DD147882A1 - STABILIZED, PHOTOGRAPHIC HALOGEN SILVER MATERIAL - Google Patents

Abstract

The invention relates to a photographic material based on haul-silver emulsions which contains additives for stabilization and fogging during production and / or processing. The aim and purpose of the invention is to achieve sufficient stabilization and fog inhibition of photographic materials without loss of sensitivity. According to the invention, the photographic material dimercaptotriazines of the formula I x = 1 or 2, R = aliphatic or cycloaliphatic radical having 1 to 6 carbon atoms, in which hydrogen atoms may be substituted by halogen or aromatic radical (formula II), R & exp1 !, R & exp5! = H, alkyl halogen, OCOR & exp6 !, R & exp2R & exp4! = H, alkyl, halogen, R & exp3! = H, alkyl, halogen, NO & ind2 !, OCOR & exp6 !, OR & exp6 !, COR & exp6 !, NHCOR & exp6 !, R & exp3! and R & exp4! and / or R & exp4! and R & exp5! can form another ring system together, R & exp6! Alkyl.

Description

VEB Filmfabrik Wolfen Wolfen, 28. 09. 1979

PN 780 Wk

- <- 2177 1

Int.Cl. ² : G 03 C 1/34

Stabilized photographic silver halide material

Field of application of the invention

The invention relates to a photographic material based on silver halide emulsions containing additives for stabilization and anti-fogging in the production and / or processing.

Characteristic of the known technical solutions

In the development of exposed silver halide emulsions, in addition to the silver image, additional blackening known as fog is known to occur. It is of the properties of the emulsion, the additives contained therein and the conditions of storage and development

dependent.

For the prevention or reduction of fog, stabilizers and antifoggants are added to the emulsion or the developer, and usually a loss of sensitivity is unavoidable. An exception is 7-hydroxy-5-methyl-1,3,4-triazaindolizine (hereinafter called triazaindolizine); This stabilizes very well and does not reduce the sensitivity, in some cases even significantly increased. "

-2- 21771

But even this connection is not against any possible

Veiling cause sufficiently effective. Bs are known to have numerous thio-substituted heterocycles with good antifogging activity, e.g. i-phenyl-5-mercaptotetrazole (see G. Kraft, Z. wiss Photogr. Photophys. Photochem.

31, 352 / T933.7) and 2-mercapto-5-aryl 1-1,3,4-oxadiazoles (U.S. Patent 2,843,491).

There are also known 1- (dialkylaminoalkyl) -5-mercaptotetrazoles and differently substituted 5-mercaptotetrazoles.

but also the disadvantage of desensitizing

Own effect. By combination with triazaindolizine

and by introducing hydrophilic groups (such as SCUH, -SOpNH ₂ , -COOH) into the mercapto-heterocycles, the desensitization tendency can be partially mitigated.

Examples of the latter case are hydrophilic substituted

2-mercapto-benzazoles (German Pat. No. 151,731) and 1- (p-sulfophenyl) -5-mercaptotetrazole (DD-PS 80 625).

In addition, the photographic activity of the mercapto group can be attenuated by having a

cleavable radical is substituted, eg _o by acyl

(DE-P 1 173 336) or alkoxycarbonyl radicals (Jap. P. 43-17 933).

Such "masked antifoggants" usually work

less desensitizing than their parent compounds.

With all the above measures, however, the problem of adequate stabilization and fog inhibition without loss of sensitivity can not be solved.

Object of the invention

The object of the invention is to achieve stabilization and haze reduction without loss of sensitivity in photographic silver halide materials.

2t77 1 9

Explanation of the essence of the invention

The invention has for its object to find substances that allow adequate stabilization and anti-fog with constant sensitivity.

This object is achieved according to the invention in that, for stabilization and haze reduction in photographic silver halide emulsions, the photographic material contains compounds of the following formula I in at least one layer,

R -

in the

X = 1 or 2

R = aliphatic or cycloaliphatic radical having 1 to carbon atoms, in which hydrogen atoms may be substituted by halogen or an aromatic radical of the formula II

II

R ¹

R = H, alkyl of 1 to 6 carbon atoms, halogen, OCOR ⁶ ,

R ² = H, alkyl of 1 to 6 carbon atoms, halogen

-4- 2177I

R = H, alkyl having 1 to 6 carbon atoms, halogen, NO ₂ , OCOR ⁶ , OR ⁶ , COR ⁶ , UHCOR ⁶ ,

R = H, alkyl of 1 to 6 carbon atoms, halogen,

Ir = H, alkyl of 1 to 6 carbon atoms,

Halogen, OCOR ⁶ , R = alkyl of 1 to 6 carbon atoms,

where R- * and R ^ and / or R ^ and R ^ can form a further ring system,

mean.

.. A particular advantage of the invention is that the claimed compounds have a very good anti-fogging effect as an additive to the emulsion and in contrast to the above-mentioned mercapto cause no loss of sensitivity.

With the compounds according to the invention, a lower fog can be achieved with the same sensitivity than with the already known antifoggants if they are added to any emulsion or auxiliary layer. The addition may be made at any point in the emulsion preparation, preferably before casting. · ·

Another advantage of the invention is that the claimed compounds can be used in conjunction with other stabilizers and antifoggants. Particularly useful is their use as an additional anti. fogging agent in addition to the basic stabilizer triazaindolizine; this achieves a more favorable ratio of sensitivity and fog than with triazaindolide alone.

21771

The compounds claimed according to the invention can be used in emulsions which contain chemical and spectral sensitizers, color couplers, curing agents, wetting agents and other photochemical additives.

The amount of the substances used according to the invention may be between 0.02 and 0.6 (preferably 0.15-0.3) mol per mol of silver halide _o

The claimed compounds can be prepared by a known process by reaction of cyanic acid star ROCli, wherein R has the abovementioned meaning, with rhodium hydrogen (see DE-PS 1 217 965).

(1) R (OCN) + 2 χ HSCN

R-

SH

h-V,

Some examples of compounds containing compounds according to the invention are given below (Table 1).

table 1: . X Fp / ⁰ C No. R (from general formula II 1 248 1 R ¹ -R ⁵ = H 1 255 2 R ¹ , R ³ = CH ₃ -, R ² , R ⁴ , R ⁵ = H 11 > 300 3 R ² = C1; R ¹ , R ³ -R ⁵ = H 1 194 4 R ³ = N0 ₂ ; R ¹ , R ² , R ⁴ , R ⁵ = H 1 207-8 VJL R ³ = CH ₃ CO; R ¹ -R ⁵ = H 1 215 6 R ¹ = OCOCH ₃ ; R ² -R ⁵ = H 1 216-8 7 R ¹ = R ³ = C ¹ , R ² , R ⁴ , R ⁵ = H 1 255-6 8th R ³ = CH ₃ 0; r1r ² , R ⁴ , R ⁵ = H 1 316 9 R ³ = NHCOC (CH ₃ ) = CH ₂ ; R ¹ , R ² , R ⁴ , R ⁵ = H 1 258-9 10 "6-naphthyl

2177t

HS

Pp: 256C

ο.

SH PP: 3 5 CTC

13 R = aliphatic radical

χ = 1

Pp: 198-200

Preparation of 2,4-dimercapto-6-phenoxy-1,3,5-triazine (compound 1).

To an aqueous solution of 15 »2 g (0.2 mol) NH.SCN, which is covered with 100 ml of ether, is added at -5 ° C with stirring and cooling, first 17 _f 8 g 55% HpSO., Then '11, Og (0.2 mol) of phenyl cyanate slowly. The product precipitates out of solution, is filtered off with suction and washed with ether (yield: 22 g = 92% of theory).

Pp: 248 ⁰ C (ethanol)

Ausführungsbeispie1

The invention is explained in more detail below by way of examples, wherein the claimed according to the invention additives 6,7 »10,12,13 have the meaning given above, while, for comparison known compounds such as i-phenyl-5-mercaptotetrazole, 2-mercapto-benzoxazole , 3-mercapto-5-methyl-4-phenyl-1,2,4-triazole and 2-mercaptobenzimidazole-5-sulfonic acid are used «

21771

example

A highly sensitive gelatin silver bromide iodide emulsion chemically sensitized with gold compounds and polyethylene oxides and spectrally sensitized with cyanine dyes is divided into 7 parts, which are provided with triazaindolizine and the other common additives except the sample used as a type, in addition to those shown in Table 2 specified amounts of the compounds 6,7,10,12,13 included.

After adjustment to pH 7, the emulsions are poured onto a support and the resulting pot materials cut into strips, either fresh or after Heizschranklagerung (10 days at 50 ⁰ C) by Sensitometer behind the daylight filter and step wedge (factor - ^ /?) Exposed and in Developed a developer of the following composition:

18.0 g 1.0 g

filled with H ₂ O to 1 1

It is then fixed, watered and dried. The sensitometric data (relative sensitivity at density 0.2 above fog and fog differences versus type) are summarized in Table 2.

It can be seen that by adding Compounds 6, 7, 10, 12, 13 at the concentrations 0.02-0.6 mmol / mol silver halide compared to that used as a type. Sample - a significant reduction in fog with no significant loss of sensitivity and almost the same gradation is achieved.

Metol 1, 5 G K ₂ CO ₃ Na ₂ SO ₃ 18 0 G , KBr hydroquinone 2, 5 G , with H

Table 2

Sample addition in mmol / mol Ag Hal ·

2) connections'

fresh

after 10 days 50 ⁰ C

rel. Eo.2

Veil-

rel. Eo.2

Λ veil

(Type ¹⁾ ) i-phenyl-5-mercaptotetrazole (0.3) 3-mercapto-5-methyl-4-phenyl-1

1,2,4-triazole (0.3)

2-Mercaptobenzimidazol-

5-sulphonic acid (0,3)

2-mercaptobenzoxazole (0.3)

Connection 7. (0.3)

Compound 7 (0.6)

Compound 12 (0.3)

Compound 10 (0.3)

Compound 6 (0.3)

Compound 13 (0.3)

1)

100 71

50

32 100 100

95

90

100

100

63

O (S = 0.16)

- 0.06

- 0.05

- 0.05 0.00

- 0.02 -0.04 -0.03

- 0.02

- 0.02

- 0.06

100 50

71

40 40

112 9595

110 110 50

O (S = 0.20)

- 0.03

- Ο, ίΟ

-0.10

0.00

-0.04

- 0.06

- 0.03

- 0.03

- 0.03 -0.10

Type = 10 mmol / mol Ag Hal · triazaindolizine

Claims (4)

21771 invention claim 1 "Stabilized Mercaptoheterocyclen containing photographic silver halide material, g e k e η η ζ e i c h η e- t characterized in that it is in at least one layer, a dimercaptotriazine of the general formula I. SH (X R- in the R = aliphatic or cycloaliphatic radical with 1 to 6 carbon atoms, in which hydrogen atoms may be substituted by halogen or aromatic radical of the formula II R ' II R = H, alkyl of 1 to 6 carbon atoms, halogen, OCOR R = H, alkyl of 1 to 6 carbon atoms, halogen R "^ = H, alkyl of 1 to 6 carbon atoms, halogen, UO ₂ , OCOR ⁶ , OR ⁶ , COR ⁶ , NHCOR ⁶ R ⁴ = H, alkyl of 1 to 6 carbon atoms, halogen - 10 - 1 77 1 f r5 = H, alkyl of 1 to 6 carbon atoms, halogen, OCOR ⁶ R = alkyl having 1 to 6 carbon atoms, χ = 1 or 2 and where Έ? and R ⁴ and / or R ⁴ and R 1 can form another ring system. 2. Stabilized photographic silver halide material according to item 1, characterized in that the emulsion additionally contains antifoggants. 3.'Stabilized photographic halogen silver material according to item 1, characterized in that the emulsion contains 7-hydroxy-5-methyl-1,3,4-triazaindolizine. 4. A stabilized photographic halogen silver material according to item 1, characterized in that the compounds in amounts between 0.02 and 0.6, preferably 0.15 to 0.3 mmol per mole of silver halide are included.