DE1806997A1 - Optically sensitized photographic light-sensitive material - Google Patents

Description

4th NOV. 1968

Gs / Stf

Optically sensitized photographic, photosensitive material

The present invention relates to photographic materials with at least one light-sensitive silver halide emulsion, the light-sensitivity of which extends to the extreme red Range of spectrum extends. The invention relates in detail to photographic silver halide materials having camera sensitivity, uniform spectral sensitization from green to yellow and red to the near infrared range of the spectrum show. Photographic materials of this type are of interest to aerial photography.

It is known the natural spectral sensitivity of photographic Silver halide emulsions expand into the green, yellow, and red regions of the spectrum by adding their incorporated suitable optical sensitizers from the class of cyanine dyes. Panchromatic silver halide emulsions

-G 426 909828 / UOO

for the usual picture photography have a sensitivity which does not exceed 700 mn.

The sensitization of photographic silver halide emulsions with camera sensitivity in the deep red area between -oü nm and about 760 nm with the aim of photosensitive materials Manufacture that are equally sensitive from the green to the far red or near infrared region of the spectrum presents a number of difficulties. Although sii.d various sensitizing dyes known for Hesen purpose. z. B. pentamethine dyes, heptamethine dyes, tetramethine merocyanine dyes and rhodacyanine dyes, however, adhere most of the dyes have serious disadvantages if they are used for the sensitization of highly sensitive silver bromide iodide or bromide chloride iodide emulsions with camera sensitivity can be used.

The pentamethine and heptamethine dyes are unsuitable for use in combination with other sensitizers in the above sense for shorter wavelength ranges. They generally deliver in camera speed photographic materials too little sensitizing effect in the deep red area, they tend to obscure the emulsion and show one inadequate storage stability.

The tetramethine merocyanine and rhodacyanine dyes are also unsuitable in connection with sensitizers for the

AG 426 - 2 -

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shorter wavelength range, as it is the inherent sensitivity in photographic materials with camera sensitivity of the emulsion and also reduce the sensitizing effect in the deep red region of the spectrum.

It has now been found that rhodacarbocyanines, together with sensitizers for the green and red regions of the spectrum, are outstandingly suitable for the production of photographic materials with camera sensitivity, namely a uniform spectral sensitivity from the green region through the yellow and red to the extremely red region of the spectrum * without desensitization is sought.

In particular, the present invention is directed to panchromatic photosensitive silver halide emulsions, whose sensitivity extends to the extremely red (or the near infrared) region of the spectrum. The emulsions acquire this property by giving them a rhodacarbocyanine incorporated, its sensitizing effect over 700 mn and that of the following general formula I corresponds, as well as at least one carbocyanine according to the overnight general formula II:

r - Z ₁ -, * 5 / S _N * 4 r - Zr - i

I. R ₁ -NO = CH-C = CC = CH-C = CH-C - & - R,

O = CN ⁺

AG 426 - 3 -

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where mean:

R-, and Rp = a typical for cyanine dyes substituent on the cyanine nitrogen atom, z. B. an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl including a substituted alkyl group such as ß-hydroxyethyl, ß-acetoxyethyl, carboxymethyl and carboxyethyl according to German patent 704,141, sulfoalkyl as described in British patent 742,112 z. B. sulfoethyl, sulfopropyl, sulfobutyl, sulfitoalkyl as described in French patent 1,149,769, for example sulfate 0 propy1 and sulfatobutyl, the group -A-CO-OB-SO ₂ -OH where A and B have the meaning given in British patent 886,271 have, for example, a sulfocarbomethoxymethyl group, a 5 sulfocarbopropoxymethyl group, a sulfocarbobutoxymethyl group, a p-sulfocarbobutoxybenzyl group, the -AW-NH-VB group in which A, W, V and B are those in British Patent 904,332 have given meaning, such as an N- (methyleulfonyl) -carbamylmethylgruppe, / ■ - (AcetylsulfamylJ-propyl, a cf- (Aeetylsulfamyl) -i3utyl'-

^ H
group «the group AP. where A is the British patent

0 OH;
font 886,270 has the meaning given} an aralkyl group such as a benasyl group including a substituted aralkyl group _; such as carboxybenzyl and sulfobenzyl, an aryl group such as phenyl including a substituted aryl group such as carboxyphenyl, a cycloalkyl group such as cyclohexyl or an allyl group,

R, «alkyl, such as ethyl including a substituted alkyl group such as ß-sulfoethyl, ß-aminoethyl, aralkyl such as benzyl

AG 426 '- 4 -

909828 / UOO

finally a substituted aralkyl such as carboxybenzyl, Aryl such as phenyl including a substituted aryl such as p-carboxyphenyl and allyl, ■

R. = an alkoxy group such as methoxy, an amino group or a substituted amino groups such as anilino and N-methyl-N-acetylamino, R ^ = hydrogen, optionally substituted alkyl, optionally substituted aralkyl or optionally substituted aryl,

Z, and Z ₂ = the non-metallic atoms which are necessary to complete a heterocyclic ring of the Ihiazolserien (z. B. thiazole, 4-methylthiazole, 4-phenylthiazole, 5-Methylthia- g zole, 5-phenylthiazole, 4, 5-dimethylthiazole, 4,5-diphenylthiazole, 4- (2-thienyl) -thiazole), or a ring from the benzothiazole series (e.g. benzothiazole, 4-chlorotenzthiazole, 5-chlorobenzthiazole, 6-chlorobenzthiazole, 7-chlorobenzothiazole, 4-methylbenzthiazole, 5-methylbenzthiazole, 6-methylbenzthiazole, 5-bromobenzthiazole, 6-bromobenzthiazole, 4-phenylbenzthiazole, 5-phenylbenzthiazole, 4-methoxybenzthiazole, 5-methoxybenzthiazole, 6-methoxybenzthiazole, 5-iodobenzole, 6-methoxybenzthiazole, Ethoxybenzthiazole, 5-ethoxybenzthiazole, 4,5,6,7-tetrahydrobenzthiazole, 5,6-dimethoxybenzthiazole, 5,6-dioxymethylenebenzthiazole, 5-hydroxybenzthiazole, 6-hydroxybenzthiazole, 5> 6-dimethylbenzthiazole), or a ring from the Nap ^ thothiazole series (e.g. naphtho [2, ld | thiazole, naphtho [Ϊ, 2-d | thiazole, 5-methoxynaphtho \ l, 2-dJ t hiazole, 5-ethoxy-naphtho [1,2-d ~ | thiazole, 8-methoxynaphtho 12,1-dJ thiazole, 7-methoxynaphtho [2,1-dJthiazole), or a pendant from the thionaphthenof7,6-d ~ [ thiazole series (e.g. 7-methoxythionaphtheno J7,6-dl thiazole),

AG 426 - 5 -

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from the series of Seleaasols (e.g. 4-Meiütylselenazol, 4-Ph.enylselen.azol), from the series of benzoselenazoles (e.g. cr> Benzoselenazole, 5-chlorobenzoselenazole, 5-methyl-6-methoxybenzo-

^ selenazole, 5-methylbenzoselenazole, 5,6-dimethylbenzoselenazole, ^ 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 4,5,6,7-tetrahydrobenzoselenazole, Sto-Dioxymethylene benzoselenazole,), from the Series of naphthoselenazoles (e.g. naphtho [2,1-dJ selenazole, Naphtho 1,2-djselenazole),

X ~ = an acidic radical such as a chloride, a bromide, an iodide, a ClO, a benzenesulfonate, a p-rtoluenesulfonate, a methyl sulfate, an ethyl sulfate, a propyl sulfate ion, where But X "is absent if R. and / or R _{2 is} an anionic group

wear, e.g. B. -SO- ^, -OSO, ^, -000 ^, -SO ₂ A = J -SO ^ CO-,

-SO ₀ -N-SO ₀ -, or -P

^{2 2} S ^ o (-)

-CH = C-CH = C ^ ^v II. A h Il I \

where mean:
R ₁ , R ₂ and X "= as stated above,

R ₆ = alkyl with preferably not more than 5 carbon atoms, e.g. B. methyl and ethyl,

Q ₁ and Q ₂ = (identical or different) sulfur or selenium and A and B = (identical or different) hydrogen, a condensed benzene ring, a tetramethylene group, a methylenedioxy group or one or more substituents such as alkyl, ζ. Β. Methyl, aryl ζ. B. phenyl, alkoxy ζ. B. methoxy, alkylthio e.g. methylthio, halogen e.g. B. fluorine, chlorine, iodine, bromine and hydroxyl.

AG 426 - 6 909828/1400

-C

OCH. _s

C-CH-C-CH-C I fl NNI ⁺ 1 C ₂ H ₅ C ₂ H ₅

CH-SO ₄ '3 4

The sensitizers of formulas I and II are _{<~ Γ}} completely compatible with each other. Emulsions such

O combinations of sensitizers contain one

r— wide uniform spectral sensitivity from blue to in the extreme red area of the spectrum. As from the following it can be seen, the rhodacyanines according to the general formula I in connection with the garbocyanines accordingly of the general formula II can be used without desensitization occurring. Rather, in some cases it is a slight increase in general sensitivity can be observed. In addition, the rhodacarbocyanines show the photographic advantage Silver halide emulsions not to obscure. In addition, the combinations according to the invention are obtained of the sensitizers a practically constant gamma value over the entire spectral sensitization range.

The rhodacarbocyanines corresponding to the general formula I and the carbocyanines corresponding to the general formula II can be prepared by any of the methods customary in cyanine chemistry.

Rhodacarbocyanines, which come under the general formula I given above and are used in the manner according to the invention

*> can are in UK patents 646 * 137 and ο

JJ 837.674 and in Belgian patent 532.028 besohrie-OO ben. The following list contains some examples of particularly suitable rhodacarbocyanines

A-G 426 - 7 -

_Λ Γ ι

0 <_N

^0CH 3 CH - C = CH -

C ₂ H ₅ O = C

C ₂ H ₅

CH ₃ SO ₄ -

H ₃ CO.

I ν

SCH-C = C ^ C = CH

O = C-N OCH.

C-- CH

^fc 2 ^H 5

C ₂ H ₅ -if

CH ₃ SO ₄

N ^ CH-C = C C = CH-C = CH-C ^ \

.N 0 * C N

CH ₃ SO ₄

Se

OCH.

ti 1

CH ₃ SO ₄

f ^H 3

C ₂ H ₅

It

N +

CH ₃ SO ₄

f ^H s

- ⁵ V

C * CH-CH = C C * CH - C II

0 * C

Ii

N. + 1

9O982-80UOO

_O H _C 2

'2 * 5

C Γ

= CH-C = C «

NO = C I

C = CH - C = CH

CH ₂ -CH = CH ₂

Ί80Β997

To the carbocyanines corresponding to the formula II those in connection used with the rhodacarbocyanines of formula I may include, for example, the following compounds:

CH ₂ -CH ₂ -OH

-CH = C-CH = C

C-CH = C-CH = C

CH

N =. C-CH = C-CH = C

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Br

Br

CH ₃ SO ₄

A-G 426

H ₅ C ₂ In.

'2 "5 p

. C-CH = C-CH = C

-CH.

H / 6.

H ₃ C

'C-CH = C-CH = C

NN \

+ I

^C 2 ^H s " ^C 2 ^H 5

-CH,

II / 7,

H ₃ CO-H ₃ C-

II / 8.

H ₃ C
H ₃ C-

Se <2 "5. ^ Se

^ C-CH = C-CH = C

Se » ^C 2 ^H 5

> C-CH = C-CH = C

ι *

Br

-CH, -CH.

[1/9.

Se? 2 ^Η 5 p

" ¹ C-CH = C-CH = C ^

C ₂ H ₅

-CH. -CH.

1T / 1O

? 2 ^H 5

Se? 25 ^ S

"C-CH = C-CH = C V ^ -CH

ϊ λ-Q-CH

1 +

C ₂ H ₅

CH ₂ -CO-N-SO ₂ -CH ₃

II / ll.

Se

? 2 ^H

2 ^H 5

H ₃ CO

> C - CH = C - CH = C U ^ N. N

(CH ₂ ) ₃ -SO ₃

C ₂ H ₅

11/12.

H ₃ C

il

.N
I +

CH.

-och, 90 9 828 / UOO

A-G 426

(CH ₂ ) ₃ -O-SO ₃
-

11/13.

/ M

Se

f2 ^H 5 Se

CH ₂ -CH ₂ -COOH

18U6997

11/14.

Se? 2 ^H 5 ^ Se.

^ "- CH = C-CH = C '

C-CH = C-CH = CV ^ N N- l * A

C ₂ H _{5 4} -SO ₂ -NH-CO-CH ₃

11/15.

11/16.

C-

₃ , p

M CH Br

11/17.

^ H ₃ C-

C ₉ Hc

L ² -CH-C-CH.C

^C 2 «5

-CH

CH -'- CHa-COOH

11/18.

3 ι 2

x: - CH * c - cn «c

N N

CH ₂ -CO-N-SO ₂ -CH ₃ C ₂ H ₅

11/19.

Se

CU

Γ3

Il

^C 2 ^H 5

^C 2 ^H 5 Br

The combinations of these dyes can be used for the sensitization of a wide variety of photographic finule ions .

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-U- 909828/1400

! MSPECTEO

In the light-sensitive material according to the present invention, various silver salts can be used, such as. B. silver chloride, silver bromide, silver iodide or mixed halides such as silver chloride bromide, silver bromide iodide and silver chloride bromide iodide. The hydrophilic colloid used as the binder for the silver halide _t may, for example, gelatin, agar-agar, be a water soluble cellulose derivative such as carboxymethyl cellulose, polyvinyl alcohol ,, poly-N-vinylpyrrolidone Öollodium. Hydrophilic synthetic or natural resins or polymeric compounds are also suitable. However, gelatin is preferred.

For the preparation of the sensitized photographic emulsions, the dyes can be incorporated into the emulsion by one of the known processes for introducing additives into hydrophilic colloid mixtures. It is useful to dissolve the dyes in a suitable water-miscible or immiscible high-boiling or low-boiling organic solvent or a mixture of such solvents and these solutions, optionally in the presence of a dispersant in the hydrophilic colloid, which is the binder of the photographic light-sensitive emulsion or a part of the binder represents to disperse. The solution mentioned can be added to the ready-to-pour emulsion itself or to one

ο aqueous, non-light-sensitive, hydrophilic colloid solution that to

optionally after the solvents used have been removed * with the photosensitive emulsion in the appropriate ** instant is mixed. More detailed information on suitable dis-

ο. pergating process necessary for the introduction of the sensitizers

are suitable in photographic emulsions, contained under AG 4-26 ■. - 12 -

including the American patent 2,304,940, the British Patents 791,219, 1,099,414, 1,099,415, 1,099,416, 1,099. 417, 1,098,594 and Belgian patents 682,413 and 705,889.

Another interesting procedure for dispersing sensitizing dyes into silver halide emulsions is to introduce the dye into an aqueous gelatin solution in the presence of a dispersant and to mix the resulting gelatin dispersion into a silver halide emulsion at the appropriate moment prior to the preparation of the layer. This M method is explained below. 100 mg of sensitizing dye and 250 ml of the sodium salt of oleyl methyl tauride are mixed for 36 hours in a vibrating mill in the presence of 100 ml of a 2% aqueous gelatin solution.

The sensitizing dyes can be added to the emulsion be added at a point in time of their manufacture. They should be evenly distributed in the emulsion. Is preferred Added after chemical ripening and just before the layer is made.

The concentrations of the rhodacarbocyanines correspond to the general Formula I and the carbocyanines corresponding to general formula II can vary within wide limits, e.g. B. between 10 mg and 1 g and preferably between 20 and 300 mg per mole of silver halide, and they will depend on the type of emulsion, the desired sensitizing effect, etc. The

As 426 -13- 909828/1400

The most appropriate concentration can be found on the basis of. Samples how they are common practice in emulsion preparation. '

The dyes are preferably added to photographic emulsions, the general sensitivity of which is determined by physical and chemical ripening was enhanced. These emulsions can be chemically sensitized by ripening carries out in the presence of small amounts of sulfur-containing compounds, such as B. allyl isothiocyanate, allyl thiourea, sodium thiosulfate, Potassium selenocyanide, etc. The emulsions can also be sensitized with the help of reducing sensitizers, such as B. with tin compounds, iminoaminomethanesulfinic acids and their derivatives, with cadmium salts and with salts of precious metals such as gold, platinum, palladium, iridium, ruthenium and rhodium.

In the preparation of the photographic emulsions it is also possible to use the usual additives, for example antifoggants, stabilizers, development accelerators, plasticizers, wetting agents and hardeners. Such additives can be incorporated into the emulsion in a customary manner.

Suitable hardeners include formaldehyde , oalogen-auDBtituierxe aldehydes that contain a carboxyl group, such as mucobromic acid, diketones, dialdehydes, etc.

Compounds useful for sensitizing emulsions suitable by acceleration of development are z. B. Connections

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of the polyoxyalkylene type, e.g. B. Alkylenoxykondenaationaprodukte as described inter alia in American patents 2,531,832 and 2,533,990, in British patents 920,637, 940.051, 945.340 and 991.608, and in Belgian patent 648.710. are, or onium derivatives of amino-N-oxides according to British patent 1,121,696.

As StabiliBatoi "s _f 4ie usual manner are used in emulsions may be mentioned mercury compounds such as in Belgian Patent 524,121, 677,337 and, as well as 707,386 (| containing the US Patent nitrogen described further heterocyclic 3,179,520 Thiooxoverbindungen as German in the Patent 1,151,731 are described, furthermore benzothiazoline-2-thione and 1-phenyl-2-tetrazoline-5-thione and compounds of the hydroxytriazolpyrimidine type such as 5-methyl-7-hydroxystriazol-3,5-pyrimidine.

The following describes the use of combinations of sensitizers will be described in accordance with the present invention.

This is done on the basis of three types of emulsion, the following composition tongue:

A: An acidic double enema silver bromochloride iodide emulsion is made by simultaneously adding two separate casts of a solution of silver nitrate and the solution of an alkali halide mixture to a gelatin solution containing small amounts of alkali halide. The emulsion contains

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AG 426 - 15 -

88.5 mole # silver bromide, 9 mole # silver chloride, and 2.5 Mol-96 silver iodide.

B: A double enema ammoniacal silver bromide emulsion is made by the simultaneous addition of two different casts of an ammoniacal silver nitrate solution and a halide mixture into a gelatin solution. The emulsion contains 95.3 mol .- # silver bromide and 4.7 mol .- # Silver iodide.

C: An acidic silver bromide-dide emulsion is prepared by adding a silver nitrate solution to the solution of a halide mixture in gelatin. The emulsion contains 94 mol .- $ silver bromide and 6 mol .- $ silver iodide.

Each of these three types of emulsion contains 1 g of S-methyl-T-hydroxy-s-triazole ^ ü ^ Z-pyrimidine as a stabilizer per mole of silver halide. The emulsions contain about 0.3 mol of silver halide per kg.

The emulsions are then applied to an ordinary substrate and dried. The layers are then exposed in a sensitometer through a step wedge with the constant 0.15 and through a yellow filter (spectral sensitivity), the permeability of which for light of a wavelength shorter than 460 mp is less than 0.1 # and for light of a wavelength greater than 520 wfx is more than 90 #. The spectral sensitivities determined in this way are shown in the table below by the number of determinable levels of the AG 426 · -16- .909828 / UOO

/ ί?

used wedge. The table contains the combinations of sensitizers used and the in the particular quantities used.

Emulsion A

attempt Used mg / mole silver
halide Sensibilisaotr sensitivity 5 Rhodacarbocyanine (I ' 100 Carbocyanines e) (II ' 5 No. 100 No. mg / mole silver
halide 5 1.0 I / l 100 - 20, 1.1 I / l 100 II / l 132 21. 1.2 I / l 100 II / 2 132 20th 1.3 I / l 100 II / 3 132 21 1.4 I / l 100 II / 4 132 21 1.5 I / l II / 5 132 21 1.6 I / l II / 6 132 21

A-G 426

- 17 -

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1.7 I / l 100 II / 7 1.8 I / l 100 II / 8 1.9 I / l 100 II / 9 l.lO I / l 100 11/10 1.11 I / l 100 ii / ii ■ 1.12 I / l 100 11/12 1.13 I / l 100 11/13 1.14 I / l 100 11/14 1.15 I / l 100 11/15 1.16 I / l 100 II / 16 + II / 17 1.17 I / l 100 II / 16 + II / 1 1.18 I / l 100 II / 16 + II / 18 1.19 I / l 100 II / 19 + II / 17 1.20 I / l 100 II / 19 + II / 1 1.21 I / l 100 II / 19 + II / 18 2.0 1/3 100 2.1 1/3. 100 II / l 2.2 1/3 100 II / 2 2.3 1/3 100 II / 3 2.4 1/3 100 II / 4 2.5 1/3 100 II / 5 2.6 1/3 100 II / 6 2.7 1/3 loo II / 7

132 20th 132 20th 132 20.5 132 21 132 21.5 132 21.5 132 22nd 132 21 132 21 66/66 21 66/66 21 66/66 22nd 66 / G6 21 66/66 21.5 66/66 21.5 - 20th 132 20.5 132 20th 132 20th 132 20th 132 20th 132 . 20th 132 21

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- 18-909828 / UOO

2.8 1/3 100 06997 2.9
2.10 1/3
1/3 100
100 co 2.11 1/3 100 2.12 1/3 100 2.13 1/3 100 2.14 1/3 100 2.15 1/3 100 2.16 1/3 100 2.17 1/3 100 2.18 1/3 100 2.19 1/3 100 2.20 1/3 100 2.21 1/3 100 3.0 1/8 100 3.1 1/8 100 3.2 1/8 100 3.3 1/8 100 3.4 1/8 100 3.5 1/8 100 3.6 1/8 100

OO N> OO

II / 8
II / 9
II / OK
Ίΐ / 11
11/12
11/13
11/14
11/15

II / 16 + II / 17 II / 16 + II / 1 II / 16 + II / 18 II / 19 + II / 17 II / 19 + II / 1 II / 19 + II / 18

II / 16 + II / 17

II / 16 + II / 1

11/16 + 11/18

II / 19 + II / 17

II / 19 + II / 1

II / 19 + II / 18

Emul_sion_B

132 132 132 132 132 132 132

20th

20th

20.5

20.5

21

20.5

19.5

132 20.5 66/66 20th 66/66 20th 66/66 20th 66/66 21 66/66 20th 66/66 20.5 • - 18th 66/66 19.5 66/66 19.5 66/66 19.5 66/66 19.5 66/66 19.5 66/66 20th

attempt Used Sensitizer Carbocyanines e) (II) sensitivity Rhodacarbocyanine (D No. mg / mole silver
halide No. mg / mole silver
halide II / l 82
II / 2 82
_ 19 - OftiGHWAi 4. .0
4.1
4.2
AG 426 I / l
I / l
I / l 82
82
82 13th
14th
13th
_ IMADCa-vrt - «*

4th .3 I / l 82 4th .4 I / l 82 4th .5 I / l 82 4th .6 I / l 82 4th .7 I / l 82 4th .8th I / l ¹ 82 4th .9 I / l 62 4th .10 I / l 82 4th .11 I / l 82 4th .12 I / l 82 4th .13 I / l 82 4th .14 I / l 82 4th , 15 I / l 82 4th .16 I / l 82 4th .17 I / l 82 4th 18th I / l 62 4th 19th I / l 82 4th 20th I / l 82 5. O 1/3 82 5. 1 1/3 82 909828 / 5.
5.
5. 2
3
4th 1/3
1/3
1/3 82
82
82 UOO 5.
5. 5
6th 1/3
1/3 82
82 5. 7th 1/3 82 • 5. 8th 1/3 82 5. 9 1/3 82

9LO

II / 3 82 13.5 II / 4 82 14 1806-997 II / 5 82 14th II / 6 82 13th II / 7 82 12.5 II / 8 . 82 12.5 II / 9 62 13.5 11/10 82 14th 11/11 82 14th 11/12 82 14th 11/13 82 14.5 11/15 62 14th II / 16 + II / 17 50/50 14th II / 16 + II / 1 50/50 II / 16 + II / 18 50/50 '.IS II / 19 + II / 17 50/50 14.5 II / 19 + II / 1
- 50/50 14th ii / 19 + ii / ie 50/50 14.5 \ '- 82 13.5 II / l 82 13.5 II / 2 82 13th II / 3 82 13.5 II / 4 82 15th II / 5 82 13th II / 6 82 13th II / 7 82 13.5 II / 8 82 13; II / 9 62 13th

Emulsion C

O CD OO

attempt Used mg / mole silver
halide Sensibilisaotr sensitivity 100 10.5 Rhodacarbocyanine (I. 50 Carbocyanines) (II) 100 13th No. 50 No. mg / mole silver
halide 100 12.5 I / l 50 - loo 13th I / l 50 ii / i 100 12th I / l 50 II / 2 100 12th I / l 50 II / 3 100 11.5 I / l 50 II / 4 100 13.5 I / l 50 II / 5 100 12.5 I / l 50 II / 6 ICO 13th I / l 50 II / 7 100 14th I / l 50 II / 8 100 13.5 I / l 50 II / 9 100 13th I / l 50 11/10 100 14th I / l 50 11/11 100 13th I / l 50 11/12 50/50 13.5 I / l 50 11/13 50/50 12.5 I / l 50 11/14 50/50 13.5 I / l 50 ΙΪ / 15 50/50 12.5 I / l 50 50/50 13th I / l 50 50/50 14.5 I / l 50 - 13.5 I / l 50 100 1 * .5. I / l 50 12th I / l 50 1/3 1/3 6.0 6.Ι δ.2 6.3 6.4 6.5 6.6 6.7 6.8 II / 16 + II / 17 6.9 II / 16 + II / 1 6.10 ΙΙ / 16 + ΙΙ / Ιδ 6.11 II / 19 + II / 17 6.12 II / 19 + II / 1 6.13 II / 19 + II / 18 6.14 - 6.15 II / l 6.16 6.17 6.18 6.19 6.20 6.21 7.0 7.1

- 21 -

7th .2 1/3 7th .3 1/3 7th .4 1/3 7th .5 1/3 7th .6 1/3 7th .7 1/3 7th .8th 1/3 7th . 9 1/3 7th .10 1/3 7th .11 1/3 7th 12th 1/3 7th 13th 1/3 7th 14th 1/3 7th 15th 1/3 7th 16 1/3 7th 17th 1/3 7th 18th 1/3 7th 19th 1/3 7th 20th 1/3

50 II / 2 100 12th 50 II / 3 100 12th 50 II / 4 100 11th 50 II / 5 100 11.5 50 II / 6 100 11th 50 II / 7 100 13th 50 II / 8 100 12th 50 11/10 100 13th 50 11/11 100 13th 50 11/12 100 12.5 50 11/13 100 12th 50 . 11/14 100 12th 50 11/15 100 13th 50 II / 16 + II / 17 50/50 11.5 50 II / 16 + II / 1 50/50 12th 50 II / 16 + II / 18 50/50 12th 50 II / 19 + II / 17 50/50 12.5 50 II / 19 + II / 1 50/50 12.5 50 ΐΐ / 19 + ΐΐ / ιε 50/50 12.5

180699

Figures 1 to 15 in the attached drawings show the spectrograms of the emulsions corresponding to tests 1.0, 1.3, 1.4, 1.7, 1.9, 1.10, 1.11, 1.12, 1.17, 1.21, 2.0, 2.3, 2.4, 2.8, 2.17, 2.21 again. They were determined in a spectrograph by exposure through a daylight compensation filter .

These spectrograms clearly show that the sensitizers according to the invention are completely compatible with one another, since all emulsions are uniformly sensitive up to 740 nm.

- 22 -

It is clear that the "ceiling in the green-yellow area of the spectrum is completely filled and that finally the intensity of the sensitization is practically independent of the wavelength"

AO 426 - 23 -

9 0 9 8 2 8 / U 0 0 bad

Claims (1)

Patent claims: 1. Optically sensitized, photographic light-sensitive material, characterized in that there is a rhodacarbocyanine color material corresponding to the following general formula I and in at least one silver halide emulsion layer Contains at least one carbocyanine dye according to the following general formula II: R ₁ -N- -C = CH-C = C O = C- 'C = CH-C = CH-C- -N -NR ₂ + ^R fi ι ⁶ C-CH = C-CH = C where mean: R ₁ and R ₈ ■ (identical or different) optionally substituted alkyl, allyl, optionally substituted aralkyl, optionally substituted aryl or cycloalkyl, A-G 426 - 24 - 909828 / UOO Rb = optionally substituted alkyl, optionally substituted aryl, optionally substituted aralkyl or allyl, R ₄ = alkoxy or an optionally substituted amino group, R ₆ = hydrogen, optionally substituted alkyl, optionally substituted aryl or optionally substituted aralkyl, R ₆ = alkyl, Z ₁ and Z ₂ = each one non-metal atom that is required to complete an identical or different, optionally substituted nuclei from the. Series of thiazole, benzothiazole, napthothiazole, selenazole, benzoselenazole or napthoselenazole, Q ₁ and Q ₂ = (identical or different) sulfur or selenium, A and B = (identical or different) hydrogen, a condensed one aromatic ring, a tetramethylene group, a methylenedioxy group or an or several substituents such as alkyl, aryl, alkoxy, alkylthio, halogen and hydroxyl, X "= an anion if R ₁ and R ₈ do not contain an anion group. AG 426 - 25 - '9 09828 / UOO 2. Optically sensitized, photographic light-sensitive material according to claim 1, characterized in that both the rhodacarbocyanine dye and the carbocyanine dye used in the silver halide emulsion layer (s) in an amount of 10 mg to 1 g per mole of silver halide will. 5. Optically sensitized, photographic photosensitive Liches material according to claim 1, characterized in that a gelatin silver bromide chloride is used as the sensitized silver halide emulsion layer - or - silver bromide iodide emulsion layer is used with camera sensitivity. AG 426 - 26 - 9098 28 / UOO Blank page