DEE0010080MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: January 12, 1955 Announced on November 22, 1956

GERMAN PATENT OFFICE

The invention relates to a photographic material comprising at least one supersensitized halosilver emulsion.

It is known to those skilled in the art of making photographic emulsions that certain Cyanine class dyes affect the spectral sensitivity of photographic emulsions of the halogen-silver-gelatin type. It is also known that the various The sensitization achieved by dyes depends somewhat on the type of emulsion treated. Further can sensitize a particular emulsion by a particular dye through modification the physical and / or chemical conditions of the emulsion can be changed. For example the sensitization by increasing the silver ion concentration or by reducing the Hydrogen ion concentration (i.e. by increasing the alkalinity) or by both measures will. For this purpose, for example, photographic plates, which have a spectrally sensitized emulsion, bathed in water or in aqueous ammonia solutions will. Such processes, in which the sensitivity of an emulsion by increasing the Silver ion concentration and / or shifted or by reducing the hydrogen ion concentration is changed, in general »hypersensitivity

609 708/308

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called bilization «. It turns out, however, that one such hypersensitization of the emulsions generally does not last long.

According to the invention, the sensitivity of the emulsions containing cyanine dyes is now to be shifted or can be changed without changing the state of the emulsion, i.e. the hydrogen ions and / or

the silver ion concentration of the emulsion is changed in a significant way. In contrast to the 65 The above procedure is intended to refer to this procedure as a certain type of "supersensitization" will.

Compounds of the formula were found to be cyanine dyes in the emulsions according to the invention

R - N (-

-Z -— _N

= CH) ^ ₁ -C = CH-C = CH-C (= CH-CH) _n ^ ₁ = NX-R ₁

(I)

suitable. In the formula, R and R ₁ each represent one

Alkyl group, e.g. B. a methyl, ethyl, n-propyl, Carbäthoxymethylgruppe, etc., R _{2 is} an aryl group, z. B. a phenyl, ο-, m- or p-tolyl, o-, m- or p-chlorophenyl group, e.g. B. a mononuclear aromatic group of the benzene series, or an α-naphthyl, / I-naphthyl, 9-phenanthryl group, etc. or a pyrryl group (simple or fused nucleus) such as a pyrryl group, an indolyl, pyrrocolyl, benzoindolyl group, etc. ., m and η each 1 or 2, X an acid residue, such as chloride, iodide, bromide, perchlorate, p-toluenesulfonate, benzenesulfonate, ethyl sulfate, methyl sulfate, etc., Z and Z ₁ each to complete a 5- to ole-membered heterocyclic nucleus required non-metallic atoms, such as a heterocycle of the thiazole series, e.g. B. thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, etc., the benzothiazole series, e.g. B. Benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, Methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 6-iodobenzothiazole, 5-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, 5, 6 -dimethoxyberizothiazole, 5-oxybenzothiazole, zaphthiazolethiazole, 6 - oxybenzo series, etc., zaphthotybenzo series. B. a-naphthothiazole, / 3-naphthothiazole, 7-methoxy-a-naphthothiazole, 8-methoxy

^v a-naphthothiazole, S-methoxy - ^ - naphthothiazole, 5-ethoxy-a-naphthothiazole, etc., the benzoselenazole series, z. B. benzoselenazole, 5-chlorobenzoselenazole, 6-methoxybenzoselenazole, 5-methoxybenzoselenazole, etc., the naphthoselenazole series, e.g. a-naphthoselenazole, / J-naphthoselenazole, etc., the benzoxazole series, e.g. B.

Benzoxazole, 5-oxybenzoxazole, 6-oxybenzoxazole, 5-chlorobenzoxazole, 5-methoxybenzoxazole, 6-methoxybenzoxazole, 5-phenylbenzoxazole, 5-bromobenzoxazole, etc., of the naphthoxazole series, e.g. a-naphthoxazole, / 3-naphthoxazole etc., the 2-quinoline series, e.g. B. 2-quinoline, 6-methyl-2-quinoline, 7-methyl-2-quinoline, 8-methyl-2-quinoline, 6-chloro-2-quinoline, 8-chloro-2-quinoline, 4-chloro-2-quinoline, 5-ethoxy - 2 - quinoline, 6-ethoxy-2-quinoline, 7-ethoxy-2-quinoline, 6-oxy-2-quinoline, 7-oxy-2-quinoline, 6-methoxy-2-quinoline, etc., der

6q 4-quinoline series, e.g. 4-quinoline, 6-methoxy-4-quinoline, 7-methyl-4-quinoline, 8-methyl-4-quinoline, etc., etc.

This is what happens now in the supersensitization

combination according to the invention a non-ionized

R ₃ -NC = CH-C = CH-CN-R ₄

Q c-o

(Π)

Dye. Suitable dyes of this type are preferably compounds of the formula

In this, R ₃ and R ₄ each represent an alkyl group, that is to say an alcohol radical, e.g. B. a methyl, ethyl, n-propyl, η-butyl, / I-oxyethyl, carbethoxymethyl, benzyl (phenylmethyl) group, etc., Q to complete an indanedione or a 5- to 6-membered heterocyclic nucleus required non-metallic atoms. Such heterocycles are, for example, nuclei of the pyrazolone series, e.g. 3-methyl-i-phenyl "5-pyrazolone, i-phenyl-5-pyrazolone, i- (2-benzothiazolyl-3-methyl-5-pyrazolone), etc., of the isoxazole series, e.g., 3-phenyl -5- (4H) -isoxazolone, 3-methyl-5- (4H) -isoxazolone, etc., of the indanedione series, e.g., i, 3-diketohydrindene, etc., of the oxindole series, e.g., the · T-alkyl -2, 3-dihydro-2-oxindoles, etc., the 2,4,6-triketohexahydropyrimidine series, e.g. barbituric acid or 2-thiobarbituric acid as well as their ι-alkyl (e.g. 1-methyl, 1 -ethyl, 1 n-propyl, tn-heptyl, etc.) or 1, 3 ^J dialkyl (e.g. 1,3-D1-methyl, 1, 3-diethyl, 1, 3-di-n-propyl, 1 , 3-diisopropyl-, i, s-dicyclohexyl-, 1, 3-di - (; 3-methoxyethyl) -etc. Or 1, 3-diaryl- (1, 3-diphenyl) -, 1,3-di- (p-chlorophenyl) -, 1, 3-di- (p-ethoxycarbonylphenyl) - etc. or i-aryl- (e.g. i-phenyl-, ip-chlorophenyl-, ip-ethoxycarbonylphenyl) or i-alkyl- 3-aryl (e.g. i-ethyl-3-phenyl, in-heptyl-3-phenyl, etc.) derivatives, cores of the rhodanine series, i.e. the 2-thio-2, 4-thiazolidinedione series, such as rhodanine, 3-alkylrhodanines, e.g., 3-ethylrh odanine, 2-allylrhodanine, etc., or 3-arylrhodanine, ζ. B. 3-phenylrhodanine etc., etc., the 2 (3H) -imidazo-i, 2-a-pyridine series, the 5, 7-dioxo-6, 7-dihydro-5-thiazol-3, 2-a- pyrimidine series, e.g. B. 5, 7-Dioxo-3-phenyl-6, 7-dihydro-5-thiazol-3, 2-a-pyrimidine etc., of the 2-TM0-2, 4-oxazolidinedione series, such as the 2-thio-2 , 4 (3 H, 5 H) -oxazoldione series, e.g. B. 3-ethyl-2-thio-2,4-oxazolidinedione etc., the thianaphthenone series, e.g. B. 2 (3H) -thianaphthenone etc., the 2-thio-2, 5-thiazolidinedione series, such as the 2-thio-2, 5 (3H ₁ 5H) -thiazoldione series, e.g. 3-ethyl-2-thio-2, 5-thiazolidinedione etc., Z ₂ means the

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Completion of a 5- to Ö-membered heterocyclic nucleus required non-metallic atoms. Such heterocyclic nuclei are, for example, those from the benzothiazole series, for example benzothiazoles 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenothiazole, 6-phenothiazole , 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 6-iodobenzothiazole, 5-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, 5, 6-dimethoxybenzothiazole, 6-benzothiazole, 6-benzyazothiazole, oxzothiazol, -oxybenzothiazole, 6-benzyzothiazol etc., the naphthothiazole series, e.g. B. a-naphthothiazole, / 5-naphthothiazole, 7-methoxy-a-naphthothiazole, 8-methoxy-a-naphthothiazole, 5-methoxy- / 3-naphthothiazole, 5-ethoxy-a-naphthothiazole, etc., of the benzoselenazole series, e.g. . B. benzoselenazole, 5-chlorobenzoselenazole, 6-methoxybenzoselenazole, 5-methoxybenzoselenazole etc., the naphthoselenazole series, e.g. A-naphthoselenazole, / J-naphthoselenazole, etc., of the naphthoxazole series, e.g. B. α-naphthoxazole, β-naphthoxazole, etc., and Z ₃ denotes that to complete a heterocyclic nucleus of the naphthothiazole series (e.g. as above
Naphthoselenazole series

listed for Z ₂ ) or the 'z. B. also as above for Z ₉

listed) required non-metallic atoms. Cyanine dyes (i.e. carbocyanine dyes) of the formula (I) when R ₂ therein is a pyrryl nucleus include dyes of the formula

R-Ni-CH =

, _! - C = CH - C = CH - C (= R ₅ -CZ ₄

■ ■ 'I J ■ ·.

In the formula, R, R ₁ , X, Z, Z ₁ , m and η have the meanings given above. R ₅ and R ₆ each denote a hydrogen atom, an alkyl group, such as a methyl, ethyl, n-propyl, n-amyl, n-heptyl, n-dodecyl, cyclohexyl, etc., group, or an aryl group such as a phenyl, o-, m- or p-tolyl group, etc. R ₆ and R ₆ together represent the non-metallic atoms required to complete a heterocyclic nucleus of the pyridine series.

Z ₄ denotes the non-metallic atoms required to complete a pyrrole nucleus, that is to say a simple or fused pyrrole nucleus such as pyrrole, indole, pyrrocoline, benzoindole, etc.

The dyes given in the formula (III) are already from US Pat. No. 2,666,761 known.

Dyes of the formula (II) which have been found to be particularly useful are dyes of the formula

(IV)

In the formula, R ₃ , R ₄ , Z ₃ and Q have the meanings given above. Among these, dyes proved to be particularly suitable in which Q 'denotes the non-metallic atoms required to complete a heterocyclic nucleus of the barbituric acid series and Z ₃ denotes the nonmetallic atoms necessary to complete a heterocyclic nucleus of the naphthothiazole series or the naphthoselenazole series.

Some of the dyes of the formula (I), when R ₂ therein denotes an aryl nucleus, have already been disclosed in U.S. Patents 1,934,659, 2,107,379, 2,112,140,: 2,369,646, 2,369,657, 2,486,173 and 2,515,913 became known, dyes of the formula (II) [or (IV)] from Belgian patent 519 147.
According to the invention, one or more of the cyanine dyes of the formula (I) or (III) are now added to the photographic emulsion together with one or more of the dyes of the formula (II) or (IV). The gelatin-halosilver emulsions that are usually used are particularly suitable as such emulsions. The supersensitization combination according to the invention is, however, also suitable for other halogen silver emulsions, that is to say for emulsions which have a carrier other than gelatin, for example a synthetic resin or a cellulose material, provided this does not damage the light-sensitive materials.

The sensitizing dyes can be used in various concentrations depending on the desired effects. As is known to those skilled in the art, the sensitivity achieved by a particular dye does not increase in proportion to its concentration in the emulsion. Rather, with increasing concentration, a maximum is passed through. In practicing the invention, the individual sensitizing dyes are preferably used in an amount slightly below their opti ^: '■

609 708/308

E 10080IVal57 b

paint concentration lies. Under "optimal" concentration is to be understood as the one in which the individual dyes are each the greatest possible Sensitivity. Namely, if any of the dyes in the supersensitization combination is used according to the invention in its optimal concentration, can in certain cases the increase in sensitivity achieved by the combination has already passed through the maximum ..

ίο The optimal concentration of each dye can as is well known to those skilled in the art, readily by determining the sensitivity of a series can be determined from samples of the same emulsion, with each sample containing the dye in a different amount contains. The optimal concentration of the supersensitization combinations can of course be in the same Manner can be determined by the sensitivity of a number of samples of the same emulsion is measured, with each sample the individual dyes of the combination in different amounts contains. It is used to determine the optimal concentration of the supersensitization combination It is advisable to first use the individual dyes in less than the optimal concentrations. The concentration of the individual dyes is then increased until the optimum concentration the supersensitization combination is reached.

In general, this is the optimal concentration

of the cyanine (that is to say the carbocyanine) dyes according to the formula (I) or (III) in the order of magnitude from 0.05 to 0.3 g per mole of halosilver in the emulsion.

The non-ionized dyes of the formula (II) or (IV) are expediently used in concentrations from 0.05 to 3.3 g per mole of halosilver used in the emulsion. The concentration ratio of the dye of the formula (II) or of the formula (IV) to the cyanine dye of the formula (I) or (III), in general spoken, in wide ranges, for example in the range from 1:20 to 3: 1 (weight ratios) vary.

Processes for incorporating the dyes into the emulsions are known to the person skilled in the art. According to the In accordance with the invention, they can be added to the emulsions either separately or together. It has proven to be most expedient to dissolve the dyes and the solutions in suitable solvents ever to admit for yourself. Methanol, ethanol, pyridine, etc. (the latter in particular) turned out to be such. as suitable for the dyes of the formula (I), (II), (III) or (IV). In certain cases acetone can also be used be applied. Pyridine proved to be a particularly effective solvent because of its use in certain cases an increased supersensitization effect occurs.

Particularly noticeable is the fact that certain dyes of the formula (II) or (IV) for themselves alone have little or no sensitization effect. However, if they are together are used with pyridine, a significant increase in sensitivity can be observed. However, it is not necessary to use pyridine in every case. Often times it is useful to Pyridine diluted with methanol or acetone as a solvent for the supersensitization combinations to use according to the invention. The dye can, for example, first in Pyridine can be dissolved, the solution is then diluted with methanol or acetone.

The dyes are expediently only added to the finished, washed emulsion. It goes without saying that they are distributed as evenly as possible in the emulsions.

The following procedure was found to be satisfactory. It becomes stock solutions of the supersensitizing dyes prepared by dissolving the dyes in one of the solvents indicated above. Thereupon a stock solution is created one of the dyes is slowly stirred into the liquid halogen silver gelatin emulsion. The emulsion keep stirring until the dye is evenly distributed. After that, the desired amount the stock solution of the second dye is slowly stirred in, stirring is continued until the second dye is also evenly distributed in the emulsion. The supersensitized emulsion will then on a suitable support, such as on glass, a cellulose derivative film, a synthetic resin film or paper, Cast in the appropriate thickness. The details of such potting processes are well known to those skilled in the art known.

The most favorable proportions of the individual sensitizing dyes in the emulsions vary depending on the emulsion used and depending on the desired effect, a little from dye to dye. The skilled worker succeeds in setting the most economical and favorable working conditions without further ado by making the appropriate tests and evaluations. The ones given so far Possibilities for introducing the sensitizing dyes into the emulsions and their proportions so serve only for explanation. The following examples are provided for further explanation of the method according to the invention. There were different servings of the same Firstly, a cyanine dye of the formula ## STR3 ## filling a photographic bromoiodosilver gelatin emulsion (I) [or (HI)] and secondly a combination of a cyanine dye of the formula (I) [or (III)] and a non-ionized dye of the formula (II) [or (IV)] is added.

In some cases a third sample coat of the same emulsion was made, with this only one of the non-ionized dyes of the formula (II) or (IV) was added. The following list shows that often this third sample layer is so low in sensitivity that this could not be measured in the spectral range passed by the filter. In the lineup these cases are marked with an asterisk.

The emulsions of some of the examples differ from those of the remaining examples. In every single one In the example, however, only emulsions from the same batch were used in each case.

For example, the sample layers of Examples 1, 2, 3 and 4 come from the same emulsion batch,

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those of Examples 5, 6 and 7 of a second emulsion batch, the sample layers of Examples 8, 9 and 10 of a third emulsion batch, the sample layers of Examples 14, 15, 16 and 17 of a fourth emulsion batch, the sample layers of Examples 18 and 19 of a fifth Emulsion batch, the sample layers of Examples' 21 through 28 of a sixth emulsion batch, the sample layers of Examples '29 to 34 of a seventh emulsion batch, the sample layers of Examples 35, 36 and 37 of an eighth emulsion batch, and the sample layers of Examples 38, 39 and 40 of a ninth Emulsion batch. The sample layers of Examples 1 to 10 and 13 to 20 contained 1 cm of pyridine per mole of AgX, whereas the sample layers of Examples 21, 22, 23, 25, 27 and 29 to 40 contained 1 cm of pyridine per mole of AgX. The emulsions were digested prior to casting a short time in a maintained at 52 ⁰ water bath. The various emulsion samples were then poured onto appropriate supports and exposed in the usual way in a spectrograph and a sensitometer (type Eastman Ib) through a filter (Wratten filter No. 25) which essentially does not allow any light of a wavelength shorter than 580 ταμ to pass through, and / or through a filter (Wratten No. 12 filter) which essentially does not allow light of a wavelength below about 495 ταμ (with the exception of about 1% between 300 and 340 ταμ) to pass through. The exposed emulsions were developed in the usual manner. The red and / or minus blue sensitivity, gamma and fog values of each of the emulsion samples were then determined. The results are compiled in the following list.

The sensitivity is given in the measurement system io / i, i being the inertia.

example

Dye (g per mole of AgX) exposure to red

Sensitive
speed

gamma

Minus blue exposure
Emp

delicacy

gamma

veil

(a)

(b)

(C)

(d)

(f)
(G)

(i) Ö)

(1)
(m)

(O)

(P)

(q)

i, 3-Diethyl-5- [di- (i-ethyl-2- (i H) - /? - naph-

thothiazolylidene) isopropylidene] -

barbituric acid (0.040)

3,3'-Diethyl-9-phenylthiacarbocyanine

iodide (0.080)

Dye (a) (0.020) plus dye (b) (0.080) 3, 3 '-Diethyl-g-phenylselenacarbocyanine-

bromide (0.080)

Dye (a) (0.020) plus dye (d) (0.080) 3, 3'-dimethyl "9-phenyl-4, 5, 4 ', 5'-dibenzo-

selenium carbocyanine bromide (0.080)

Dye (a) (0.020) plus dye (f) (0.080) .., 3, 3'-dimethyl "9-phenyl-4, 5, 4 ', 5'-dibenzo-

selenathiacarbocyanine iodide (0.080)

Dye (a) (0.020) plus dye (h) (0.080) 3, 3'-dimethyl-9-phenyl-4, 5, 4 ', 5'-dibenzo-

thiacarbocyanine bromide (0.080)

Dye (a) (0.020)

Dye (j) (0.080) plus dye (a) (0.020) .. i-ethyl-5- [di- (i-ethyl-2- (i H) - /? - naphtho ~

thiazolylidene) isopropylidene] -

barbituric acid (0.020)

Dye (j) (0.080) plus Dye (m) (0.020) 5 - [(3-Ethyl-2- (3 H) -cc-naphthothiazolylidene) -

(i-ethyl-2- (1 H) -ß-naphthothiazolylidene) -iso-

propylidene] -i-methyl-2-thiobarbitur-

acid (0.020)

Dye (j) (0.080) plus dye (o) (0.020)

Dye (j) (0.080)

i, 3 "diethyl-5 - [(3-ethyl-2- (3 H) -benzo-

'thiazolylidene) - (1 -methyl-2- (1 H) -ß-naphtho-

selenazolylidene) isopropylidene] -2-thio-

barbituric acid (0.020)

Dye (j) (0.080) plus Dye (r) (0.020) 9.0

1.72

7.6 3.12 25.5 3.07 6.8 2.79 27.0 3.02 6.2 2.92 31.0 2.82 3.9 2.49 22.0 2.87 13.5 3.00 7.1 1.76 52.0 3.02 * * 44.0 3.20 6.6 2.68 29.5 3.48 11.8 3.28 9.2 3.24 24.0 3.32

0.05 0.05

0.05

0.05 0.05

0.05 0.06

0.05 0.06

0.07 0.05 0.07

0.05 0.07

0.05 0.07 0.07

0.05 0.07

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E 10080 IVa / 57b

example

. Red exposure gamma Minus blue
exposure gamma Emp Emp sensitive sensitive speed speed

veil

ίο (ν)

(W)
II (X)

(y)

(a ')
(b ')

(C)

(d ')
(C)
(f)

(G')

(i ')

Ö ')

(k ')
ΐ6 (Γ)

(n ')

(O')
ΐ8 (ρ ')

(s')

(u ')
(V)

(χ ')

5 - [(3-Ethyl-2- (3 H) -benzothiazolylidene) - (3-ethyl-2- (3 H) -a-naphthothiazolylidene) -isopropylidene] -i-methyl-2-thiobarbituric acid (0.020)

Dye (j) (0.080) plus Dye (t) (0.020) ...

5- [Di- (i-Ethyl-2- (iH) - / 3-naphthothiazolylidene) isopropylidene] -i-methyl-2-thiobarbituric acid (0.020)

Dye (j) (0.080) plus dye (v) (0.020). .

Dye (j) (0.080) -

2- [Di- (i-Ethyl-2- (iH) - / 3-naphthothiazolylidene) isopfopylidene] -i, 3-indandione (0.080)

Dye, (j) (0.080) plus Dye (y) (0.020) ..

Dye (j) (0.040)

4- [Di- (i-Ethyl-2- (1 H) - / 3-naphthothiazoiylidene) isopropylidene] - ^ - phenyl-S- (4 H) -isoxazolone (0.080) .... ".

Dye (j) (0.080) plus Dye (b ') (0.040) ..

Dye (j) (0.080)

Dye (b ') (0.040)

Dye (j) (0.080) plus Dye (b ') (0.020) ..

9- (i-ethyl-2,5-dimethyl-3-pyrryl) -3,3'-dimethyl-4, 5, 4 ', S'-dibenzothiacarbocyanin iodide (0.080)

Dye (a) (0.020)

Dye (g ') (0.080) plus Dye (a) (0.020) ..

3,3'-Diethyl-9- (i-ethyl-2, 5-dimethyl-3-pyrryl) -4, 5, 4 ', 5' ~ dibenzothiacarbocyanin iodide (0.080)

Dye (a) (0.020) plus dye (j ') (0.080) ..

9- (3-indolyl) -3, 3'-dimethyl-4, 5, 4 ', 5'-dibenzothiacarbocyanin iodide (0.080)

Dye (Γ) (0.080) plus dye (a) (0.020) ..

3,3'-dimethyl-9- (2-methyl-6, 7-benzo-3-indolyl) -4, 5, 4 ', S'-dibenzothiacarbocyanine-p-toluenesulfonate (0.080)

Dye (n ') (0.080) plus Dye (a) (0.020) ..

Dye (a) (0.020)

3,3'-Dimethyl-9- (3-pyrryl) -4, 5, 4 ', 5'-dibenzothiacarbocyanine bromide (0.080)

Dye (q ') (0.080) plus Dye (a) (0.020) ..

3, 3 '-: Dimethyl-9- (3-pyrryl) -4, 5, 4', 5'-dibenzoselenacarbocyanine bromide (0.080)

Dye (s') (0.080) plus Dye (a) (0.020) ..

3-ethyl-3'-methyl-9- (2-methyl-3-indolyl) -4 ', 5 ', 6, 7-dibenzoxacarbocyanine-. perchlorate (0.080)

Dye (y) (0.080)

Dye (u ') (0.080) plus Dye (y) (0.040) ..

Dye (j) (0.080)

6.6
16.5

6.3
18.5
10.2

3, o
38.0

16.0

7, i

3i, 5

14.8
30.0

23.0
42.0

22.5
31.0

10.0

17.0

4.9

2.12 - - 2.74 - - 3, ΐ -. - 2.84 ¹ - - 1.84 7.6 2.68 2.80 * * - 27.0 2.60 II, 0 2.8 - · 21.5 3.24 - ■ 30.0 2.67 - ' _ ■ _ - - - 2.84 - · - · 1.76 -. - 2.69 - - 2.97 .— · - 2.93 • - - 3, ΐ4 3, ο8 - - · 3.12 * * 3.32 16.0 3.44 - 47, ο 2.62 II, 0 3.09 - 31.0 v2.86 - · - - - * 6.2 2.87 ΐ, 54 2.87

0.04 0.07

0.04

0.07 0.06

0.06 0.06 0.06

0.06

0.08

0.07 0.06

0.08

0.07

0.05

0.07

0.07 0.07

0.06 0.07

0.07

0.07

0.06

0.06 0.06

0.05 0.06

0.04 0.05 0.05

0.04

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E 10080IV a / 57 b

example

Dye (g per mole of AgX)

Red exposure

Emp

delicacy

gamma

Minus blue exposure
Sensitive
speed

gamma

veil

22nd (a ") (b ") 23 (C ") (d ") 20th 24 (e ") (f ") (JS ") 25th (H") 25th (i ") 26th (J ") (k ") 3D 27 (I ") (m ") 35 28 (n ") (O") 29 (P ") (q ") 40 (r ") 30th (S ") (t ") 45 31 (U ") (V ") 32 (W ") 50 (X ") 33 (Y ") 55 34 (a '") (b '") 35 (C ") 60 (d "')

i, 3-Diethyl-5 - [(i-Ethyl-2- (i H) - / 3-naphthothiazol3diden) - (i-methyl-2- (iH) - / 3-naphthothiazolylidene) isopropylidene] barbituric acid (0.080)

Dye (j) (0.080) plus Dye (y ') (0.020) ..

5 - [Di- (1-Ethyl-2- (1 H) - / 3-naphthothiazolylidene) isopropylidenj-i-n-heptylbarbituric acid (0.080)

Dye (j) (0.080) plus Dye (a ") (0.020) ..

5- [di- (i-ethyl-2- (iH) - / 3-naphthothiazolylidene) isopropylidene] -i, 3-di - (/ 3-methoxyethyl) barbituric acid (0.080)

Dye (j) (0.080) plus Dye (c ") (0.020) ..

Dye (j) (0.080) ...

Dye (c ") (0.080).

Dye (j) (0.080) plus Dye (c ") (0.020) ..

5- [di- (i-ethyl-2- (iH) - / 3-naphthothiazolylidene) isopropylidene] -1 - η - heptyl - 3 - phenylbarbituric acid (0.080)

Dye (j) (0.080) plus Dye (h ") (0.020) ..

Dye (h ") (0.080)

Dye (j) (0.080) plus Dye (h ") (0.020) ..

i, 3-Dicyclohexyl-5 - [(i-ethyl-2- (i H) - / 3-naphthothiazolylidene) isopropylidene] barbituric acid (0.080)

Dye (j) (0.080) plus Dye (1 ") (0.020) ..

Dye (1 ") (0.080) ■

Dye (j) (0.080) plus Dye (1 ") (0.020) ..

Dye (a) "(0.040)

i, i'-Dimethyl-io-phenyl-2,2'-carbocyanine bromide (0.040)

Dye (a) (0.015) plus dye (q ") (0.040)

i, i'-Diethyl-io-plienyl-2, 2'-carbocyanine-

iodide (0.040)

Dye (a) (0.015) plus Dye (s ") (0.040) ..

io-p-Chlorophenyl-i, i'-dimethyl-2,2'-carbocyanin iodide (0.040)

Dye (a) (0.015) plus dye (u ") (0.040)

i, i'-dimethyl-io- (o-tolyl) -2, 2'-carbocyanine-

iodide (0.040)

Dye (ä) (0.015) pl ^us Dye (w ") (0.040) I, i'-diethyl-io- (o-tolyl) -2, 2'-carbocyanine-

iodide (0.040)

Dye (a) (0.015) plus dye (y ") (0.040) i, i'-diethyl-io-a-naphthyl-2,2'-carbocyanine-

iodide (0.040)

Dye (a) (0.015) plus dye (a '") (0.040)

Dye (a) (0.030) .-

1 ', 3-diethyl-9-phenylthia-2'-carbocyanine-

iodide (0.040)

Dye (a) (o; oi5) plus dye (d '") (0.040)

2.85 7.6 3, i 2.5 32.0 2.72 1.9 28.0 2.1 2.85 48.0 3, P5 1.0 10.2 0.81 2.86 40.0 3.5 2.58 5.4 ■ 3, i. * * * 2.70 35.5 3, o 1.92 40.0 2.1 2.8 47, o 3.2 * * * 2.88 3!, O 3.0 1.26 7, ¹ . 1.72 3.08 50.0 2.86 * * 3.2 29.0 3.2 1.18 - - * 1.68 - - *
1.8 - - * , _ i, 45 - - * : 2.1 . - - * • _ 2.2 - - * _ 1.9 '· ■ - - ■ o, 53 '- ^: - 1.06 i, 55 - -

0.04 0.05

0.06.

0.05

0.05 0.05

0.03

0.04 0.05

0.05 0.05 0.04 0.05

0.05 0.05 0.05 0.05

0.05

0.04 0.05

0.04 0.05

0.04 0.05

0.04 0.05

0.04 0.05

0.04 0.05 0.05

0.05 0.05

609 708/308

E 10080 IVa / 57b

example

Dye (g per mole of AgX)

Rotbel
Emp
sensitive
speed icht
gamma Minu
belicl
Emp
sensitive
speed jblue-
iteration
gamma 2.5
12.3 0.96
1.56 - - 3.6
8.4
4, i 1.46
1.27
1.98 - - 6.8
21.5 2.72
1.62 - - 23.0
25.5 1.87
i, 73 - - 12.6
24.5 2.7
1.29 - -

veil

36 (f ")

10 37 (D
(H'") 15th 38 (i '")
(j '")
(k '") 20th 39 (I '")
(m '") 25th 40 (n '")
(O'")

1 ', 3-diethyl-9- / 3-naphthylthia-2'-carbocyanine-

iodide (0.040)

Dye (a) (0.015) plus dye (f ") (0.040) ι ', 3-diethyl-9 ~ (9-phenanthryl) -thia-2'-carbo-

cyano iodide (0.040)

Dye (a) (0.015) plus dye (h '") (0.040) Dye (j) (0.080)

5 - [(1 - ethyl -2- (iH) -j3- naphthothiazolylidene) - (3-methyl-2- (3 H) -α-naphthoxazolylidene) -isopropylidene] -1, 3-di- (ß-methoxy ethyl) barbituric acid (0.080)

Dye (j) (0.080) plus dye (k '") (0.080)

5-- [(1 - Ethyl - 2 -. (1 H) -ß - naphthothiazolylidene) (3-methyl-2- (3 H) -ß-naphthoxazolylidene) isopropylidene] -1, 3-di - (/ 3 methoxyethyl) barbituric acid (0.080)

Dye (j) (0.080) plus dye (m '") (0.080)

5 - [(1 - Ethyl - 2 - (1 H) -ß - naphthothiazolylidene) (3-methyl-2- (3 H) -a-naphthothiazolylidene) -isopropylidene] -i, 3-di - (- /? - methoxyethyl) barbituric acid (0.080)

Dye (j) (0.080) plus Dye (o '") (0.080) 0.05
0.05

0.05
0.05
0.05

0.05
0.07

0.05
0.08

0.05
0.07

In the drawings, for example, is the supersensitizing effect of three of the new dye combinations according to the invention in bromoiodosilver gelatin emulsions shown. Each figure in the drawing contains a diagram of two or, in the case of FIG. 1, three spectrograms. The sensitivity of the cyanine dye The emulsion sample containing the formula (I) [or (HI)] is represented by a solid curve. The top curve of each figure, shown in broken lines, shows the sensitivity of the Combination of the cyanine dye of the formula (I) [or (HI)] and the non-ionized dye of Emulsion sample containing formula (II) [or (IV)]. The one shown in Fig. 1 in dash-dotted lines third curve shows the sensitivity of an emulsion sample containing only one non-ionized dye Formula (II) [or (IV)] contains. In Fig. 2, this third curve has been omitted because it is related to the specified third curve of FIG. 1 is identical. In Fig. 3, the third curve has been omitted because it is just not emulsion containing ionized dye alone has insufficient sensitivity.

Fig. 1: Curve A shows the sensitivity of an ordinary silver bromide gelatin emulsion which is sensitized with 3,3'-diethyl-9-phenylthiacarbocyanine iodide; Curve B shows the sensitivity of the same emulsion when it contains 1,3-diethyl-5- [di- (i-ethyl-2 (iH) - /? - naphthothiazolylidene) isopropylidene] barbituric acid; Curve C shows the sensitivity of the same emulsion when it contains both the 3, s'-diethyl-g-phenylthiacarbocyanine iodide and the, 3-diethyl-5- [di- (i-ethyl-2 (iH) - _/ 3- contains naphthothiazolylidene) isopropylidene] barbituric acid. The sensitometric evaluation of these emulsions is given in Example 1 in the list above.

Fig. 2: Curve D shows the sensitivity of a conventional bromoiodosilver gelatin emulsion which is sensitized with 3,3'-dimethyl-9-phenyl-4, 5, 4 ', s'-dibenzothiacarbocyanine bromide; Curve E shows the sensitivity of the same emulsion when it contains both the 3,3'-dimethyl-9-phenyl-4, 5, 4 ', 5'-dibenzothiacarbocyanine bromide and the 1,3-diethyl-5- [di- (i ethyl-2 (1 H) -SS- naphthothiazolyliden) isopropylidene] barbituric acid contains. The sensitometric values of this emulsion are given in Example 5 of the list given above.

Fig. 3: Curve F shows the sensitivity of a conventional bromoiodosilver gelatin emulsion which is sensitized with 3,3'-diethyl-9- (3-pyrryl) -4, 5, 4 ', 5'-dibenzothiacarbocyanine bromide; Curve G shows the sensitivity of the same emulsion when it contains both 3,3'-diethyl-9- (3-pyrryl) -4, 5, 4 ', 5'-dibenzothiacarbocyanine bromide and 1,3-diethyl-5 - [di- (i-ethyl-2 (1 H) - /? - naphthothiazolylidene) isopropylidene] -barbituric acid contains. The sensitometric values of these emulsions are listed in Example 18 of the list given above.

For the invention come primarily the commonly used evolvable halosilver gelatin emulsions, for example chlorosilver gelatin, Silver chlorobromide gelatin, silver chloroiodine gelatin, bromoiodochlorosilver gelatin, silver bromide

708/308

E 10080IVal 57 b

Gelatin, silver bromoiodide gelatin emulsions. Although in the list given above Only silver bromide gelatin emulsions can also have excellent results Chlorobromosilver gelatin emulsions can be achieved. Also suitable for the method according to Invention emulsions in which the latent image is formed essentially within the halide silver grains as become known from U.S. Pat. No. 2,456,956.

The emulsions can be on any carrier, for example on glass, cellulose nitrate film, Cellulose acetate film, polyvinyl acetal resin film, paper or metal.

The silver halide photographic emulsions can be used in addition to the supersensitization combination according to the invention still further additives, such as chemical sensitizers, for example sulfur compounds, z. B. allylthiocarbamide, urea, allyl isothiocyanate, cystine, etc., also various Gold compounds, such as potassium chloroaurate, auritrichloride, etc. (USA patents2 54oo85,2 597856, 2597915), various palladium compounds, such as palladium chloride (U.S. Patent 2540086), Potassium chlorpalladate (U.S. Patent 2,598,079), etc., or mixtures of such sensitizers. Furthermore, the emulsions can contain, for example, anti-fog agents such as ammonium chloroplatinate (U.S. Patent 2,566,245), ammonium chloroplatinite (U.S. Patent 2,566,263), benzotriazole, Contain nitrobenzimidazole, 5-nitroindazole, benzidine, mercaptans or mixtures thereof (see Mees, "The Theory of the Photographic Process", Macmillan Pub., P. 460). The emulsions can also Hardeners, such as formaldehyde (USA.-Patent ι 763 533), chrome alum (USA.-Patent 1763533), Glyoxal (U.S. Patent 1,870,354), dibromoacrolein (British Patent 406750) etc., color couplers (e.g. U.S. Patent 2,423,730) or Contain mixtures of such additives. You can also use dispersants for color couplers as they come from U.S. Patents 2,322,027 and 2,304,940 can be used.

From the above listing it can be seen that, in certain examples, those in the supersensitization combinations The dye concentrations used do not match the concentrations when the dye was used correspond alone. This is precisely what can be seen under "supersensitization" according to the Invention is to be understood, namely that phenomenon that the combination of dyes gives greater sensitivity than either dye on its own at any concentration. Hence, in some cases, the dye concentration when it is used alone (optimal concentration), is not identical to the concentration in which it is in the supersensitization combination is used. There were in each case in the examples given in each of the test layers as far as possible the optimal conditions are chosen. Higher dye concentrations in the Supersensitization combinations are unnecessary and in some cases even harmful.

Claims (1)

PATENT CLAIMS: i. Photographic material with. at least one supersensitized halogen silver emulsion, preferably with at least one halogen silver gelatin emulsion, characterized in that the emulsion is a supersensitizing combination of at least one carbocyanine dye the formula Z ₁ - R-N (-CH = CH) _n ^ ₁ -C = CH-C = CH-C (= CH-CH) _m _. ₁ = NX -R ₁ and of at least one non-ionized dye of the formula NO, C = CH-C = CH-C = X Θ Q C-O contains. In the formulas, R and R ₁ each represent an alkyl group, preferably an alkyl group containing 1 or 2 carbon atoms, R ₂ preferably an aryl group or a pyrryl group, X an acid radical, m and η each 1 or 2, Z and Z ₁ the to complete a 5- to 6-membered heterocyclic nucleus, preferably one of the thiazole series, the benzothiazole series, the naphthothiazole series, the benzoselenazole series, the naphthoselenazole series, the benzoxazole series, the naphthoxazole series, the 2-quinoline series or the 4-quinoline series, required non-metallic atoms, R ₃ and R ₄ each have an alkyl group, preferably an alkyl group containing 1 or 2 carbon atoms, Z ₂ the nonmetallic atoms required to complete a heterocyclic nucleus of the benzothiazole series, the naphthothiazole series, the benzoselenazole series, the naphthoselenazole series or the naphthoxazole series, Z ₃ the nonmetallic atoms required to complete a heterocyclic nucleus of the naphthothiazole series O of the non-metallic atoms required for the naphthoselenazole series, Q the non-metallic atoms required to complete a nucleus of the indanedione series, the barbituric acid series, the thiobarbituric acid series or the isoxazolone series. 609 708/308 E 10080 IVa / 57b 2. Material according to claim ι, characterized in that the non-ionized dye is a compound the formula X = CH-C = CH-C = —R ₄ ■ \ / R, Q ^ s Θ C-O is, in which R ₃ and R ₄ each have an alkyl group containing ι or 2 carbon atoms, Z ₂ the nonmetallic atoms required to complete a heterocyclic nucleus, preferably the naphthothiazole series or the benzothiazole series, the benzoselenazole series, the naphthoselenazole series or the naphthoxazole series, and Q the to complete a core of the indandione series; the barbituric acid series, the thiobarbituric acid series or the isoxazolone series mean required non-metallic atoms. 3. Material according to claims 1 and 2, characterized in that the carbocyanine dye is a Compound of formula R-Ni-CH = CH) ₇ ^ ₁ -C = CH-C = CH-C (= CH-CH) ^ ₁ = NR ₁ c-,. x ζ _Δ is, in which R and R ₁ each have an alkyl group having 1 or 2 carbon atoms, R ₅ and R ₆ each a hydrogen atom, an alkyl group or an aryl group, Z ₄ the non-metallic atoms required to complete a pyrryl nucleus, m and w each ι or 2, X is an acid residue, Z and Z _{1 are} each used to complete a heterocyclic nucleus of the thiazole series, the benzothiazole series, the naphthothiazole series, the benzoselenazole series, the naphthoselenazole series; the benzoxazole series, the naphthoxazole series, the 2-quinoline series or the 4-quinoline series required non-metallic Atoms mean. 4. Material according to claims 1 to 3, characterized characterized in that the emulsion is a supersensitization combination of at least one Carbocyanine dye of the formula = CH-C = CH-C = NX-R ₁ R-N- and of at least one non-ionized dye of the formula -Z ₃ -. = CH-C = CH-C = - R ₄ \ Θ C-O contains. In the formulas, R and R _{1 are} each an alkyl group C _n H _{2n + 1} , η = ι or 2, R _{2 is} a mononuclear aromatic group of the benzene series, X is an acid residue, Z and Z _{1 are} each to complete a heterocyclic nucleus of the naphthothiazole series required non-metallic atoms, R ₃ and R ₄ each an alkyl group C TT w = i or .2, Z ₃ the 708/308 E 10080 IVa / 57b standing of a heterocyclic nucleus of the naphthothiazole series required non-metallic Atoms and Q are those required to complete a nucleus of the barbituric acid series non-metallic atoms. 5. Material according to claims 1 to 4, characterized characterized in that the emulsion is a supersensitization combination of at least one Carbocyanine dye of the formula R —N = CH-C = CH-C = N - R ₁ and of at least one non-ionized dye of the formula = CH-C = CH-C: contains. In the formulas, R and R _{1 are} each an alkyl group C _n H _{2n + 1} , η = ι or 2, R _{2 is} a mononuclear aromatic group of the benzene series, X is an acid residue, Z and Z _{1 are} each to complete a heterocyclic nucleus of the naphthothiazole series required non-metallic atoms, R ₃ and R ₄ each have an alkyl group C _m H _{2m + 1} , w = i or 2, Z ₂ the non-metallic atoms required to complete a heterocyclic nucleus of the benzothiazole series or the naphthoselenazole series and Q the non-metallic atoms required to complete a nucleus of the 2 -Thiobarbituric acid series required non-metallic atoms. = N -R ₄ \ Θ C-O 6. Material according to claims 1 to 5, characterized in that the emulsion is a supersensitization combination from at least one carbocyanine dye of the formula , .- Z-, ^Λ 2, .- Z ₁ -, R-NC = CH-C = CH-C = NR ₁ V X and at least one non-ionized dye the formula contains. In the formulas, R and R _{1 are} each an alkyl group C _n H _{2n + 1} , η = ι or 2, R _{2 is} a pyrryl group, X is an acid residue, Z and Z _{1 are} each the non-metallic atoms required to complete a heterocyclic nucleus of the naphthoxazole series, R ₃ and R ₄ each represent an alkyl group C _m H _{21n + 1} , W = I or 2 and Z ₃ the non-metallic atoms required to complete a heterocyclic nucleus of the naphthothiazole series and Q the non-metallic atoms required to complete a nucleus of the indanedione series. 7. Material with at least one supersensitized bromoiodosilver gelatin emulsion according to claims ι to 6, characterized in that the emulsion is a supersensitization combination from 3, 3'-dimethyl-9-phenyl-4, 5, 4 ', 5'-dibenzothiacarbocyanine bromide and 1,3-diethyl-5 - [(3-ethyl-2 (3 H) -benzothiazolylidene) - (i-methyl-2 (1 H) - /? - naphthoselenazolylidene) -isopropylidene] -2-thiobarbituric acid. 8. Material with at least one supersensitized bromoiodosilver gelatin emulsion according to claims ι to 6, characterized in that the emulsion is a supersensitization combination from 3, 3'-dimethyl-9-phenyl-4, 5, 4 ', 5'-dibenzothiacarbocyanine bromide and 1,3-diethyl-5 ~ [di- (i-ethyl-2 (1 H) - / 3-naphthothiazolylidene) isopropylidene] - contains barbituric acid. 9. Material with at least one supersensitized bromoiodosilver gelatin emulsion according to claims ι to 6, characterized in that the emulsion is a supersensitization combination from 3, 3'-dimethyl-9-phenyl-4, 5, 4 ', 5'-dibenzothiacarbocyanine bromide and 5 - [(3-ethyl-2 (3 H) -a-naphthothiazolylidene) - (1-ethyl-2 (1 H) - / 3-naphthothiazolylidene) -isopropylidene] -1 -methyl-2-thiobarbituric acid. 609 708/308 E 10080IV a / 57 b ίο. Material with at least one supersensitized bromoiodosilver gelatin emulsion according to claims ι to 6, characterized in that the emulsion is a supersensitization combination of 3,3'-dimethyl-o, -phenyl-4, 5, 4 ', 5'-dibenzothiacarbocyanine bromide and 5 - [di- (i-Ethyl-2 (iH) - ß - naphthothiazolylidene) - isopropylidene] - 1, 3 - di - (/ S-methoxyethyl) -barbituric acid contains. 11. Material with at least one supersensitized Bromiodilber gelatin emulsion according to Claims 1 to 6, characterized in that the Emulsion a supersensitization combination of 3-ethyl-3'-methyl-g- (2-methyl-3-indolyl) -4 ', 5', 6, ^ -dibenzoxaecarbocyanine perchlorate and 2- [di- (i-ethyl-2 (1 H) - / 3-naphthothiazolylidene) isopropylidene] -i, Contains 3-indandione. 1 sheet of drawings © 609 708/308 11.56