DE1170626B - Process for the production of colored gelatin - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Boarding school Class: C 08 h

GERMAN

PATENT OFFICE

EDITORIAL

German class: 39 b-17

Number:
File number:
Registration date:
Display day:

C 26540 IVd / 39 b

March 20, 1962

May 21, 1964

High demands are often made on colored gelatins for photographic purposes with regard to Lightfastness, transparency, staying clear in the various processing baths, but above all in with regard to diffusion fastness. The fastness to diffusion of a colored gelatin, i.e. H. the property in swollen form when pouring the layers and in the various treatment baths not in penetrating the neighboring layer cannot always be achieved without other properties, such as a high solubility of the dye in water or aqueous gelatin or the lack of Tendency to flocculate or the lightfastness, are impaired or even lost /

It has now been found that reactive dyes, which reduce their reactivity to mobile halogen atoms owe to chemically bond with gelatin under suitable conditions and the so colored Gelatins have very valuable properties, such as clarity and no tendency to become cloudy later and usually high diffusion fastness and light fastness. In the gelatins colored in this way In general, the sensitivity of the silver halide and that of the colored layer is also determined is incorporated, not degraded. The invention accordingly provides a method for Production of colored gelatin, and the process is characterized in that the gelatin with water-soluble reactive dyes that reduce their reactivity to mobile halogen atoms owe.

When choosing the dyes, two things must be taken into account, namely the constitution of the mobile Reactive groups containing halogen atoms and that of the remaining part of the molecule, which the Process for making colored gelatin

Applicant:

CIBA Aktiengesellschaft, Basel (Switzerland)

Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse and
Dipl.-Chem. Dr. rer.nat. E. Frhr. v. Bad luck man,
Patent Attorneys, Munich 9, Schweigerstr. 2

Named as inventor:
Dr. Walter Anderau, Münchenstein,
Dr. Karl Seitz, JSTeu-Allschwil,
Dr. Paul Dreyfuss, Basel (Switzerland)

Claimed priority:

Switzerland of March 21, 1961 (3366)

contains chromophoric and auxochrome groups. Depending on the intended use of the gelatin you can various such groups come into consideration. So z. B. for the silver dye bleaching process such dyes are used, which by photo image silver depending on its presence Amount to be bleached, for example azo or azoxy dyes or phthalocyanines. What the Regarding reactive groups, dyes, in particular azo dyes, are preferred which contain at least contain a chlorotriazine residue, e.g. B. a residue of the formula

N-C

-C

where X is a chlorine atom, an alkoxy group or a 45 - NH - phenyl (the phenyl radical can also optionally be further substituted amino group, e.g. by a sulfonic acid group - NH ₂ , - NH - alkyl, - NH - oxyalkyl,

- N

Alkyl

Alkyl

- Ν

Oxyalkyl

Alkyl

means. Except dyes with hair triazine residues There are also other dyes which may or may not reduce their reactivity Halogen atom, in particular a mobile ChIo atom, owe. Below are a few more groups such reactive dyes.

409 590/519

H -SO ₃ H N Cx -Cl \ W. H
I. /
HO ₃ S - C
I. I.
Cx -Cl I.
- C \
C.
Il Il
C.
/ \
N
Il Il
C.

λ N ^ Nx -Cl Cl- A. -C - \ C. -Cl -C N
Il Il
N \ \
C.
π Il
C.

a) Dyes which have a trichloropyrimidine or a nitro group, a nitrile group or preferred dichloropyrimidine radical contain: wise a sulfonic acid group, z. B.

Cl Cl

I I s

N C-Cl Cl-C N

- C C-Cl -C C-Cl

Cl Cl

N CH HC N

I Il Il I

- c c - ci - c c - ci

Vt / X _x / ^V KX /

^X N ^XX N ^X ao \ sK

b) dyes that form the remainder of a low molecular weight

Haloalkyl carboxylic acid, e.g. B. a chloroacetic f) dyes that contain a trichloropyridazine residue

acid, ß-chloropropionic acid or α, / ί-dichloro keep z. B.

propionic acid residue, contain: 25

-CO-CH ₂ Cl, -CO-CH ₂ -CH ₂ Cl,?

- CO - CHCl - CH ₂ Cl;

c) Dyes that contain a monochlorotriazine residue: 30

/ ^N \

- c c — ci X / ^ c '

NN ₃₅ Cl Cl
\ _c /

I The reactive groups can, for. B. over a

fj nitrogen atom to the remainder of the dye molecule be bound. It's a big one today

d) dyes that contain the remainder of a dichloropyrimidine * ° ^{number of} reactive dyes with mobile halosulfonic acid or carboxylic acid, e.g. B. of the 2,6- ^diatom s are known, and otherwise these color chloropyrimidine-4-carboxylic acid or -5-sulfonic ^{substances can} contain acid according to conventional methods known per se: be prepared.

'"Surprisingly, the reactive color

Q 45 reacts relatively easily with gelatine. this

I applies in particular to the halotriazine radicals

Q holding dyes too. Such reactive dyes

/ \ are expediently in aqueous with gelatin

HC N medium, for example at temperatures from 10 to 6O ⁰ C

Il I 50 and advantageously in the presence of an acid-binding agent

C C C Cl means, reacted.

Il ^ N ^ S ° can be used, for example, at a 5- to 20% strength

O liquefied aqueous gelatin at 35 to 40 ⁰ C the

required amount of reactive dye, optionally in

/ N \ ₅₅ Form of an aqueous solution, add and that

O HC C Cl Leave the whole thing to stand for a while. Very often it is

11 π I the reactivity of the dye so great that

§ Q N without further action the implementation is practically complete

Il \ / f is constant because the gelatine contains larger amounts of the

O 9 60 absorb liberated hydrogen halide

I can without the pn value falling below 5.

Cl is usually an advantage by adding

acid-binding agents, such as. B. Sodium bicarbonate,

e) dyes that contain a pyrimidine residue, sodium carbonate, sodium phosphate, sodium acetate, in one of positions 2 and 6 to the remainder 65 sodium borate, sodium hydroxide or the entdes The dye is bound in the other speaking potassium compounds, the implementation these two positions a chlorine atom and in to promote and accelerate. The implementation 5 position a negative substituent, such as times can at temperatures of 18 to 32 ° C im

In the case of dyes containing dichlorotriazine residues 2 to 10 hours and for monochlorotriazine residues containing dyes are 4 to 24 hours.

When the reaction has ended, the colored material is optionally in the molten state, for example at 40 to 60 ⁰ C, with an acid such as hydrochloric acid, acetic acid or citric acid, so that the pH z. B. goes back to 5.6 to 5.8, whereupon the gelatin is allowed to solidify again.

The gelatin can now be crushed, e.g. B. brought into noodle form and according to methods known per se be freed from unbound dye and salts by soaking. There can be very high color yields can be obtained, which can be seen from the fact that the wash water soon runs off colorless, a Signs that only a little dye has not reacted with the gelatin. If necessary, can the result by adding suitable aids, such as. B. reaction products of higher molecular weight aliphatic amines with ethylene oxide.

Given the conditions permissible for this reaction (the reactive dye must be brought into contact with the gelatine with the greatest possible care), it was by no means foreseeable that the reaction would result in a chemical, homeopolar bond between the dye and the gelatin; but above all it is surprising that the reaction takes place to a very large extent and only small amounts of unchanged or saponified dyes are ultimately present. The evidence for the implementation can be seen in the fact that after washing out a small amount of unbound dye, the color gelatin no longer bleeds and no more dye diffuses out, furthermore in the fact that in the implementation relatively large amounts of reactive dye with regard to gelatin, in particular in the case of dyes containing halotriazine residues, a very strong increase in the viscosity of the gelatin solution and an increase in the melting point of the aqueous gelatin solution up to 98 ^° C. can take place.

The following also suggests that there is a homeopolar bond: If an azo dye is used, that in the remainder of the diazo component has a chlorotriazine residue and at least one sulfonic acid group contains, in the manner indicated above with gelatin and subjects the colored gelatin in As is known, the silver dye bleaching process, the reduction product of the azo component formed by reduction can easily be washed out will. In this case, however, the diazo component would also be dissolved out if it were not attached to the gelatin would be bound. However, this is the case, because by diazotization and coupling, the bleached Gelatin can be converted back into the colored state. The according to the present procedure colored gelatins obtained can e.g. B. for the production of durable filters, but in particular can be used for color layers of three-color photography.

Gelatin which has been applied to a suitable carrier and reacted with reactive dyes can be used sensitize for example with alkali dichromates or alkali dichromates and then expose, whereby the gelatin is hardened under the influence of light, so that after removal of the unhardened gelatin in can be tanned in a warm water bath.

The gelatins reacted with reactive dyes can also be mixed with silver halide emulsions or silver halide can be directly generated in the colored gelatin. After this Exposure, a silver image can be developed. One arrives at by tanning silver bleaching a tanning pattern that can be washed out. Is used to react with the gelatin reactive azo dyes, such gelatin can also be used for the silver dye bleaching process will.

Furthermore, the color gelatins reacted with reactive dyes can also be used during production of mixed grain emulsions.

In the examples below, unless otherwise noted, parts are parts by weight and the percentages are percentages by weight.

example 1

3 g of the reactive dye of the formula

HO3S

NH-C
Μ Cl c - HN - < / ^S Il
N
\ N N = N \ HO ₃ S

are dissolved in 50 ecm cold water, and the solution is added to a 40 ⁰ C warm gelatin solution of 20 g gelatin in 200 ecm water. By adding about 15 ecm of a 4% sodium hydroxide solution, the original pH value is brought from 5.6 to 10.5 under control. Now the mixture is left to its own devices for 12 to 24 hours at room temperature. Thereafter, bringing the product at 40 to 45 ° C to melt and set by the addition of about 7.5 cc of 10% acetic acid a SO3H _HN _ _CO _ _C3H7

SO3H

pH from 5.6 to 5.8. The mass is allowed to solidify in the refrigerator and the jelly is cut into fine pieces, which are then freed from the salts and the unfixed dye in running cold water until the wash water runs off practically colorless.
A vivid blue-red colored gelatin is obtained,

which can be used as follows:
By trial casting on a glass plate, the

optical density of the red colored gelatin determined.

This is then adjusted to a certain density with colorless gelatine and, if necessary, with Halide silver emulsions mixed.

The concentration of gelatine can be increased by freezing part of the water. The gelatine can also be dried, and then put back into water to swell normally. In comparison to the starting gelatin, the fixation of this dye reduces the viscosity and the Melting point increased only a little.

The red colored gelatin solution has ηΐμ at 546, for example. Wavelength measured an optical Density of 2.69 if 10 ecm of it is poured onto a 13 cm χ 18 cm glass plate. By Diluting with the same amount of 5% colorless gelatin reduces the density by half when you again 10 ecm of colored gelatine (diluted) is poured onto the 13 cm χ 18 cm glass plate.

A. This glass plate is now dried and in the dark with a 2% aqueous-alcoholic Treated solution of ammonium dichromate for 2 minutes and then dried. Under a Partial color negative is exposed to strong actinic light through the glass plate. After that, will watered the plate. The gelatin was hardened imagewise under the influence of light. By treating the remaining soluble gelatine floats with warm water. You get a red positive that is called Partial image of a three-color image can be combined with other partial images, e.g. B. by transmission on gelatinized paper.

B. You can also use the above-mentioned color gelatin with a density of 2.69 in the same amount Mix and apply a light-sensitive, optionally sensitized silver bromide emulsion a suitable carrier, e.g. B. acetyl cellulose film, shed.

After exposure, a silver image is developed with a commercially available negative developer and fixed the image with sodium thiosulfate solution. Thereafter, a conventional silver dye bleach bath is included Hydrobromic acid and thiourea, allowed to act for 10 to 20 minutes. In proportion to the amount of silver present, the red azo dye is destroyed and highest in the places Silver density bleached to completely colorless gelatin. After soaking, the remaining silver is in Silver bromide is converted back to the copper sulfate and by treatment with an aqueous bath Contains potassium bromide. After a short soak, it is fixed with sodium thiosulphate solution and watered again and dried. A red partial image is obtained. This can be one of the layers of a three color material be.

The same red partial picture, after the described ones Processes produced are obtained when the reactive dye is the red dye of the formula

H ₂ N

C-N

H ₂ N

C · —HN

C = N

Cl

is used.

C. A plate produced with silver halide as described under A can after exposure with a tanning developer, for example pyrocatechol sodium carbonate, to form a tanning pattern be guided. The silver picture mentioned under A can also be bleached with the help of a tanning agent

With the reactive dyes of the formulas

SO ₃ H

N = N
HO

SO ₃ H

Treat solution containing potassium dichromate, copper sulfate, potassium bromide and a little hydrochloric acid. After fixing, soaking and drying, a tanning pattern of the gelatine can develop in the warm water will. The soluble gelatin floats away.

NH ₂

HO ₃ S

HN-C-CH ₃ O NC

NH-C N

N = C
Cl

(3)

NH ₂

HO ₃ S

N = N

H ₃ C

SO ₃ H

N-C

y \

NH-C N

N = C

Cl

(4)

ίο

yellow-colored gelatins are obtained which, as described above, are used for tanning images or the silver color bleaching process, in the latter case z. B. can also be used in three-layer material.

Example 2
One of the following dyes is used here as reactive dye:

a) dye of formula (1) —red—;

b) dye of the formula

Cl

C-N

SO ₃ H

HO
C-

Cl

-N

N = N-

SO ₃ H

C = N

- yellow-

c) dye of the formula

Cl

N-C

- Red-;

d) copper phthalocyanine further substituted in the 3-, 3'-, 3 "and 3"'positions, with an average of 2.5 HO ₃ S groups and 1.5 CI-CH2 — CH ₂ —HN-O2S groups in the molecule there are —blue “.

1 to 2 g of dye are stirred in 50 ecm of water, 1 g of anhydrous sodium acetate (crystalline) is added, and the resulting solution is added to a gelatin solution of 20 g of gelatin in 200 ecm of water. It is kept in the water bath for 2 to 6 hours at 35 to 40 ^° C. The gelatin is then solidified and cut into noodle form and then washed out with cold water for several hours. The colored gelatine can be dehydrated by freezing the water. They can be used to produce colored layers for photographic purposes, as described in Example 1 above.

The dichlorotriazine granules show a strong increase in viscosity and desiccant at the same time Melting point of the aqueous color gelatins detectable.

Example 3

0.25 part of the reactive dye of the formula

NH ₂ HO ₃ S

Cl

N = N

N-C

NH-C

CH

HO ₃ S

are stirred in 25 parts of cold water, and the solution is added to a ^{gelatin which is melted at 40 °} C. and which contains 10 parts of gelatin in 100 parts of water. The mixture is left to themselves, or at 18 to 2O ⁰ C for 24 to 48 hours kept for 12 hours at 30 to 35 ° C. the

65 N = C
Cl

Chilled, solidified gelatine is made into noodle form and washed with cold water to remove the unfixed dye. She is lively Dyed blue-red and can be used in the construction of color photographic material. the The strength of the coloring can be increased

409 590/519

if the gelatin as a catalyst for the reaction of the formula with the reactive dye 0.05 part of N, N-dimethylhydrazine the formula

Nn

H ₃ C

H ₃ C

N-NH ₂

H ₂ C CH ₂ CH ₂

I I I

H ₂ C CH ₂ CH ₂

or the same amount of 1,4-diazabicyclo- (2,2,2) -octane can be added.

Example 4

0.3 part of the blue dye of the formula is dissolved

O NH ₂

SO ₃ H

SO ₃ H

in 30 parts of water, gives the solution to 100 parts an aqueous gelatin which contains 10 parts of gelatin and adds 0.03 part of KN-dimethylhydrazine added. The gelatin is poured onto a glass plate, for example 10 ecm on an area of 13 cm χ 18 cm. After drying the gelatin and After 24 hours of storage, the unbound dye can be dissolved out of the gelatin with water will. After repeated drying, a blue gelatin layer is obtained on the glass. She can in be converted into a gelatin tanning pattern and wash-out relief in a known manner, e.g. B. by raising awareness with ammonium dichromate, copying and developing with water.

Example 5

33 parts of a silver bromide emulsion which contains 45 parts of silver bromide in 1000 parts of a 6- to 7% ^{gelatin are added at 35 °} C. to 33 parts of a 10% strength aqueous gelatin. To this are added 10 parts of a dye solution containing 1.2 parts of the dye of the formula

SO ₃ H

N = N-

contains dissolved in water. If desired, 10 parts of a 1 to 4% solution are added Wetting agent or dispersant too.

10 g of such a mixture are poured onto a glass plate 13 cm × 18 cm and dried. After a few days, most of the dye is chemically bound to the gelatin. The layer

HO C-N

SO ₃ H

(10)

can be used in the silver dye bleaching process and as a partial image of a three color material. Man receives a yellow partial image. The small portion of the dye that is not bound to the gelatine can easily be washed out in the course of the development process.

13 14

EXAMPLE 6 0.25 to 0.3 parts of dye of the formula are added at 35 ° C. to 100 parts of 10% strength aqueous gelatin

H ₂ N

Cl-CH ₂ -CH ₂ -CO-HN

SO ₃ H

(H)

SO ₃ H

dissolved in 25 parts of water. The mass is allowed to ^{react at 18 °} C. for hours or at 35 ^° C. for 6 hours. The reaction times can be shortened by adding the catalysts as listed in Example 3.

The color gelatine is deep-frozen and finely washed to remove the unbound Dye and for further processing by freezing partially dehydrated and with fresh, uncolored gelatine brought to the desired color density. This red colored gelatin can can be used to build up the purple layer in the three-layer material.

Instead of the reactive dye of the formula (11)

The reactive dyes of the formulas below which contain other reactive groups can also be used, can be used to produce purple-colored sub-layers for the three-color material.

NH ₂

(12)

SO ₃ H

CN NH ₂

HO ₃ SC

C = N

Cl

SO ₃ H

(13)

NC SO ₃ H

NH ₂

Cl-C

C-SO ₂ -HN

N-C

Cl

Claims (5)

Patent claims: 1. Process for the production of colored gelatin, in particular for the silver dye bleaching process, characterized in that gelatin is reacted with water-soluble reactive dyes which change their reactivity Owe halogen atoms. 2. The method according to claim 1, characterized in that gelatin with such dyes converts which contain at least one chlorotriazine residue. 3. The method according to claim 2, characterized in that one gelatin with chlorotriazine residues containing azo dyes. SO ₃ H ^H0 (14) SO ₃ H 4. The method according to claim 2 and 3, characterized in that gelatin with dyes converts the at least one atomic grouping of the formula Cl N-C - C C N = C
X
contain, in which X is a chlorine atom, an alkoxy 15 16 group or an optionally further substituted 6. The method according to claim 1 to 5, characterized ated amino group means. characterized by the fact that the gelatin is 5. The method according to claim 1, characterized by gerigem medium at temperatures between 10 and indicates that gelatin with dyes, 60 ° C, optionally in the presence of an acidic especially with copper phthalocyanines, binding agents, with reactive dyes sets that implements. Cl - CH ₂ - CH ₂ - HN - O ₂ S - groups _ _. _,, ._ Considered print sections: contain. German patent specifications No. 740 708, 1 041 355. 409 590 / S19 5.64 @ Bundesdruckerei Berlin