DE1547733C - Use of compounds with beta vinylsulfonyl ethyl groups for hardening photographic emulsions - Google Patents

Description

RN

or R ₂ N · Χ ^θ

in which R is an alkyl radical with 1 to 4 carbon atoms and X® is an acid anion, _r

Z is a polyvalent organic residue of valence η and

η 2 to 6,

for hardening photographic emulsions containing gelatine and / or carboxylated polymers.

2. Use of compounds according to claim 1, characterized in that these the Formulas

R ² R ²

and

CH ₂ = CHSO ₂ CH ₂ CH ₂ -N-R ¹ -N-CH ₂ CH ₂ SO ₂ CH = CH ₂

R ² R ²

CH, = CHSO, CH, CH, —N — R ¹ —N — CH, CH, SO, CH = CH,

2X «

(III)

R ³ R ³

correspond to, in which means

R ^{1 is} an alkylene chain with 1 to 10 C atoms which may have unsaturated bonds or is interrupted by an arylene or cycloalkylene radical, O or S atoms or amide groups,

R ² and R ^{3 are} alkyl radicals with 1 to 4 carbon atoms, both radicals R ^2, together with the two nitrogen atoms on which they are located, can form a heterocyclic ring,

X ^{e is} an acid anion.

3. Use of

N, N'-bis (2-vinylsulfonylethyl) piperazine; N, N'-bis (2-vinylsulfonylethyl) piperazine-

bis (methyl perchlorate);
N, N'-bis (2-vinylsulfonylethyl) -N, N'-dimethyl-2-butene-1,4-diamine-

bis (methyl p-toluenesulfonate) or N, N'-bis (2-vinylsulfonylethyl) -Ν, Ν'-dimethylethylenediamine- bis (methyl p-toluenesulfonate)

according to claim 2.

The invention relates to the use of compounds with / S-vinylsulfonylethyl groups for curing Gelatin and / or carboxylated polymers containing photographic emulsions.

The utility of compounds with olefinically unsaturated bonds as curing agents for hardening gelatin is known.

So is z. B. from German patent specification 1 100 942 and the USA patent specification corresponding to this 2,994,611 the use of aromatic, at least compounds containing two vinylsulfonyl groups in the molecule for hardening protein bodies, z. B. photographic gelatin layers are known. Those known from these patents However, aromatic vinylsulfonyl compounds have the disadvantage that they are comparatively few are water-soluble, which makes their use in photographic systems difficult, that they also have a have a comparatively low hardening effect, as is evident from swelling tests in water, as well as that they lead to a brownish discoloration of the materials to be hardened.

From the German patent specification 872 153 is also the use of divinyl sulfone for hardening of Glue and gelatin layers known, but the technical application of divinyl sulfone fails its harmful physiological properties, e.g. B. its toxicity.

The object of the invention is to provide hardening agents with improved hardening effect even when used containing in comparatively low concentrations for gelatin and / or carboxylated polymers indicate photographic emulsions which are characterized by good water solubility and are non-toxic, the sensitometric. Properties of the emulsions, in particular their sensitivity, are not disadvantageous influence and do not lead to any disadvantageous discoloration of the emulsion layers.

The invention is based on the knowledge that the specified object is particularly advantageous Way can be solved in that compounds of a precisely defined structure with two to six / i-vinylsulfonylethyl groups can be used as curing agents.

The invention thus relates to the use

of compounds with / 3-vinylsulfonylethyl groups the formula

(CH ₂ = CHSO ₂ CH ₂ CH ₂ A -) "Z
where means

A is an oxygen atom or a radical of the formulas Z is a polyvalent organic radical of the valent

speed η and

/ e / η 2 to 6,

RN or R ₂ N · Χ ^Θ

\ \ 5 for hardening gelatin and / or carboxylated poly

photographic emulsions containing merizates.

in which R is an alkyl radical with 1 to 4 carbon atoms. Particularly suitable groups of compounds

and Χ ^{θ is} an acid anion, are as follows:

R ²

CH ₂ = CHSO ₂ CH ₂ CH ₂ -N-R ¹ -N-CH ₂ -CH ₂ SO ₂ CH = CH ₂

R ²

CH ₂ = CHSO ₂ CH ₂ CH ₂ -N-R ¹ -N-CH ₂ CH ₂ SO ₂ CH = CH ₂ · 2X ©

R ³

where means

R ^{1 is} an alkylene chain with 1 to 10 C atoms which may have unsaturated bonds or is interrupted by an arylene or cycloalkylene radical, O or S atoms or amide groups,

R ² and R ^{3 are} alkyl radicals with 1 to 4 carbon atoms, where both radicals R ² with the two nitrogen atoms on which they are attached can form a heterocyclic ring,

X ^e. An acid anion.

Further typical hardening agents which can be used according to the invention are e.g. B.

VO (CH ₂ ) _O OV

VOCH ₂ CH ₂ SO ₂ Ch ₂ CH ₂ OV
VOCH ₂ CH ₂ NHCONHCH ₂ CH ₂ Ov VO (CH ₂ CH ₂ O) _P V

CH, OV

VOCH ₂ C = CCH ₂ OV

(VOCH ₂ ) ₃ CCH ₃

(VOCH ₂ ) ₄ C

OH

VOCH, I CH ₇ OV

VOCH ₂ I CH ₂ OV

(VOCH ₂ CH ₂ ) ₃ N and
(VOCH ₂ CHi) ₃ ³ NR ⁴ ■ X-

CH ₃
VOCH ₂ CH ₂ NV and

40

45

50

55

60 CH ₃ VOCH ₇ CH, -N-V

R ⁴

V —N N-V and

R ⁴ R ⁴

V — NN — V ■ 2X '

R ⁴ R ⁴

V —Ν— (CH ₂ ) _O —Ν — V · 2 C ₇ H ₇ SO ₃ ^e R ⁵ R ⁵

CH ₃ CH ₃

VN-CH ₂ C = CCH ₂ - NV • 2 C ₇ H ₇ SO ₃ Q CH ₃ CH ₃

CH,

CH,

V — Ν — CH ₂ - / "" V-CH ₂ -Ν — V ■ 2Χ ^Θ

R ⁴
where means

R ⁴

V is a ß-vinylsulfonylethyl group of the formula CH ₂ = CHSO ₂ CH ₂ CH ₂ ,

R ⁴ and R ^{5 are} alkyl radicals with 1 to 4 carbon atoms, X is an acid anion, in particular that of p-toluenesulfonate, perchlorate or monomethyl sulfate,

ο = 2 to 10 and

p = 1 to 4.

The hardening agents to be used according to the invention, even in very small amounts, have an effect in Gelatin solutions cause hardening. However, it has been found to be useful to use the hardening agent in quantities from 0.5 to 15 percent by weight, based on the weight of the binder, in particular the gelatin, to use.

The invention achieves that not only emulsions with gelatin as the only binder, but also emulsions in which carboxylated polymers such. B. ethyl acrylate, acrylic acid and Butyl acrylate-acrylic acid copolymers or mixtures thereof, preferably in combination with gelatin, are present as binders, are curable in a particularly effective manner, the curing agents conveniently in the form of aqueous solutions, possibly in combination with antifoggants, are applicable, and the sensitivity of the emulsions not only not affected, but in is usually even increased.

The compounds which can be used according to the invention are in particular for hardening color photographic materials Recording materials suitable. When using these hardeners, as already mentioned, the risk of discoloration is reduced without adverse sensitometric effects occurring, such as this when using known hardening agents, e.g. B. also those of the aldehyde type, for example at Use of formaldehyde and mucochloric acid, often the case. There were neither adverse effects In relation to the color of the dye, the stability of the emulsion can still be determined.

No protection is sought here for the preparation a) to i) described below of curing agents to be used according to the invention.

a) Production of N, N'-bis (2-vinylsulfonyläthvl) -

piperazine

To a solution of 52 parts of divinyisulfone in 100 parts of dry chloroform, which is cooled to 10 ° C a solution of 17.2 parts of anhydrous became dropwise with stirring at 10 to 15 ° C Piperazine added in 100 parts of chloroform. Included A cloudy solution formed which was stirred for 7 hours and then allowed to stand overnight. Subsequently the mass was treated with charcoal and filtered. The filtrate became under reduced Pressure concentrated on a water bath. The crude product was made from ethyl acetate and then three times recrystallized from acetone. A colorless product with a melting point of 125 bis was obtained 126 ° C.

b) Production of N, N'-bis (2-vinylsulfonylethyl) -

piperazine bis (methyl perchlorate)

A solution of 9.7 parts of N, N'-bis (2-vinyisulfonylethyl) piperazine and 16.7 parts of methyl p-toluenesulfonate in 50 parts of acetonitrile was stirred at room temperature for 2 hours and then overnight cooked on the walnut cooler. The solution was treated with charcoal and filtered. The filtrate was concentrated under reduced pressure on a water bath to half its volume and then in Poured ether. An oily precipitate was obtained, which was washed with ether, with a very slight Diluted amount of water and then with a concentrated solution of about 20 parts of sodium perchlorate was treated in 10 parts of water. The compound which crystallized out was filtered off and off recrystallized from a small amount of water. The colorless compound obtained had a melting point from 191 to 192 ° C.

c) Preparation of N, N'-bis (2-vinylsulfonylethyl) -N, N'-dimethyl-2-butene-1,4-diamine-bis (methyl-

p-toluenesulfonate) (A)
and the corresponding bis (methyl fluorate) (B)

The methyl p-toluenesulfonate was in the under b) described manner. Instead of vinylsulfonylpiperazine however, N, N'-bis (2-vinylsulfonylethyl) -N, N'-dimethyl-2-butene-1,4-diamine used. The colorless compound (A) had a melting point of 235 to 236 ° C.

Part of the compound (A) was converted to the fluoborate by adding aqueous fluoboric acid to the Compound (A) was allowed to act. The obtained colorless compound (B) had a melting point of about 288 ° C with decomposition.

d) Preparation of N, N'-bis (2-vinylsulfonylethyl) -

N, N'-dimethylethylenediamine bis (methyl p-toluenesulfonate)

The compound was prepared as described under c), but Ν, Ν'-dimethylethylenediamine was used as the starting compound. The melting point of the compound was 197 ° C.

e) Production of 1,2-bis (2-vinylsulfonyIethoxy) -

ethane

A few drops of a solution which was prepared by reacting sodium with an excess of ethylene glycol were added with stirring to a solution of 6.2 parts of ethylene glycol in 23.6 parts of freshly distilled divinyisulphone stabilized with less than 0.1 percent by weight of hydroquinone. A rapid rise in temperature indicated that a reaction had occurred. A few crystals of hydroquinone were added at a temperature below 35 ° C. After 48 hours, the reaction mixture was neutralized with glacial acetic acid, the volatile constituents were ^{evaporated off in vacuo (0.5 mm Hg, 30 °} C., 5 hours) and the reaction product was filtered off. The reaction product had an average molecular weight of about 293.

fj Production of 1,4-bis (2-vinylsulfonylethoxy) butane

The connection was established like connection e). However, there were 24 parts with divinyisulfone 9 parts of 1,4-butanediol in 20 parts of dry dichloromethane reacted with one another as a reaction medium. It became a liquid reaction product with an average molecular weight of about 227.

g) Preparation of bis [2- (2-vinyIsulfonyläthoxy) -äthyl] sulfone

The compound was prepared according to the procedure described using 25 parts of divinyisulfone and 15.4 parts of bis (2-hydroxyethyl) sulfone in 20 parts of dry dimethyl sulfoxide using made of a sodium ethylate catalyst. It became a liquid reaction product with a average molecular weight of about 325 obtained.

h) Preparation of N, N'-bis [2- (2-vinylsulfonylethoxy) ethyl] urea

25 parts of divinyl sulfone and 14.8 parts of N, N'-bis (2-hydroxyethyl) urea were in 25 parts of dried acetonitrile and 15 parts of dimethyl sulfoxide using a sodium ethylate catalyst implemented together. It became a reaction product having an average molecular weight obtained from about 384.

i) Preparation of l, 14-bis (vinylsulfonyl) -3,6,9,12-tetraoxatetradecane

According to the process described, 25 parts of divinyl sulfone and 15 parts of triethylene glycol were mixed with one another implemented. The reaction product obtained had an average molecular weight of 309

example 1

Samples of curing agents a) to d) became

different proportions of a highly sensitive SiI

J)) berbromidiodide emulsion was added, which had been sensitized panchromatically with 3-carboxymethyl - 5 - [(3 - methyl - 2 - (3 H) - 3 - thiazolinylidene) isopropylidene] rhodanine. that a support area of 1 dm ^{2 contained} an amount of silver halide corresponding to 49.40 mg of silver and 111.94 mg of gelatin.

Samples of the recording materials obtained were then exposed in an Eastman 1 B sensitometer, 5 minutes in a developer of the following composition:

Water (50 ⁰ C) '. 500 cm ³

p-methylaminophenol sulfate 2.5 g

Sodium sulfate, anhydrous 30.0 g

Hydroquinone 2.5 g

Sodium metaborate 10.0 g

Potassium bromide 0.5 g

Made up to 1 liter with water.

developed, fixed, washed and dried. The results obtained are shown in Table I below reproduced:

Table I.

Hardening agents Hardening agents
concentration Relatively sensitive
measured at gamma veil developer % Swelling To wash a density of 0.3 1100 940 (g / mol AgX) over the veil 920 780 820 Fixer 630 Control sample 0.0 100 1.20 0.11 420 540 330 a) 2.4 110 1.22 0.13 1200 450 810 b) 7.2 132 1.12 0.22 1000 390 700 a) 14.4 120 0.98 0.28 690 240 510 Control sample 0.0 100 1.22 0.10 460 560 360 b) 2.4 120 1.22 0.07 - 510 800 b) 7.2 115 1.28 0.05 - 370 660 b) 14.4 107 1.27 0.05 - 270 510 Control sample 0.0 100 1.32 0.15 - - 720 c) 4.8 123 1.28 0.18 - - 750 c) 14.4 112 1.23 0.18 - - 520 c) 4.8 123 1.30 0.18 - - 360 c) 14.4 129 1.30 0.17 - d) 4.8 102 1.30 0.13 - d) 14.4 76 0.93 0.08 -

The "% swelling" given in the table was determined by first determining the thicknesses of dry photographic materials were determined. The materials were then exposed, developed, fixed and washed. The thicknesses were measured again after each treatment stage. the The values given in the table indicate the swelling of the materials after each process stage in%.

Example 2

Samples of hardeners e), f), h) and i) were added to various proportions of a highly sensitive SiI-berbromidiodide emulsion. The emulsion samples were applied to cellulose acetate supports in such a way that an amount of silver halide corresponding to 49.40 mg of silver and 111.94 mg of gelatin were ^{applied to a support area of 1 dm 2.} Samples of the recording materials obtained were exposed in a 1B sensitometer, developed for 5 minutes in a developer of the composition already indicated, fixed, washed and dried. The hardening agents used, their amounts and the test results obtained with fresh film samples are given in Table II below.

209 584/410

Table II

10

Hardening agents Hardening agents
concentration Relative sensitivity,
measured at a density gamma veil % Swelling (g / mol AgX) of 0.3 above the veil Control sample 0.0 100 1.23 0.13 750 e) 2.4 95 1.18 0.12 420 7.2 89 1.13 0.12 270 14.4 85 1.12 0.10 220 Control sample 0.0 100 1.32 0.20 750 f) 14.4 87 1.20 0.14 300 H) 14.4 82 1.18 0.16 230 Control sample 0.0 100 1.25 0.19 760 i) 7.2 105 1.20 0.16 340

Example 3

This example shows the superiority of the hardening agents which can be used according to the invention the hardening agents known from German patent specification 1,100,942.

To carry out these comparative experiments, samples of a photographic emulsion were made according to the invention Usable compound 1,2-bis (2-vinylsulfonylethoxy) ethane, their preparation under e) and their use are described in Example 2 or from the specified German Patent known compound 1,3 - dimethyl-4,6-di (vinylsulfonyl) benzene, its use as a hardening agent is described in the examples of this patent, incorporated the coating compositions obtained applied to the support and the photographic recording materials obtained tested for hardening effect and sensitometric properties. In addition, there was also the water solubility of the hardening agent to be investigated.

The photographic emulsion used was a high sensitivity, negative one Silver bromide iodide emulsion with 3-carboxymethyl-5 - [(3-methyl-2- (3H) -thiazolinylidene) isopropylidene] - rhodanine had been sensitized panchromatically. Since the compounds to be examined are comparable Having molecular weights, they were equal to the emulsion samples, from the one given below Table III incorporated concentration apparent. The resulting emulsion samples were then applied made of cellulose acetate layer support applied in such a way that per square meter of support surface an amount of silver halide corresponding to 4.94 g of silver and 11.2 g of gelatin were omitted. For comparison purposes a hardener-free photographic material was prepared.

The obtained photographic materials were then in a conventional, under The sensitometer known under the name "Eastman 1 B" is exposed, then for 5 minutes in a developer the composition given in Example 1 developed and finally in the usual known Way fixed, washed and dried. The tests indicated were then carried out. The results obtained are shown in Table III below.

Table III

solubility in water Hardening agents
concentration Relatively sensitive gamma veil Swelling Hardening agents (Weight percent, measured at
a density of 0.3 in water based on dry over the veil - Gelatin) 1.35 0.18 (%) Control sample bad 0 100 1.50 0.17 730 A *) bad 1 55 1.43 0.14 580 A *) bad 3 25th 1.53 0.12 440 A *) excellent 6th 22.5 1.42 0.26 340 B **) excellent 1 105 1.38 0.22 340 ■ B **) excellent 3 115 1.27 0.21 460 B **) 6th 110 340

*) A = 1,3-dimethyl-4,6-di (vinyIsulfonyl) benzene, known from German Patent 1,100,942. **) B = 1,2-bis (2-vinylsulfonyIethoxy) ethane, usable according to the invention.

The results show that the 1,2-bis (2-vinylsulfonylethoxy) ethane which can be used according to the invention is used in Use in a concentration of 1 percent by weight based on dry gelatin, an essential It also has a stronger hardening effect than the well-known 1,3-dimethyl-4,6-di (vinylsulfonyl) benzene the sensitometric properties of the cured recording materials are not only not disadvantageous influences, but even improves, whereas the known hardener has a very disadvantageous, has a concentration-dependent influence on the sensitometric properties and that it is in

IO

Water is much more soluble than the known hardening agent.

It was also found that the hardening agent which can be used according to the invention was distinguished by that there is no discoloration, e.g. B. no tanning, the hardened layers caused, as well as the fact that it advantageously no harmful physiological properties, e.g. B. no toxic properties, exhibited.

Example 4

As can be seen in Example 3, when used according to the invention, preferred per se occasionally occur Curing agents of the compound class (II) a clear veil, which leads to an impairment of the finished recording material. It will now be shown how this difficulty arises can be met in a simple manner.

The hardening agent N, N'-bis (2-vinylsulfonylethyl) piperazine which can be prepared by the specified procedure a) was used in the concentrations used in Example 1 in combination with the known Antifoggant, the sodium salt of 4 - hydroxy - 6 - methyl - 1,3,3a, 7 - tetrazaindene, various Samples of a highly sensitive silver bromide iodide emulsion made with 3-carboxymethyl - 5 - [(3 - methyl - 2 - (3 H) - 3 - thiazolinylidene) - isopropylidene] rhodanine panchromatically sensitized was added. The emulsion samples obtained were applied to a cellulose acetate film Layer support applied in such a way that a corresponding 4.95 g of silver per square meter of support surface Amount of silver halide and 11.2 g of gelatin accounted for.

In each case a sample of the recording materials obtained was in the fresh state on a Eastmann-1 B-sensitometer exposed, whereupon it for 5 minutes in the developer specified in Example 1 Composition was developed and then fixed, washed and dried. The sensitometric and swelling tests were then carried out in the manner indicated. The received Results are shown in Table IV below.

Table IV

Hardening agents
concentration
(g / mol AgX) Antifoggant
concentration
(g / mol AgX) Relatively sensitive
measured at
a density of 0.3
over the veil gamma veil developer Ό swelling
Fixer To wash Control sample
2.4
7.2
14.4 0.0
3.0
3.0
3.0 100
110
135
107 1.20
0.97
1.12
0.77 0.11
0.14
0.14
0.15 1100
1100
930
660 560
470
410
330 870
820
670
490

A comparison of the results obtained with the advantageous ways to suppress the

The results obtained in Example 1 indicate that fogging leads to practically no other effects

that common known antifoggants adversely affect the sensitometric properties

hardening agents 40 to be used according to the invention, are usable together and that this in particular

Claims (1)

Patent claims: 1. Use of compounds with / 9-vinylsulfonylethyl groups the formula (CH ₂ = CHSO ₂ CH ₂ CH ₂ A -) "Z (I) wherein means IO A is an oxygen atom or a residue of the formulas