DE1161138B - Color photographic color correction process and photographic material therefor - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: G 03 c

German class: 57 b - 18/08

Number: 1161138

File number: G 37656IX a / 57 b

Filing date: May 3, 1963

Opening day: January 9, 1964

The invention relates to a method and a material for producing color photographic images and in particular a method of color correction using an integral masking method.

It is known that those formed by color development in multicolor photographic subtractive images have Dyes do not have the desired absorption spectrum. The blue-green dye, the red light absorb and transmit green and blue light, next to most of the red absorbed Light usually also a small part of green and blue light. The purple dye, the green one Should absorb light and transmit blue and red light, next to most of the absorbed green light usually also has a considerable part of the blue light and a small part of the red light Light. The yellow "dye that absorbs blue light and is supposed to transmit green and red light, usually satisfies these requirements Dimensions.

Because of these undesirable secondary absorptions of the dyes formed during color development it is practically impossible to achieve a true reproduction of the original colors.

It is therefore desirable to mask the undesired secondary absorptions when copying to undertake. This is usually achieved by using color masks, which increase the density make the undesired absorptions in the unexposed image areas equal to those in the exposed image areas. Since separate masks are difficult to register with the see-through color image it is advisable to use masks that are integral to the color image.

A process for the production of a photograph! - see color image to which the mask belongs integrally, is in Belgian patent specification 597 617 as well as in German patents 1 063 900, 1 109 522 and 1,119,666.

The latter patent describes a process for producing a color-corrected image in a photographic material which contains a halogenated silver emulsion layer and a color coupler (particularly a color coupler of the naphthol type) which can react with the oxidation product of an aromatic amino developing agent to produce a primary color image by color development (in particular a blue-green color image) which contains a major part of light in one region of the visible spectrum (especially the red light) and undesirably also a smaller part of light in at least one other region of the visible color photographic color correction process
and photographic material therefor

Applicant:

Gevaert Photo-Producten N.V., Mortsel,

Antwerp (Belgium)

Representative:

Dr. W. Muller-Bore

and Dipl.-Ing. H. Gralfs,

Patent attorneys,

Braunschweig, Am Bürgerpark 8

Named as inventor:

Dr. Jan Jaeken, Hove,

Hugo Vital van Goethem, Berchem, Antwerp (Belgium)

Claimed priority:
Great Britain 4 May 1962
(No. 17 249)

absorbable spectrum (especially the green light) by exposing and developing color photographic element containing an oxidizing solution (especially a photographic Bleach bath) treated in the presence of a 4-aminopyrazolinone-3 compound, which oxidatively with the rest of the color coupler, creating a secondary color image (especially a purple image) whose gradation is opposite to that of the primary color image and the light in at least one of the named undesired secondary absorption areas (in particular the green Light), but absorbs practically all light in the stated main absorption range (especially the red light) lets through.

A method has now been found for producing a color corrected photographic image in a photographic material comprising at least one halide silver emulsion layer and one Contains color coupler which, during development, reacts with the oxidation product of an aromatic primary amino developing agent forms a primary color image which is a major part of light in a region of the visible spectrum and, undesirably, also a smaller part of light

309 778/298

3 4

used in at least one other area of the visible my formula:

Spectrum absorbed, by treating the photo- q ^ ^ £,

graphic material after image-wise exposure
and color development with an oxidizing solution

in the presence of a mask-forming compound, 5 —CO — NH— ■

characterized in that the mask-forming process ~ SO ₃ M

bond a 3-aminoguanidine compound of the following formula is used:

RNC-NH-NH _{2 10} ^Y

in which X means an oxygen atom, a sulfur atom,

r / NH one - NH - CO group, one - CO - NH -

Group, a - SO ₂ - NH group, a - NH -

in which R denotes a hydrogen atom, an alkyl radical, ^so a group, a

a substituted alkyl radical. an aralkyl radical, a 15 ^ Alkvlgrutroe

substituted aralkyl radical, an aryl radical, a ""

substituted aryl radical, a heterocyclic radical

or a substituted heterocyclic radical and or a sulfonyl group, Y is a hydrogen atom or

R 'represents a hydrogen atom or an acyl group, e.g. B. a halogen atom, D a diffusion-proofing

an acetyl group or a benzenesulfonyl group, 20 group, e.g. B. an aliphatic hydrocarbon

where by the oxidative coupling of this 3-amino radical with 5 to 20 carbon atoms, preferably

guanidine compound with the remaining color coupler with 14, 16 or 18 carbon atoms, and M a

a secondary color image is generated, which in at least a hydrogen atom, an alkali metal atom or a

the un-ammonium group in a region of the visible spectrum.

Desired secondary absorptions of the primary color 25 Suitable compounds with which good results

image compensated. and those of the above formula

In particular, a procedure was established for the cor- responding to:

position of a color-corrected blue-green dye sodium salt of l-oxy-N- (2'-n-hexadecyloxy-

image found, in which an integral, orange-5'-sulfophenyl) -2-naphthamids,

colored to red mask image in a photograph! - 30 sodium salt of l-Oxv-4-chloro-N- (2'-n-hexadecyl-

rule coloring material, in a rotsensibihsierten oxy-5'-sulfophenyl) -2-na _P hthamids

Halos overemulsion layer or in one of these _vr . ,,, ^ * _r - ",,,

Emulsion layer adjacent water-permeable sodium salt of 1-Oxy-M2 -n-hexadecylmercap-

non-light-sensitive colloid layer a blue-too-suIfopheny1) -2-naphthamids,

green color coupler of the phenol type, preferably the 35 sodium salt of l-oxy-4-bromo-N- (2'-n-hexadecyl-

Naphthol type, contains, according to the following stages, mercapto-5'-suIfophenyl) -2-naphthamids,

generated: imagewise exposure, color development with the sodium salt of] -Oxy-4-chloro-N- (2'-n-hexadecyl-

an aromatic primary amino developer mercapto-5'-suIfophenyl) -2-naphthamids,

and treatment of the coloring material before or after the sodium salt of l-oxy-N- (2'-palmitoylamino-

Fixation in a sufficiently strong oxidizing 40 4'-sulfophenyl) -2-naphthamids,

Solution z. B a photographic potassium hexasodium salt of l-oxy-4-chloro-N- (2'-methyl-n-

cyanoferrate (III) containing bleach bath, in the presence of hexadecylamino-S'-sulfophenvO ^ -naphthamids,

a j-aminoguamide compound as above. ,,,, _ »," ,, ",,,, ..,

ben, which with the remaining blue-green color coupler sodium salt of l-oxy-N- (2-n-hexadecylsulfonyl-

oxidative coupling, creating a mask image 45 ⁵ -suifophenyD-2-naphthamids,

whose gradation is that of the primary dye sodium salt of I-oxy-4-chloro-N- (2'-n-hexadecyl-

The opposite picture and the undesirable sulfonyl-5'-sulfophenyl) -2-naphthamids.

Secondary absorption of the blue-green color image in the sodium salt of 1-oxy-N- (4'-n-hexadecyIsulfonyl-

blue and at least partially in the green area 3'-sulfophenyl) -2-naphthamids.
of the spectrum compensated. 50

According to a preferred embodiment of these cyan color couplers can, for. B. by

Invention are the oxidative coupling condensation of l-oxy-2-naphthoic acid or its

bonds, in the following also as mask-forming derivatives with the suitable aromatic amines

Connections designated, preferably in combination after that in the German patent specification 1 121 061

tion can be produced with cyan color couplers of the following general 55 described processes.

Suitable mask-forming compounds to be used in the method of the invention are those given in Table I.

Table I.

1. H ₂ NC-NH-NH ₂

NH

2. H, C - NH - C - NH - NH ₂

NH

Table I (continued)

;> - NH - C - NH - NH ₂

NH

4th

OCH.

$> - NH - C - NH - NH ₂
NH

5.

CH ₃ - O - r> - NH - C - NH - NH ₂

NH

6. H, C - CO - NH- i

> —SO.

H ₃ C: N-C-NH-NH ₂

NH

The compounds of the formulas 1 to 6 are not resistant to diffusion. You can use one of the treatment baths, e.g. B. the developing bath or bleach bath, be incorporated. They are preferably used as bicarbonates, that is to say in a more or less diffusion-resistant form incorporated into the photographic emulsion layer.

Mask-forming compounds according to the above formula can also be a diffusion-proofing Group, like a long aliphatic carbon chain. Examples of diffusion resistant Compounds which are preferably incorporated into the emulsion layer are given in Table II.

1.

Table II
H ₃ C - (CHa) ₁₅ - NH - C - NH - NH ₂

2. H ₃ C - (CHa) ₁₅ - O - / V - NH - C - NH - NH ₂

3. H ₃ C - (CHa) ₁₅ - SO ₂ - ^ V - NH - C - NH - NH ₂

X = / ι

Although the above masking compounds are preferably used in conjunction with cyan color couplers attention is drawn to the fact that these mask-forming Oxidative coupling of compounds also with purple color couplers of the pyrazolone class to produce Dyes that mainly absorb in the wavelength range from 380 to 430 ηιμ and so in mask the blue part of the visible spectrum.

The masking compounds used in the process of the invention are photographic inert and do not cause a veil.

To explain the production of mask-forming compounds according to the invention in the following both detailed preparation examples of these compounds and literature references specified.

Manufacturing 1

1 - (0 - Methoxyphenyl) - 3 - aminoguanidine iodine hydrate is made as follows:
9 g of N- (o-methoxyphenyl) thiourea and 10 cm ³

Methyl iodide is refluxed for 5 minutes in 100 cm ^{3 of} dry acetone. After the acetone has been distilled off, dry ether is added to the residue. A solid precipitate of N- (o-Methoxyphenyi) -S-methylisothiouro-

nium iodide, which is sucked off. Melting point: 125 ° C (decomposition).

15.5 g of the thiouronium iodide obtained in 100 cm ^{3 of} pyridine is treated with 3 cm ^{3 of} hydrazine hydrate for 4 days.

After the pyridine has been distilled off, the solid residue is washed with isopropanol and removed from acetonitrile recrystallized. The obtained l- (o-methoxyphenyl) -3-aminoguanidinjodhydrat melts at 176 ° C.

7 8

Preparation 2 washed with a little dry ether. Melting

The compound 6 of Table 1 (l- [N-4-acetyl ^pU ?} ^U ! Ίη ^ α u ι tu- ■ ■ aa

sulfanilylH-methyl-3-aminoguanidine) is produced. ^ on leave 16, g of the thiouronium iodide obtained as described by A. Greer, J. Am. Soc, 76 m 15 cm ³ Pyndm 3 days with 0.5 cm «hydrazine hydrate Π 954Ί S 1141 to 1145 room temperature react. By pouring out

"The l- (p-n-hexadecyloxyphenyl) - formed falls on ice

TT, j -j 3-aminoguanidine. The aminoguanidine is filtered off with suction and recrystallized from acetonitrile. Schmelzl-n-hexadecyl-3-aminoguanidinjodhydrat as point: 90 ⁰ C. prepared as follows: io Preparation 5

51 g dry ammonium thiocyanate and 70 cnr

Benzoyl chloride is refluxed for 5 minutes with 1- (p-n-hexadecylsulfonylphenyl) -3-aminoguanidine

cooling heated in 450 cm ³ dry acetone (cf. is prepared as follows:

R. Frank, Organic Synthesis, 23, p. 89). The solution containing benzoyl isothiocyanate is prepared as described in Preparation 3, starting with 145 g of n-hexadecylamine, 18.8 g of ammonium thiocyanate and 26.6 cm ^{3 of} ben-15 minutes in 2100 cm ^{3 of} dry acetone are refluxed heated. zoylchlorid in 200 em ³ acetone. After filtration, a solution of 84.6 g of pn-hexa-600 cm ^{3 of} water is gradually added to the reaction mixture. The precipitated Nn-hexadecyldecylsulfonylaniline in 800 cm ^{3 of} acetone. N'-benzoylthiourea is terminated and the reaction is filtered off with suction by recrystallizing for a further 1 hour under re-ethanol. Melting point: 63 ⁰ C. Flow cooling heated. After cooling and a solution of 125 g of the thiourea obtained, the reaction product is poured into water, the compound and 12.5 g of sodium hydroxide in 1875 cm ^{3 of} precipitate of N- (pn-hexadecylsulfonyl-ethanol) is refluxed for 1 hour The reaction mixture is poured into water, a brief boiling with a solution of 45 g, whereupon the precipitate formed is suctioned off and ^{recrystallized from sodium hydroxide in 700 cm 3 of} water to give pn-hexa-isopropanol. decylsulfonylphenylthiourea saponified. The product After a further recrystallization from Acetoni- the Nn-hexa- ethylene glycol monomethyl ether formed is purified by rinsing and recrystallization from tril or ethyl acetate. Melt decylthiourea at 140 ⁰ C. 30 point: 158 ° C.

75 g of Nn-hexadecylthiourea and 290 cm ^{3 of} Me-8.4 g of the thiourea compound obtained

thyl iodide are heated for 3 hours in 750 cm ^{3 of} acetone under reflux cooling with 20 cm ^{3 of} methyl iodide in 50 cm ^{3 of} dry acetone. ^ The precipitate formed is heated under reflux cooling for 2 hours. After that it is suctioned off and washed with ether. After cooling, the precipitated N- (pn-hexa-recrystallizing is from ethyl acetate to obtain Nn-He- decylsulfonylphenyO 35-S-methylisothiouroniumjodid abxadecyl-S-methylisothiouroniumjodid Melting point: vacuumed and washed with dry ether melting point 87 ^0C.: 13O ⁰ C.

56 g of the thiouronium iodide obtained and 6.8 cm ^{3 are} heated IV for ₂ hours 5.6 g of the obtained

Hydrazine hydrate are ^{refluxed in 280 cm 3 of} ethanol iodide with 1 cm ^{3 of} hydrazine hydrate in 50 cm ^{3 of} methanol for 2 hours. After cooling 40 under reflux. The precipitate formed is filtered off with suction by pouring it into water and the l- (pn-hexadecylsulfonylphenyl) acetonitrile formed is recrystallized. The obtained 1-n-hexa- from aminoguanidine 3 that is ablated from ethyl acetate umkristallidecyl-3-aminoguanidinjodhydrat melts at 103 ⁰ C. Melting point: about 120 ° C (decomposition (decomposition). Decomposition).

Manufacture 4 ⁴⁵ ^ ^ur ^ ^e practical implementation of the invention

according to the procedure are the color couplers and

l- (p-n-hexadecyloxyphenyl) -3-aminoguanidine is preferably one of the mask-forming compounds prepared as follows: photographic silver halide emulsion containing

A solution of benzoyl isothiocyanate is prepared using the one commonly used for this purpose as described in Preparation 3, starting from 50 colloids prepared, for example gelatin, 8.5 g ammonium thiocyanate, 5 cm ³ benzoyl chloride, polyvinyl alcohol, collodion or other natural in 50 cm ³ acetone . At the boiling point, drop or artificial colloids are used. The silver halide emulsion assigns a solution of 16.7 g of pn-hexadecylaniline in 50 cm ^{3 of} acetone, preferably on a transparent support. After pouring into water, which consists of glass, nitrocellulose, cellulose, the precipitate formed is sucked off by N- (pn-hexa esters, such as cellulose triacetate, polyester, polystyrene or decyloxyphenyl) -N'-benzoylthiourea and other natural or synthetic resins 15 minutes in a solution of 8 g of sodium and part of a photographic material with a hydroxyd in 70 cm ^{3 of} water under reflux or several emulsion layers, heated. The saponified product precipitates immediately. A multilayer color photographic material

The reaction mixture is neutralized and the 60 usually comprises the following aspirated onto a support pn-hexadecyloxyphenylthiourea. After applied layers: a red-sensitive emulsion recrystallization from benzene melts the product sion layer with a cyan color coupler, a green-sensitive emulsion layer with a purple ^{color at 129 0 C.}

3.92 g of the thiourea compound obtained becomes a color coupler and a blue-sensitive emulsion with 10 cm ^{3 of} methyl iodide in 40 cm ^{3 of} dry acetone 65 layer with a yellow color coupler. Heated to reflux between 1 hour. After the blue-sensitive emulsion layer and the green cooling, the N- (pn-hexadecyloxy-sensitive emulsion layer that is formed is usually a phenyl) -S-methylisothiouronium iodide is suctioned off and a yellow filter is arranged, which is usually made of a gelatin

9 10

layer, the dispersed, colloidal silver of the red-sensitive emulsion layer remains during contains. It is not only possible to leave the color couplers unaffected in color development. The Farbentdie The material is then wrapped before or after the photosensitive halide silver emulsion layer incorporated themselves, but they can also be fixed in an oxidative photographic bleaching neighbor not photosensitive colloid layer brought 5 bath, in which the metallic silver itself be incorporated or dissolved in a non-photosensitive and the mask-forming compound oxidative Layer that couples from the light-sensitive emulsion to the non-exposed areas of the layer through a water-permeable colloid layer red-sensitive emulsion layer still available, is separated. remaining cyan color coupler. That way

An orange-red mask image is created on the back of the transparent carrier,

usually an antihalation layer applied. which is caused by the secondary absorption of the blue-green

When producing the color photographic image according to the invention in the blue and green areas

multilayer graphic material, the difference in absorption in this is in the blue and green areas

Invention used mask-forming compound of the spectrum between the exposed and un-

preferably compensated for the red-sensitive areas exposed to a blue-green 15.

Naphthol-type color couplers containing halogen- The following aromatic primary amines

incorporated silver emulsion layer. use yourself as a developer for such a material:

The mask mono-, bi- and triaminoaryl compounds to be used according to the invention, in particular

Forming compounds can also be used together with their Ν, Ν-dialkyl-p-phenylenediamines, for. B. Ν, Ν-Di-

one of the mask-forming compounds according to the ao ethyl-p-phenylenediamine and N, N-diethyl-2-methyl-

German patent 1 119 666 can be used, p-phenylenediamine, and derivatives thereof, z. B. N, N-Di-

which describes the manner in which purple alkyl-N'-sulfomethyl-p-phenylenediamines or N, N-di-

Make-up images that mainly contain the undesirable alkyl-N'-carboxymethyl-p-phenylenediamine. As a

In addition to absorption of a blue-green image in the green, suitable monoamino developers may be mentioned:

Compensate the area of the spectrum with oxidative 25 phenols and aminocresols or their halogen derivatives

Coupling of a 4-aminopyrazolinone-3 compound and also the aminonaphthols,

the following formula: The bleach bath usually contains potassium bromide,

Borax, boric acid, magnesium sulfate and especially potassium hexacyanoferrate (III). These ingredients are

¹ 30 dissolved in precisely defined amounts of water, so that

'get a solution with a certain pH above 7

/ N \ will.

R ₃ . C ^X NR ₂ The following examples illustrate the invention.

Il I

H ₂ NC C = O ³⁵ Example 1

For 500 cm ^{3 of} a red-sensitized bromoiodosilver binder, R ₁ signifies a lower alkyl group, R ₂ an emulsion (2% iodide) which contains 1.6 moles of halosilver lower alkyl group, an aryl group of the benzene series, if 10 g of sodium salt or a substituted aryl group is used as a color coupler the benzene series and 40 of the l-oxy-N- (2'-n-hexadecylsulfonyl-5'-sulfophenyl) -R _{3 to} a diffusion-proof, aliphatic radical 2-naphthamide, dissolved in 193 cm ³ of at least 5 and at most 20 carbon atoms distilled , Water and 7 cm ^{3 of} 2 n sodium hydroxide.
obtained with blue-green color couplers of the naphthol type. Further, this emulsion is used as a mask-forming agent

will. In this way you can choose a combination of 5 g of ln-hexadecyl-3-aminoguanidine, which gives a blue-green image, the 45 of which is set, dissolved in 12.5 cm ^{3 of} sodium hydroxide and undesirable secondary absorptions in the blue as in the 37.5 cm ³ ethylene glycol monomethyl ether. The green area of the spectrum is acidified practically completely with 32.5 cm ^{3 of} η-acetic acid to pH 5.7, pensified. gives the usual additives, for example hardening

The method for producing a masked agent and wetting agent, adds and fills the emulsion of the photographic color image according to the invention 50 with distilled water up to 1000 cm ³ . This takes place as follows: A photosensitive multi-emulsion is applied to a suitable support layered color material, as described above, which is dried in and. After exposure through one of the red-sensitive halide silver emulsion layers Graukeil with the constant 0.15, the material is developed both a cyan color coupler of the naphthol type for 9 minutes at 20 ^° C. in a color development bath and an oxidative 55 used in this invention of the following composition:
containing coupling mask-forming compound is
exposed according to a colored original. This exposed anhydrous sodium hexameta-

Material becomes phosphate 2 g in a standard color developer bath

developed, with the light- Ν, Ν-diethyl-p-phenylenediamine-

sensitive emulsion layers the halogen silver 60 chlorohydrate 3 g

Is reduced to silver by an aromatic anhydrous sodium sulfite 4 g

primary amino developer, the oxidation of which is anhydrous sodium carbonate .... 57 g

product with the one in the emulsion layers .... . _TT,, . ,,

essential color coupler. This gives anhydrous hydroxylamine chlorine

in the red-sensitive emulsion layer a blue-65 ydrate, g

green color image, mainly the red light, Potassium Bromide Anhydrous Ig

but also undesirable a little blue and green water up to 1000 cm ³

Absorbs light. The mask-forming compound in (pH = 10.6)

Claims (10)

11 12 This material ^c for 30 minutes at 18 to 20 C above red-sensitized emulsion layer containing cyan rinsed and 5 minutes at 20 ⁰ C in a fixer color coupler, a gelatin intermediate layer, a green the following composition fixed: sensitized emulsion layer with purple color Anhydrous sodium thiosulphate ... 200 g kuppter, a yellow filter layer, a blue-sensitive one " _R -. -vT · ι · ίο, / 5 emulsion layer with yellow color coupler and closing Anhydrous sodium bisulfite 25 g _{] and a gelatin} overlay that _{serves as a} protective layer. Kahumalaun-24-Wasser 20 g _After exposure through a gray wedge with the Sodium Biacetate 20 g constant 0.15 becomes the photographic material Anhydrous boric acid 7.5 g developed as in Example 1 and treated further. Man Water up to 1000 cm ^{3 10} in the red-sensitized layer next to one (p _H = 4 0) cyan image also has a purple and an orange mask image that has a gradation that Then the material is again 10 minutes that of the blue-green image and the opposite Rinsed at 18 to 2O ⁰ C and then 5 minutes in an undesirable secondary absorption of the blue-green Treated bleach bath of the following composition: 15 Image in both the blue and the green area Anhydrous potassium hexacyano- compensated for ^{the spectrum.} ferrate (III) 100 g ^ S *! WHAT? ^u ™ ^bramid . :::::: St. p - *** = Boric acid anhydrous 5 g Water up. 1000 cm ³ * Process for the production of a photographic (p _H = 8 8) graphic color corrected image in a photographic material which contains at least one Then the material is again 10 minutes with halogen silver emulsion layer and a color 18 to 20 ⁰ C rinsed and 5 minutes at 20 ⁰ C in a 25 coupler that contains during the development Fixed bath of the following composition: reaction with the oxidation product of an aromatic Ethylenediaminetetraacetic acid 1 g of primary amino developer substance Anhydrous sodium thiosulphate ". '.'. 130 g ^{Primary F. ArWA} * ™ **> one main part of ^B light in a region of the visible spectrum Anhydrous sodium carbonate .... 6 g 30 and, in an undesirable manner, also a smaller anhydrous sodium bicarbonate .. 14 g part of light in at least one other range Anhydrous sodium sulfite 10 g of the visible spectrum absorbed by water up to 1000 cm ³ after treatment of the photographic material (p _H _ § m imagewise exposure and color development with an oxidizing solution in the presence of a Finally, the material is again masked for 10 minutes, rinsed through at 18 to 20 ⁰ C, whereupon it is dried. oxidative coupling of the mask compound with. In the exposed and treated the remaining color coupler, a secondary color material is obtained in addition to a blue-green image, an orange image is generated, the mask image colored in at least one area (absorption maxima at 480 and 40 of the visible spectrum, the undesired 530 πιμ), which has a gradation which is opposite to that of the secondary absorption of the primary color image and which is unpensated, characterized in that the desired secondary absorption of the blue-green image in the mask-forming compound is a 3-amino blue and partly in the green area of the guanidine compound spectrum compensated according to the following formula. 45 turns: Example 2 A solution of 9 g of the sodium salt of 1-oxy-N- (2'-n-hexadecylsulphonylphenyl) -2-naphthamide is added to ¹ _{l of 2 kg of a red-sensitized bromo-iodide emulsion (2% iodide) which contains Ve moles of halosilver} a mixture of 175 cm ^{3 of} water and 6.3 cm ^{3 of} 2 n sodium hydroxide, a solution of 2 g of l, 2-dimethyl-4-amino-5-nonylpyrazolinon-3 in 20 cm ^{3 of} ethanol with a little sodium hydroxide and a solution of 2.5 g of ln-hexadecyl-3-aminoguanidine in 6.25 cm ^{3 of} sodium hydroxide and 18.5 cm ^{3 of} ethylene glycol monomethyl ether. After acidification with 1 η-acetic acid to pH 6 and after adding the usual additives, e.g. B. hardeners and wetting agents, distilled water is added up to a total of 1000 cm ³ . When applied, this emulsion forms part of a multilayer photographic material which consists of the following layers, superimposed in the order given: an antihalation layer, a transparent cellulose triacetate support, an adhesive layer, the R - N - C - NH - NH ₂
R 'NH in which R denotes a hydrogen atom, an optionally substituted alkyl radical, an optionally substituted aralkyl radical, an optionally substituted aryl radical or an optionally substituted heterocyclic radical and R 'is a hydrogen atom or an acyl group. 2. The method according to claim 1, characterized in that a color photographic material with a red sensitized halosilver emulsion layer, in which emulsion layer or in an adjacent non-light-sensitive, water-permeable colloid layer a naphthol type cyan color coupler is included. 3. The method according to claim 2, characterized in that the red-sensitized halosilver emulsion layer of the photographic material contains a naphthol-type cyan color coupler of the following general formula: OH Ä. X-D ■ CO - NH- \ κ SO, M 10 in which X denotes an oxygen atom, a sulfur atom, a - NH - CO - group, a - CO - NH - group, a - SO ₂ NH group, an --NH - SO ₂ group, a - N - alkyl group or a sulfonyl group, Y a hydrogen atom or a halogen atom, D a diffusion-proofing, aliphatic hydrocarbon radical with 5 to 20 carbon atoms and M is a hydrogen atom, an alkali metal atom or an ammonium group. 4. The method according to any one of claims 1 to 3, characterized in that the mask-forming Compound incorporated into a water-permeable colloid layer of the photographic element will. 5. The method according to claim 4, characterized in that the water-permeable colloid layer a red sensitized silver halide emulsion layer is used. 6. The method according to any one of claims 1 to 5, characterized in that as oxidizing Solution used an alkaline photographic bleaching bath containing potassium hexacyanoferrate (III) will. 7. The method according to any one of claims 1 to 6, characterized in that the red-sensitized Halogen silver emulsion layer of the photographic material is a 4-aminopyrazolinone-3-compound bond of the following general formula contains: R. -C H ₈ N- C- NR ₂
= 0 R ₁ denotes a lower alkyl group, R ₂ denotes a lower alkyl group, an aryl group of the benzene series or a substituted aryl group of the benzene series and R ₃ denotes a diffusion-proof, aliphatic straight-chain hydrocarbon radical of more than 5 and less than 20 carbon atoms. 8. Multilayer color photographic material with superimposed and for different Ranges of the visible spectrum sensitized halogen silver emulsion layers, for the process according to claim 1, characterized in that the red-sensitive emulsion layer or an adjacent, water-permeable colloid layer, a naphthol type cyan color coupler and a A mask-forming compound of the formula of claim 1 contains. 9. Color photographic multilayer material according to claim 8, characterized in that it contains a naphthol type cyan color coupler represented by the general formula of claim 3. 10. Multilayer color photographic material with superimposed and for different Regions of the visible spectrum sensitized halogen silver emulsion layers for the process according to claim 1, characterized in that the red-sensitive emulsion layer or an adjacent water-permeable colloid layer a cyan color coupler of the formula of claim 3, a masking compound of the formula of claim 1 and a masking compound of the formula of claim 7 contains.