DE1234521B - Process for curing photographic gelatin layers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN # 07 ¥ W PATENT OFFICE Int. Cl .:

G03c

EDITORIAL

German class: 57 b-8/02

Number: 1234 521

File number: C 26685IX a / 57 b

Filing date: April 6, 1962

Opened on: February 16, 1967

The invention relates to a method for hardening photographic gelatin layers.

It is known to dilute aldehydes, preferably formaldehyde, chromium salts and alums to add aqueous solutions either to the ready-to-pour gelatin-containing emulsion or to use them as To be used before or during the treatment process.

The disadvantage of this is that the effect of the chromium salts is often highly dependent on the pH of the cast Is emulsions. Alums in processing baths show the same disadvantage.

The aldehydes lead to fogging, especially in the case of highly sensitive silver halide layers. Color haze can also be caused by the hardener. When adding the known The hardening agent for the ready-to-pour emulsion often has a time-dependent influence on the viscosity a, so that the viscosity gradually increases in the course of the casting process, causing fluctuations Layer thicknesses are caused.

The object of the invention is to provide a method for hardening photographic gelatin layers, in which one uses hardening agents that are added to the ready-to-pour emulsions without the viscosity changes in the course of casting, but that after completion of the recording material within 1 to 2 days or, if desired, hardening does not occur until 15 to 40 days, which is normal use and testing of the recording material and that, on the other hand, long-term storage does not lead to strong Cornification leads. In addition, these hardeners should not produce a fog and face each other behave neutrally to the color couplers and other additives.

The subject matter of the invention is a process for hardening photographic gelatin layers and is characterized in that the curing agent used is colorless compounds, the at least one acidic, water-solubilizing group, at least one of 3 to 4 carbon atoms and 3 to 2 nitrogen atoms and at least one heterocyclic six-membered ring contain a carbon atom of this six-membered ring bonded halogen atom, is used.

As acidic, water-solubilizing groups, the hardeners can be a carboxylic acid, sulfonic acid or an acidic sulfuric acid ester group, as a six-membered heterocyclic ring, they can be one Triazine, pyridazine or pyrimidine ring and contain bromine or chlorine atoms as halogen atoms.

Method of holding photographic
Gelatin layers

Applicant:

CIBA Aktiengesellschaft, Basel (Switzerland)

Representative:

Dr. F. Zumstein, Dr. E. Assmann,

Dr. R. Koenigsberger

and Dipl.-Phys. R. Holzbauer, patent attorneys,

Munich 2, Bräuhausstr. 4th

Named as inventor:

Dr. Walter Anderau, Münchenstein;

Dr. Alfred Oetiker, Basel (Switzerland)

Claimed priority:

Switzerland of 7 April 1961 (4074)

What is achieved by the invention is that the hardening does not occur until after the drying of the treated according to the invention Gelatin layer and an additional residence time occurs. The implementation of the invention The compound used in the gelatin layer is released due to its halogen content The amount of hydrogen halide is so small that it is smoothly buffered by the excess gelatin.

The amount of the halogen compound, based on the amount of gelatin, is expediently 1 to 5%. Hardening also occurs when the compound used according to the invention is only a single reactive compound Has halogen atom. There are several in the molecule of the compound used according to the invention reactive halogen atoms are present, an extensive crosslinking occurs, strong hardening of the gelatin. The water-solubilizing groups have the effect of the invention The compound used had good swelling properties despite the hardening. By hardening the The gelatin layer remains the sensitivity of the silver halide and the reactivity of color couplers or dyes unaffected.

According to one embodiment of the invention, halogen-1,3,5-triazine compounds are used as hardeners used. According to a further embodiment of the

709 509/406

Invention are called halogen - ^^ - triazine compounds those of the formula

Ri

C - halogen

R ₂

wherein Ri is an organic radical with at least one acidic, water-solubilizing group and R2 is a halogen atom, an organic radical with a acidic, water-solubilizing group, a hydrocarbon radical or an oxygen atom, Means sulfur atom or nitrogen atom bonded to the triazine ring substituents is used.

According to a further embodiment of the invention, halogen-1,3,5-triazine compounds are used in which at least one of the radicals Ri and R2 is an oxygen or oxygen bonded to the triazine ring Nitrogen atom, a hydrocarbon radical, preferably an aliphatic hydrocarbon radical, a carboxylic acid, sulfonic acid or acid sulfuric acid ester group means.

According to a further embodiment of the invention, halogen-1,3,5-triazine compounds are used in which one of the radicals Ri and R2 is a halogen atom, denotes an oxy, a methoxy or an optionally substituted phenoxy or amino group.

Examples of such groups are:

-HN

r --oar

HN-J-4-SO ₃ H

O —CH ₂ —COOH

CH ₃

/ C ₂ H _{5 /}

^ C ₂ H ₅ ^ H

/ CH ₂ -CH ₂ -OH

- n (- n <

^ CH ₂ -CH ₂ -OH

- N

CH ₃

CH ₃

, CH ₂ -CH ₂ -OH

^ CH ₂ -CH ₂ -OH ^ CH ₃

40

Also bridges that connect two 1,3,5-triazine rings to each other connect, e.g. B. those that differ from diamines such as 1,4-diaminobenzene or alkylenediamines derive come into consideration.

Examples of acidic, water-solubilizing groups (radicals Ri or R ₂ ) are:

- NH-CHa-

-NH-

O - SO ₂ - OH COOH

-HN

-HN

- O

SO ₃ H

COOH

COOH

SO ₃ H

-HN

-HN

- O

55

SO ₃ H COOH

SO ₃ H

65

COOH - HN "ι / - O - CH ₂ - COOH

SO ₃ H -S-CH ₂ -COOH

According to a further embodiment of the invention, the halogen-1,3,5-triazine compound is a chlorine-1,3,5-triazine compound used. The following compounds can be used as hardeners: Cl

HN

SO ₃ H

35 Cl Cl

SO ₃ H ⁸ C-HN-K '> (b)

Cl Cl

45

SO ₃ H X - HN - <V- SO ₃ H (C)

50 I Cl

Cl

C-HN-CH ₂ -COOH

Cl Cl

I Cl

C-HN-CH ₂ - CH ₂ - O - SO ₂ - OH

SO ₃ H (g)

HO ₃ S

SO ₃ H

HN

X: H, SO ₃ H, COOH

Cl Cl

-Cx /, C - N *

NH-C

C-HN

HN - CH ₂ - CH ₂ - NH Cl

^X C = N ^X SO ₃ H

Cl

X: CH ₃ , Cl

HO ₃ S

NH-C

HO ₃ S

NH-C

SO ₃ H

HN-CH _{2 -COOH}

O - C

Cl
I. N = c / CH ₂ - N
\ Cl
I. NC _V \ N HN - CH ₂ - ^ C = ! NH

C - O

SO ₃ H

SO ₃ H (n)

1 234 52 1 Cl //
N
\ \
/ - *
/ HN Cl Cl
I. //
N c—
/ HN \ ¹ ^ C = N ⁷ /

SO ₃ H

SO ₃ H

SO ₃ H

HO-CH ₂ -CH ₂ -NH

Cl

Cl

HO ₃ S

NH-C

C-HN

SO ₃ H

HN - CH ₂ - CH ₂ - NH

COOH

SO ₃ H (S) The heterocyclic compounds used in the process according to the invention, in particular the halogen - !, 3,5-triazines, can be prepared in weakly acidic solution by condensation of an aminobenzenesulfonic acid with freshly precipitated cyanuric chloride. To replace a second halogen atom with the remainder of an amine or an aminosulfonic acid, the primary condensation product obtained in this way can be ^{reacted with the amine or the aminosulfonic acid at 30 to 40 °} C. in a neutral to weakly alkaline medium.

In the following examples, parts mean parts by weight, unless otherwise noted, and the percentages percentages by weight. Parts by weight are related to parts by volume as grams to milliliters.

SO ₃ H (t)

Cl-C

example 1

Prepare an aqueous solution containing 5% des Curing agent of the formula (b) (2,4-dichloro-6-phenylamino-1,3,5-triazine-3'-sulfonic acid) contains.

2, 4 or 6 parts of this are added to a silver bromide chloride emulsion, which contains 120 parts of iO parts of gelatine.

Mixtures are obtained which contain 1, 2 or 3% hardening agent, based on dry gelatin. A glass plate measuring 13 × 18 cm is coated with 10 ecm each of these mixtures, dried and (u) 6o determines the melting points of the layers in water of increasing temperature after 24 to 48 hours.

SO ₃ H

Amount of hardener in%, based on gelatin

O%

1%

Melting point of the layer

up to 32 C.

37 ³ C

75 to 80 ⁰ C

85 to 90 ⁰ C

With similar results, instead of the compound of formula (b), the compounds of Formulas (a), (c), (e) and (g) are used in the manner indicated above as hardening agents for gelatin layers will. By replacing a chlorine atom in the dichlorotriazine compounds, e.g. B. by use of the compound of formula (f), the activity can be reduced, and the hardening

takes full effect only after a long period of time.

Example 2

To 100 parts of a silver bromide emulsion having lO ° / pc alcohol content of gelatin are added at 40 ⁰ C 0.2 parts of the disazo dye of the formula

H ₂ N OH

H ₃ CO

HO ₃ S

N = N

O - CH ₃ HO NH ₂

N = N

SO ₃ H

HO ₃ S

dissolved in 20 parts of water, also 6 parts of a 3% strength Saponin solution and 2 parts of 2,4-dichloro-6-phenylamino-1,3,5-triazine-2 ', 4'-disulfonic acid of formula (c) dissolved in 30 parts of water.

After coating a support, drying and storing for 24 to 48 hours, you have one blue colored silver halide layer which develops into a blue image after the silver dye bleaching process leaves and those with a melting point above 8OC are those that place heavy demands on the gelatine Resists treatment baths well.

Example 3

To a red-sensitized silver halide emulsion containing 30 parts of silver chloride per 1000 parts by volume, 70 parts of gelatin and 15 parts of a color coupler of the formula

OH X

SO ₃ H

CO-HN

SO ₃ H

HOOC

NH - C - CH ₂ - C -

HN - OC - (CH ₂ ) J ₆ - CH ₃

where X is a diffusion-preventing radical, ζ. Β. one of the formula

-C ₂ H ₅

- N <

means, 1.4 parts of one of the curing agents of the formulas (a), (b), (c) or (k) are added.

After coating, drying and storage for 1 to 2 days, a hardened gelatin layer is obtained, which withstands the attacks of numerous baths for a color reversal material without the Activity of the color coupler is inhibited.

Example 4

A bath is prepared containing 2 to 10 parts of one of the hardening agents of the formulas (a), (b), (c), (e) or (g) Contains dissolved in 100 parts of water.

The recording material to be hardened is treated with it for 5 to 20 minutes and rinsed for 2 to 5 minutes and dries. A well-hardened recording material is obtained after 24 hours.

The hardening agents of the formulas (i), (1), (m) and (n) are more inert in their effect. Leave with these Depending on the amount used, from 2 to 6% of the weight of the gelatin, melting points from 40 to Set 65 ° C, with a great tendency to swell, which z. B. may be desirable for suction processes.

Example 5

4 parts of the curing agent of the formula (o) are dissolved in 100 parts of cold water. 10 parts of this solution are added to 100 parts of an 8 to 10% aqueous gelatin solution or a corresponding silver halide emulsion at a temperature of 35 to 38 ^° C. A glass plate of 13-18 cm is coated with 10 cm ^{3, allowed to solidify and dry} . The melting point of a comparison layer without the use of the curing agent is 32 ⁰ C. A layer of curing agent after 24 hours shows a melting point of 42 ^C, which increases in the course of a few days to values of 58-62 ° C.

Example 6

Add 2 to 5%, calculated on gelatin, to a gelatin solution according to the instructions in Example 1, the curing agent of formula (p).

This increases the melting point of the gelatine to around 40C. Further hardening is only achieved after a certain storage time. The reaction with the compound of the formula (p) has a particularly favorable effect in the subsequent production baths and a subsequent hot drying.
Slow hardening is also achieved if the gelatin is reacted in the manner indicated with the hardening agent of the formula (q).

Example 7

As indicated in Example 1, the hardener is left of formula (r) act on a gelatin solution. The melting point of the gelatin layer will be 62 to 68 ° C 24 hours after coating and drying and rises to over 90 "C.

709 509/406

45

Example 8

A gelatin solution is in the manner indicated in Example 1 with the hardening agent of Formula (s) implemented. It takes a long time for the gelatin layer to reach its maximum hardness will.

A similar effect is obtained with the hardening agent of formula (t).

The pyrimidine compounds of the formulas (s) and (t), which are much more sluggish than the triazine compounds, increase within the time that must be applied to the shedding of large approaches that The viscosity of the casting compounds is not. The freshly poured and dried layers have melting points around 40 C. The melting points only rise after prolonged storage.

The pyridazine compound of the formula (u) acts even more slowly as a hardening agent.

Example 9

5 parts of the clearest possible gelatin are dissolved in 100 parts of distilled water at 4OC. This Solution, 5 to 20 parts by volume of a solution of 1 part of filter dye in 100 parts of distilled Water and 20 parts by volume of an aqueous 2% solution of the compound of the formula (a) were added. A plane-parallel ground glass plate is coated with it, dried and placed on the coated one Side applied a second plane-parallel glass plate. The filter plate can then be placed on the desired Formats can be cut. The filters obtained in this way are extremely heat-resistant. You turn out especially in reproduction technology and where there are no colored glasses that make you feel completely show certain absorption range are known to be valuable. The known filter dyes are used Dyes tartrazine, brilliant purple 10 B, real acid fuchsine, chlorantine light green BL and direct sky blue mentioned.

Example 10

180 parts of commercially available barite white with a water content of 30 ° / ₀ , 30 parts of water and 6 parts by volume of glycerol are mixed in a kneading apparatus. To this are added the to 6O ⁰ C warmed up to 50 solution of 18 parts of swollen gelatin in 75 parts of water, the mixture is stirred until the mass is homogeneous, and then 0.4 parts of the curing agent of formula (a) or the equivalent amount of (b), (c) or (e), which have previously been suspended or dissolved in 10 parts of water. After further stirring, the desired viscosity is set by adding water. Raw paper is coated with this barytaic compound on the casting machine and then dried. Obtained cured, firmly adhering layers of high wet strength at temperatures up to about 8O ⁰ C.

Claims (6)

Patent claims: 1. A method for hardening photographic gelatin layers, characterized in that that the curing agent is colorless compounds which have at least one acidic, water-solubilizing group, at least one heterocyclic six-membered rings consisting of 3 to 4 carbon atoms and 3 to 2 nitrogen atoms and contain at least one halogen atom bonded to a carbon atom of this ring, used. 2. The method according to claim 1, characterized in that the curing agent used is halogen-1,3,5-triazine compounds used. 3. The method according to claim 2, characterized in that there is used as halogen-l, 3,5-triazine compounds those of the formula Ri - halogen = N ' R-2 wherein Ri is an organic radical with at least an acidic, water-solubilizing group and R-2 is a halogen atom, an organic radical with an acidic, water-solubilizing group, a hydrocarbon radical or a by one Oxygen atom, sulfur atom or nitrogen atom attached to a triazine ring substituent means used. 4. The method according to claim 2, characterized in that one halogen-l, 3,5-triazine compounds, in which at least one of the radicals Ri or Ro is bound to the triazine ring Oxygen or nitrogen atom, a hydrocarbon radical, preferably an aliphatic one Hydrocarbon radical, a carboxylic acid, sulfonic acid or acid sulfuric acid ester group means used. 5. The method according to claim 4, characterized in that one halogen-1,3,5-triazine compounds, in which one of the radicals Ri and Ra is a halogen atom, an oxy, a methoxy or denotes an optionally substituted phenoxy or amino group is used. 6. The method according to claim 2, characterized in that one chlorine-l ^ S-triazine compounds used.