DE2148425B2 - Spectrally sensitized silver halide photographic emulsion - Google Patents

Description

C ₂ H ₅ each

C ₂ H ₅

7. Photographic silver halide emulsion, characterized in that it is a sensitizing combination from the dyes A, C and 1 or H and 1 or E and 4 or I and 4 contains.

to obtain spectral sensitivity distribution. In numerous cases, however, this is the case when it is used two or more sensitizing dyes available in combination low!

than it occurs when the dyes are used individually The so-called supersensitivity is even less common tion achieved with the use of two sensitizing dyes. The application of such a sensibili control technology is used, for example, in the USA.

■ ο Writings 2 533 426, 2 688 545 and 2 751298, dei German Patent 1 547 641 and in German Offenlegungsschrift 1 813 001.

The joint use of merocyanine dyes and carbocyanine dyes has also already been established tries. Merocyanine dyes are becoming more general adsorbed only flat on the silver halide, so that the formation of the I-aggregate of the carbocyanine dye is inhibited, so that with merocyanines generally no particularly high color sensitivities can be obtained.

From the French patent specification 994 762 and from the publication by M. Schouwenaars ir May be. et. Ind. Phot. 1944.15, pp. 146 and 147 is known Mixtures of a merocyanine dye and a carbocyanine dye for spectral sensitization to use.

The disadvantage of the known sensitizer mixtures is that the attainable spectral sensitivity wedge the sensitized silver halide emulsion layer still leaves something to be desired and that when used of the spectrally sensitized layers for the production of master copies for printing plates inadequate dot quality.

The object of the invention is therefore panchromatically sensitized silver halide emulsions indicate that there is an increased spectral and general sensitivity and, in particular, a high one Have sensitivity in the red wavelength range and when used in manufacture Master copies for printing plates deliver excellent dot quality.

The invention is based on a spectrally sensitized silver halide emulsion containing a combination of sensitizers from a predominantly red-sensitizing carbocyanine dye with two heterocyclic ones Cores from benzothiazole, benzoselenazole, / f-naphthoselenazole and ß-naphthothia zollinie, the formula

•so

55

The invention relates to spectrally sensitized photographic silver halide emulsions containing a Sensitization mixture of a predominantly red sensitizing carbocyanine dye and a predominantly green sensitizing merocyanine dye is spectrally sensitized

It is known that for a continuous, panchromatic spectral sensitization usually at least two sensitizing dyes, namely a predominantly red-sensitizing and a predominantly green-unsensitizing sensitizer dye must be used together to achieve the desired

C = CH-C = CH-C

• (D

where R ₁ and R _{2 are} each a lower alkyl group, A is a methyl or ethyl group, Z, and Z _{1 are} each the non-metallic atoms required to complete a benzothiazole, benia selenazole, / J-naphthoselenazole or / J-Ni phthothia zolkeras, X _{1 is} an anion and m is the number 0 or 1, where m = 0 if an intermolecular salt is formed and at least one, predominantly green-sensitizing merocyanine dye and optionally a further green-sensitized cyanine dye and

is characterized in that as a merocyanine dye a tetrazole merocyanine of the formula

N - Ν --Β

CH-CH

Z ₃ (11)

N
R ₃

15th

where R ₃ and R ₄ each represent a lower alkyl group, B a lower alkyl or aryl group, Z ₃ the group = N —R ₅ , an oxygen atom or sulfur atom and R ₅ a lower alkyl group.

The carbocyanine dyes which correspond to the general formula I have a sensitization maximum between 595 and 690 nm, many of which have high red sensitivity. Many Sensitizing dyes which correspond to the general formula II have a sensitization maximum between 460 and 560 nm, while others did not have a remarkable spectral sensitization effect even when used together with a silver iodide emulsion. With the dyes of the formula II a tetrazole derivative nucleus and a merocyanine nucleus are linked via a dimethine chain.

In the above formulas I and II, R ₁ and R _{2 represent} a lower alkyl group, e.g. B. methyl, ethyl, propyl, y-sulfopropyl, y-sulfobutyl, o-sulfobutyl,, 3-hydroxyethyl, ß-carboxyethyl, allyl or similar groups, A is a lower alkyl group, preferably methyl or ethyl group, Z ₁ and Z _{2 are} the non-metallic atoms required to complete a benzothiazole benzoselenazole, ß-naphthoselenazole or / i-naphthothiazole nucleus, the nuclei optionally being replaced by a halogen atom, e.g. B. chlorine or bromine, a lower alkyl group, e.g. B. methyl or ethyl group, alkoxy group, e.g. B. methoxy or ethoxy group, alkoxycarbonyl group, e.g. B. methoxycarbonyl or ethoxycarbonyl group, aryl group, e.g. B. phenyl or toluyl group, X _{1 is} an anion, ζ. B. chloride, bromide, iodide, methyl sulfate, p-toluenesulfonate, and R ₃ and R ₄ each represent a lower alkyl group, e.g. B. methyl, ethyl, n-propyl, γ-sulfopropyl, γ-sulfobutyl, "5-sulfobutyl, jff-hydroxyethyl," 5-carboxybutyl or allyl, B is a lower alkyl group, z. B. methyl or ethyl group, or an aryl group, e.g. B. phenyl or toluyl group, Z ₃ the group = N - R ₅ , oxygen or sulfur, where R _{5 is} a lower alkyl group, e.g. B. means ethyl and / i-hydroxyethyl group.

The invention achieves that the sensitivity to red, which the carbocyanine dyes of general formula I, and the general sensitivity to white light is remarkable is increased. The spectrally sensitized emulsions of the invention also provide images of excellent dot quality.

The use of a specific combination of a carbocyanine dye of the general formula I. and a merocyanine dye of the general formula II having a maximum sensitivity in one Wavelength range not exceeding 500 nm, i.e. H. only in the blue area, also results in a photographic one Emulsion that is highly sensitized to the red wavelength range and sensitive to red Layer of color photographic materials is particularly suitable.

The increased sensitivity to red shows that the merocyanine of the general formula II the J band of the carbocyanine sensitizing dyes of the general Formula I reinforced.

The tendency to the mentioned J-band amplification as a result of the oversensitization effect and the The effect of preventing desensitization is achieved through the use of an additional orthochromatic Sensitizing dye, e.g. B. 2,2'-cyanine or pseudocyanine, not affected.

The sensitizing dyes of the general formula I do not result in any deterioration in dot quality, as is often the case with lith development which is used for the production of master copies for printing forms.

The merocyanine dye of the general formula II significantly enhances the lith development and is essential for achieving good dot quality responsible. Accordingly, the oversensitization technique according to the invention is particular for panchromatic sensitization of light-sensitive silver halide emulsion layers useful, which are subjected to a lith development for the production of master copies for printing forms should be

Preferably at least one of the N-substituents of the heterocyclic nuclei of the carbocyanine dye is a sulfoalkyl or carboxyalkyl group or Z _{3 of} the general formula II is an oxygen atom or A of the general formula I is a methyl group and Z _{3 of} the general formula II is a sulfur atom.

A particularly advantageous embodiment of the invention consists in that the carbocyanine dye is selected from the group of dyes A to L listed below and the merocyanine dye is selected from the group 1 to 10 listed below:

Sensitizing carbon cyanine dyes

A.

11

Cl

CH ₃

> = CH- C = CH

(CHj) ₃ SO ₃ H

QH ₅

s _x !

V = CH-C = CH

VAn / (CHj) ₃ SO ₃ HN

C ₂ H ₅ CH-C = CK

12th

\ (CHj) ₃ SO ₃

/ SxAs

CH ₃

(CHj) ₃ SO ₃ -

Cl

N '

Cl Cl

cio;

(CHj) ₂ OH

(CH ₂ ) jOH

C ₂ H ₅

CH - C = CH

S _n A

H, C0

(CHj) ₃ SO ₃ HN (QH ₅ ) ₃ (CH ₂ ) ₃ SO ₃ "

GH

COO <

0ΓΙ5

VAn / QH ₅ CH - C = CH

(CHj) ₃ SO ₃ -

C ₂ H ₅ CH - C = CH

SoA.

/ C ₂ H ₅ COO

QH ₅

\ = CH - C =

CH

(CH ₂ ) ₃ SO ₃ "

SoA

N ^ VA

(CH ₂ ) JSO ₃ -

(CH ₂ ) ₃ SO ₃ HN (QH ₅ ) ₃

QH ₅

H ₃ C

(CH ₂ ) ₃ SO ₃ H

ί CH ₃

(CH ₂ J ₃ SO ₃ -

J.

13th

CH ₃

_N / ^GH - ^c - ^a - ^ _N / vy

Br "QH ₇

(CH ₂ J ₂ COOH

14th

K.

CH ₃

V = CH- C = CH-C _{+ Ν} / ^ n

(CH ₂ ) ₂ CHCH ₃

CH ₂ - CH = CH ₂

L. CH ₁

) = CH-C = QH ₅

H, C

QH ₅

Sensitizing merocyanine dye N - N-CH ₃

Il I

N
QH ₅

CH ₂ -CH = CH,

J = CH-CH

ONS

4th

N-N-CH ₃

N
QH ₅

N - N - Il
N

\
N

QH ₅

CH - CH == i

ONS QH ₅

CH - CH = t N - QH ₅

55

6th

ONS CH,

N N-CH ₃

CH-CH

ONS

CH ₂ CH - CH ₂ QH ₅

NN - CH ₃

CH-CH

(CH ₂ J ₂ OH 'ONS QH ₅

N N-CH ₃

Il

QH ₅

CH = T S

NS QH ₇

ONS
CH ₂ -CH = CH ₂ C ₂ H ₅

N
Il -N-CH ₃ N CH = t- S. N
\ J = CH- I. N CH ₃ I. / \ Ä O N S CH ₁ COOH

N - N

C ₂ H ₅

N-N-CH ₃

Il

C ₂ H ₅

= CH - CH == r S.
■ N I. I. / \ A C ₂ H ₅ 0 N S (CH ₂ ) ₂ SO ₃ K

35 A method introduced Usually, the dyes in a solvent such. B. methanol, ethanol, water, cellosolve, water-soluble ketones or the like, dissolved and added to an emulsion. On the other hand, the dyes can be dissolved in an oil which is sparingly soluble in water, and added and dispersed in water or hydrophilic colloid.

The molar ratio of the sensitizing carbocyanine to the sensitizing merocyanine contained in an emulsion can vary in a wide range from 9: 1 to 1: 9 depending on the desired effect. The amount of each of these dyes is preferably in the range of 1 x 1 (T ⁶ to 1 x 10 ^-3 moles per mole of silver in accordance with the nature of the emulsion used.

The photographic emulsion according to the invention can moreover undergo hypersensitization or Supersensitization can be subjected in a known manner. In the manufacture can use common Additives, e.g. B. chemical sensitizers, stabilizers, anti-bronzing agents, hardeners, surfactant, antifoggant, plasticizer, development accelerator, color coupler, Fluorescent brightening agents or the like, more commonly used in the photographic emulsion according to the invention Way to be included.

The photographic emulsion according to the invention can be coated in a conventional manner a suitable carrier, e.g. B. a glass plate, a film or a sheet of cellulose derivatives, synthetic Resins, on baryta paper or paper coated with resin.

The invention is explained in more detail below with the aid of examples.

40

These embodiments of the invention achieve particularly advantageous effects.

The sensitizing carbocyanine dyes according to of the invention can be used by those skilled in the art with ease on the basis of the provisions that in U.S. Patents 2,238,231, 2,503,776, and 3 177 210 and in German patents 929 080 and 1,072,765 or in German patent specification 1,019,418.

The spectral sensitization according to the invention is for gelatin-silver halide photographic emulsions useful. It can also be used for an emulsion that has a different hydrophilic polymer contains as gelatin, e.g. B. agarcollodium, water-soluble cellulose derivatives, polyvinyl alcohol, polyvinyl pyrrolidone copolymer and other synthetic hydropWle resins, natural hydrophilic polymers or gelatin derivatives.

The photographic emulsion of the present invention is appropriate a mixed silver halide emulsion containing at least two components of silver chloride, silver chromide and silver iodide. To the Preparation of the spectrally sensitized photographic emulsion according to the invention is the Sensitizing dye according to the invention in a photographic emulsion according to an ordinary one

Examples

Halogen silver photographic emulsions were prepared by adding the dyes separately to the sensitizer mixture according to the invention to an iodobromide silver emulsion (AgI: AgBr = 7 mol: 93 mol) manufactured. In addition, a photographic silver halide emulsion, which according to the invention is one of the Carbocyanine dye and the merocyanine dye contained. Each of these emulsions was made applied as a coating to a triacetyl cellulose film base and dried, followed by white light using 64 lux daylight and at the same time through a red filter that is permeable to light with longer wavelengths than 580 nm, or a blue filter that allows light to pass through door with wavelengths im Range is between 400 and 490 nm and has a percentage maximum transmission at 450 nm, exposed and developed at 20 ° C for 8 minutes. The developer used here has the Composition given in Table 1 below.

Table I.

Metol 2 g

Sodium sulfite 100 g

Hydroquinone 5 g

Borax 2 g

Water, rest on 11

Il

In Table II below are the inherent white light sensitivity and red sensitivity, by the independent addition of the sensitizing dyes, as described above, and / or were obtained by adding them together, and the Eigeaensensitivity with Indicated in relation to that of the starting emulsion.

Table II

request
No. example
No. Sensitizing dye
Additional amount (ICT ⁵ mol / kg
the emulsion) 1 (2) emulsion Maxim.
Sensitive
ization Relative
White sensitivity Relative
Red recept. Personal perception Spectrogram 1 (4) (nm) 1 A (2) 1 (8) AgBr / J 600 90 35 94 A (4) 1 (4) AgBr / J 630 100 90 90 Fig. 1 A (8) 1 (4) AgBr / J 632 130 120 80 Curve 5 1 (4) AgBr / J 540 82 0 100 11 (4) AgBr / J 540 88 0 116 Curve 1 1 (4)
12 (4) AgBr / J 540 102 0 120 1 A (4) 9 (2) AgBr / J 632 140 120 120 A (8) 9 (4) AgBr / J 632 170 146 120 Curve 6 2 2 A (4) 9 (8) 9 (4) AgBr / J 630 164 120 116 3 3 A (4) 9 (4) AgBr / J 630 155 120 110 4th 7 (2) AgBr / J 542 80 0 94 7 (4) AgBr / J 542 84 0 100 7 (8) AgBr / J 542 86 0 100 4th A (4) 7 (4) AgBr / J 632 120 100 100 A (8) 7 (8) AgBr / J 632 150 120 100 5 8 (2) AgBr / J 540 90 0 110 8 (4) AgBr / J 540 96 0 116 8 (8) AgBr / J 540 100 0 116 5 A (4) AgBr / J 610/630 120 100 105 A (4) AgBr / J 610 150 100 116 6th AgBr / J 530 74 0 90 8 (4) AgBr / J 530 76 0 88 8 (4) AgBr / J 530 76 0 88 L (2) AgBr / J 600 70 25th 94 L (4) AgBr / J 630 90 60 88 L (8) AgBr / J 630 110 90 80 6th L (4) 6 (2) AgBr / J 628 100 68 88 L (8) 6 (4) AgBr / J 628 125 100 80 7th B (2) 6 (8) AgBr / J 655 95 75 85 B (4) 6 (4) AgBr / J 660 110 135 88 Fig. 6 B (8) 6 (4) AgBr / J 665 130 170 78 Curve 15 AgBr / J 535 80 0 110 AgBr / J 535 100 0 110 Curve 9 AgBr / J 545 107 0 96 7th B (4) 6 (4) AgBr / J 660 135 175 88 Curve 16 B (8) 6 (8) AgBr / J 665 160 210 80 8th J (2) AgBr / J 600 85 30th 100 Fig. 4th J (4) AgBr / J 630 100 88 100 Curve 10 J (8) AgBr / J 630 128 105 98 8th J (4) AgBr / J 630 135 108 110 Curve 11 J (4) AgBr / J 612 140 100 110

continuation

rsuch
No. example
No. Sensitizing dye
Additional amount (10 ~ ⁵ jno '/ kg
the emulsion) 2 (2) emulsion Maxim.
Sensitive
ization Relative
White sensitivity Relative
Red recept. ligen-receiving Spectrogram 2 (4) (nm) 9 I.
C (4) 2 (8) AgBr / J 654 100 100 95 Fig. 2 C (6) 2 (4) AgBr / J 658 108 120 92 Curve 3 C (8) 2 (8) AgBr / J 660 110 130 90 3 (4) AgBr / J 70 0 100 3 (8) AgBr / J 76 0 105 3 (4) AgBr / J 85 0 116 Curve 2 9 C (6) 3 (8) AgBr / J 660 135 135 98 C (6) AgBr / J 660 152 146 100 Curve 4 10 AgBr / J 520 80 0 94 AgBr / J 520 88 0 90 10 C (6) 3 (4) AgBr / J 660 118 130 94 C (6) 3 (8) AgBr / J 660 118 140 94 11 G (1) AgBr / J 634 60 30th 94 ~ Fig. 5 G (2) AgBr / J 640 76 43 90 Turn 13 G (4) 5 (2) AgBr / J 640-645 78 66 85 11 G (2) 5 (4) AgBr / J 655 82 60 90 G (2) 5 (8) Agbr / J 655 82 73 90 12th D (6) 5 (4) AgBr / J 660 105 150 85 D (8) 5 (8) AgBr / J 660 112 160 80 AgBr / J 500 80 0 100 AgBr / J 500 90 0 100 AgBr / J 500 94 0 104 12th D (6) 5 (4) AgBr / J 660 140 170 85 D (6) 5 (8) AgBr / J 658 145 175 100 13th F (2) 4 (4) AgBr / J 650 73 45 98 F (4) 4 (8) AgBr / J 650 96 60 98 F (8) 4 (4) AgBr / J 650 98 60 95 13th F (4) 4 (8) AgBr / J 640 108 100 100 F (4) 4 (4) AgBr / J 640 108 76 100 14th 4 (8) AgBr / J 500 80 0 100 Fig. 5 AgBr / J 500 83 0 104 Curve 12 14th F (4) AgBr / J 642 110 88 94 F (4) AgBr / J 642 110 83 104 15th 15th G (2) 6 (4) AgBr / J 640-660 80 54 90 Curve 14 G (2) 6 (4) AgBr / J 655 85 70 90 16 K (2) AgBr / J 600 75 30th 94 K (4) AgBr / J 630 90 85 94 K (8) AgBr / J 630 110 105 90 16 K (4) 2 (4) AgBr / J 630 135 100 100 Fig. 3 K (8) 2 (8) AgBr / J 030 148 110 100 Curve 7 17th H (1) 5 (4) AgBr / J 686 80 164 88 H (2) 5 (8) AgBr / J 686 85 172 82 H (4) AgBr / J 686 85 188 60 17th H (1) AgBr / J 684 90 210 90 H (1) AgBr / J 684 94 210 104 Curve 8 18th 18th H (1) AgBr / J 686 90 208 94 H (1) AgBr / J 686 90 170 98

continuation

Is

attempt
No. example
No. Sensitizing dye slofT
Additional amount (1 (T ⁵ mol / kg
the emulsion) 1 (4) emulsion Maxim.
Sensitive
ization Relative
White sensitivity Relative
Red recept. Personal perception 1 (8) (nm) 19th I (4) AgBr / J 650 80 120 86 I (6) AgBr / J 650 85 135 82 I (8) AgBr / J 650 85 140 75 19th I (6) 5 (4) AgBr / J 650 96 152 90 I (6) 5 (4) AgBr / J 650 110 178 104 20th E (2) 10 (4) AgBr / J 650 90 73 92 E (4) 10 (8) AgBr / J 650 96 88 88 E (8) 10 (4) AgBr / J 650 100 104 85 20th E (4) 10 (4) AgBr / J 650 108 94 94 E (8) 10 (4) -,
11 (4) J. AgBr / J 650 110 110 98 21 AgBr / J 540 85 0 106 1 (4) AgBr / J 540 96 0 110 21 L (4) 1 (4) 1 AgBr / J 628 120 72 96 L (8) 11 (2) 1 AgBr / J 628 138 108 94 22nd 22nd L (4) AgBr / J 628 146 108 96 23 A (6) \
C (0.3) J 7 (4) AgBr / J 632 120 120 86 23 A (6) 1
C (0.3) / AgBr / J 632 152 152 108 24 24 A (6) 1 6 (4) AgBr / J 630 178 152 102 C (0.3)} 25th H (Dl
1 (4) 1 1 (4) AgBr / J 670 108 260 86 25th H (1) 1
I (4) 1 AgBr / J 670 124 268 100 26th η (in
A (4) 1 AgBr / J 680 100 164 84 26th η (in
A (4) 1 AgBr / J 680 120 178 98 27 H (1) 1
B (4) 1 AgBr / J 680 118 200 27 H (1) 1
B (4) 1 AgBr / J 680 140 234 82 96

In Table II above, the white light sensitivity and the red sensitivity are relative to the corresponding sensitivities when exposed to a daylight source without a filter or through a red filter using a sample containing 4 * 10 "* mol / kg emulsion des Sensitizing Dye C obtained and taken as 100 are reported. The intrinsic sensitivity is relative to the sensitivity indicated, which was obtained on exposure of the starting emulsion through a blue filter and with 100 was accepted.

From the results in Table II above, it can be seen that the white light sensitivity and

the sensitivity to red caused by the use of the sensitizing dye Invention obtained, essential than the corresponding sensitive ^ the separated or independent

Dyes were obtained.

As in Examples 2, 3 and 22 in de Table II shows the durc nation of at least one of the Ca substances and at least one of the Meroc obtained sensitization effect not if, in addition, an already known table sensitizing dye, z. B. specified below, also used <

chromatic sensitizing dyes which can be used together with the sensitizing dyes according to the invention are used are e.g. 2,2'-cyanine and pseudocyanine dyes (e.g. 2'-thiacyanine) of those below given chemical structural formula, however other similar dyes are used can get.

Comparative example

There were the carbocyanine dyes B and H used according to the invention and those according to the invention Merocyanine dyes I and VI used with the dye combination according to the French patent 994 762, which are given below as dyes Xl and XTlI, compared:

CH-CH

1 kg of the emulsion was placed in a pot which was heated to 45 ° C. to dissolve the emulsion became. The sensitizing dyes were added individually and in combination to the emulsion. In

In the same way, the sensitizing dyes became XI and XIII added to the emulsion. Then 40 ecm of a 1% aqueous solution of 2-methyl-4-hydroxy-1,3,3a, 7-letrazainden added as a stabilizer. Then 40 ecm became one

, ο 0.5% aqueous solution of polyoxyethylene laurine ester (n = 40) and 20 ecm of a 2% aqueous solution of the sodium salt of 6-hydroxy-2,4-dichloro-triazine added and the emulsion used finally obtained, the emulsion was stirred at 45 ° C. The resulting emulsion was coated on a polyethylene terephthalate film and dried to have a dry thickness of 6 microns. This film was cut into strips, which are subjected to wedge exposure using a sensitometer of a color temperature of 5400 ⁰ K. Three common filters, namely a blue filter, a green filter, and a red filter, were used. On the surface of the photographic material, a gray contact grid for positive use was closely applied at 150 lines / 2.5 cm. The exposed recording material was developed and fixed using the following developer solution, which is generally used for lithographic development, at 20 ° C. for 1.5, 2.5 and 4 minutes.

The sensitivity is given relative to the corresponding sensitivities achieved by an exposure when the optical density of the stripes was less than 1.50.

35

40

45

CH ₃

> CH = C-CH = <

Br

(XIlI)

As a photographic silver halide emulsion, a silver chlorobromoiodide emulsion having the following composition was used:

Bromine ion content 17 mole percent Iodine ion content 0.2 mole percent Silver content 1.3 mol / kg

emulsion

Average diameter of the Silver halide particles ... about 0.6 μm

Composition of the developer solution

Water 500 ecm

Hydroquinone 15g

Addition product of formaldehyde and sodium hydrosulfite .. 50 g

Potassium carbonate 35 g

Triethanolamine 90 g

Sodium sulfite 2.5 g

Boric acid 5.0 g

Potassium bromide 2.0 g

1000 ecm of water

Composition of the fixing solution

Water 600 ecm

Sodium thiosulfate 360 g

Ammonium sulfate 60 g

Anhydrous sodium sulfite 15g

Glacial acetic acid 13.5 g

Boric acid 7.5 g

Potassium alum 15 g 1000 ecm of water

The quantities added as well as the recovered * Results are from Tables I below and IV as well as from the accompanying FIGS. 7, 8, 9 and evident.

The point quality was according to the German Areas A, B and C according to the point edge sharpness, with A being the sharpest.

25th

26th

Table III

Dye and amount used - B. Mol / kg emulsion) - Relative white re (ICT ⁵ - sensitivity emp H 2 - 100 GXIII) 4th - 100 8th PCI) 4 100 8th 96 12th 96 H 4th 80 4th 8th 74 pain) 4th 4th 96 8th 8th 96 8th - 92 2 - 88 B. 4th - 120 8th 6 4 134 8th 134 12th 100 4th 100 4th 8th 96 B. 4th 4th 145 8th 1 4 150 - 8th 150 12th 100 4th 96 4th 8th 96 4th - 170 1 - 160 2 2 4 100 - 8th 100 12th 96 - 96 I. 8th 92 1 4th 130 2 144 140

Sensitizing dye

and amount used

(1 (T ⁵ moles)

H 2 1 4th 1 - H 2 2 pcm) 4th 8th 16

Relative red

0 25 36 40

0 40 36 40 40

60 100 120

135 135 156

135 130

94 120

125 125 162

Table IV

Self-sensitivity

Relative sensitivity when developing during

1.5 min. BGR

8th
16
8th
16

87

4-

4-

4-

4-

87 108 270

4- 145 210

4-

215
200

2.5 min
BGR

100

96

4-

66

76

145

155

166

170

170

100

100

50

94

145

160

200

380

263
500

350

340

4-

132

380455

4 min. G 100 100 86 80 84 60 56 80 76 80 68

112 112 108

110 114 116 120 120

110 110 100

760 660 580 740 960 850 880 730 750 800

2850
2700

700
1350
4570

veil

14 min. BGR

Spectrogram

0.06 Fig. 7 No. 1 0.06 0.08 Fig. 7 No. 2 0.09 0.08 0.09 F i g. 7 No. 3 0.11 0.10 0.10 0.11 0.12 Fig. 8 No. 4 0.06 0.09 Fig. 8 No. 5 0.09 0.06 0.06 Fig. 8 No. 6 0.08 0.09 0.09 F i g. 9 No. 7 0.09 0.06 0.06 Fig. 9 No. 8 0.08 0.09 Fig. 10 No. S 0.09 0.06 Fig. 10 No. H 0.06 0.06 0.06 Fig. 10 No. 1 0.06 0.06 0.06 0.06

Point quality

λ5Μιη. BGR

B B

AA A ACBC

4 min. BGR

B B A Λ A

Sensitizing fiber

and amount used

(1 (Γ ⁵ mol)

P (IlI) 8

(XI) 8 16

(Xl) 8 16

27

continuation

ffe

28

Relative sensitivity when developing during

, 5 min. R. 2.5 min B. G G ₊ 80 120 ₊ + 105 220 + + 225 485: 130 + 240 475: 145

R. B. 1050 + 1400 217 950 210 1050

4 min. G

260

480

9500

9450

2000 1850

Point quality

1.5 min.

, 5 Wed 1 R. B. 4 min B. G C. Ci B. B. - C. C. B. B. C. C. C. B. B. C. C. C. B. B. C.

The dot quality was classified into 3 levels A, B and C in the order of the dot edge sharpness (A has the greatest Sharpness) in comparison with that of the strips divided for 2.5 minutes after development.

1 sheet of drawings

Claims (6)

Patent claims: 1. Spectrally sensitized silver halide photographic emulsion; containing a sensitizer combination of a predominantly red sensitizer Carbocyanine dye with two heterocyclic nuclei from the benzothiazole and benzoselenazole ß-naphthoselenazole and / J-napbthothiazole series, the formula R, = CH-C = CH-C where R ₁ and R _{2 are} each a lower alkyl group, A is a methyl or ethyl group, Z ₁ and Z _{2 are} each the non-metallic atoms required to complete a benzothiazole, benzoselenazole, / 3-naphthoselenazole or / S-naphthothiazole nucleus, X ₁ is an anion and m is the number 0 or 1, where m = 0 if an intermolecular salt is formed, and at least one, predominantly green-sensitizing merocyanine dye, and optionally a further green-sensitized cyanine dye, characterized in that the merocyanine dye is a IO 20th 35 tetrazole merocyanine of the formula
NN ~ B N
R ₃ CH = | Z ₃ (11) Ä Λ
ONS R ₄ where R ₃ and R ₄ each represent a lower alkyl group, B a lower alkyl or aryl group, Z ₃ the group - N - R ₅ , an oxygen atom or sulfur atom and R ₅ a lower alkyl group. 2. Photographic silver halide emulsion according to claim 1, characterized in that at least one of the N-substituents of the heterocyclic nuclei of the carbocyanine dye Is sulfoalkyl or carboxyalkyl group 3. Photographic silver halide emulsion according to claim 1, characterized in that Z _{3 of} the general formula II denotes an oxygen atom. 4. A photographic silver halide emulsion according to claim 3, characterized in that A of the general formula I represents a methyl group and Z _{3 of} the general formula II represents a sulfur atom. 5. A photographic silver halide emulsion according to claim 1, characterized in that the carbocyanine dye from the group of dyes A to L and listed below the merocyanine dyes are selected from group 1 to 10 listed below: Sensitizing carbocyanine dyes C ₂ H ₅ (CH ₂ J ₄ SO ₃ - B. (CH ₂ J ₃ SO ₃ H (CH ₂ J ₃ SO ₃ / V ^S \ ' / ^S V \ I V = CH-C = CH ^ _+] 1 Cl (CH ₂ J ₃ SO ₃ HN (CH ₂ J ₃ SO ₃ - Cl Cl QH ₅ 'V = CH-C = C (CH ₂ ) ₂ OH QH ₅ H, C0 V = CH-C = (CH ₂ ) ₃ SO ₃ HN (QH _S ) 3 ClO ₄ T (CH ₂ J ₂ OH Cl J * (CH ₂ ) jSO ₃ COOCH ₃ (CH ₂ ) ₃ SO ₃ - QH ₅ / S COOH (CH ₂ ) j SOj H. Ct QH ₅ (CH ₂ ) jSOjHN (QH ₅ ) ₃ (CH ₂ ) jSO ₃ - J. H ₃ C QH ₅ (CH ₂ ) ₃ SU ₃ H CH ₃ (CH ₂ ) ₃ SO., CH ₃ CH - C = CH Br " I QH ₇ (CH ₂ ) ₂ COOH κ. CH ₃ S _x I V = CH-C = C N ⁷ (CH ₂ J ₂ CHCH ₃ SO ₃ " CH ₂ - CH = CH ₂ L. / v ^s CH ₃ CH-C = C ₂ H ₅ H ₁ C C ₂ H ₅ Sensitizing microcyinine dye N- N : h = | S.
I. Il
N
\ I. I. C ₂ H ₅ / \ / Λ ON
I. S. I.
CH , -CH = CH, - Ν - CH ₃ , I = CH-C 2nd N.
I! N- - CH ₃ CH = J \,
N Il
N
\ -CH- O N
j
C ₂ H ₅ -0 Λ
S. C ₂ H ₅ 3. N - N- < H ' NC ₂ H ₅ Λ Λ ONS CH ₃ 4 ° 45 CH-CH = 5. N-N-CH ₃ ! I (CH ₂ ) ₂ OH -0 ONS C ₂ H ₅ 6. N - N-CH ₃ II N
C ₂ H ₅ ONS C ₃ H ₇ 7. NN - CH ₃ CH-CH = T S IN IN - I. ONS CH, -CH = CH, C ₂ H, 4. N N-CH ₃ I! I. N U CH- CH ι ι Λ λ ONS CH ₃ -CH = CH; CH. SN - N - CH ₃ CH-CH N
I.
CH, ONS i CRCOOH (CH ₂ ) ₂ SO ₃ K 6. A photographic silver halide emulsion according to claim 1, characterized in that the additionally contained orthochromatic sensitizing dye is a 2,2'-cyanine or a Pseudocyanine of the formula