographic is prepared similarly to example 12, but
in one emulsion layer it is added sensitizing dye of the formula (III) (A = C
2H
5, B = 4,5-thieno, B
1 = 6-OCH
3, 5-C
6H
5, R = R
1- (CH
2)SO
3- [K]
+ = HN
+(C
2H
5)
3) in an amount of 75,0 ml of 0,10% alcohol solution and monosodium salt of 2-mercapto-benzoxazole-5-sulfonic
acid in an amount of 20 ml of the 0,05% solution as an activator of spectral sensitization.
[0047] In other emulsion layer as a sensitizing dye it is added compound of the formula
I (A
2 -CH
3, A, A
1 together - CH
2C(CH
3)
2CH
2, B - 5,5'-di-OCH
3, 6,6 '-di-SCH
3, R - C
2H
5, X = CH
3C
6H
4SO
3 -, n = 0) in an amount of 60 ml of 0,02% alcohol solution and the compound of the formula
I (A,A
2 = H, A
1 = OCH
2CH
2CH
2SO
3-, B = H, R = C
2H
5, n = 1, X is absent)..
Example 14.
[0048] False colour silver halide photographic material is prepared similarly to example
13, but all light-sensitive layers are prepared from silver bromide-iodide photographic
emulsion with an average size of flattened crystals 1,5 µm at aspect ratio 1:5.
Example 15.
[0049] False colour a photographic material is prepared similarly to example 13, but all
light-sensitive silver halide emulsion layers are prepared from a mixture of silver
bromide-iodide photographic emulsion with octahedral microcrystals with an average
grain size d = 0,7 µm and silver bromide-iodide photographic emulsion with flattened
microcrystals with d = 1.2 µm in the ratio 1:1.
Example 16.
[0050] False colour silver halide photographic material is prepared similarly to example
15, but in one light-sensitive layer it is added as a sensitizing dye a compound III
(A = C
2H
5, B = 4,5-benzo, B
1 = 5'-OCH
3, R = R
1-(CH
2)
3SO
3, [K
+] = HN
+ (C
4H
9)
3), in an amount of 120 ml of 0,1% alcohol solution and as an activator of spectral
sensitization diperchlorate of 3,3'-[1",2"-bis(ethoxy)-ethyl]-bis-(1-ethylbenzoimidazolium)
in an amount 45 ml of the 0,2% solution. Then 375 g of (5,7%) dispersion of a cyan
coupler ZG-97 ((2,4-di-tret-amylphenoxy)-butylamide of 1-oxy-2-naphtoic acid) obtained
on high pressure homogenizer on the following prescription: ZG-97 - 57,2 g, dibutylphtalate
- 55 g, ethylacetate - 260 g, gelatin solution with mass concentration 60 g/L - 790
g, solution of emulgator with mass concentration 40 g/l - 98 g.
[0051] Also it is added 75 g of 6.2% dispersion of a yellow coupler N-596 ([2-chloro-5-[γ-2,4-di-tret-amyl(phenoxy)-butiroylamino)anilide
of α-n-carboxyphenoxypyvaloylacetic acid), prepared on high pressure homogenizer according
to the prescription: N-596 - 62,3g, tricresylphosphate - 31,2 g, N-azoamylphtalimide
- 31,1 g, ethylacetate - 250 g, gelatin solution with mass concentration - 80 g/L
- 779 g, solution of emulgator with mass concentration 40 g/L - 96,4 g.. As a hardener
20 ml of the 3% solution of sodium salt of 2,4-dichloro-6-oxy-triazine-1,3,5 is added.
[0052] Gelatin interlayer is prepared from a following composition: per 1 L of desalinated
water 50 g of gelatin, 30 ml of 4% sodium salt of di-2-ethylhexyl ether of sulfosuccinic
acid and 10 ml of 0,1 M solution of dipotassium salt of diether of a mixture of polyglycerides
of alkenylsuccinic acids as the surfactants and 35 ml of the 3% solution of a hardener
1,3,5-triacryloylhexahydrotriazine are added.
[0053] In the other light-sensitive silver halide layer per 1 kg of emulsion it is added
as a sensitizing dye 33 ml of 0,02% alcohol solution of compound of the formula I
(A,A
1 together = CH
2C(CH
3)
2CH
2, A
2 = CH
3, B = 5,5'-di-OCH
3, 6,6'-di-SCH
3, R = C
2H
5, X = CH
3C
6H
4SO
3- , n = 0) and before than sensitizing dye it is added 75 ml of the 1% solution of
disodium salt of 4,4'-bis(4,6-dihenoxy-1-3-5-triazinyl-2-amino)stilbene of 2,2-disulfonic
acid as a supersensitizer and 5 ml of the 0,5% solution of 2-heptyl-5-methyl-7-oxytriazaindolycine.
Then 500 g of a dispersion of a magenta coupler (ZP-24) (1-(2,4,6-trichlorophenyl)-3[2,4-ditret-amyl-phenoxyacetylamido)-benzoamido]-pyrazolone-5)
is added obtained on high pressure homogenizer according to the prescription: ZP-24
- 56 g, tricresylphosphate - 28g, N-isoamylphtalimide - 28 g, gelatin solution with
mass concentration 60 g/L - 773 g, solution of emulgator sodium salt of dodecylbenzensulfonic
acid with mass concentration 40 g/L - 115 g.
[0054] A protective layer is prepared from the composition: per 1 L of desalinated water
50 g of gelatin and 30 ml of 4% solution of sodium salt of di-2-ethylhexyl ether of
sulfosuccinic acid and 10 ml of 0,1 M solution of dipotassium salt of diether of a
mixture of polyglycerides of alkenylsuccinic acids as the surfactants and 30 ml of
the 3% solution of sodium salt of 2,4-dichloro-6-oxytriazine-1,3,5 as a hardener.
Example 17.
[0055] False colour silver halide photographic material is prepared similarly to example
16, but gelatin interlayer between light-sensitive layers is not introduced; in one
light-sensitive layer it is added 490 g of a dispersion of cyan coupler ZG-97 and
145 g of a dispersion of a yellow coupler Y-488 (2-chloro-5-[(γ-2',4'-di-tret-amylphenoxy)
butiroylamino)-anilide of α-benzylhydantoylpyvaloylacetic acid), obtained on high
pressure homonizer according to the prescription: 69,7 g of a yellow coupler, 32 g
of dibutylphtalate, 99 g of ethylacetate, 780 g of a gelatin solution with mass concentration
60 g/l, 119 ml of the 4% solution of sodium salt of dodecylbenzenesulfonic acid as
an emulgator.
Example 18.
[0056] False colour silver halide material is prepared similarly to example 16, but between
light-sensitive layers a gelatin interlayer without colour couplers is coated. In
other layer instead of a dispersion of a magenta coupler ZP-24 500 g a dispersion
of a magenta couplers ZP-24 and N-651 is added, obtained as a joint dispersion prepared
on high pressure homogenizer according to the prescription: 120 g of tricresylphosphate,
360 ml of ethylacetate, 2400 ml of a gelatin solution with mass concentration 60 g/L,
530 ml of an solution of a sodium salt of dodecylbenzensulfonic acid with mass concentration
40 g/L as an emulgator.
[0057] A protective layer contains per 1 L of desalinated water 55 g of gelatin, 30 ml of
the 4% solution of sodium salt di-2-ethylhexyl ether of sulfosuccinic acid and 10
ml 0,1 M solution of dipotassium salt of diether of a mixture of polyglycerides of
alkenylsuccinic acids as the surfactants and 34 ml of the 3% solution of the sodium
salt of 2,4-dichloro-6-oxy-triazine-1,3,5 as a hardener.
Example 19.
[0058] False colour silver halide photographic material is prepared similarly to example
2, but after spectral sensitizers in one layer it is added 570 g of a dispersion of
a yellow coupler N-609 (2"-chloro-5"(3",5"-dicarbomethoxyphenylsulfamido)anilide of
α-(3',5'-dicarbomethoxyphenoxy-2-octadecyloxybenzoylacetic acid) obtained on high
pressure homogenizer according to the prescription: 207,5 g of N-609, 45 g of 2,5-di-tret-octylhydrochinone,
45 ml of tricresylphosphate, 1650 ml of gelatin solution with mass concentration 60
g/L, 260 ml of the 4% solution of sodium salt of dodecylbenzenesulfonic acid as an
emulgator and 370 ml of ethylacetate.
[0059] In the other layer after spectral sensitizers it is added 490 g of a dispersion of
a cyan coupler ZG-97 ((2,4-di-tret-amylphenoxy)butylamide-1-oxy-2-naphtoic acid) obtained
on high pressure homogenizer according to the prescription: ZG-97 - 10 parts by weight,
dibutylphtalate - 8 parts by weight, ethylacetate - 16 parts by weight, gelatin water
solution with mass concentration 100 g/L - 65 parts by weight, water solution of sodium
salt of dodecylbenzensulfonic acid -12 parts by weight, oil-soluble surfactant - 0,3
parts by weight.
[0060] In the third light-sensitive layer it is added after spectral sensitizers 540g of
a joint dispersion of magenta couplers ZP-24 and N-651 prepared in high pressure homogenizer
according to the prescription: 120 g of ZP-24, 60 g of N-651, 180 ml of tricresylphosphate,
360 ml of ethylacetate, 2400 ml of a gelatin solution with the mass concentration
60 g/L and 530 ml of sodium salt of dodecylbenzensulfonic acid as an emulgator.
[0061] In gelatin interlayers and protective layer the colour couplers are not added. A
material is exposed and processed on process C-41, as in an example 11. The properties
are represented in the table.
Example 20.
[0062] False colour silver halide photographic material is prepared similarly to example
19, but all light-sensitive layers are prepared from a mixture of two emulsions: silver
bromide-iodide emulsion with octahedral microcrystals with an average grain size d
= 0,7 µm and silver bromide-iodide emulsion with flattened microcrystals (aspect ratio
1:5) with an average grain size 1,2 µm.
[0063] In the one light-sensitive layer it is added 660 g of a dispersion of a yellow coupler
N-609, in the other light-sensitive layer 500 g of a dispersion of a cyan coupler
ZG-97 and in the third light-sensitive layer 550 g of a dispersion of magenta couplers
ZP-24 and N-651. The properties are represented in the table.
Example 21.
[0064] False colour silver halide photographic material is prepared similarly to example
16, but in the one light-sensitive layer as sensitizing dye the compound (III) (A
= C
2H
5, B = 4,5-benzo, B
1 = 5-OCH
3, R = R
1-(CH
2)
3SO
3, [K]
+ = 3,3'-diethylthiazolyneocarbocyanine) in amount of 130 ml of 0,1 % alcohol solution
is added and in the other layer the compound (I) (A = A
2-H, A
1 = O-i-C
3H
7, R = R
1 = C
2H
5, n = 1, X = J) in an amount of 35 ml of 0,02% alcohol solution is added.
Example 22.
[0065] False colour silver halide photographic material is prepared similarly to example
19, but before introduction of a dispersion of a yellow coupler in the one light-sensitive
layer as a sensitizing dye a compound (III) (A = C
2H
5, B = 4,5-benzo, B
1 = 5-Cl, R = R
1 = (CH
2)
3SO
3), [K
+] - N
+H (C
2H
5)
3) in an amount of 140 ml of 0,1% alcohol solution is added and in the other layer
as a sensitizing dye a compound (I) (A
2 = CH
3, A and A
1 together - CH
2C(CH
3)
2CH
2, R = R' = C
2H
5, B = 5,5'-di-OCH
3, 6,6'-di-SCH
3, X = CH
3SO
3-) is added.
Example 23.
[0066] It is similar to an example 22, but in the one light-sensitive layer as a sensitizing
dye it is added the compound (I) (A and A
1 = CHC(CH
3)
2CH
2, A
2 = H, R = R
1 = (CH
2)
3SO
3-, X = Na) in an amount of 100 ml of 0,02 % alcohol solution, and in the other layer
it is added the compound of the formula (III) (A = C
2H
5, B = 4,5 = benzo, B
1 = 5-CH
3, R = (CH
2)
3SO
3-, R' = CH
2CH(OH)CH
2SO
3, [K]
+ = HN
+(C
2H
5)
3) in an amount of 50 ml of 0,05 % alcohol solution.
[0067] As it follows from the table, the false colour material according to the invention
has a high resolving power (R = 140-145 MM
-1), i.e. higher than material according to the prototype (R = 68 MM
-1) and higher light sensitivity. This effect is achieved by application in a material
of special silver halide emulsions or their mixtures, spectral sensitizers and/or
their compositions, ensuring a variation of sensitization zone as well as application
of appropriate activators of spectral sensitization and stabilizers.
[0068] This invention can be applied in a photographic industry for production of colour
photographic materials used for registration of objects in visible and infra-red area
of a spectrum.
Table
| Example |
Sensitometric properties |
Resolving power, R, mm-1 |
| |
Sensitivity, S0.85 |
Contrast coefficient, γ |
Fog density, Do |
|
| 1 |
30 |
1.6 |
0.30 |
68 |
| 2 |
130 |
2.4 |
0.25 |
110 |
| 3 |
200 |
2.0 |
0.20 |
100 |
| 4 |
200 |
2.2 |
0.20 |
110 |
| 5 |
250 |
2.0 |
0.20 |
145 |
| 6 |
270 |
2.2 |
0.15 |
145 |
| 7 |
310 |
2.8 |
0.25 |
120 |
| 8 |
250 |
2.0 |
0.15 |
145 |
| 9 |
300 |
2.3 |
0.18 |
145 |
| 10 |
400 |
2.2 |
0.25 |
100 |
| 11 |
320 |
1.9 |
0.17 |
120 |
| 12 |
500 |
2.1 |
0.21 |
110 |
| 13 |
480 |
2.0 |
0.16 |
110 |
| 14 |
700 |
1.7 |
0.25 |
100 |
| 15 |
600 |
2.3 |
0.20 |
110 |
| 16 |
600 |
1.8 |
0.21 |
110 |
| 17 |
600 |
1.95 |
0.20 |
110 |
| 18 |
600 |
1.95 |
0.20 |
110 |
| 19 |
200 |
1.9 |
0.20 |
120 |
| 20 |
250 |
1.9 |
0.23 |
110 |
| 21 |
550 |
1.9 |
0.20 |
110 |
| 22 |
250 |
1.9 |
0.20 |
120 |
| 23 |
300 |
2.0 |
0.18 |
135 |