SU467671A1 - Method of sensitization of panchromatic layers of cine and photo materials - Google Patents

Description

one

The invention relates to the sensitization of halide-silver emulsions with high sensitivity to the red part of the spectrum.

It is known that cationic anionic dyes containing chromophores in the cationic and anionic parts of the dye molecule have a somewhat greater sensitizing effect than similar compounds with a chromophore only in the anionic part of the molecules.

For example, for the day region of the spectrum, 3,3-dialkyl-9-ethyl-4,5,4,5-dibenzothiocarbocyanine is used to sensitize the layers of a variety of grades of black and white panchromatic photographic materials or color panchromatic layers of multi-layer color film photographic materials with internal masking with activators or 2- (3carbidopropyloxyamylthiazolindanthion-2OH-4-or-den-5) -3-n-butyl-5 - (3-ethyl-4-phenylthiazolinylidene-2-ethylidene) -inazolidino-4.

A significantly greater effect of increasing the sensitivity of halide-silver photomaterials can be achieved with the use of cation-anion dyes of building I and II.

 o- itsSg- Cil-J j,

vT

(Sn Ul

fiij; n

zln

$ 0h

sz

2l

((1H UH

N

N -R. R

A is alkyl or aryl;

e

B - alkoxy and others;

BI - benzo, tieno-3,2 and thieno-2, 3;

p -2-4;

Z - residues of 5- or 5,6-alkyl, alkoxy, aryl-substituted benzotnazoles, benzoselenozol, unsubstituted in hetero-residues, and also 5-alkoxy-substituted naphtho- (1,2-с) thiazoles, thieno (3,2-е) and thieno ( 2,3-e) benzothiazoles and others;

Zz - thiazoline, benzthiazole,

Zi and benzimidazole, quinoline and

others;

m -O-1 ...;

AI - H, alkyl,

R - alkyl, alkoxy, etc. With the introduction of dyes I, II, both in highly sensitive negative ammonium bromodocerebral and in various ammonia-free emulsions, photographic layers are obtained that in sensitivity greatly exceed the corresponding layers containing similar dyes with a chromophore only in the anionic part molecules, and in some cases also layers, containing the most effective or known sensitizers used for a given spectral region.

III

HjC - V --- Y18Ns5 g (eE. CON- (j-CONH (ljeH3j, j-CONHCi7H3s, Ci7H35;

And others, VN, NN-Ar or (30 in a case P).

The photosensitivity of the layers, sensitized dyes of structure I, II and containing these components, does not change during the standing of the emulsion at the refund before watering.

Thus, emulsions sensitized with dyes of buildings I, II can be used to obtain highly sensitive black-and-white and red-sensitive layers of colored multilayer films, including with internal masking.

The proposed dyes are introduced into the emulsion before being irrigated in an alcohol solution, and their optimal concentrations are 128-10-1-192-10-e mol of the dye per 1 mol of silver halide.

The components are introduced in the amount of 10-12 g per 1 liter of the emulsion in the form of aqueous or hydroalcoholic alkaline solutions.

Example 1. In 1 liter of molten ammonia bromide-silver emulsion, 225 ml of a 0.026% solution of the triethylamine salt of 3,3-di-7-sulfopropyl-9-ethyl-6methoxy-4, 5,4,5 - dibenzothiocarbocyanine betaine are introduced. After standing for 30 minutes in a thermostat at 40 ° C, glass plates were poured with a sensitized emulsion (5 ml of emulsion on a 9X X12 cm plate) (experiment 1 in the table). The second portion of the sensitized emulsion after the application of the dyes of building I, II makes it possible to obtain highly sensitive panchromatic cinematographic materials with a maximum sensitization at 670-695 and a border of sensing zone 690-710.

The sensitizing effect of these dyes remains practically unchanged or slightly increased in the presence of conventional and masking non-diffusing components, in particular, amides of 1,2-hydroxy naphthoic acid or pyrazolone-5 structure III and IV, respectively.

Ojh

IV

2-methyl-octadecylamino-5-sulfoanilide-1-hydroxy-2-naphthoic acid (component 1) or the mixture of the latter with the corresponding aryl-producing compound (component 2, run 1a) is introduced for 30 minutes. A photographic material is obtained, sensitized to the zone of the spectrum of 550-700 with a maximum at 680 pm.

Example 2. Analogously to the previous example, 225 ml of a 0.021% solution of the salt of 3,3-di-7-sulfopropyl-9-ethyl-6-methoxy-4,5,4,5-dibepzothiacarbocyanine betaine and 3 were introduced into a 1 liter emulsion; 1-diethyl-6-methyl-5-methoxythiachino-2-monometinine and component 1, as described in example 1 (experiment 2 and 2a).

A photographic material is obtained more than 3 times more sensitive than in the previous example, sensible to the zone of the spectrum of 500-710 nm with a maximum at 680 nm.

Example 3. Analogously to the previous example, 225 ml of a 0.027% solution of the triethylamine salt of 3,3-di-7-sulfopropyl-9-ethyl-6,6-dimethoxy-4, 5-benzo-4,5 was introduced into a 1 l emulsion. - (thieno-2,3) thiacarbocyanine betaine and in the second portion of the emulsion, the component 1 is introduced (experiment 3 and Za). Get insensitive photographic material.

Example 4. Analogously to the previous example, 225 ml of a 0.020% solution of the salt of 3,3-di-7-sulfopronyl-9-ethyl-6, 6 - dimethoxy-4,5 - benzo4, 5- (thieno -2.3) thiacarbocyanine betaine and 1, G-diethyl-2,2-quinocyanine (test 4 and 4a).

A highly sensitive photographic material is obtained, sensible to the spectral range of 500-710 nm with a maximum sensitization of 690 nm.

Example 5. Analogously to the previous example, 225 ml of a 0.019% solution of the salt Z.Z.-di- -sulfopropyl-9-ethyl-6, 6 - dimethoxy-4,5-benzo4, 5- (thien-6 2,3) thiacarbocyaninebetaine and 3,3-diethylthiazolinocarbocyanine (test 5 and 5a).

Get a photo material sensitized to the area of the spectrum of 500-720 nm with a maximum of 695 nm.

Example 6. In a similar manner to the previous example, 225 ml of a 0.021% solution of the salt of 2,3-di-v-cyphopropyl-9-ethyl-6, 6-dimethoxy-4,5-benzo4, 5- (thieno -2.3) thiacarbocyanine betaine and 3, G-diethyl-6-methyl-5-methoxythiahino-2 monomethine cyanine.

A highly sensitive photographic material is obtained, sensible to the range of the spectrum 500-710 JiM with a maximum sensitization at 690 nm.

Example 7. Analogously to the previous example, 225 ml of a 0.026% solution of the pyridine salt of 3,3-di-7-sulfopropyl-9-ethyl-6,6 - dimethoxy-4, 5,4,5 - bis were introduced into a 1 l emulsion. (thieno - 2,3) thiacarbocyanine betaine.

A photographic material with very low sensitivity is obtained (experiment 7).

Example 8. Similarly to the previous example, 225 ml of a 0.020% solution of the salt of 3,3-di-y-sulfopropyl-9-ethyl-6, 6 - dimethoxy - 4,5,45-bis (thieno- 2,3) thiacarbocyaninebetaine and 1L-diethyl-2, 2-quinocyanine (test 8 and 8a). A highly sensitive photographic material, sensible to the zone of 500–710 nm, creeps with a maximum at 680 nm.

Example 9. Similarly to the previous one, 225 ml of 0.032% solution of the salt of 3,3-di-y-sulfopropyl-9-ethyl-6, 6-dimethoxy-4,5,4,5-bis (thieno -2.3) thiacarbocyanine betaine and 3,3-Diethylthiazolinocarbocyanine (test 9 and 9a). A photographic material is obtained, sensible to the spectral zone of 500-700 nm with a maximum at 695 nm.

Example 10. In a manner similar to the previous example, 225 ml was injected into a 1 l emulsion

0,021% solution of the salt of 3,3-di-y-sulfopropyl - 9-ethyl-6,6 - dimethoxy-4,5,4,5bis- (thieno-2,3) thiacarbocyaninebetaine and 3, G-diethyl-6 -methyl - 5-methoxythiahino-2 monometincyanine. A highly sensitive photographic material is obtained, sensible to the spectral range of 500-710 nm with a maximum of 680 nm.

Example 11. Analogously to the previous example, 225 ml of a 0.025% solution of the pyridine salt of 3,3-di-7-sulfopropyl-9-ethyl-6,6-dimethoxy-4, 5,4,5 - dibenzothiocarbocyaninebetaine was introduced into a 1 l emulsion. (experience 11 and Pa).

An insensitive photographic material is obtained, sensible to the spectral zone of 540-700 nm with a maximum of 680 nm.

Example 12. Similarly to the previous, 225 ml of a 0.02G% solution of the salt of 3,3-di-7-sulfopropyl-99til-6, 6 - dimethoxy - 4,5,4,5-dibenzothiocarbocyaninebetaine and 3 were injected into a 1 l emulsion. , 1-diethyl-6-methyl 5 - methoxythiachino - 2 - monomethine cyanine (test 12 and 12a). A highly sensitive photographic material is obtained, sensible to the spectral range of 500-710 nm with a maximum of 68 (5 nm.

Example 13. Analogously to the previous example, 225 ml of a 0.029% solution of the salt of 3,3-di-7-sulfopropyl-9-ethyl-6, b - dimethoxy-4,5,4,5-dibenzothiocarbocyaninebetaine and 3,3-diethylazolinocarbocyanine (test 13 and 13a). A highly sensitive photographic material is obtained with a sensitization zone of 500-710 nm with a sensitization maximum of 695 nm.

Claims (2)

1. A method for sensitizing panchromatic film layers of both black and white multi-layered and color masking, by introducing an emulsion of dyes, characterized in that, in order to obtain photographic layers having a high sensitivity to the red rays of the spectrum, a dye of the general formulas I and II is used as a dye ("Jx - to j: l, g A is alkyl or aryl; where B is alkoxy; BI - benzo, tieno-3,2 or tieno-2,3; 2-4; Z - residues of 5- or 5,5-alkyl, alkoxy, aryl, substituted benzotriazoles, benzoselenozools, unsubstituted in hetero-residues, and also 5-alkoxy-substituted naphtho- (1,2-) thiazoles, thieno- (3,2-e) thieno, (2,3-e) benzthiazoles; thiazoline, benzthiazole, benziZ and Zo midazole, quinoline; t 0.1; A is hydrogen, alkyl; R is alkyl, alkoxy. 2. A method according to claim 1, characterized in that non-diffusing color components are derivatives of 1,2-hydroxy naphthoic acid or pyrazolone-5 as masking agents.