DE1914955C - Method of crosslinking hydrophilic colloids - Google Patents

Description

The present invention relates to a method for crosslinking hydrophilic colloids, which hydroxyl, Sulfhydryl, amino or imino groups contain, by means of organic crosslinking agents, the at least contain two groups reactive with the colloid, at least one of which is a halogen atom represents.

From the German patent specification 1 113 807 is a Process for hardening gelatin layers known, in which substances are used as hardening agents, which contain at least two chlorohydrin groups, in which the hydroxyl group and the Halogen atom are bonded to adjacent carbon atoms, optionally together with others Hardeners and / or accelerators.

US Pat. No. 2,983,611 discloses diaziridinyl-azines known as a hardener for gelatin. You can also be in the presence of yourself in the emulsion any stabilizing dead are applied. These stabilizers are tertiary, but not basic nitrogen compounds, so that they do not accelerate the crosslinking process.

The inventive method for crosslinking hydrophilic colloids, which hydroxyl, sulfhydryl, Contain amino or imino groups, by means of organic Crosslinking agents which contain at least two groups which are reactive with the colloid, of which at least one represents a halogen atom, is characterized in that the crosslinking in The presence of a basic tertiary nitrogen compound or its salt is carried out.

According to this process, a wide variety of hydrophilic colloids can be crosslinked, provided they are with the halogen-containing crosslinking agent) are able to react. The method is particularly suitable for crosslinking gelatine, but also gelatine derivatives, primarily gelatine for photographic use should be mentioned. It can but also other aqueous colloids such as polyvinyl alcohol or alginates are crosslinked. Also can gelatine other natural or synthetic polymers capable of forming aqueous colloidal solutions, such as copolymers of acrylic acid. Acrylamides. Acrylonitrile. Acrylic esters. Vinyl acetate. Vinylpyridine and / or vinylpyrrolidone and ethyleneimines. can be added. Thus, with the present Process such organic substances that are reactive with the halogen-containing crosslinking agents use which are able to form colloidal solutions in an aqueous medium or with absorption of water are swellable.

So that the compounds used as crosslinking agents can fulfill their purpose, they should contain at least two reactive groups in the molecule, at least one of which is a halogen atom has, preferably a chlorine or bromine atom. Compounds with halogen atoms are therefore preferred, which are at an activated point on the molecule and, for example, at a carbon atom are bound. The crosslinking agents should be in the temperature range from 10 to 80 ° C. in particular from 20 to 60 "C, react with the crosslinkable groups of the aqueous colloids.

Examples of highly useful crosslinking agents are compounds which contain at least one of 3 to The six-membered heterocyclic ring formed by 4 carbon atoms and 3 to 2 nitrogen atoms aromatic character and at least one halogen atom bound to a carbon atom of this ring, preferably at least two such halogen atoms, and optionally also further substituents contain. Particular mention should be made of halogen-1,3,5-triazine compounds, Halopyrimidine compounds, haloquinoxaline compounds and haloquinazoline compounds, especially the dihalogen compounds of the formula

or compounds z. B. a ring skeleton of the formulas

c-

C. C.

have, where X is a bromine atom or preferably a chlorine atom and R is a what. stifle or one by a carbon atom. Oxygen atom, sulfur atom or nitrogen atom on the heterocyclic ones Ring bound organic radical or one to the

Heterocyclic ring-bonded hydroxyl group or primary amino group mean.

In general it is recommended. Apply crosslinking agents that have sufficient water solubility have so that they can be supplied to the substances to be hardened as aqueous solutions ν earth. Accordingly the compounds of the formulas (I), (2) and (3) acidic water-solubilizing groups such as Carboxylic acid groups or, in particular, sulfonic acid groups contain, preferably to benzene or

Naphthalene residues are bound. It should also be noted that the radical R of these compounds z. B. may be an aliphatic, aromatic or heteroeyclic radical, preferably an unsubstituted or with halogen atoms. Alkyl groups. Alkoxy groups.

Aryloxy groups, aralkoxy, aralkyl groups, hydroxyl groups, Carbalkoxy groups, alkenyl groups, secondary or tertiary amino groups or the already mentioned acidic water-solubilizing groups substituted, directly or via an oxygen, Sulfur or nitrogen atom attached to the heterocyclic radical, alkyl, cycloalkyl, benzene or Naphthalene resin.

Also suitable for the present process are crosslinking agents which have at least one Oxygen or nitrogen atom, a methylene, carbonyl or sulfonyl group bonded, optionally Contain unsaturated aliphatic hydrocarbon radical with a maximum of 3 carbon atoms.

9i4955

ier has at least one bromine or, preferably, chlorine atom bonded to the η- or / - (- carbon or ioffiite atom. This radical can be a halomethyl radical optionally substituted with a methyl group or with further halogen atoms, e.g. a chloroacetyl group, or a corresponding Haloleiiathyirest such as

- CO - CH ₂ - CH ₂ - Cl

-CO-CHCl-CH ₂ Cl

: .. Jer

-CO-CHBr-CH ₂ Br

Jcr also a corresponding ethylene radical such as

-CO-CBr = CH ₂

■: Orders are also received from networking materials from the

■ a species that is considered to be via an oxygen : .r nitrogen atom bonded hydrocarbon ■ ic / {- contain halogen ethyl radicals, such as

-NH-CH ₂ -CH ₂ -CI

-NlCH ₂ -CH ₂ -Cl) ₂
1 -'scr

- O-CH ₂ -CH ₂ -Cl

A variety of halogen-containing crosslinking agents are known per se, and others can be used according to customary Methods are made.

For example, the reaction products of Halogeniria / .incn are suitable for the present process or halopyrimidines. preferably the chlorine compounds such as cyanuric chloride, with aliphatic or aromatic amines. Hydroxycarboxylic acids, or carboxylic acids, with lower aliphatic Alcohols, with ammonia or water or with gelatine itself. Such reaction products are advantageous chosen which still have two reactive chlorine atoms on the triazine or pyrimidine ring contain. The compounds of the formula may be mentioned in particular

Cl

25th

C - R

14)

Cl
where R is one of the following radicals:

- HN - <f y - SOjNa

MN

- HN

COOH

SO ₃ K

-HN-CH ₂

, CH ₃ -H ₃ Cv

-NH ₁ -N

¹ ^ CH ₁ -H ₁ C

I ^ -Dichloroquinazoline-o-carboxylic acid chloride are also suitable and reaction products of gelatin and cyanuric chloride or!, ^ - dichloro-o-phenylamino-1,3,5-triazine-4'-sulfonic acid.

Mention should also be made of crosslinking agents which contain at least one halovinyl group, 2. B. Compounds containing at least one acidic water-solubilizing group and at least one n, / i'-ethy! enically unsaturated u-halocarboxamide radical contain.

Compounds of the formula should also be mentioned

- HN - CH, - CH ₂ - OH - ONa

HN-CR ₁

■ = S = O (5)

HN - C - R ₂
O

wherein R ₁ and R ₂ each denote a radical bonded to the - CO - group and containing mobile hydrogen atoms to form homopoly bonds, at least one of the radicals R ₁ and R _{2 being bonded to the - CO - group} has reactive halogen atom.

As compounds which «-halogen-methyl-carbonyl radicals contain, z. B. are mentioned: Dibromo-diacetyl and the reaction products of Ciiloracetylchlorid, u./i-Dichlor- or «./f-Dibromopropionic acid chloride with aliphatic and aromatic diamines. The reaction products can optionally also have acidic water-solubilizing agents Groups included.

Also reaction products from acyl isocyanates. for example from chloroacetyl isocyanate, with amino

so hydroxyalkanes, diaminoalkanes or dihydroxyalkanes come into question. On the other hand, the reaction products of chloroacetyl isocyanate are suitable with suitable reactants, such as acrylic acid amide. Glycidol, ethylenimine, bis - ^ - chloroethylamine or // - chloroethanol, as well as those containing hydroxy and amino groups Polymers for the proposed process.

Used in place of chloroacetyl chloride or isocyanate / i-chloropropionyl chloride or isocyanate

fio, one obtains completely analogous products which, like similar / i-Halogenäthylcarbonylreste containing Compounds suitable for the present process.

Particular mention should be made of compounds of the formula

R-C-NH-C-X (6)

- O-CH, -0-C ₂ H ₅

- C ₂ H,

wherein R is a remainder of the composition

H ₂ CY - CH ₁ - or H ₂ CY - HCY -

(where Y is a chlorine or bromine atom) and X is one through a hetero atom to the - CO - group bound, reactive radical with compounds containing mobile hydrogen atoms.

The individual reactive groups can be found once or several times in the molecule of the crosslinking agent happen. If this contains only a single reactive halogen atom, at least a second must group reactive with the colloid be present, e.g. B. an acrylic, vinylsulfonyl, aldehyde, epoxy, Ethyleneimine or anhydrin group. Furthermore can also two or more than two different halogens Groups exist. In general it is enough. when a crosslinking agent has two -active moieties contains. However, polymeric crosslinking agents can also be used in the present process will.

As basic, tertiary nitrogen compounds or their salts, which are used in the present process are required, those containing at least one nitrogen atom can suitably be used have that to alkyl or cycloalkyl radicals or an aralkyl or aryl radical or to an optionally further nitrogen atom substituted with lower alkyl radicals is bonded or that belongs to a ring with an aromatic character. So there come Amines. Alkylhydrazines and compounds with ring nitrogen of the specified type are considered. The basic one A nitrogen compound can contain, for example, a nitrogen atom attached to two carbon atoms is bound and together with these a part of at least five members, z. B. five- or six-membered, Ring forms, which as further ring members also oxygen, sulfur or additional nitrogen atoms may contain. The basic nitrogen compounds can be used as further substituents in alkyl groups, such as methyl or ethyl, alkoxy groups such as methoxy or ethoxy, or optionally with alkyl groups carry substituted amino or hydroxyl groups, the alkyl groups generally from 1 to 5 carbon alum included. For example, are preferred Compounds of the formula

amino group further substituted by I to 2 low molecular alkyl groups and Y a —CH ₁ -, - O—, - NH- or

AlkyK

where R ₁ and R ₂ are optionally substituted low-molecular-weight alkyl groups and R are optionally substituted low-molecular-weight alkyl groups or an amino group, where R ₁ and R ₂ together with the nitrogen atom or R ₁ , R ₂ and R 2 together with the nitrogen atom form a cyclic system can form. Cyclic compounds of this type correspond, for example, to the formula

/ CH ₂ - H ₂ C _x

R, -N "(Y) ₁₁ -, (8)

^x CH, - H ₂ C /

wherein R _{-1 is} a hydrogen sulfide, a primary or an N-bridge

means, where R ₊
may be if Y

only then a hydrogen atom

- N -

Alkyl

and η is 1 or 2.

The following nitrogen compounds should be mentioned in detail:

Trimethylamine.

Triethylamine.

N-ethyl-N-di-isopropylamine,
Dimethyl dodecylamine.

p-dibenzylaminobenzaldehyde,

N-methyl-N-diethylamine,

1.5-diaza-bicyclo- (4.3,0) -5-noncn,

N-methyl pyrrolidine.
N-methylpiperazine.

N-methylmorpholine,

Dimethylethanolamine,

N-methyl-N-ethyl-ethanolamine,

Methyl diethanolamine.
- ⁱ⁰ n-picoline.

Quinaldin.

N.N-diethylhydrazine.

N.N-Di - (/ i-'hydroxyäthyI) -hydrazine,

as well as the following other hydrazine compounds:

N-aminopyrrolidone,

N-aminopiperazine.

N-aminomorpholine.

The basic organic nitrogen compounds can therefore not only e ^; n, but also contain more than one nitrogen atom in the molecule. They do not need to be volatile, and the boiling point of the nitrogen compounds under normal pressure can also be higher than 125 C. Even high molecular weight compounds can be considered. The nitrogen compounds can, in suitable solvents, e.g. B. in water, dissolved in water-miscible or immiscible solvents, added to the aqueous colloid. If necessary, the solutions are to be brought into finely dispersed uniform distribution in the colloid in a manner known per se.

The use of diffusion-resistant amines, e.g. B. those with high molecular weight or sehi long rtlkylkettcn. can help achieve a differentiated Hardening effect in different layers can be advantageous. As a result, one can otherwise be very slow and hard-to-harden layers are rapidly brought into the same hardening state as an adjacent hardened one no-time hardenable layer. This comes e.g. B. when using certain emulsion additives, such as certain color couplers or plasticizers.

In general, however, it is advantageous to use the aqueous colloids, especially those for the formation of photographic Materials certain gelatin preparations. to add such nitrogen compounds, which are at most weakly colored and sufficiently water-soluble that they are not visible in the

Layer precipitate or crystallize. Especially for this suitable are e.g. B. lower alkylamines such as triethylamine, N-methylmorpholine. 1,4-diaza-bicyclo- (2,2,2) octane and also hydrazines such as. B. N.N-dimethylhydrazine. Various nitrogen compounds can also be used used for the same colloid in combination with one another.

The nitrogen compounds can also be in the form of their salts with acids, e.g. B. carboxylic acids with a maximum of 6 carbon atoms, such as oxalic acid and citric acid or mineral acids, such as hydrohalic acids, Sulfuric acid and nitric acid. can be applied. These salts can be added in isolated form to the solution of the colloid or by dissolving the tertiary amine and Addition of an appropriate amount of acid can be formed in solution. There are also nitrogen compounds into consideration, in addition to the tertiary nitrogen atom, one or more quaternary Have nitrogen atoms with common quaternizing agents. like alkyl halides. Benzyl halides. Ethylene halohydrins. Epihalohydrins. Haloacetamides or cyanuric chlorides. or such as alkyl sulfonates or toluenesulfonic acid esters. manufactured will.

The basic nitrogen compounds and their salts can be applied simultaneously in the same layer or in a neighboring layer, possibly simultaneously or in direct succession, They can also be used later by re-moistening the material with a solution of the amine, ζ B by an immersion or Spray-on process (thereby steaming the material are fed

With respect to the quantitative ratio between crosslinking agents and basic nitrogen compound is to be found that the application is stoichiometric Amine amounts are by no means required. It is in (On the other hand, mostly advantageous, a much lower one Amount of nitrogen compound to be applied, than that of the given amount of the halogen-containing crosslinking agent equivalent amount. The amount of the organic nitrogen compound, for. B. at most 20 percent by weight and preferably 0.05 to 10 percent by weight the amount of crosslinking agent Without any influence on the result is in general, whether the basic nitrogen compound feeds the colloid first and then the crosslinking agent or whether to proceed the other way round.

The present procedure is particularly suitable good for networking under acidic to at most weak alkaline conditions, ζ B. in such a way that the pH value of the water-containing colloid during crosslinking no more than "7.5. For example no more than 6 amounts to.

There are various possibilities for carrying out the method, of which are below some particularly important ones are circumscribed:

1. The aqueous colloid are simultaneously the Crosslinking agent and the nitrogen compound supplied.

2. The aqueous colloid becomes the crosslinking agent first and then the nitrogen compound fed.

3. The nitrogen compound is added first to the aqueous colloid and then fed the crosslinking agent.

4. One works according to 2. the nitrogen compound ersi immediately before the preparation of the Layer is supplied to the aqueous colloid.

5. One works according to .1. wherein the crosslinking agent only immediately before the production of the layer is added to the aqueous colloid.

6. Work according to 2. where the nitrogen compound is added to the layer of aqueous colloid containing the crosslinking agent.

ίο 7. One works after .1. wherein the crosslinking agent is supplied to the layer of the aqueous colloid containing the nitrogen compound.
8. The crosslinking takes place in multilayer materials, the crosslinking agent and the

■ 5 nitrogen compound initially in different Layers are in place.

Thus, the crosslinking acceleration effect achieved in the present process can be greatly improved

ίο be realized in different ways. To 2 and 3 can the aqueous colloid only with one of the two additives, for. B. the ineffective in itself Nitrogen compound, let stand a few minutes to several hours and the other Only then add Zw »tz when the actual release the crosslinking process is desired immediately afterwards be added at this point, either all at once, e.g. B to the colloid in the storage vessel. or

u> continuously. 1. B. into the flow of the outflowing colloid preparation in a well-coordinated dosage. For the production of photographic materials, such a metering can be done, e.g. in the inflow to a casting tray or a metering casting system. as described in US Pat. No. 2 ⁷ M 418. According to 8, when producing materials with several layers, one can apply one layer with the crosslinking agent and then the overlying layer with the nitrogen compound either one after the other or at the same time, it is essential that at least one of the two substances within the layer of association can diffuse Of course one can also proceed the other way round. ie first pour the layer with the nitrogen compound and then the layer with the crosslinking agent.

Furthermore, you can create layer intrinsic crosslinking effects, z. B one layer more than the other harden if one of the two substances is diffusion resistant is. Both substances can also be separated into two different colloid preparations before they are brought together are available and then poured together at the desired time «ground. The networking agents and the nitrogen compounds can be added to the colloid in the solid state or as a solution will. Also a gassing of already spread out layers with volatile nitrogen bases wit Trimethylamine comes into consideration, in all cases isi however, a sufficient distribution of both substances is wrong

ίο to watch out for colloid. This can be done by a sufficient!

Water solubility already largely guaranteed As mentioned, it is advantageous to use relatively ge

Use small amounts of nitrogen compound so that at the moment of addition none are noticeable «:

or at least no detrimental change in temperature, viscosity, concentration, and especially the pH value occurs. Only the connection reaction itself should lead to such changes. By dii

combined use of basic nitrogen compounds and crosslinking agents !! is over a wide pH range, generally from 3.5 to II. In particular from 4 to 7.5. achieved a substantial acceleration of hardening. The hardening effect is largely independent of the prevailing pH value of the colloid medium. The pH value can therefore be adapted to the requirements of the photographic system at hand without having to fear that the hardening process will be impaired. In practice, the advantage of the present process is primarily to be seen in the fact that when crosslinking agents of the specified type are used, without having to accept disadvantages in processing and the properties of the material, the action of the basic nitrogen compound causes either the same Hardening state is reached faster or a higher hardening state is reached in the same time.

Example I.

Mm represents a 6% gelatin solution in water in the usual way at 40 ° C. likewise a 1% solution of the sodium salt of 2,4-dichloro-6-phenylamino-1.3.5-triazine-4'-sulfonic acid (crosslinking agent. hardener) and a 1% solution of ;, 4-I> iaza-bicyclo- (2.2,2) -octane (amine) in water 25 d.

Mix 100 ml of the 6% gelatin solution with 20 ml of the 1% in the order given Hardener solution and 0 to 2 ml of the solution of the dia / abicyclo-octane at 40 'C. Pour 10 ml of it onto a subbed glass plate of 13 χ 18 cm. leaves this Dry for 2 hours at 32 C and store the glass plate for another:! 4 hours at 20 to 22 C and 50 to 55% Humidity The original solution is kept at 40 C. until it solidifies and becomes lumpy can no longer be stirred with a glass rod. This point should be referred to as "fixed". In In one case, the pH was adjusted to 6 with 0.4 g of citric acid.

The melting points are determined by immersion in a stirred water bath with successive heating from room temperature to the boiling point. The melting point is the temperature at which the crelatin layer becomes detached from the substrate by dissolving. The results of crosslinking carried out in this way are recorded in Table I.

■ amine solution Table I. fluid : Casting . fixed _: Melting . fixed Point No ml solution . fixed in C O . fixed n.icti 0.5 24 hours 1 • 85 I.I -) ^: > 95 1.2 Could? ; > 95 1.3 0.4 2 > 95 1.4 Lemons > 95 1.5 acid. after 24 hours pH 6 after SO min after 40 min after 15 min after 60 min

Example 2

A 6% gelatin and 1% hardener solution prepared in the same way as Example I is used, and a solution of diaza-bicyclo-octane (amine) in water prepared analogously to Example 1 is used. First 33 ml of 6% gelatin solution and ml of 1% hardener solution are mixed at 40 "C and then 0 to 20 ml of the 0.05% amine solution are added, ίο It is then made up to 100 ml with water. Such a solution contains 100 g gelatine 5 g hardening agent and 100 g hardening agent 0 to 10 g amine Immediately after the addition of the amine solution, as described in Example 1, 10 ml are poured onto a glass plate, dried and the melting point determined.

The remaining solution is maintained at 4O ⁰ C and determines the pH at the start, after 2 and 18 hours aiii conventional manner. The results obtained are recorded in Table II.

No.

2.1
2.2
2.3
2.4
2.5
2.6

Amine solution

ml

1.25

2.5

5.0

10.0

20.0

Table I. 0 I. solution 18th hours 4.4 Melting point IH hours > 95 pH after 4.7 4.3 in C. 42 > ^l > 5 4.8 2 4.6 4.3 2 80 > 95 4.8 4.6 4.2 90 > 95 4.8 4.4 4.2 95 > 95 4.8 4.3 4.2 > 95 > 95> 95 4.8 4.2 I 3 4.8 spat Be

The same solutions and procedure as in Example 2 are used.

Add 5 ml of I% hardener solution and 0 to 5 ml of amine solution to 33 ml of 6% gelatin solution. Results: see Table III.

Table III

No

3.1

3.4

r ι

Amine solution

m!
0

0.3025

1.25

5.0

solution

pH after

hours

Molding

5.1

5 y

5.1

5.1

5.0 4.9 4.S 4.8

36

60 95

B e i s ρ i e i 4

The same solutions and the sleic Procedure as in Example 2 used. Add 10 ml of hard to 33 ml of gelatin solution. solution and 5 ml of amine solution used.

The pH is adjusted with 10% aqueous water Citric acid solution immediately after addition c Amine solution. Results: see Table IV.

1% 0.05% HSrUT- Amine No. solution solution mi ml 4.1 10 0 4.2 10 5 4.3 10 5 4.4 10 5

11th Oh 4.0 Ou B 5 4th C after Table IV 2 3.9 Melting point in hours 20th solution hours 4.1 2 34 pFI ι 4.0 4.2 39 35 0 4.0 ρ i e 1 32 95 69 4.25 36 95 > 95 4.5 80 > 95 By S 85

The same solutions and procedure as in Example 4 are used.

5 ml hardener and 1.25 ml amine solution are used for 33 ml gelatin solution.

The pH is also adjusted with 2N sodium hydroxide solution. Results: see table V.

Table V

solution
pH after

1% 0.05% 0 Shepherd Amine No. solution solution ml ml 5.1 5 5.2 '5 5.3 5 5.4 5 5.5 5 5.6 10 , 25 , 25 .25 .25 .25

hours

4.0
4.5
5.0
6.2
7.0
6.9

4.1

5.0 5.6 5.9

OuD

Melting point in C.

2 I 20 hours

34

40

85

> 85

> 85

39

38

from 45> 95> 95> 95

Example 6

The same solutions and procedure as in Example 2 are used.

U) ml hardener and 0 to 0.625 ml amine solution are used for 33 ml gelatin solution. Results: see table VI.

Table Vl

No. 1% lliirtcriösuhg 6.1 10 6.2 10 6.3 10 6.4 10

0.05% amine solution

Casting melting point

in C after 4 hours

0 85

0.156 94

0.312> 95

0.625> 95

Example 7

Completely analogous to Examples I to 6, 10 ml of 1% hardener solution and 10 ml of 0.05% strength are used Amine solution obtained the following results.

Table VII

Amine solution none Melting point '. 4S in No. Diethyl ethanolamine after Dimethyl cyclohexylamine 2 hours to do 7.1 Ethyl diisopropylamine 35 78 7.2 Dimethylaniline 45 95 7.3 N-ethylmorpholine 64 93 7.4 Dodecahydro-1.4.7,9b-te- 39 90 7.5 trazophenaline 38 90 7.0 Pyridine 38 95 7.7 N.N-dimethylhydrazine 42 90 7.8 50 91 7.9 90 90

Example 8
To 33 ml of 6% gelatin solution are added 20 ml of a 1% solution of the compound of the form «

KO ₃ S

H, C = BrC-C-HN-> -HN-C-CBr = CH ₂

SO ₅ K

fr \ water and 40 ml of 0.05 ⁿ pc solution of M-diaza-bicyclo-octane-lZ.IJl in water and FuIIt Tnit water to 100 mL. 10 ml are, as described in Example 2, poured onto a glass plate, dried and stored at room temperature for 5 days. The melting point of the gelatin is 7? C. E comparison without amine solution melts at 38 C.

Example 9

In 33 ml of 6% gelatin solution, at 40 ° C., the reaction of the Hartungsmutel is added

either 5 ml of a 2% change in the pH value listed below within the first

Hardener solution or 10 ml of a 1% hardener solution. 65 2 hours while holding the gelatin solution!

now 20 ml of 0.05% M-Diaza-bicyelo-li ^ Ji-octane holds at 40 C, similar to that described in Example 2

Add the solution and adjust the pH to 7.5 to 7.8 using 2N sodium hydroxide solution. To yerfolben is.

Hardener solutions:

H ₂ C = HC — C — HN — C — NH — C — CH ₂ —CH ₂ —C1

14th

1% in ethanol

CH ₂ -O-Co-NH-CO-CH ₂ -CH ₂ -CI CH-O-CO-Nh-CO-CH ₂ -CH ₂ -Cl

CH ₂ -O-Co-NH-CO-CH ₂ -CH ₂ -CI

_ OO

/ ° \ Il Il

H ₂ C CH-H ₂ COC-NH-C-CH ₂ -CH ₂ -CI

Table VIII

1% in ethanol

2% in ethanoi

Hardener solution Ainin solution pll a 9.1 With 9.1 without 9.2 With 9.2 without 9.3 With 9.3 without

7.7 7.5 7.7 7.7 7.8 • 7.5

example

In 33 ml of 6% gelatin solution are added. as described in example 8. 5 ml of a 1% solution of the given hardener and 10 ml of a 0.05% solution of 1,4-diaza-bicyclo- (2,2.2) -octane in water and < works as otherwise stated there, compared with a corresponding solution without the tertiary amine.

end difference 6.1 -1.6 6.2 - -1.3 6.5 -1.2 6.7 -1.0 6.9 -0.9 6.8 -0.7

1% in ethanoi

Cl

CN
y ν
\ / CO-CH ₃ BrH-CCC-CH ₂ Br
¹ I II Il
O \ /
C = N
I. Il
O Cl CI
I. CN
/ V
K C-NH ^^ I. I.
COOH Cl

1% in ethanol

1% in water with the addition of so much 2N NaOH,
that the carboxylic acid is dissolved

i% in methanol

Table IX

louder- Amine solution solution 10.1 With 10.1 without 10.2 With 10.2 without 10.3 With 10.3 without 10.4 With 10.4 without i

Melting point in C.

56 after 5 hours 86 after 20 hours 35 after 5 hours 36 after 20 hours

> 95 after 3 hours 34 after 3 hours

> 95 after 3 hours 34 after 3 hours 66 after 5 hours 62 after 5 hours

Example Il

1.0 ml of a 1% solution of the compound is added to 3.3 ml of 6% gelatin solution at 40.degree formula

H ₂ C CH-OC-Hn-C-NH-OC-CH ₂ -CH ₂ -Cl

11.1

in ethanol and 1.0 ml of a 0.05% aqueous solution of 1.4-diaza-bicyclo- (2.2.2) -octane and fills with water to 10 ml. It is poured onto a glass plate, as described in Example 2, and the procedure is otherwise identical stated there. After 15 hours of drying, a melting point of S6 C. is determined during a corresponding sample without 1.4-diazo-bicydo- (2.2.2) -octane after this line melts at 37 ° C.

B c i s ρ i e 1 I2 4c

To 1 kg of a highly sensitive silver bromide iodide emulsion With a Gclatine content of 7%, a red sensitizer is added at 40 ° C. in a known manner and the usual casting additives such as stabilizer.

SO, H

OH

SO ₁ II

Wetting agent but not a hardening agent, as well as the cyan image dye of the formula

-CO-NH

OH

12.1

HO ₃ S

SO ₃ H

50 ml of a 0.5% aqueous, with Cilronensäuic Aqueous 1.4-diaza-bicyclo- (2.2.2) -octane solution (amine) adjusted to pH 6.5 are also used stirred into the mixture. It is then filtered and the required amount of water is added the viscosity adjusted to the desired value. The pH value in the ready-to-pour mixture is also 6.5. On a photographic base, at a pouring temperature of 40 C and a Casting speed of 6 m min. A layer 6 μ thick (in the dry state) is produced.

A colorless gelatin layer 2μ thick (when dry) is poured over this layer in the usual way. Based on dry gelatin, this layer contains 5.9% 2,4-dichloro as a crosslinking agent (hardener) - 6 - phenylamino -1.3.5 - triazine - 4 '- sulfonic acid Sodium. The pH value in the ready-to-pour mixture is 6.0.

A corresponding intermediate layer system is used for comparison produced, which differs from the one described only in that it is in the Emulsion layer does not contain an amine as a hardening accelerator.

Analogous materials are produced with green-sensitive layers, with a green sensitizer and the purple image dye of the formula

NH-OC-NH

NH,

CO

12.3

also with blue-sensitive layers, unsensitized and the yellow image dye of the formula

SO., HO-CH., O-CH ₁ SO., H

-N = N-

SO, H

N = N

SO ₃ H

12.4

After a storage time of 4 hours in one, the melting points in water are determined. Indoor climate of 20 C and 55% relative humidity. The following values are obtained:

Tubelle X Cyan Stomach do Yellow C. 50 C 45 ^: C 47 ' C. Without e accelerator > 8 (TC > 80 C > 80 With accelerator game 13 By S

6 ml each of a 6% strength prepared in the usual way Gelatin solution are mixed at 40 ° C. with 2 ml each of a 1% strength aqueous solution of 2,4-dichloro-6-phenylamino - 1,3,5 - triazine - 4 '- sulfonic acid - sodium salt (hardener) and 0.25 ml of a 0.02N aqueous Solution of the compounds 13.1 to 13.5 are added, the resulting mixture is diluted with 2 ml of water and poured onto a 13 × 18 cm glass plate subbed in the usual way. The panels produced in this way are then dried for 2 hours at 36 C and the melting points as in Example 1 aiiüCizeben determined.

-N H bark Xl Melting point
the shift
in C "after
2 hours No i
H Iornici > 95 3.1 > 95 3.2 > 95
> 95 }.}
3.4 , COO
SO ₄ "- > 95 3.5 C ₂ O ₄ he Br CII
J_
2 1
2

40

An otherwise identical layer without the ammonium salt had under the same conditions after 2 hours a melting point of 72 C.

B e i s ρ i c I 14

6 ml of a gelatin solution prepared in the usual way are mixed with 2 ml of a 1% strength aqueous solution at 40.degree Breaking the connection 10.2. 0.5 ml of a 0, () 2N aqueous solution of the compound 13.1 and 1.5 ml of water were added and poured onto a subbed glass plate measuring 13 × 18 cm. After a drying period after 2 hours at 36 ° C, the melting point of the S 'has not risen to above 95 ° C.

Example 15

1.5 ml of a 2% solution of the hardener from Example 1 and 0.3 (15.1), rcsp. **> p, 75 ml (15.2) cinerO, () 2N aqueous solution of 1,4-diazabicyclo- (2,2,2) -octane added. The mixture produced in this way is diluted with water up to a total weight of 15 g, poured onto a glass plate of 13 × 18 cm subbed in the usual way, and this is dried at 36 ° C. for <> 5 for 2 hours. The melting points are determined as in Bcispici I. At 15.1 they are 58 C. at 15.2 55 C.

A layer produced in the same way without the addition of amine has a melting point of 34 ³ C

B is ρ ie! 16
s

6 ml each of a 6% gelatin solution prepared in the usual way are mixed with 2 ml each at 40.degree a 1% aqueous solution of 2,4-dichloro-6-phenylamino-1,3,5-triucin-4'-sulfonic acid sodium salt (Crosslinking agent), each 2 ml of water and 0.25 ml of a 0.02N aqueous solution of the compounds 16.1 to 16.4 offset. The mixtures thus obtained are then poured onto a glass plate of 13 × 18 cm subbed in the usual way and the plates produced in this way were dried at 36 ° C. for 2 hours.

The melting points are given as in Example 1 definitely. The results are shown in Table XIl.

Table XiI

formula

Melting point of the layer in C after 2 hours

16.1 y N

N - CH ₃

Cl

16.2 NN -CH, - CH ₁

Br

16.3 I N

16.4 N N - CH,

CT

OC H_,

OCH,

Cl

> 95

> 95

> 95

> 95

An identical layer without an ammonium compound has a melting point under otherwise identical conditions from 72 'C.

Example 17

6 ml each of a 6% strength prepared in the usual way Gelatin solution are mixed at 40 C with 2 ml of a pure solution of 2,4-dichloro-6-methoxy-1,3,5-iriazine (Crosslinking agent), 2 ml each of water and 0.5 ml of a 0.02N aqueous solution of the compounds 16.1 and 16.3 offset. The mixtures thus obtained are then poured onto a customary substrate glass plate of 13 χ 18 cm and the Plates produced in this way were dried at 36 ° C. for 2 hours. The melting points were determined as in Example 1. They are above 95 "C in both cases.

An identical layer without an ammonium compound has a melting point under otherwise identical conditions of 72 "c.

i 914955

(t

Example 18

Per 6 ml of a solution prepared in a conventional Weiie 6% gelatin solution at 4O ⁰ C 2 each of the hardener solution from Example 16 and 0.3 ml to 2.0 ml of a solution of the compound 0,004n 16.2 and 16.3 and added with water to 10 ml supplements. The mixtures obtained in this way are then poured onto subbed glass plates measuring 13 × 18 cm, and the plates produced in this way are dried at 36 ° C. for 2 hours. After this time, as in the example! 1 indicated, the melting points determined. In all cases they are above 95 "C.

An identical layer without an ammonium compound has a melting point under otherwise identical conditions from 72 ° C.

Example 19

6 ml each of a 6% strength prepared in the usual way Gelatin solutions are added to the at 40 C by adding 10% citric acid solution or IN NaOH set the desired pH, each 2 ml of hardener solution from Example 16 and 0.25 ml of a 0.02N aqueous Solution of the compounds 16.1 and 16.3 and mixed with water up to a total volume of 10 ml diluted. After 3 minutes, the pH values of the solutions are determined in the usual way at 40 C, then the solutions are placed on substrate glass plates of 13 χ 18 cm poured, the plates 2 hours at 36 C gct / ocknet and then the melting points as in the example ! definitely. The results are shown in Table XIH.

Table XIII SchniL'l / punkl n; i Addition of 2 hours in C Connection no. pll-VVcrl 37 to 42 <an addition 4.5 39 to 41 5.4 70 6.3 52 6.5 90 to 95 16.1 4.6 > 95 5.3 > 95 5.9 > 95 6.1 > 95 6.6 82 16.3 4.6 85 5.4 > 95 5.8 > 95 6.1

Example 20

10 grams each of a 6% aqueous polyvinyl alcohol solution are with 1.5 ml of a 2% aqueous solution of the hardener from Example 16 and 0.3 bis 1.5 ml of a 0.02N solution of compound 16.1 or 16.3 offset. The mixtures obtained are diluted with water up to a total weight of 15 g and poured onto substrate glass plates of 13 18 cm. Without a drying time of 2 hours at 36 ° C, as described in Example I, the Melting points determined. The results are shown in Table XIV.

Table XIV

Mo! accelerator Melting point in <- ' Connection no. Per 100 g hardener after! hours 16.1 0.02 52 16.3 0.02 62 0.05 70 0.10 70

A corresponding layer without accelerator has a melting point of 34 ³ C under the same conditions.

Claims (7)

Patent claims: 1. Method for crosslinking hydrophilic colloids, which hydroxyl, sulfhydryl, amino or Imino groups contain, by means of organic crosslinking agents, the at least two with the Contain colloid reactive groups, at least one of which is a halogen atom, characterized in that the Crosslinking carried out in the presence of a basic tertiary nitrogen compound or its salt will. 2. The method according to claim 1, characterized in that gelatin in the manner indicated is networked. 3. The method according to any one of claims I or 2, characterized in that the crosslinking in Layer materials, especially in photographic layers, which contain aqueous colloids, is performed. 4. The method according to any one of claims 1 to 3, characterized gekennzeichnci that the basic tertiary Nitrogen compound has at least one nitrogen atom attached to alkyl or cycloalkyl radicals or an aralkyl or aryl radical or an optionally substituted by lower alkyl radicals another nitrogen atom is bonded or which is a ring with aromatic character listened to. 5. The method according to claim 4, characterized in that the basic nitrogen compound the formula R., - N where R ₁ and R 2 optionally further substituted low molecular weight alkyl radicals or optionally further substituted cycloalkyl radicals and R ₃ optionally further substituted low molecular weight alkyl radical or an amino group, where R ₁ and R 2 together with the nitrogen atom can form a heteroyclic ring system. 6. The method according to claim 5, characterized in that the basic nitrogen compound the formula R4-N (Y) -, ^ CH ₂ - H ₂ C corresponds to where R _{d is} a water vent. one primary amino group or amino group further substituted by I to 2 low molecular weight alkyl radicals and Y a - CH ₁ -, - O - - NH - or AIkyK N bridge means, where R _{4 is} only a hydrogen atom may be if Y - N - Alkyl
is, and »i is 1 or 2. , 7. The method according to claim 6, characterized in that the basic nitrogen compound 1,4-Diaza-bicyc | o- (2,2,2) -octane of the formula H ₂ CH ₃ C CH ₂ H ₁ CH ₁ C CH ₁ χ // ■ is used.