DE1077531B - Process for the formation of a blue-green dye image in a photographic layer - Google Patents

Description

GERMAN

The invention relates to color photography and, more particularly, to silver dye-B recourse proceedings.

This method, important for making color photographs, is based on the following general principle Procedure:

A photographic silver halide emulsion layer, usually a gelatin-halogen emulsion layer, contains a suitable dye as a uniform dispersion. This layer is exposed or the latent silver image is produced in some other way, followed by development into the silver image. the The layer is then treated with a bleach bath, which oxidizes the silver and at the same time the dye reduced or bleached at the location of the silver image. The silver salts and the excess silver will be then removed from the layer, which is then only that which is complementary to the original silver image Contains dye image.

Many modifications of this procedure are possible. So z. B. the layer after exposure or colored with the dye after the development of the silver image. Furthermore, the dye be contained in a special gelatin layer which covers the emulsion layer. A big Number of patents have been granted on this process; the main details of which can be found in the British Patents 397 159 and 397 188 can be found.

In order to produce a color image, one must in principle use a multi-layer material that contains three light-sensitive halogen silver layers, one of which is only sensitive to blue light and the other to green and red light. To prevent, that the latter two layers are still on next to the light to which they are sensitized To respond to blue light, it is common to place a blue absorbing filter layer between the latter Layers and turn on the blue sensitive layer. A common type of layer arrangement is the following:

a) carrier layer,

b) red-sensitive emulsion layer,

c) green-sensitive emulsion layer,

d) blue absorbing filter layer,

e) blue sensitive emulsion layer.

Layer d) is not always necessary because layer e), if it is colored yellow, is the blue one Holds back light enough.

Multi-colored light falling on layer e) causes the formation of the latent silver image in layers e), c) and b), each showing the method of production

of a cyan dye image

in a photographic layer

Applicant:
JR Geigy A.-G., Basel (Switzerland)

Representative: Dr. F. Zumstein,

Dipl.-Chem. Dr. rer. nat. E. Assmann

and Dipl.-Chem. Dr. R. Koenigsberger, patent attorneys,

Munich 2, Bräuhausstr. 4th

Claimed priority:

Great Britain 29 April 1957

and dated April 9, 1958

Dr. Ernst Keller, Binningen,

Dr. Peter Hmdermann, Basel,

and Dr. Jean-Pierre Jung, Riehen (Switzerland),

have been named as inventors

blue, green and red parts of the incident Light in these layers.

In the silver dye bleaching process, as is customary is applied, the layer b) is blue-green (cyan), the layer c) magenta (red-violet) and the layer e) colored yellow. As a result, the finished picture contains after exposure and development (This creates the silver images first, which are then subjected to the necessary bleaching process whereupon the remaining silver salts and the silver are removed,) "positive" yellow, magenta and blue-green images, which add to the "negative" silver images created by development are complementary, so that a faithful reproduction of the original to be imaged is produced.

The silver dye bleaching process, however, suffers from a number of difficulties. One of them is in the selection of suitable dyes. Several hundreds have already been suggested but most proved unsatisfactory in more ways than one.

One of the main difficulties is to prevent the colorant from getting out of the gelatin emulsion

909 753/374

I UYYÖ31

Layer into which it is incorporated diffuses out. Various proposals have been made to circumvent this difficulty, e.g. B. the layers Add pickling substances. Furthermore, the dyes should be quickly due to the bleach baths used Be bleached, and in addition, they should reduce the sensitivity of the emulsion layer in which they are embedded, do not affect them too much. Then each dye should be red, blue, and green Only absorb light in one spectral range and should also absorb the other two spectral ranges let through or reflect completely.

A particular difficulty in using disazo dyes is that they are bleached the reductive cleavage of only one azo group can occur, with a hue change results. When using azo dyes in color photography, however, it is essential that the hue remains unchanged at the various degrees of fading.

The invention relates to a new class of cyan dyes used in the silver dye bleaching process are very suitable because they largely meet the above requirements.

In accordance with the invention, the method for forming a cyan dye image consists in one photographic layer in that there is a light-sensitive halosilver-gelatin emulsion layer or a special gelatin layer overlying the halogen silver layer, a blue-green one Incorporated dye of general formula I,

of the formula A - NH ₂ and coupling the same with a middle component of the formula

OR

HO.

NH ₂

OH X

A-N = N-.

SO ₃ H

wherein A is the radical of an aryl carboxylic acid alkyl ester, the ester group of which is in the m- or p-position to the azo group, the alkyl group of which contains at least 5, preferably at least S carbon atoms, R a lower, optionally substituted alkyl group, X a hydroxyl or an NHRj group, in which the radical R _{1 is} hydrogen or an R ₂ CO group (in which R _{2 is} an alkyl, aralkyl or aryl or a halogen-substituted alkyl, aralkyl or aryl group), and η is 1 or 2 creates a latent silver image in the mentioned layer, develops it, subjects the developed silver image to such a treatment which fades or removes it and which at the same time decolorizes the dye locally and then removes the remaining silver salts and the silver therefrom.

The dyes used according to the invention stand out in comparison with the dyes that for the same purpose in the German patent specification 952 146 are described and only partially through the replacement of the phenyl ether group by the alkyl ester group differ from these by an improved affinity for gelatin.

Methods for representing the aforementioned class of dyes are discussed in detail later. Basically, this class of dyes is made in the usual way by diazotizing an initial component shown. The amino monoazo dye obtained is further diazotized and with an end component the formula

OH X

- (SO ₃ H) _n

coupled, where the symbols have the meaning given above. The present invention further relates a gelatin-halosilver layer as an element of a multilayer photographic material, which is sensitive to red and contains a cyan dye as defined above. The multilayer Photographic material also contains photographic emulsion layers which overlay blue and green light are sensitive and colored with yellow and magenta dyes, respectively. Of the The blue-green dye can optionally also be in a special layer instead of in the red-sensitive layer Gelatin layer are located, which this silver layer rests on.

In particular, the invention relates to a color photographic material in which the aforesaid blue-green layer b) belongs to a layer sequence which consists of

a) a carrier layer,

b) a red-sensitive, blue-green colored emulsion layer,

c) a green-sensitive, blue-red colored emulsion layer,

d) a blue absorbing filter layer,

e) a blue-sensitive, yellow-colored emulsion layer

and if necessary from one or more usual ones, colloidal separating layers exist between some or all of the enumerated layers.

Those dyes according to the invention of the above formula are preferred in which R is methyl or Represents ethyl group, the sulfonic acid group of the middle naphthalene ring is in the 6- or 7-position, preferably in the 6-position, and wherein in the l-amino-8-hydroxynaphthalene ring of the end component one sulfonic acid group in the 4- or 6-position, the optionally present second sulfonic acid group is in the 2-, 3- or 4-position.

Preferred end components are the 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid compounds or the l-amino-8-hydroxynaphthalene-3,6-disulfonic acid compounds.

The bleaching of the cyan dye of the present invention can be performed with any of the im Silver dye bleaching processes are carried out using the usual bleach baths.

The use of acid alone, e.g. B. of bromic or hydrochloric acid, it is possible to use these acids

1 U / / OD 1

but work too slowly. An additional use of salts of the hydrohalic acids accelerates the bleaching process, but such bleaching baths still work too slowly. The usage a solvent for the silver halide, such as thiourea or pyridine, speeds up the process strong, and through the use of accelerators and catalysts the speed can be increased again increase. In this context, British patents 397159 and 490451, which describe suitable bleach baths are referred to.

The following example, for the sake of simplicity, only applies to one material with a single den refers to the cyan dye-containing layer, the invention is intended to illustrate.

Examples
Representation of the dyes

example 1

COOC ₁₀ H ₂₁

OCH ₃

HO3S

OH NHCOCH,

S0, H

SO ₃ H

36.9 parts of 3-amino-4-phenoxybenzene-1-carboxylic acid decyl ester are dissolved in 30O parts of alcohol at room temperature. Then 40 parts of concentrated hydrochloric acid is added to the mixture and it is cooled. The chlorohydrate then precipitates. Then 40 parts of ice are added, and the whole thing is ^{diazotized at 0 to 5 °} C. with a concentrated, aqueous solution of 6.9 parts of sodium nitrite. After it has been stirred for 2 hours at 0 to 5 ° C. and the small excess of nitrous acid has been destroyed, the pale yellow clear diazo solution is converted into a suspension of 25.3 parts of 1-amino-2-methoxynaphthalene-6-sulfonic acid within 2 hours and 60 parts of sodium acetate poured into 500 parts of water and 500 x parts of ice. This happens at 0 to 5 ° C. The coupling takes place immediately and the color changes to red. The whole is stirred at this temperature for 6 hours, then the acid is neutralized by gradually adding 32 parts of sodium carbonate, and the precipitated dye is then filtered off with suction. Then it is washed on the suction filter with a 5% sodium chloride solution. The brownish red monoazo dye is dissolved in 4000 parts of boiling water in the presence of 2 g per liter of the condensation product of dodecyl alcohol and 20 mol of ethylene oxide as a dispersing agent. 6.9 parts of sodium sitrite are then added, the reaction mixture is then cooled to 25 ° C. and 40 parts of concentrated hydrochloric acid are added. After stirring for 15 hours at 25 to 30 ° C, a small excess of nitrous acid is destroyed with sulfamic acid. The yellowish-brown gelatinous Diazoemulsion is acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid then at 15 to 20 ⁰ C in a 36.1 parts of l ^, 80 parts Natriumaeetat, 1000 parts of water and 250 parts of pyridine poured containing solution. The coupling takes place immediately and the color turns blue-green. The mixture is then stirred for a further 4 hours at the same temperature, 600 parts of sodium chloride are added, whereupon the dye precipitates and is filtered off with suction. Then it is first washed with 500 parts of a solution consisting of 50 parts of pyridine, 25 parts of sodium chloride and 3'50 parts of water, then with 500 parts of pyridine and finally with 200 parts of acetone, whereupon it is dried at 80 ° C ..

The dye is a blue powder, which turns blue-green in water and concentrated in water Sulfuric acid with a blue color dissolves.

The 3-amino-4-phenoxybenzene-1-carboxylic acid decyl ester used as the starting component is made by condensation of 4-chloro-3-nitrobenzene-1-carboxylic acid with an excess of phenol in the presence of 2.2 moles of sodium hydroxide at one above 100 ° C is shown. The free 4-phenoxy-3-nitrobenzene-1-e carboxylic acid is then isolated and converted into the carboxylic acid chloride with thionyl chloride. The chloride is then with n-decyl alcohol converted to the deeyl ester, and finally the nitro group is used in aqueous ethyl alcohol Amino group reduced.

The following table contains some more suitable ones Disazo dyes which can be prepared by the method described above.

If the starting materials are homologous and isomeric or analogous compounds, they too can can be represented according to the method described above.

C00C _in H.

10 ^iJ -21

N = N

Example 2

OCH.

OH NH,

SO ₃ H

SO ₃ H

36.9 parts of 3-amino-4-phenoxy-1-carboxylic acid n-decyl ester are diazotized by the method described in Example 1 and coupled with 25.3 parts of 1-amino-2-methoxynaphthalene-6-sulfonic acid. This brown-red monoazo dye is dissolved in 400O parts of boiling water in the presence of 2 g per liter of the condensation product of 1 mole of dodecyl alcohol and 20 moles of ethylene oxide as a dispersant. 6.9 parts of sodium nitrite are then added, the temperature is cooled to 25 ° C. and 40 parts of concentrated hydrochloric acid are added to the mixture. After stirring for 1 hour at 20 to 25 ° C, the small excess of nitrous acid is destroyed. The yellow-brown diazo suspension is then poured at 20 to 25 ° C. into a solution of 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and 80 parts of sodium acetate in 1000 parts of water and 250 parts of pyridine. The coupling takes place immediately and the color changes to blue-green. The mix will

then stirred for a further 6 hours at 10 to 15 ° C and then treated with 600 parts of potassium chloride, the Dye suspension is heated to 40 ° C. The precipitated blue disazo dye is suctioned off and first with a solution containing 50 parts of pyridine, 25 parts of sodium chloride and 350 parts of water, then

washed with 500 parts of pyridine and finally with 200 parts of acetone, whereupon the dye im Vacuum is dried at 70 to 80 ° C.

The dye is a blue powder, which turns blue-green in water and concentrated in water Dissolves sulfuric acid with a deep blue color.

Example 3

OCH ₃

OH NH ₉

H ₂₁ C ₁₀ OOC-

-N = N

-N =

HO ₃ S

SO ₃ H

S0 "H

27.7 parts of 4-aminobenzene-1-carboxylic acid n-decyl ester are suspended in 200 parts of water and 30 parts of hydrochloric acid and at 0 to 2 ° C with 6.9 parts Sodium nitrite diazotized. The clear solution of the diazonium component is then at 0 to 5 ° C in portions in a suspension of 25.3 parts of 1 - amino - 2 - methoxynaphthalene - 6 - sulfonic acid and 60 parts of sodium acetate poured into 500 parts of water and 500 parts of ice. The clutch takes place immediately instead, and the color changes to red. After stirring for hours at 0 to 5 ° C, the acid becomes neutralized by adding 32 parts of sodium carbonate. The precipitated red dye is then Sucked off and washed on the suction filter with a 5% sodium chloride solution. The red-brown one Monoazo dye is dissolved in 3000 parts of boiling water and 6.9 parts of sodium nitrite are added. The solution is then cooled to 25 ° C. and 40 parts of concentrated hydrochloric acid are added. After stirring for 20 hours at 20 to 25 ° C, a small excess of nitrous acid is mixed with sulfamic acid destroyed. The diazo component is precipitated by adding 750 parts of sodium chloride and filtered off and washed out with a saturated saline solution. The diazo component is 1000 parts Suspended ice water, and the suspension is in portions at 15 to 20 ° C to a solution of 31.9 parts of 1-amino-S-hydroxynaphthalene-Sjo-disulfonic acid and 40 parts of sodium acetate in 1000 parts of water and 250 parts of pyridine were added. the Coupling takes place immediately and the color turns blue-green. After stirring for 4 hours 400 parts of potassium chloride are added to the dye solution at 15 to 20 ° C and the mixture is heated to 40 ° C. The precipitated blue dye is then filtered off and first with 300 parts of 20% sodium chloride solution, then washed with 300 parts of pyridine and finally with 200 parts of acetone. Then the Dyestuff dried in vacuo at 80.degree.

The dye is a blue powder that turns blue-green in water and in concentrated form Sulfuric acid with a blue color dissolves.

Example 4

OCH ₃

H ₁₇ C ₈ OOC-

-N = N

OH NH ₂

S0 "H

SO ₃ H

34.1 parts of S-amino-o-phenoxybenzene-1-carboxylic acid octyl ester are diazotized as described in Example 1 and with a l-amino-2-methoxynaphthalene-6-sulfonic acid coupled. The brown-red monoazo dye is dissolved in 4000 parts of boiling water and 6.9 parts of sodium nitrite are added. The temperature is lowered to 25 ° C and the mixture mixed with 40 parts of a concentrated hydrochloric acid solution. After stirring and destroying for 20 hours of the excess of nitrous acid, the precipitated diazo compound is filtered off and with a Washed 20% saline solution. The diazo compound is then suspended in 1000 parts of ice water. This suspension is at 20 to 25 ° C in portions to a solution of 31.9 parts l-Amino-8-hydroxynaphthalene-3,6-disulfonic acid and 40 parts of sodium acetate in 1000 parts of water and 250 parts of pyridine added. The clutch takes place immediately instead, and the color turns blue-green. After stirring for an hour at 20 to 25 ° C, the dye solution becomes 180 parts of potassium chloride are added and the mixture is heated to 35.degree. Then the fancy blue one Sucked off disazo dye. It is washed and dried at 70 to 80 ° C in a vacuum as in the example 1 described.

The dye is a blue powder, which turns blue-green in water and concentrated in water Sulfuric acid dissolves with a dark blue color.

9 10

The following table shows further correlations with this invention. You correspond games of dyes compiled, which in one of the formula I:

OR OH X

A - N = N- / "V-N = N-

(SO ₃ H) _n I.

A '

SO, H

Position of the SO ₃ H groups in the final component

(tert.)

B H

(tert.)

the same
the same
the same
the same

the same

the same

the same

O-

-COOC ₁₀ H ₂₁

COOCoH ₁

-COOC ₁₂ H ₂₅

-O-

COOC ₁₀ H ₂₁
-0- / V-COOC ₆ H ₁₁

-O

COOCoH ₁

CH,

CH ₃ CH ₃ CH ₃

CH,

CH,

CH,

CH,

CH,

CH,

CH,

CH,

CH,

OH

NH ₂
NH,

NHCOC ₆ H ₅

NH,

NHCOCH

NHCOCH ₂ O

NH,

NH,

NH ₂

NH,

NH,

Cl

3: 6

2: 4

3: 6 4: 6

3: 6

3: 6

3: 6

3: 6

3: 6

3: 6

3: 6

3: 6

909 759 / 3W

\ - .y 11 -COOC ₈ H ₁₇ R. 12th Position of
SO ₃ H- '
groups
in the
End
component Color
stofi
No. Cl- / y A. COOC ₁₀ H ₂₁ CH ₃ X 3: 6 18th COOC ₁₀ H ₂₁ COOC ₁₀ H ₂₁ CH ₃ NH ₂ 3: 6 19th ° <) COOC ₁₀ H ₂₁ CH ₃ NH ₂ 3: 6 20th ./ " \. / -C ₂ H ₅ NH ₂ 3: 6- 21 ° - \ > -CH ₂ COOH NH ₂ 3: 6 '' 22nd _ \ NH ₂

g of the dye according to Example 1 and 5 g of dodecyl sodium sulfate are dissolved in 550 cm of water with heating. This dye solution is then added to an iodine-bromide silver emulsion which contains 13 g of silver as halogen silver. This mixture is then distributed on a film base in such a way that the resulting filter layer contains 15 mg of halogenated silver, dissolved as silver, and 7 mg of dye per dm ² .

The dried layer is exposed and the captured image is developed at 20 ° C as follows :

1. Develop the silver image by treating it for 2 minutes in the following developer:

Metal 0.75 g

Sodium sulfite, crystall 25 g

Hydroquinone 3 g

Sodium carbonate, crystall 40 g

Potassium bromide Ig

Water on 1 1

2. Flush for 30 seconds.

3. Fix for 3 minutes in 20% sodium thiosulphate solution,

4. Rinse for 30 seconds,

5. Hardening in 4% formalin,

6. Soak for 10 minutes, ⁵ ^

7. Bleach the dye in the following bath for 8 minutes:

Hydrochloric acid (specific gravity 1.19) 100 ecm

Potassium bromide 12.5 g

Thiourea 10 g

2,3-dimethylquinoxaline 0.1 g

Water on 1 1

8. Soak for 5 minutes ^:

9. Treat 5 minutes for silver bleaching with the following bath:

Copper sulfate, crystall. 100 g

Sodium chloride 100 g

Hydrochloric acid, conc 50 ecm

Water on 1 1

10. Soak for 5 minutes,

11. Fix for 3 minutes in 20% thiosulphate solution,

12. Soak for 10 minutes and then dry.

In this way a colored reversal image is obtained.

Operations 4 and 5 can be omitted if the emulsion layer is hardened or, with is provided with a hardened gelatin coating.

Similar results are obtained by using other dyes falling under the general formula used; the dyes of Examples 2, 3 and 4 may be mentioned in particular. Will the procedure with a similar but uncolored silver halide emulsion applied to the dye emulsion is carried out, a microscopic examination shows that there is practically no dye - neither in the production nor in the processing of the film - from the colored to the uncolored Layer diffuses.

All the dyes mentioned have a satisfactory hue, do not migrate to other layers, bleach rapidly and thoroughly and as a whole are suitable for the silver-dye bleaching process in color photography excellently suited.

Claims (8)

Patent claims: 1. Process for the production of a cyan dye image in a photographic layer, characterized in that there is a photosensitive halosilver gelatin emulsion layer or a special gelatin layer, which is adjacent to the halogen silver layer, a blue-green one Incorporated dye of general formula I, OR OH X A N-N < SO ₃ H where A is the remainder of an Arvlcarbonsäurealkvl- represents esters, the ester group of which is in the m- or p-position to the azo group, the alkyl group of which contains at least 5, preferably at least 8 carbon atoms, R is a lower, optionally substituted alkyl group, X is a hydroxyl or NHRj group, in which the radical R ₁ Is hydrogen or an R ₂ CO group (where R _{2 is} an alkyl, aralkyl or aryl or a halogen-substituted alkyl, aralkyl or aryl group), and η is 1 or 2, a latent silver image in the above-mentioned layer is generated, this is developed, the developed silver image is subjected to a treatment which fades it out or removes it and which at the same time locally decolorizes the dye and then removes the remaining silver salts from it. 2. Color photographic method according to claim 1, characterized in that said Gelatin-silver halide coating is sensitive to red light and that it is the coating of a multilayer photographic material, which also consists of a photographic, sensitive to blue or green light and with yellow or blue-red dyes colored emulsion layer, and in which the blue-green dye of the formula I der mentioned red sensitive layer or a special gelatin layer, which this silver layer is present, is incorporated. 3. The method according to claim 2, characterized in that the dye I containing Layer b) belongs to the following layer sequence: a) carrier layer, b) red-sensitive, blue-green colored emulsion ^ 5 layer, c) green-sensitive, bluish-tinted emulsion layer, d) blue absorbing filter layer, e) blue-sensitive, yellow-colored emulsion layer, a particular colloidal separating layer preferably being located between some or all of the layers is located. 4. Process according to Claims 1 to 3, characterized in that in the dye I the ester group of A has an alkyl radical of at least 8 carbon atoms, that R is a methyl or Is ethyl group and in which in the l-amino-8-hydroxynaphthalene ring of the end component the one sulfonic acid group in the 4- or 6-position, the optionally present second sulfonic acid group in 2-, 3- or 4-position. 5. Photosensitive gelatin-halosilver emulsion layer for carrying out the process according to claims 1 to 4, characterized by the content of a dye of the following Formula I: OR > _N = N— r SO, H OH X Λ ^ - -i ~ (SO ₃ H), wherein A represents the radical of an arylcarboxylic acid alkyl ester, the ester group of which is in the m- or p-position to the azo group, the alkyl group of which contains at least 5, preferably at least 8 carbon atoms, R a lower, optionally substituted alkyl group, X a hydroxyl or NHR ₁ -GrUpPe in which the radical R _{1 is} hydrogen or an R ₂ CO group (in which R _{2 is} an alkyl, aralkyl or aryl or a halogen-substituted alkyl, aralkyl or aryl group) and η is 1 or 2. 6. Multilayer photographic material according to claim 5, containing a red-sensitive, blue-green colored A layer of gelatin-halosilver emulsion with a dye according to claim 5, a blue-sensitive, yellow-colored gelatin-halosilver emulsion layer and a green-sensitive, bluish-tinged red-colored gelatin-halosilver emulsion layer. 7. The multilayer photographic material of claim 6, wherein the cyan colored Layer b) is arranged in the following layer sequence: a) carrier layer, b) red-sensitive, blue-green colored emulsion layer, c) green-sensitive, bluish-tinted emulsion layer, d) blue absorbing filter layer, e) blue-sensitive, yellow-colored emulsion layer, a colloidal separating layer preferably between some or all of the layers is located. 8. Photo material according to Claims 5 to 7, characterized by the content of a dye according to claim 4. Considered publications:
German patent specification No. 952 146. 909 759/374 3.