SU268325A1 - HALOGEN-AID SILVER GELATIN - Google Patents

Description

A halide-silver gelatin photographic material is known for the method of bleaching dye with silver, consisting of a substrate and at least one emulsion layer containing various azo dyes. The purpose of the invention is the use of dyes resistant to diffusion and recovered to passenger car decomposition products, characterized by purity of tone and color fastness. This is achieved by using a dye of general formula I as azo dyes in the emulsion layer.

50zN

where B and BI are the benzene or naphthalene residue bound in the 1.4 position with -N-N- and -NH groups;

A, EI and D is the residual residue;

DI and D2 are a monocyclic residue bound through an acyl group to the group-iNH;

SO; lH

VN-N-BrNH i -D

p, r S are integers not more than 2; the sum of r and s is at least 3; the amount of azogroup in the molecule is (g-l) + (s-1) -b (p-1) (g-1) (S-1)

Especially valuable are the linear azo dyes of the formula

rii-n

Jc,

D, -N

L

(BUT,

-HN50зН

(g)

-HN

N N-B-NH l (2-p) (lVl) (S-l)

vG

g-1

N f-BrNH; where B2 is a benzene residue linked to the -N, N- and -NH groups in the 1.4 position;

AO and E3 are the acyl residue of a carboxylic or sulfonic acid, for example, the residue R is -CO- or Rg-SOg, where Ri is hydrogen, alkyl, alkoxy, carboxyalkyl or vinyl, or a substituted benzene, furan, thiophenyl or pyridine residue;

Ra is an alkyl or substituted benzene residue;

DICO-, an aliphatic, aromatic or heterocyclic dicarboxylic acid residue, or a substituted 1,3,5-triazine or pyrimidine residue; and D4 is a benzene residue bound

-N N In addition, D may also be a residue -CO-Fa-SOg-, where F2 is a substituted benzene residue, a methylene or halomethylene residue.

The acyl residues A, EI, AE and 2 are derivatives of anhydrides and, above all, halides of monobasic acylating agents. As galogenoangidridov applied, e.g., acetyl chloride, propionyl chloride, 3-sulfobenzoilhlorid, benzolsulfohlornd, / z-toluenesulfonyl chloride, chloroacetyl chloride, the acid chloride of acrylic acid chloride of phenylacetic acid, p-nitrobenzoyl chloride, Z-trifluoromethylbenzoyl chloride, 4-chlorobenzoyl chloride, furoyl chloride, thionyl chloride, nicotinic acid, chloroformate ethyl ester or chloroformic acid diethylamide.

The acyl residues D and D are derivatives of anhydrides and especially dihalides of dibasic acylating agents.

through a klOiNyl or sulphonyl group with -NH-grunya;

p, g and S are integers not more than 2, or, the sum of r and S is not less than 3;

the amount of azogruy in the molecule is (r-l) + (s-l) + (p-l) (r-l) (s-l);

DI can be CO-F-CO- or -SOa- -FI-SO-2, where F is an alkylene residue with 2-10 carbon atoms, a benzene residue substituted with amino, nitro, sulfonic or sulfamide group, furan, thiophene or pyridine residues, a diphenyl sulfone residue or a —CH — CH- residue,

FI is a substituted benzene residue.

The remainder -DS-N N-D4- corresponds to the formula

SOa

.CO- Og2-.

.:five

-№N

As anhydrides, for example, succinic anhydride, succinic anhydride or glutaric anhydride are used.

However, preferably D, D, -DI-N N-D2-, and -O3-N N-D4- are derivatives of, for example, phosgene, thiophosgene, succinic, glutaric, adipic, pymeric, chloric succinic and fumaric acids; terephthalic acid, isophthalic acid chloride, 5-nitroisophthalic acid; thiophene-2,5-dicarboxylic acid dichlorides, pyridine-2,6-dicarboxylic acid, azobenzene-3,3-dicarboxylic acid, 4,4-dichloroisobenzene - 3,3-dicarboxylic acid, 2,2-dimethylazobenzene-5,5 - dicarboxylic acid, 4-methoxyazobenzene-3,4-dicarboxylic acid, 3,3-dichloroisobenzene-4,4-dicarboxylic acid, azobenzene-4,4-disulfonic acid, diphenylsulfone- (1, G) -4,4-dicarboxylic acid ; benzene-1,3-disulfonyl chloride; diphenylmethane-4,4-dicarboxylic acid dichlorides, diphenylsulfide 4,4-dicarboxylic acid; cyanuric chloride; 4,6-dichloropyrimidine; 1-fevil-3,5-dichloro-with lg-triazine or 1-methoxy-3,5-dichloro-lh-triazine.

The residues BI and Br are the azo-constituent residues, for example the following: aminobenzene, 1-amino-2-methylbosol, 1-amino2, 5-dimethylbenzene, 1-amino-2-methoxybenzene, 1-amino-2-p-oxoxy-toxy- 5-methylbenzene, la-2-p-hydroxyethoxy-5-chlorobenzene, 1-amino-2-rmethoxyethoxy-5-methyl benzene, 1-amino-3-acetylaminobenzene, 1-amino-3-isobutyrylaminobenzene, 1-amino-3 -acetylamino-6-methylbenzene, 1-amino-2-acetylamino-5-methoxybenzene, 1-amino-2- | methoxy-5-methylbenzene, 1-amine -2-chloro-5-methoxybenzene, 1-amino-2-methoxy-5 chlorobenzene, 1-amino-3-methoxybenzene, 1-amino-2, 5-diacetylaminobenz ol, 3-aminophenylmochesin, 3-amino-4-methylphenoxyacetic acid, 1-a1 Minonaphthalene-5-sulfonic acid or 1-aminonaphthalene.

Acylamino dyes of formulas I and II can be obtained by various methods.

Linear azo dyes of formula I can be used in photographic materials for the method of bleaching an image dye with silver. So usually get photographic materials containing on the substrate at least one layer with the dye of formula I.

These dyes can be used in multilayer materials that on the substrate contain a layer dyed with blue-green dye and sensitive to red light, a second one dyed with magenta dye and sensitive to green light and a third layer colored with yellow dye sensitive to blue light. You can also enter the dye of formula I in the auxiliary layer or adjacent to the photosensitive layer. Dyes have different spectral characteristics.

Yellow dyes have a good spectral absorption curve, which makes it possible to combine these dyes with a magenta or blue-green dye. In this case, a neutral gray tone is achieved in the layer with good density.

In addition, the dyes of the formula I are resistant to oxidizing agents used in photographic baths for the oxidation of silver.

Example 1. 154 parts of 6-acetylamino-2-aminonaphthalene-4, 8-disulfonic acids obtained by acylation of 6-aminonaphthalene-4,8-disulfonic acids, nitration and reduction of nitro groups with sodium sulfide, are dissolved in 2500 parts of water containing 500 hours ice. Then, 80 parts of 30% hydrochloric acid and 80 parts of 4N are added at 0 ° C. sodium nitrite solution, and the diazonium salt precipitates as a white emulsion. After vigorous stirring for 2 hours. excess nitrite is removed by sulfamic acid.

57 parts of 3-amino-4nmethoxy-1-methylbenzene are dissolved in 3000 parts of water and 30 parts of 30% hydrochloric acid at 55 ° C, then cooled to 0 ° C. The azo-component is then added to the diazo compound. After adding the required amount of potassium acetate buffer, the combination begins. The reaction mass is stirred overnight and filtered. The filter cake is washed with 200 hours. 2 n. a solution of soda and 1000 hours of water. After pouring in, another 3,500 parts of water are heated to 65 ° C. The dye solution is filtered and 200 parts of sodium chloride are added, then cooled to 20 ° C and filtered. The filter cake is washed with 4000 parts of acetone and dried at. 141 parts of an orange-red powder are obtained.

6 parts of the azoamine obtained above are dissolved in 200 parts of water with 6 parts of crystalline sodium tetraborate. 1 part of thiofenedicarboxylic acid dichloride is heated to 120 parts of acetone and added to the azoamine solution, then stirred for 20 hours. at room temperature and at 60 ° C poured 20 hours 7 n. acetate solution calp. The precipitated dye is filtered off, the precipitate is dissolved in 1500 parts of water at 90 ° C, and after a clear filtrate is obtained, 250 hours are added. potassium acetate solution and 100 parts of methanol. The precipitate formed is filtered off and washed with methanol. After drying, 4.8 parts of dye are obtained.

The same dye is obtained by combining 2-nitro-6-aminaphthalene 4,8-disulfonic acid with 3-amino-4-methoxy-1-methylbenzene, followed by the interaction of thiofendicarboxylic acid dichloromethane with an amine,

reduction and acylation of both the resulting nitro groups.

In both cases, the calpevic salt of dye N ° 1 is obtained (see Table 1). Other dyes are similarly isolated.

are given in table. 1. Dye number 2 is obtained by treatment with cyanuric chloride according to example 8.

Example 2. 1 part of azoamip, obtained by combining 6-acetylamino-2-aminonaphthalene4, 8-disulfonic acids with 2-acetylamino-5-methoxyaniline, is heated in 5 parts of N-methylpyrrolidone and 0.5 parts of pyridine and then filtered. Next, 0.2 parts of terephthalic acid dichloride are added at 50 ° C and at

this temperature is stirred for 30 minutes, then cooled to room temperature and the dye is precipitated for 5 parts of a 20% potassium acetate solution in alcohol and 5 parts of methanol. The precipitate is filtered, boiled in

methanol and after filtration, washed with methanol. Get 0.3 hours of the potassium salt of the dye jYe 12 (see tab. 1).

When 1. 3. 10 parts of azoamine prepared by combining 6-acetylampno-2-aminonaphthalene 4, 8-dpsulfonic acid with 3-amiNO-4-methoxy-1 methylbenzene is dissolved with 5 parts of crystalline sodium tetraborate in 500 parts of water, then 10 including 30% solution of sodium hydroxide solution to RP 10, heated to 50 ° C and

dyes of the general formula

-I- --SP, CJ

15

la The precipitate formed is filtered off, washed with methanol, and the residue is dissolved in 500 parts of water at 50 ° C. The dye is planted again, adding 30 h. 7 n. of potassium acetate solution and 100 parts of methanol, then filtered, the precipitate is mixed with 400 parts of methanol, esh, filtered and dried under vacuum at 60 ° C. Hi NH-C with COHFs ° The properties of this dye are the same as dye No. 1, but during the second condensation after 24 hours of reaction at 50 ° C, they are heated for another 2 hours at 70 ° C. Table 5 Example 9. 0.7 vol. including 1% aqueous dye No. 1 solution (see Table 1) was added to 3.3 vol. including 6% aqueous solution of gelatin at 40 ° C. Then add 3.3 vol. including bromo-silver emulsion in gelatin at 40 ° C, and 1-2 vol. including aqueous solution of saponin and tanning agent, for example dimethylol urea. This mixture is poured onto a 13x18 cm glass plate and dried. Then it is exposed behind a step wedge, a silver image is developed in a developer containing 1-methylamino-4-hydroxybenzenesulfate and hydroquinone, and then fixed.

Table 1

268325

sixteen

Receive 3.5 hours in the form of a red-brown powder of potassium salt dye No. 1 (see tab. 5).

If 2,4-dichloro-6-methoxy-1-3,5-triazine is used instead of trichlorotriazine, then dye No. 2 is obtained, which is given in table. 5, of the formula 20 25 30 35 40 45 - / N N- fVNHCOCHj OSYGNGON In a bath containing 1000 vol. hours from 30 to 100 vol. including 32% hydrochloric acid, from 40 to 120 parts of potassium bromide, from 30 to 50 parts of thiourea and from 0.001 to 0.01 parts of 2-amino-3-oxyphenazine; bleach the dye of the image depending on the amount of silver. After intermediate washing with water, excess silver is removed in a bath containing 1000 vol. including 100 parts of sodium chloride, 100 parts of crystalline copper sulphate and 50 vol. including 37% hydrochloric acid. The remaining amount is fixed. A yellow wedge is obtained, which: in relation to the original silver wedge, is a reverse image and is completely bleached compared to the original highest density of silver. Such a yellow image is achieved in the case of a multicolor material. Similar results are obtained if, instead of dye N ° 1, other dyes are used that are listed in Table. 1-5. Example 10. The following layers are successively applied to an adhesive film provided with an adhesive layer: a) a red light-sensitive bromide-silver emulsion in gelatin containing a blue-green dye of the formula

d) bromide-silver emulsion sensitive to blue light in gelatin, containing dye No. 3 (see Table 1).

Gelatin layers may contain additives, for example wetting, tanning agents or stabilizers. Each layer contains 0.5 g of the corresponding dye and 1 -1.2 g of silver contained in the corresponding amount of silver bromide per 1 m of film. The film is exposed through a color slide with red, green and blue light.

A copy is developed as follows:

a) 6 minutes in a bath containing in 1 l of water 50 g of anhydrous sodium sulfite, 0.2 g of 1-phenyl-3-nirazolidone, 6 g of hydroquinone, 35 g

(Lg)

-HN- /

50zN

; EG)

SOjH where B and BI is a benzene or naphthalene residue, linked in the 1.4 position with the N, N- and -NH groups; AI, EI and D - acyl residue; 45 DI and D2 - monocyclic residue, st Compiled by E. A. Ramzova Editor LK UshakovTehred V.I. Rybakov Order 3537/1 Circulation 480 TsNIIPI Committee for Inventions and Discoveries: at

anhydrous soda, 4 g of potassium bromide and 0.3 g of benztriazole;

b) washed with water for 5 minutes;

c) 6 minutes are fixed in a solution of 200 g of sodium thiosulfate (crystalline) and 20 g

potassium metabisulphite in 1 liter of water.

Subject invention

A silver halide gelatin photographic material for the silver dye bleaching process, consisting of a substrate and at least one emulsion layer containing an azo dye, characterized in that a dye of the general formula is used as azo dye.

N N-B-NH- (2-p) (r-l) (s-i) BI

r-i

-N N-BI- JH - D.

(p-) i-j) frs-l

Proofreader O. I. Usovanova through an acyl group with the group —NH; p, z and s are integers not more than 2; the sum of / - and S is at least 3; the number of azo groups in the molecule is (g-1) + (5-) + (p-I) (g-1) (s-I). Subscription to the USSR Council of Ministers

Date: 27/09/2001

Number of pages: 2

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