SU1761747A1 - Benzylcarbamoyl-n@@@-sec-aminocaramates as tanning agents for gelatin-containing layers of halogen-silver photographic materials - Google Patents

Abstract

Usage: tanning agent for gelatin-containing halogen-silver photographic materials. Essence: benzylcarbamoyl-M -v-aminocarbamates of the formula SbNb CH20-C (0) -N- (H) -C (0) -NR2, where R2 - C2Hs or NRa - together mean a morpholine or piperidine residue. Reagent 1: sec-amino-carboxylic acid halide. Reagent 2: carbamic acid benzyl ester. The process is carried out with cooling to 5 ° C in a solvent. 1 tab.

Description

This invention relates to new chemical compounds, in particular to benzyl-carbamoyl-M-sec-amino-carbamate of formula I

CfiH5CH20-C-N-C-NR7 L 5 Ln, 1 (Z

IT

where R is C2H5 or NR2 together mean a residue of morpholine or piperidine, which can be used as tanning agents for gelatin-containing layers of halogen-rib photographic materials.

Known organic products based on amides of dicarboxylic acids of the formula

CH2 0-C-N-OR 2, OH

where R, CH2 is CH2Hal (1). However, photographic materials hardened by these compounds have relatively low values of strength and temperature of deformation of the swollen gelatin layers (strength - 250-300 g, T def. ° C - 60-70).

Acylurea derivatives are known which are used as tanning agents for gelatin-containing photosensitive layers (2). Photographic materials hardened by these compounds have insufficiently high physicomechanical indices.

In addition, amides of the formula: CICH2CH2C (0) 2NH (3) are known. The disadvantages of using these compounds as a tanning agent are relatively high swelling and low strength of the swollen gelatinous layers of photographic materials.

The aim of the invention is to find new benzylcarbamoyl-L-sec-amino-carbamates of formula (I), which provide photographic materials with increased strength and deformation temperature while maintaining photographic properties during storage.

WITH

with

Vj o

XI

NJ

This is achieved by introducing benzylcarbamoyl-M-sec-amino-carbamates of the general formula 1 as an tanning agent into the emulsion and protective gelatin-containing layers of a halogen-silver photographic material.

 Compounds of formula 1 are prepared in a known manner by reacting a sec-amino-carboxylic acid nhydride halogen with carbamic acid benzyl ester prepared according to method (4).

The following is an example of the preparation of compounds of formula 1.

Example 1. To a solution of 12 g of N2CO3 in 120 ml of desalted water, 0.1 M (15 g) of benzyl ester of carbamic acid is added and 0.1 M (15 g) of morpholinecarboxylic acid chloride is added dropwise with cooling to + 5 ° C in 120 ml benzene. After the addition is complete, the mixture is stirred for 30 minutes at room temperature, the organic layer is washed with water, dried and benzylcarbamoyl N-morpholino carbamate is separated. A white crystalline product is obtained with an mp. 108-110 ° C, yield 85%, (20.4 g).

Found,%: C 58.86. 58.78; H 5.90; 6.05; N 10.54; 10.62.

Benzylcarbamoyl-M-morpholinocarbamate C1 HN | b # 04.

Calculated,%: C 59.08; H 6.10; N 10.60.

Example 2. It differs from Example 1 in that instead of morpholine carboxylic acid chloride, piperidine carboxylic acid chloride is taken in the same weight ratios. Get a crystalline product with T. pl, 132-134 ° C, yield 78% (20.4 g).

Found,%: C 63.80, 64.01; H 6.90, 6.95; N 10.40. 10.55.

Benzylcarbamoyl-M-piperidinocarbat CuHi8N203.

Calculated,%: C 64,10; H 6.91: N 10.67.

Example 3. It differs from Example 2 in that instead of morpholine carboxylic acid chloride, diethylaminocarboxylic acid chloride is taken in the same weight ratios. Get a crystalline product with So pl. 86-88 ° C, yield 81% (18.7 g).

Found,%: C 61.95, 62.15; H 6.92,7.16; N10,95,11,01.

Benzylcarbamoyl-M-diethylaminocarbamate C1 H 1 B NO.

Calculated,%: C 62.55; H 7.26; N 11.22.

The study of the oak effect of compounds of general formula 1 was carried out as follows.

Irrigation additives are introduced into the molten photographic emulsion: stabilizer F-2 - bis- (1-phenyl-tetrazolyl-5) -disulfide, wetting agent CB-133 - dipotassium salt of the polycondensation product 1 mol of 2-ethylhexynyl succinic acid octaglyceride with 2 mol of 2-ethylhexyl succinic anhydride, the wetting agent CB-1147-disodium salt of diethyl ether N- y -decyloxypropyl-M- ((3-carboxy- / - sulfopropyl)) aspartic acid,

polysaccharide-dextran, glycerin, see F-1 emulsifier - Trilon-B, and as tanning agent

- compounds of general formula 1.

The resulting emulsion is applied onto a cellulose triacetate base, a protective layer is applied over the emulsion layer,

including gelatin, wetting agent SV-102

sodium di-2-ethylhexyl ester of sulfo succinic acid, phenol, glycerin, potassium nitrate,

phenyl-5-mercaptoterazole, triethanolamine and, as a tanning agent, a compound of general formula 1.

Tanning agents are introduced in the amount of 0.4-2.0 g / kg of the emulsion and in the amount of 0.2-1.8 g / kg

the composition of the protective layer.

Photo material after drying and aging

within 24 hours at 20 ± 2 ° С and humidity p

50-65% tested by indicators

So.ssP, Until, the strength of the swollen emulsion layer (G), deformation temperature (° C), swelling (g / cm). Tests on photo properties are performed in archival storage after 2, 10 and 30 days.

The examples below illustrate the use of compounds of general formula 1 as tanning agents for black and white halogen-silver photographic material.

Example 4. 100 g of a standard halogen-silver emulsion made according to Specifications 6-17-909-77, containing 15% gelatin, are melted at 40 ° C, prepared for irrigation on a substrate, for which, during mixing, the irrigation additives are introduced into it (g / kg emulsion):

- stabilizer

F-2, 4% aqueous solution of 0.6-0.7

-polyglukin, 15%

water solution 35,0-47,0

- glycerin, 50%

water solution 0,5-1,5

- wetter SV-133, 4%

water solution 0,28-0,66

- wetting agent SV-1147, 4%

water solution 0.12-0.72

-cm smitel

F-1, 20% water

solution 0,5-1,0

-dubitel formula 1,

5% aqueous solution0.4

After thermostating and standing for 3 to 5 hours, the emulsion is poured onto the TAC-base. At the same time, a protective layer of the composition (g / kg of the composition of the protective layer) is applied over the churned emulsion layer:

- gelatin 20-40

- glycerin, 50%

water solution 5,0-10,0

Phenol, 50%

water solution 2,5-7,5

- potassium nitrate,

20% aqueous solution 4.0-10.0

-phenyl-5-mercaptotetrazol, 0.01%

alcoholic pp 0.05-0.15

triethanolamine

99% aqueous solution 5.0-15.0

- wetter SV-102,4%

aqueous solution of 0.6-1.2

 dubitel formula

1a, 5% aqueous solution

0.2

Photographic material after drying and keeping for 24 hours at 20 + 2 ° C and humidity (p 50-65% is tested according to indicators So.ssP, Dc, strength of the swollen emulsion layer (g), deformation temperature (° C), swelling ( g / cm).

The test results are shown in the table. Photovoltaic tests were conducted in archival storage through the 2nd, 10th and 3th day.

Examples 5-11. Also, as in Example 4, the emulsion, irrigation additives and protective layer components are taken in the same ratios, the difference is that the tanning agents of formula 1 are taken for introduction into the emulsion layer (g / kg emulsion, 5% aqueous solution) and the composition of the protective layer (g / kg of the composition, 5% aqueous solution) in the amounts indicated in the table. Sun sequence of operations as in example 4.

Example 12. Comparative TU 6-17-909-77. As in Example 4, the emulsion, irrigation additives and protective layer components are taken in the same ratios, the difference is that hexahydrotriacryloyltriazine-1,3,5 (Du-801) is taken as tanning agent (g / kg of emulsion, 2.5% water-alcohol solution) 0.325, and for introduction into the protective layer (g / kg of the composition of the protective layer, 2.5% aqueous-alcoholic solution) - 0.11. Sun sequence of operations

as in example 4. The results are shown in the table.

Example 13. In the same way as in example 4, the emulsion, additives, irrigation and components

the protective layer is taken in the same ratios, the difference is that they take di- (3-LOR-ethyl en-boxbox) -amin (g / kg emulsion, 5% aqueous solution) as a tanning agent - 04, and for introduction into protective

layer (g / kg of the composition of the protective layer, 5% aqueous solution) - 0.2. The test results are shown in the table.

Example 14. The tests are the same as in example 4, the emulsion additives irrigation

and the components of the protective layer are taken in the same ratios, the difference is that penta-isopropoxymethyl-carbamyl urea (g / kg emulsion, 5% water-alcohol solution) is taken as 0.8, and

for introduction into the protective layer (g / kg of the composition, 5% aqueous alcohol solution) - 0.4.

The test results are shown in the table.

The analysis of the data in the table suggests that using emulsion and protective layers of benzylcarbamoyl-M-sec-amino-carbamates of general formula 1 as tanning agents allows obtaining samples of photographic material with improved physicomechanical properties. The temperature of the deformation, the strength of the swollen layers and the swelling capacity are higher than those of the prototype. At the same time, no deterioration of photographic indicators is observed in the course of monthly archival storage.

The introduction of compounds of formula 1 in quantities below the optimum does not give improved physical and mechanical properties, and the introduction in quantities exceeding the optimal ones leads to a noticeable deterioration of photographic indicators (growth

Claims (1)

veils, falling sensitivity). Claims of the Invention Benzylcarbamoyl-M-V-aminocarb mats of the general formula 50 sdn, cH2o-c-j-c-NR2 I it where R2 - (C2Hs) 2 or NR2 together means a morpholine or piperidine residue, as tanning agents for gelatin-containing layers of halogen-silver photographic materials. 14 0.8 0.4 ; 2 / 560 560 560 0.04 0.04 0.04 420 95 4.0