SU1657505A1 - Derivatives of 1-(morpholinocarbonyl)- or 1-(morpholinocarbonyloxy) -pyridinium chloride as tanning agents for gelatine-containing layers of silver-halide photographic materials - Google Patents

Abstract

The invention relates to heterocyclic compounds, in particular the invention relates to new chemical compounds, namely, derivatives of 1- (morpholinocarbonyl) - or 1- (morpholinocarbonyloxy) -pyridinium chloride of the formula O R. W II of these derivatives of 1- (morpholinocarboxylic - nyl) - or 1- (morpholinocarbonyloxy) - pyridium chloride, f-type o R. / & II © (. 0 (/ - С- (0); ГЦ -РГС1С У- Rl where or 1 IR | is methyl, vinyl, or R (and R is each - H and RЈ is vinyl, which can be used as tanning agents for desirable layers of halogen-silver photographic materials. The purpose of the invention is to find compounds having useful properties. The preparation is carried out by the reaction of morpholinecarboxylic acid chloride with 2-methyl-5-vinyl pyridine, 4-vinyl pyridine or their N-oxides in methylene chloride environment. Table 1 where p; 0 or 1; methyl; hydrogen; vinyl or R | and RJ, each is hydrogen; vinyl, Ri is R2R3S (L o el vj SL O SL possesses properties of gelatin that can be used as tanning agents for gelatin-containing layers of halogen-silver photographic materials.

Description

The aim of the invention is to obtain new compounds based on 2-methyl-5-vinylpyridine, 4-vinylpyridine or their N-oxides, which provide a photographic material with increased strength and high temperature distortion while maintaining photographic properties during storage.

Example 1. Preparation of 1- (mor folinocarbonyl) -2-methyl-5-vinylpy-, ridinium chloride.

To a solution of 0.02 mol of 2-methyl-5-α-vinylpyridine in 20 ml of methylene chloride, 0.02 mol of morpholine-M-carboxylic acid chloride was added while cooling to 0 ° C. After stopping the dropping, the mixture is stirred for 1 hour at room temperature. The resulting crystals are washed with acetone and ether, dried over the melting point of the target product 110-112 ° C, yield 84%.

Found,%: C 57.97, 58.02; H 6.12, 6.26; N 10.17, 10.27; C1 12.96, 13.07.

C ,, H, 7NeCl04

Calculated,%: C 58,12; H 6.37; N 10.42; C1 13.19.

Example 2. Preparation of 1- (morpholinocarbonyl) -4-vinyl pyridinium chloride.

ten

15

6575054

EXAMPLE 4. Preparation of 1- (morpholino carbonyloxy) -4-vinyl pyridinium chloride.

, Carried out analogously to example 1

using 4-vinylpyridine N-oxide instead of 2-methyl-5-vinylpyridine. Get the crystalline product from the t. Pcs. 141-142 ° C, yield 87%.

Found,%: C 53.75, 53.98; H 4.62, 4.80; N 10.29, 10.40; C1 13.01, 13.14.

CttH, 5N4ClO

Calculated,%: C 54.01, H 4.86; N 10.42; C1 13.19.

The structure of all the compounds obtained was confirmed by IR and NMR spectra.

The study of the oak effect of the proposed compounds is carried out as follows.

Irrigation additives are introduced into the molten photographic emulsion: stabil ор bis (1-phenyltetrazolyl-25 -5) disulfide, wetting agent CB-133 кали dicalium salt of the polycondensation product 1 mol of 2-ethylhexynyl succinic acid with 2 mol of 2-ethylhexyl succinic anhydride , wetting agent CI-1147 disodium salt of diethyl ester N-U-decyloxy-propyl-H- (| 3-carboxy-A-sulfopropionyl) ac vapor of aga ny acid, polysaccharide, dec. countries, glycerin, as

20

thirty

Carried out analogously to example 1 35 of the Dubitel compound of the proposed

using 4-vinylpyridine instead of 2-methyl-5-vinylpyridine.

Get the crystalline product with so pl. 127-128 ° C, yield 87%.

Found,%: C 56.17, 56.32; C 6.23, 6.32; N 10.87, 10.94; C1 13.70, 13.84.

C, zH, 5NtCl04

Calculated,%: C 56.36; H 6.36; N 10.95; C1 13.86.

Example 3. Preparation of 1- (morpholinocarbonyloxy) -2-methyl-5-vinylpyridinium chloride.

Carried out as in Example 1, using its N-oxide instead of 2-methyl-5-vinylpyridine. Get the crystalline product with so pl. 132-133 ° C. Yield 92%.

Found,%: C 54.89, 55.02; H 5.50, 5.62; N 9.70, 9.85; 0112.70, 12.82.

,

Calculated,%: C 55.03; H 5.69; N 9.90; C1 12.84.

40

formulas.

The resulting emulsion is applied onto a TAC base, a protective layer is applied over the emulsion layer, including gelatin, wetting agent CB-102 sodium salt of di-2-ethylhexyl sulfonic acid ester, hair dryer glycerol, potassium nitrate, phenyl 45 -5-mercaptotetrazole, triethanolamine and as a tanning agent - the compound of the proposed formula. Tanning agents in an amount of 0.2-1.8 g / kg emulsion and in an amount of 0.1-1.5 g / kg of the protective layer composition.

Photographic material after drying and expelling for 24 hours at a moisture content of Cf - 50–65% is tested according to S0) geM, De, strength on the swelled emulsion layer (g), deformation temperature (° С), swelling (g / cm). The tests are carried out in archival storage after 2, 10 and 30 days.

50

5 dubitel connection proposed

0

formulas.

The resulting emulsion was applied onto a TAC-base, and a protective layer was applied over the emulsion layer, including gelatin, wetting agent CB-102 sodium salt of di-2-ethylhexyl sulfonic acid ester, phenol, glycerin, potassium nitrate, phenyl-5 -5-mercaptotetrazole , triethanolamine and as a tanning agent - a compound of the proposed formula. Tanning agents are introduced in the amount of 0.2-1.8 g / kg of the emulsion and in the amount of 0.1-1.5 g / kg of the composition of the protective layer.

Photographic material after drying and aging for 24 hours at a Cf humidity of 50-65% is tested in terms of S0) geM, De, strength of the swollen emulsion layer (g), deformation temperature (° C), swelling (g / cm ). The tests are carried out in the process of archival storage after 2, 10 and 30 days.

0

Example 5. 100 g of a standard halogen-silver emulsion containing 15% gelatin, melt at 40 ° C, are prepared for irrigation on a substrate, for which, during mixing, the irrigation additives are introduced, g / kg emulsion:

F-2 stabilizer

(4% aqueous solution) 0.6-0,)

Poliglkzhin (15%

water solution) 35.0-47.5

Glycerin (50%

water solution) 0.5-1.5

Wetting SV-133

(4% water

solution) 0,28-0,68

Wetting SV-1147

(4% water

solution) 0.12-0.72

Wetting F-1

(20% water

solution) 0.5-1.0

The tanning agent is a compound of the formula (I (p O, R is methyl; R is hydrogen and KS vinyl, obtained according to example O,

5% water

solution0,2

After thermostating and standing for 3 to 5 hours, the emulsion is poured onto a triacetate substrate. At the same time, a protective layer of the composition, g / kg of the composition of the protective layer, is applied over the chilled emulsion layer:

Gelatin 20-40

Glycerin (50%

water solution) 5.0-10.0

Phenol (50%

water solution) 2,5-7,5

Potassium nitrate

(20% water

solution) 4.0-10.0

Phenyl-5-mercaptoterazole (0.01%

alcohol solution) 0.05-0.15

Triethanolamine

(99% aqueous solution) 5.0-15.0

Wetting SV-102

(4% water

solution) 0.6-1.2

The tanning agent of the formula (I)

(Rj - CH RZ. H,

R 3 -). Oh 1

Photographic material after drying and holding for 24 hours at 20 + 2 ° С and humidity of the CP 50-65% is tested according to the indicators SgggP-D,. ,, strength

swollen emulsion layer (g), deformation temperature (° С), swelling capacity (g / cm).

The test results are shown in the table.

The tests were carried out during archival storage after 2.10 and 30 days.

Examples 6-16. Similar to Q example 5. The tannins used in each example and their quantities are listed in the table.

Example 17 (comparative). Analogously to Example 5, as a dub-5 body, take hexagndrotriacryloyl-triazine-1,3,5 (Du-801) (g / kg emulsion, 2.5% aqueous alcohol solution) 0.325, and for insertion into a protective layer ( g / kg of the composition of the protective layer, 0 2.5% water-sprint solution)

0.11.

Example 18 (by a known method). Analogously to example 5. As a tanning agent, 1- (mor-5-folinocarbonyloxy) -3-glycoline chloride (g / kg emulsion, 5% aqueous solution) is taken 0.3, and for introduction into the backing layer (g / kg layer, 5% aqueous solution) 0.2).

An analysis of the data in the table suggests that, when using emulsion and protective layers of black and white photographic material of compounds of formula (I) as tanning agents, the samples of the photographic material have high physicomechanical properties. The temperature of the deformation, the strength of the thin layers and the swelling properties are higher than those of the known tanning agents. At the same time, there is no deterioration of photographic properties in the process of monthly 5 archival storage.

The introduction of compounds of formula (I) in an amount less than optimal does not improve physical and mechanical properties, and the introduction in quantities exceeding the optimal 0 leads to a noticeable deterioration of photographic parameters (growth of the veil, a drop in sensitivity).

Claims (1)

5 claims Derivatives of 1- (morpholinocarbonyl) or 1- (morpholinocarbonyloxy) - pyridium chloride of the formula ABOUT oQN-c otkj-rrcf ten where n is 0 or 1; K is methyl; K2 is hydrogen; RJ - VINIL or R, and R3 each is hydrogen; Kg - vinyl ,, as tanning agents for gelatin-containing layers of halogen-silver photographic materials. Hexahydrotriacryloyl-simm-triazine. 1- (Morpholinocaroneyl) -3-picolinium chloride. 1657505 10 Continuation of the table