DE2046672C3 - Light-sensitive, spectrally sensitive silver halide photographic emulsion - Google Patents

Description

R ₁ N (CH-CH) _m ., C = CH-CH = C C-CH = CH-Q = CH-CH) _n ^ NR ₂

in which R ₁ and R ₂ each denote an optionally substituted alkyl radical having 1 to 18 carbon atoms, an alkenyl radical having 2 to 4 carbon atoms or an optionally substituted aryl radical; R _{3 is} an optionally substituted alkyl, aryl or alkoxycarbonyl radical; Q the atoms required to complete an optionally substituted ethylene radical; X is an acid anion; Z and Z ^{1 are} the atoms required to complete heterocyclic rings typical of cyanine dyes, and m and η each = 1 or 2.

2. Photosensitive photographic silver halide emulsion according to claim 1, characterized in that it contains a tricarbocyanine dye of the formula given, in which R and R _{2 are} each an alkyl radical having 1 to 4 carbon atoms, and R _{3 is} an alkoxycarbonyl radical having 1 to 4 carbon atoms in the alkoxy group and Z and Z ¹ the atoms required to complete benzothiazoles benzoxazole or naphthothiazole rings and in which Q, X, m and η have the meanings already given.

3. Photosensitive photographic silver halide emulsion according to claims 1 and 2, characterized in that it contains one of the following tricarbocyanine dye salts: a 3,3'-diethyl-10,12-ethylene-11 - (4-methyl-1-piperazinyl) oxatricarbocyanine-; 3,3'-diethyl-10,12-ethylene -11 - (4-methyl -1-piperazinyl) -thiatricarbocyanine-; 3,3'-diethyl-10,12-ethylene-II- (4-phenyl-

I - piperazinyl thiatricarbocyanine-; 3,3 '- diethyl 10.1 2 - ethylene -11 - (4 - ethyl -1 - piperazinyl) oxatricarbocyanine; 3,3 '- diethyl - 10.12 - ethylene

II - (4 - ethyl -1 - piperazinylhiatricarbocyanine-; 11 - (4 - ethoxycarbonyl -1 - piperazinyl) - 3,3 '- diethyl 10,12 - ethyleneoxatricarbocyanine-; 11 - (4 - ethoxycarbonyl -1 - piperazinyl) -3,3 '- diethyl - 10.12 - ethylthiatricarbocyanine-; Anhydro - 11 - (4 - ethoxycarbonylpiperazin - 1 - yl) -10.12 - ethylene - 3,3 '- di (3 - sulfopropyl) thiatricarbocyanine hydroxide; Anhydro -11- (4 - ethoxycarbonylpiperazin - 1 - yl) -10.12 - ethylene - 3,3 '- bis- (3 - sulfopropyl) - 5.6; 5 ', 6' - dibenzothiatricarbocyanine hydroxide or an anhydro -11 - (4 - ethoxycarbonylpiperazine - 1 - yl) - 10.12 - ethylene-3,3 '- bis (3 - sulfopropyl) - thiatricarbocyanine hydroxide salt.

The invention relates to a photosensitive silver halide photographic emulsion containing a content on a tricarbocyanine dye which spectrally sensitizes the silver halide.

It is known e.g. B. from U.S. Patents 2,705,234 and 2,735,770 that carbocyanine dyes, whose mesocarbon atom is substituted by an amino group, as filter dyes and sensitizers suitable for sensitizing photographic silver halide emulsions. The known Carbocyanine dyes sensitize conventional silver halide emulsions up to a range of about 530 to 685 nm. This sensitization has proven to be sufficient in some cases. she is however z. B. inadequate if the emulsion has good red and infrared sensitivity arrives.

For deep red or infrared sensitization in areas of over 700 nm, e.g. B. from 730 to 800 nm, Tricarbocyanines have proven particularly advantageous, e.g. B. S.S'-diethylthiatricarbocyanine and 3,3 '- diethyl - 6,6' - diethoxythiatriacarbocyanin, as described e.g. B. in Glafkide's "Photographic Chemistry" London 1960, Vol. II, pp. 895-896. Disadvantages of these known infrared spectral sensitizers is, however, that they have a comparatively strong desensitization in the natural, at about 400 nm sensitivity range of photographic silver halide emulsions. There large amounts of long chain tricarbocyanine sensitizing dyes not only to a more effective sensitization of the silver halide in the sensitization area, but also to impairment of latent image formation and to desensitization lead in particular in the natural sensitivity range of silver halide, must at infrared sensitization is always a compromise

closed with regard to the amount of dye used and the optimal attainable sensitivity. Of the known tricarbocyanines you can therefore only comparatively small amounts are used and consequently only comparatively low infrared sensitization reflections can be expected to reduce the loss of sensitivity in the natural sensitivity range to keep photographic silver halide emulsions within reasonable limits. This disadvantage known infrared sensitizers is particularly noticeable when the to be sensitized Silver halide emulsion other substances which have a beneficial effect on sensitization, e.g. B. Supersensitizers contains.

The object of the invention is to provide light-sensitive photographic silver halide emulsions, which by adding a spectral sensitizing tricarbocyanine dye also against the longer wavelength region of the spectrum, d. H. compared to wavelengths of over 700 nm, spectrally are sensitized without their natural sensitivity to blue even in the presence of supersensitizers suffers too much and without reducing its sensitivity in the infrared region of the spectrum decreases too much over longer periods of storage.

The invention is based on the knowledge that the stated object can be achieved in that tricarbocyanine dyes, whose mesocarbon atom of the methine bridge is substituted by a 1-piperazinyl radical is to be used as sensitizers.

The invention relates to a light-sensitive photographic silver halide emulsion comprising a Content of a tricarbocyanine dye which spectrally sensitizes the silver halide, which thereby is characterized in that it contains a tricarbocyanine dye of the following formula:

H ₂ C

H ₂ C CH ₂

..— ζ -. c ζ ¹ —-

R ₁ - Ν (- CH = CH) ^ r ₁ C = CH - CH = CC - CH = CH - C (= CH - CH) _n = ^ fN - R ₁ Χ ^θ

Vq /

in which R ₁ and R ₂ each denote an optionally substituted alkyl radical having 1 to 18 carbon atoms, an alkenyl radical having 2 to 4 carbon atoms or an optionally substituted aryl radical; R _{3 is} an optionally substituted alkyl, aryl or alkoxycarbonyl radical; Q the atoms required to complete an optionally substituted ethylene radical; Χ ^θ an acid anion; Z and Z ^{1 are} the atoms required to complete heterocyclic rings typical of cyanine dyes, and m and η each = 1 or 2.

The tricarbocyanine dyes which can be used according to the invention have two 5- or 6-membered nitrogen containing heterocyclic rings, as are typical for cyanine dyes, the two Rings linked by a straight chain with seven methine residues. That is what Mesocarbon atom of the methine chain is attached to a 1-piperazinyl radical, with particularly good results can be obtained with dyes in which the carbon atoms of the two methine radicals correspond to the mesocarbon atom the methine chain are adjacent, are bound to an ethylene radical. Particularly advantageous Results are also obtained when the tricarbocyanine dyes used have one Have 1-piperazinyl radical, which consists of a 4-alkoxycarbonylpiperazin-1-yl radical exists, with the proviso that the alkoxy group of this radical is a short-chain group, and when the heterocyclic rings these dyes consist of benzoxazole, benzthiazole and / or naphthothiazole rings.

By the invention it is achieved that silver halide emulsions available si hen that im Range from about 560 to 850 nm and above are sensitized and their maximum sensitivities are generally from about 730 to about 800 nm, the silver halide emulsions of the invention to those sensitized with known, structurally similar tricarbocyanine dyes are characterized by the fact that they can be sensitized to a wider range of wavelengths are that they are stronger in the infrared range, since they can be sensitized with larger amounts of sensitizer, without their natural sensitivity to blue being impaired in a particularly disadvantageous way, and that they only have a very low level of veil both in the fresh and in the incubated state exhibit.

If in the given formula R ₁ and R ₂ each have the meaning of an alkyl radical, this can, for example, be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl -, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexydecyl, heptadecyl or octadecyl radical. Preferably, R ₁ and R _{2 have} the meaning of short-chain alkyl radicals with; 1 to 4 carbon atoms or substituted alkyl radicals, for example hydroxyalkyl radicals, e.g. B. ß-hydroxyethyl, γ-hydroxypropyl, / i-hydroxypropyl, γ-hydroxybutyl or o) -hydroxybutyl or alkoxyalkyl, z. B. / i-methoxyethyl, / i-ethoxyethyl, / f-butoxyethyl, y-methoxypropyl, w-ethoxypropyl, w-methoxybutyl, w-ethoxybutyl or y-butoxybutyl or carboxyalkyl, e.g. B. carboxymethyl, / i-carboxyethyl,) -carboxypropyl or «t-carboxybutyl radicals or sulfoalkyl

leftovers, ζ. B. / ϊ-sulfoethyl, j-sulfopropyl, j-sulfobutyl or m-sulfobutyl or sulfatoalkyl, z. B. /) '- sulfatoethyl, γ-sulfatopropyl, γ-sulfatobutyl or fo-sulfatobutyl or alkanoyloxyalkyl, z. B. / J-Acetoxyäthyi-, / i-Propionyloxyäthyl, / i-Butyryloxyäthyl-, γ-Acetoxypropyl-,; -Propionyloxypropyl-, ω-Acetoxj butyl-, ru-Propionyloxybutyl- or ω-Butyryloxybutylreste, alkoxycarbonyl radicals or. B. Methoxycarbonylmethyl-, / i-Meihoxycarbonyläthyl-, _t i -Äthoxycarbonyläthyl-, γ - Methoxycarbonylpropyl-, γ-Äthoxycarbonylpropyl-,

(u-Methoxycarbonylbutyl or ιυ-Äthoxycarbonylbutylresten or aralkyl radicals, e.g. B. benzyl or phenethyl radicals.

If R ₁ and R ₂ are alkenyl radicals, these can for example consist of allyl, propenyl, 1-butenyl or 2-butenyl radicals.

If R ₁ and R ₂ are optionally substituted aryl radicals, these preferably consist of those of the phenyl or naphthyl series, that is to say in this case R ₁ and R _{2 can be,} for example, phenyl, naphthyl, ToIyI-. Ethylphenyk XyIyI-. Methoxyphenyk chlorophenyl, suifophenyl or carboxyphenyl radicals.

If R _{3 has} the meaning of an optionally substituted alkyl or aryl radical, this can be a radical as defined for R ₁ and R ₂ .

_{R 3} is preferably an alkoxycarbonyl radical in which the alkoxy group has 1 to 12 carbon atoms, for example a methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl radical.

The ethylene radical completed by Q can be substituted by one, two or more radicals, for example alkyl radicals preferably having 1 to 4 carbon atoms, e.g. B. methyl, ethyl, propyl, Isopropyl and butyl radicals and / or halogen atoms, e.g. B. chlorine and bromine atoms and or alkoxy radicals preferably having 1 to 4 carbon atoms, e.g. B. methoxy, ethoxy, propoxy, isopropoxy and butoxy radicals.

X is any acid anion, as is typical for cyanine dyes, for example a chloride. Bromide-, Iodide, thiocyanate, sulfamate, perchlorate, p-toluene sulfonate, methyl sulfate or ethyl sulfate anion.

If appropriate, however, the acid anion can also be present in one or both of the radicals R ₁ and or R ₂ , for example when R ₁ and R _{2 represent} sulfoalkyl or carboxyalkyl radicals.

Z and Z ¹ preferably represent the atoms which are necessary to complete optionally substituted 5- or 6-membered nitrogen-containing heterocyclic rings, as are customary in the case of cyanine dyes. This means that Z and Z ¹ can, for example, represent the atoms necessary to complete a thiazole ring, e.g. B. a thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazo! - or a 4- (2-thienylthiazole ring);
a benzothiazole ring, e.g. B. a benzothiazole, 4 - chlorobenzothiazole, 5 - chlorobenzothiazole,

6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole-, 6-methyl-'oenzothiazole-, 5-bromobenzothiazole, 6-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothi azole, 6-methoxybenzothiazole, 5-iodobenzothiazole-6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-Dioxymethylene benzothiazole, 5-hydroxybenzothiazole or a 6-hydroxy benzothiazole ring;

a naphthothiazole ring, e.g. B. of a naphtho [2, l-d] thiazole, naphtho [l, 2-d] thiazole, 5-methoxy

ίο naphtho [2,3-d] thiazole, 5-ethoxynaphtho [1,2-d] thiazole, 7-methoxynaphtho [2, ld] thiazole or an 8-methoxynaphtho [2, ld] thiazole ring;
a thionaphtheno-7 ', 6', 4,5-thiazole ring, e.g. B. a 4'-methoxythianaphtheno-7 ', 6', 4,5-thiazole ring;
an oxazole ring, e.g. B. an oxazole, 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole or 5-phenyloxazole ring;
a benzoxazole ring, e.g. B. a benzoxazole, 5-chlorobenzoxazole, 5-AJethy] benzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-methoxyben / oxa7ol-, S. Ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole or a 6-hydroxybenzoxazole ring;
a naphthoxazole ring, e.g. B. a «-naphthoxazole or (i-naphthoxazole ring;
a selenazole ring, e.g. B. a 4-methylselenazole or 4-phenylselenazole ring;

a benzoselenazole ring, e.g. B. a benzoselenazole, 5 - chlorobenzoselenazole, 5 - methoxybenzoselenazole, 5-hydroxybenzoselenazole or a tetrahydrobenzoselenazole ring;
a naphthoselenazole ring, e.g. B. a u-naphthoselenazole or / i-naphthoselenazole ring;

a thiazoline ring, e.g. B. a thiazoline or 4-methylthiazoline ring;

a 2-pyridine ring, e.g. B. a 2-pyridine or a 5-M, thyl-2-pyridine ring;

a 4-pyridine ring, e.g. B. a 4-pyridine or 3-methyl-4-pyridine ring;

a 2-quinoline ring, e.g. B. a 2-quinoline, 6-chloro-2-quinoline, 8-chloro-2-quinoline, 6-methoxy-2-quinoline, 8-ethoxy-2-quinoline or an 8-hydroxy-2-quinoline ring;

a 4-quinoline ring, e.g. B. a 4-quinoline, 6-methoxy-4-quinoline, 7-methyl-4-quinoline or 8-chloro-4-quinoline ring;
a 1-isoquinoline ring, e.g. B. a 1-isoquinoline or 3,4-dihydro-1-isoquinoline ring;

a 3-isoquinoline ring, e.g. B. a 3-isoquinoline ring;

a 3,3-dialkylindoleran ring, e.g. B. a 3,3-di-

methylindolenine, 5 - nitro - 3,3 - dimethylindolenine, 6 - nitro - 3,3 - dimethylindolenine, 5 - cyano - 3,3 - dimethylindolenine, 6 - cyano - 3,3 - dimethylindolenine, 3.3 , 5 - trimethylindolenine or 3,3,7 - trimethylindolenine ring;
an imidazole ring, e.g. B. an imidazole, 1-methylimidazole, 1-ethylimidazole, 1-butylimidazole, 1-methyl-4-phenylimidazole or a l-methyl-4,5-dimethy limidazole ring;

a benzimidazole ring, e.g. B. a benzimidazole, 1-methylbenzimidazole or an i-phenyl-5,6-dichlorobenzimidazole ring;

a naphthimidazole ring, e.g. B. a 1-methyl-M-naphthimidazole, 1-ethyl-n-naphthimidazole, 1-butyl-a-naphthimidazole, 1-phenyl-a-naphthimidazole-,

S ^ diety.ylenlH ^ mety 1 -piperazinyl ioxathiatricarbocyanine perchlorate;

3,3'-pibutyl-10,12-ethylene-l l- (4-methyl-l-piperazinyl) oxathiatricarbocyanine perchlorate;

25th

30th

l-phenyl-zif-naphthimidazole or a 1-methyl-5-methoxy-a-naphthimidazole ring, or a benzindole ring, e.g. B. a 1 H-Benz [e] indole, 3H-Benz [f] indole or a 3 H-Benz [g] indole ring.

If R _{3 is} an alkyl radical, this radical preferably has 1 to 12, in particular 1 to 4, carbon atoms and consists, for example, of a methyl, ethyl, propyl, isopropyl or butyl radical.

If R _{3 is} an alkoxycarbonyl radical, this radical preferably has 2 to 5 carbon atoms and consists, for example, of a methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl or butoxycarbonyl radical.

The tricarbocyanine dyes used according to the invention can consist of symmetrical as well as of unsymmetrical tricarbocyanine dyes.

_{Tricarbocyanine dyes in which R: is} an alkoxycarbonyl radical have proven to be particularly advantageous. These dyes have proven to be particularly advantageous spectral sensitizing dyes with a particularly low fog level.

Except for typical advantageous symmetrical tricarbocyanine dyes which can be used according to the invention the dyes described later are:

3,3'-dimethyl-10,12-ethylene-11 - (4-ethoxycarbonyl-1 -piperazinylj-oxatricarbocyanine-

perchlorate;
3,3'-dibutyl-10,12-ethylene-11 - (4-ethoxycarbonyl-

1 -piperazinylj-oxatricarbocyanine perchlorate; 3,3'-diethyl-10,12-ethylene-11 - (4-butoxycarbonyl-

1 -piperazinyO-oxatricarbocyanine perchlorate; 3,3'-diethyl-10,12-ethylene-11- (4-propyl-1-piper-

azinyl (oxatricarbocyanine perchlorate; 3,3'-diethyl-10,12-ethylene-11- (4-butyl-1-piper-

azinyl joxatricarbocyanine perchlorate; 3,3'-diethyl-10,12-ethylene-11 - (4-phenyl-1 -piper-

azinyl joxatricarbocyanine perchlorate; 3,3'-diethyl-10,12-ethylene-11 - (4-propyl-1 -piper-

azinyl thiatricarbocyanine perchlorate; 3,3'-diethyl-10,12-ethylene-11 - (4-butyl-1 -piper-

azinydthiatricarbocyanine perchlorate; 3,3'-dimethyl-10,12-ethylene-11 - (4-ethoxycarbonyl-1 -piperazinyl-thiatricarbocyanine-

perchlorate;
3,3'-Dipropyi-10,12-ethylene-11 - (4-ethoxycarbonyl-1 -piperazinylj-thiatricarbocyanine-

perchlorate;
3,3'-dibutyl-10,12-ethylene-II- (4-butoxycarbonyl-1-piperazinylj-thiatricarbocyanine per-

chlorate;
3,3'-diethyl-10,12-ethylene-II- (4-methyl-l-piper-

azinyl selenium tricarbocyanine perchlorate; 3,3'-diethyl-10,12-ethylene-II- (4-a1iioxy-

carbonyl-l-piperazinylj-selenate tricarbocyanine-

perchlorate

Typical, advantageous asymmetrical tricarbocyanine dyes for the production of a light-sensitive photographic silver halide emulsions according to the invention are:

3-ethyl-3'-butyl-10,12-ethylene-1 l- (4-methyl-

1 -piperazinyooxatricarbocyanine perchlorate;
3-ethyl-3'-butyl-10, l 2-ethylene-1 l- (4-methyl-

1 -piperazinyothiatricarbocyanine perchlorate;
3,3'-diethyl-10,12-ethylene-l l- (4-phenyl-

1 -piperazinyl ioxathiatricarbocyanine perchlorate; 3,3'-Diethyl-10,12-ethylene-11 - (4-ethyl-1-piper-

azinyl dioxathiatricarbocyanine perchlorate;
3,3 '-Diethyl-10,12-ethylene-1 l- (4-ethoxycarbony 1-1 -piperazinyO-oxathiatricarbocyanine per-

chlorate;
3,3'-dibutyl-10,12-ethylene-l l- (4-ethoxy-

carbonyl-l-piperazinyl) -oxathiatricarbo-

cyanine perchlorate;
3,3'-diethyl-10,12-ethylene-l l- (4-methoxy-

carbonyl-1 -piperazinylj-oxathiatricarbocyanine-

perchlorate;
3,3'-diethyl-10,12-ethylene-11 - (4-butoxycarbo-

nyl-i-piperazinylj-oxathiatricarbocyanine-

perchlorate;
3,3'-diethyl-10,12-ethylene-II- (4-methyl-

l-piperaziny ^ oxaselenatricarbocyanine-

perchlorate;
3,3'-diethyl-10,12-ethylene-II- (4-butyl-l-piper-

azinyooxase selenate tricarbocyanine perchlorate;
3,3'-diethyl-10,12-ethylene-11 - (4-methyl-1 -piper-

azinyl) selenathiatricarbocyanine perchlorate;
3,3'-diethyl-10,12-ethylene-11 - (4-ethoxy-

carbonyl-1 -piperazinylj-oxaselenatricarbo-

cyanine perchlorate;
3,3'-diethyl-10,12-ethylene-11 - (4-ethoxycarbonyl-piperazinylj-selenathiatricarbocyanine per-

chlorate.

Symmetrical tricarbocyanine dyes useful for preparing a light-sensitive silver halide photographic emulsion according to the invention can be prepared by condensing a nitrogen-containing heterocyclic compound represented by the following formula:
.- Z

R ₁ - N (= CH -

40

45 ? RC - CH = CH - NR ₄ R ₅

X ⁽¹ (II)

in which m. R, X and Z have the meaning already given, R _{4 is} a hydrogen atom or an acyl radical, for example acetyl, propionyl, butyryl or benzoyl radical, and R _{5 is} an aryl radical, e.g. B. a phenyl or tolyl radical, with an enamine salt of the following formula:

/
H ₂ C

H ₂ C
\

CH ₂

CH ₂
/

Xf

(ΠΙ)

H ₂ C

CH ₂

where R ₃ and Q have the meanings already given, and X _{1 is} an acid anion

309 648/368

9 10

The asymmetrical fertilizers which can be used according to the invention and whose production is also well known

Tricarbocyanine dyes can be seen as follows The preparation of the preparation of the dyes

produce: used enamine salts of formula III will be used later

1 mol of a compound of the formula II will be described in more detail with

one mole of an enamine salt of the formula III to 5 The dyes used according to the invention are

a compound of the following indicated in an advantageous manner of the washed, ready-made

Formula IV implemented: incorporated silver halide emulsion and

R ₃ thoroughly distributed therein The addition of the dyes

I to the emulsion is carried out in accordance with customary known methods

N 10 methods. For example, the dyes can

/ \ incorporated in the form of solutions of the emulsion

H ₂ C CH ₂ , whereby of course such solution

I I means to be used that do not have any detrimental effects

H ₂ C CH ₂ exert influence on the emulsion, e.g. B. methanol.

/ 15 isopropanol, pyridine and the like, or mixtures of these

N solvent.

I leave with the new dyes described

^ --Z ---- ^ C the usual known photographic silver

_{Sensitize @} S "X / \ halide emulsions that are

Ρ _Μ —Ν (—CH-CH) ₁ ^ rC-CH = CH-CH CH ₂ ίο use of commonly known hydrophilic colloids

/ as a dispersant for the silver halide

Χ ^θ% * Q ', for example using natural substances such as gelatine, albumin, agar-agar.

(IV) gum arabic, alginic acid, or hydrophilic synthetic binders, e.g. B. polyvinyl alcohol, polyvinyl pyrrolidone, Cellulose ethers, partly hydrolyzed

1 mol of the compound IV is then treated with a cellulose acetate and the like

further moles of the compound of the formula II. The concentration of the compounds used according to the invention

which, however, can be very different from the compound of the required new dyes in the emulsion

mel II, which are used to make the compound of 30 different. The dyes are useful

Formula IV used differs. On these in concentrations of about 5 to about 100 mg prc

An unsymmetrical tricarbocyanine liter of flowable emulsion is used. The individual

dye obtained. In formula IV, R ₁ , R ₃ , Q have the most favorable concentration depends somewhat on the type

and X and Z have the meanings already given. the photosensitive emulsion used and

Advantageously, the condensation will produce the desired effects. In the individual case,

reactions for the production of both the symmetrical, most favorable concentration can be carried out in the usual way

as well as the asymmetrical dyes can be easily determined through a series of tests. The emulsions

inert solvent medium, for example Ν, Ν-Di- can then be applied to the usual known layer supports'

methylacetamide, ethanol or acetic anhydride, can be applied, e.g. B. made of paper, glass, cellulose

accomplished. The condensation is preferably carried out acetate-cellulose acetate propionate cellulose nitrate, poly

in the presence of a customary basic condensate, a polyester, a polyamide and the like

sation means, e.g. B. a trialkylamine, for example Gelatine-Silbev

as triethylamine, tripropylamine, triisopropylamine halide emulsions, for example, as follows mi

u. The like., Or a Ν, Ν-dialkylaniline, z. B. Ν, Ν-Di- one of the dye used according to the invention

To sensitize methylaniline, Ν, Ν-diethylaniline or an N-alkyl 45:

piperidines, e.g. B. N-methylpiperidine or N-ethyl- A certain amount of the dye will
piperidine. The condensation is preferably carried out using a suitable solvent! solved, whereupon e; furthermore at elevated temperatures, in particular a certain volume of the solution obtained, especially at the reflux temperature of the reaction mixture, about 5 to 100 mg of dye slowly added to about 1000 mixture In most cases; the dyes from the reaction mixtures suffice from 10 to about 23 mg of dye per liter of emulau and can be extracted or recrystallized by one or more times to achieve a maximum sensitization, extraction or recrystallization using conventional gelatin-silver solvents 55 halide emulsions whose silver halide, for example, in the case of the production of symmetrical dyes from silver chloride, silver bromide, silver bromo, the one reaction component iodide, silver chlorobromide or sflberc morobromide, may consist in a slight excess over the other iodide en can.

Reaction components are used, d. H. in the case of fine-grain emulsions, to which

a concentration which is above the calculated stoichio- 60 most common gelatin-supchloride emulsions

metric concentration is preferably, slightly higher concentrations can be used

about two moles + a 10% excess of a dye are necessary to achieve optimal sensitivity

To achieve heterocyclic compound of the formula II with a filling effect. The information provided

Of course, moles of an enamine salt of the formula III are not converted to the use of

In the case of the production of asymmetrical dyes 65 gelatin-silver halide emulsions are limited

the reaction components in molar equivalents also apply to emulsions in which the

valenten used The heterocyclic starting binders are not or only partly made of gelatine

Compounds of the formula II are known compounds

If necessary, however, the dyes can also be obtained by bathing photographic recording materials in a solution of the one or more dyes be incorporated into the light-sensitive emulsions of these recording materials.

The tricarbocyanine dyes used according to the invention are also more advantageously suitable Way of making so-called false color films or so-called false sensitized photographic ones Color films such as those found in US Pat. No. 2,763,549 and the magazine Photo Methods for Industry ”, May 1963, pp. 48, 62 and 63. are known. Are those used according to the invention Tricarbocyanine dyes for the preparation of such photographic materials used, they are particularly suitable for the production of such false color films which contain an infrared-sensitive layer.

The superhalide photographic light-sensitive emulsions of the present invention wherein it be coarse-grained, medium-grained or fine-grained emulsions or emulsions from mixtures of such Can act emulsions can be prepared by customary known methods, d. h., z. B. so-called single enema emulsions or so-called double enema emulsions being. The emulsions can also be so-called Lippmann emulsions or of ammoniacal emulsions Emulsions consist of or ripened in the presence of a thiocyanate or thioether Emulsions such as those described in U.S. Patents 2,222,264, 3,320,069, and 3,271,157 are known, or from super halide emulsions with cubic silver halide grains such as, for example in the Journal of Photographic Science, Vol. 12, 1964, pp. 242 ff., and the Journal of Photographic Science, Vol. 13, 1965, pp. 85-89.

In addition, the photosensitive soverhalide emulsions according to the invention can be so-called Outer grain and inner grain emulsions such as those disclosed in U.S. Patents 2,592,250. 3 206 313 and 3 367 778 and Belgian patent 704 255 are known. If necessary, it can The emulsions according to the invention are also those which are composed of mixtures of external grain or surface grain and inner grain emulsions, such as those from the U SA. patent 2,996,382 are known.

Finally, the dyes used according to the invention are suitable both for the production of negative emulsions as well as for the production of direct positive emulsions, such as those for example are known from USA patents 2 184013. 2541472, 3 367 778, 2456953 and 2 861885 and British patent 723 019 and French patent 1520821.

The superhalide photographic light-sensitive emulsions of the present invention cannot emulsions washed or washed to remove soluble salts. So can the soluble salts may have been removed, for example, by quenching and leaching the emulsion or by washing the coagulated emulsion, d. H. for example, according to procedures as they are from the U.S. Patents 2,618,556, 2,614,928, 2,565,418, 3,241,969, and 2,489,341 are known.

The superhalide photographic emulsions of the present invention can also be through Addition of so-called chemical sensitizers, e.g. B. reducing compounds, sulfur, selenium or tellurium compounds, gold, platinum or palladium compounds, or combinations thereof be sensitized. Chemical sensitization process that is used for chemical sensitization of the emulsions according to the invention can be used are, for example, from the USA patent specifications 1 623 499, 2 399 083, 3 297 447 and 3 297 446 are known.

The superhalide photographic light-sensitive emulsions of the present invention can be further contain sensitivity-increasing compounds, e.g. B. polyalkylene glycols, cationic surface-active compounds and thioethers or combinations thereof, the use of which

For example, it is known from U.S. Patents 2,886,437, 3,046,134, 2,944,900 and 3,294,540.

The superhalide emulsions according to the invention can furthermore be prepared in the customary manner protected by a veil and stabilized against loss of sensitivity during storage will. Suitable antifoggants and stabilizers, alone or in combination with one another For example, the thiazolium salts of U.S. Patents 2,131,038 and 2,694,716 of U.S. Patents

2,444,605 and 2,886,437 azaindenes known from U.S. Patent 2,728,663 Mercury Salts Obtained from the U.S. Patent

3 287135 known urazoles from the USA patent 3,236,652 known sulfocatechols; that from British patent specification 623 448 known oximes, also those known from U.S. Patents 2,403,927, 3,266,897 and 3,397,987 Nitroindazoles as well as mercaptotetrazoles and nitrone; those known from U.S. Patent 2,839,405 polyvalent metal salts; the thiuronium salts known from US Pat. No. 3,220,839 and finally, the palladium compounds known from U.S. Patents 2,566,263 and 2,597,915. Platinum and Gold salts.

Optionally, after the light-sensitive photographic superhalide emulsions developer compounds may also be incorporated into the invention, e.g. B. Hydroquinones, catechols, Aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and phenylenediamines.

The light-sensitive photographic silver halide emulsions of the present invention can also be used in photographic recording materials are in contact with layers containing such developer compounds contain. The developer compounds can be in the form of solutions ir suitable solutions or in the form of dispersions, as described in U.S. Pat. No. 2,592,368 and dei French patent 1505 778 is known in the emulsions are incorporated.

The photographic silver halide emulsions according to the invention can also be used harden the usual known organic and inorganic hardening agents, e.g. 8. using uni of hardeners made from aldehydes, so-called

blocked aldehydes, ketones, carboxylic acids and carboxylic acid derivatives, sulfonate esters, sulfonyl halo geniden and Vmylsulftraen, compounds with active Halogen atoms, epoxy compounds, aziridines, ak

tive olefins, isocyanates, carbodiimides curing agents with different functional groups, e.g. B. aldehyde and halogen or epoxy groups, and so-called polymeric hardeners, e.g. B. oxidized polysaccharides, such as dialdehyde starch, Oxyguargum and the like

For the production of the emulsions according to the invention As already explained, a wide variety of colloids can be used as binders, namely naturally occurring substances such as proteins, for example gelatin and gelatin derivatives, Cellulose derivatives, polysaccharides, e.g. B. dextran, gum arabic and the like, as well as synthetic Polymers, e.g. B. water-soluble polyvinyl compounds. z. B. polyvinylpyrrolidone and acrylamide polymers or present in latex form, dispersed polyvinyl compounds, especially those used for Contribute to increasing the dimensional stability of the photographic recording material to be produced. Synthetic polymers suitable as binders are, for example, from the USA patents 3,142,568, 3,193,386, 3,062,674, 3,220,844, 3,287,289 and 3,411,911 are known. As particularly effective Polymers are the water-insoluble polymers of alkyl acrylates and alkyl methacrylates, Acrylic acid, sulfoalkyl acrylates and sulfoalkyl methacrylates have been shown to network for crosslinking are suitable, which facilitates the hardening of the emulsions, as well as such polymers with repeating Sulphobetain units, such as those known from Canadian patent 774 054, for example are.

Finally, the emulsions according to the invention are also suitable for the production of photographic ones Recording materials which have antistatic or conductive layers, e.g. B. layers with or from soluble salts, e.g. B. Chlorides. Nitrates and the like, vapor-deposited metal layers, layers of ionic Polymers such as those known from U.S. Patents 2,861,056 and 3,206,312 are, or layers of insoluble inorganic salts, as they are e.g. B. from the USA patent 3,428,451 are known.

The light-sensitive photographic silver halide emulsions according to the invention can finally be coated on a wide variety of conventionally known supports, e.g. B. those made of cellulose nitrate, cellulose esters, polyvinyl acetals. Polystyrene, polyethylene terephthalate, polycarbonates and. The like., As well as further glass, paper, and metal. The like. For example, the emulsions on flexible substrate, in particular made of paper, which is optionally partially acetylated be coated or on coated paper support with baryta and / or a layer made of an α-olefin polymer, in particular a polymer made of an -olefin having 2 to 10 carbon atoms, e.g. B. polyethylene, polypropylene, an ethylene-butene copolymer or the like.

Optionally, the photosensitive photographic silver halocenide emulsions of the present invention can also contain plasticizers or plasticizers and lubricants, e.g. B. polyalcohols, e.g. B. glycerol and diols, as they are known, for example, from US Pat. No. 2,960,404, or fatty acids or fatty acid esters, such as are known, for example, from the USA, Patents 2,588,765 and 3,121,060, and also silicone resins, such as they are known for example from British patent specification 955 061, included.

Finally, the light-sensitive silver halide photographic emulsions of the present invention can be used ons also contain surface-active compounds, e.g. B. saponin or anionic compounds, e.g. B. the alkylarylsulfonates or amphoteric compounds known from US Pat. No. 2,600,831, as for example from the USA patent specification

ίο 3 133 816 are known.

Finally, the light-sensitive photographic silver halide emulsions of the present invention can be used also contain matting agents, e.g. B. starch, titanium dioxide, zinc oxide and silica particles and those known from U.S. Patents 2,992,101 and 2,701,245, or are in contact with layers of a recording material which contain such matting agents contain.

The light-sensitive photographic silver halide emulsions of the present invention are useful also for the production of photographic recording materials, which include an optical brightener, e.g. B. a brightener consisting of a

■ 25 stilbene, triazine, oxazole or coumarin compounds contain. To produce such recording materials, for example, the water-soluble optical brighteners known from German patent specification 972 067 and USA patent specification 2,933,390, as well as brightener dispersions such as those described in German patent specification 1,150,274 and in the USA, can be used . Patent 3,406,070.

The photosensitive photographic photosensitive of the present invention Silver halide emulsions can also be used for the production of photographic recording materials are used that contain light-absorbing substances or filter dyes, as they are, for example, from the USA 3,253,921, 2,274,782, 2,527,583, and 2,956,879 are known. The dyes can optionally be used pickled, for example as is known from US Pat. No. 3,282,699.

The process used to produce a light-sensitive photo-

The sensitizing dyes used in the graphic silver halide emulsion according to the invention and, if appropriate, other emulsion formulations can be added to the emulsion from aqueous solutions or solutions with organic solvents, it being possible, for example, to use methods such as those described in U.S. Patents 2,912,343, 3,342,605, 2,996 287 and 3,425,835 are known. The dyes can be dissolved separately from one another or together in a solvent, where the optionally combined solutions of the silver halide emulsion can be incorporated or whereupon an emulsion applied to a layer support can optionally be bathed with such a solution.

The silver halide photographic emulsions of the present invention can be prepared by conventionally known methods, e.g. B. by dip coating, coating by means of an air knife, a so-called Curtain coating, by extrusion coating using a coating funnel, such as for example, from U.S. Patent 2,681,294 is known, and the like., Can be applied to conventional known substrates. If necessary, you can do this

^ 633

Coating processes can also be used in which two or more layers are applied at the same time a layer support can be applied, for example, from US Pat. No. 2,761,791 and British Patent 837095 are known.

The light-sensitive photographic silver halide emulsions of the present invention are useful excellent for making photographic materials for colloid transfer process such as it is known, for example, from US Pat. No. 2 716059, or for the production of recording materials for the silver salt diffusion transfer process, as found in U.S. Patents 2,352,014, 2,543,181, 3,020155, and 2,861,885 is known, as well as for the production of recording materials for color image transfer processes, as described, for example, in U.S. Patents 3,087,817, 3,185,567, 2,983,606; 3,253,915 3227 550, 3 227 551, 3227 552, 3415644, 3415645 and 3 415 646 are known, and also for the production of recording materials for the suction transfer process, as is known, for example, from U.S. Pat. No. 2,882,156.

The silver halide photographic light-sensitive emulsions of the invention are useful Finally, for the recording of copy-out images, as is the case, for example, from the USA patent

2 369 449 and Belgian patent 704 255 is known for recording direct copy images, as is known, for example, from U.S. Patent Nos. 3,033,682 and 3,287,137, and the like. The silver halide emulsions according to the invention are also suitable, for example, for production <on recording materials that are developed by the action of heat, such as it for example from U.S. Patents 3,152,904.

3,312,550 and 3,148,122 and British Patent 1 110046 is known. Finally, «are suitable the emulsions are also used for the production of recording materials, which are produced by physical development should be developed, as for example from British patent specification 920 277 and 1 131238 is known.

The light-sensitive photographic silver halide emulsions of the present invention are useful also excellent for the production of color photographic recording materials, for example such recording materials which contain color couplers, such as those from the USA patents 2,376,679, 2,322,027, 2,801,171, 2,698,794, 3,227,554 and 3,046,129 are known, as well also for the production of recording materials which are developed with the aid of solutions which Contain color couplers such as those disclosed in U.S. Patents 2,252,718, 2,592,243 and 2 950970 is known.

Exposed silver halide photographic emulsions according to the invention can be prepared according to conventional methods known methods are developed, for example using alkaline developer solutions with usual developer compounds, e.g. B. hydroquinones, catechols, aminophenols, 3-pyrazolidones, phenylenediamines, ascorbic acid derivatives, hydroxylamines, hydrazines and the like. Finally, they can also be developed with the help of so-called ribbon development processes, such as it is known from the USA patent specification 3 179 517, or by a so-called stabilization development, as it is obtained, for example, from the PSA-Journal, Vol. 16 B, August 1950. Finally you can also so-called one-baths, as they are for. B. in the magazine Phot. May be. and Eng., Vol. 2, No. 3, October 1958, and U.S. Patent 3,39,2019 be used. Optionally, the silver halide photographic emulsions of the present invention can be used can also be developed using developers containing hardeners, as known, for example, from US Pat. No. 3,232,761, and in transport rollers developing devices such as those described in U.S. Patent 3,025,779 be, or by a surface development, as for example from Example 3 of the U.S. Patent 3,418,132 is known.

The light-sensitive photographic silver halide emulsions of the present invention are useful also excellent for making lithographic printing plates, e.g. B. by colloid transfer the undeveloped and uncured areas of an exposed and developed emulsion layer on a suitable support, e.g. B. of the type known from the USA patent specification 2,763,553, wherein relief images are obtained (see US Patents 3,402,045 and 3,053,658) or wherein relief printing plates as is known from U.S. Pat. No. 3,271,150, for example.

The tricarbocyanine dyes used according to the invention can optionally also be used together can be used with other known sensitizing dyes. For example, if necessary achieve an additional spectral sensitization that the emulsion with a solution another sensitizing dye in an organic solvent or with a dispersion another dye is treated, for example from the French patent 1 482 774 is known. Of course, solutions of the tricarbocyanine dyes used according to the invention can also be used can be used, which contain another dye. Besides the tricarbocyanine dyes used according to the invention The dyes used can also be used in the finished emulsion or at an earlier stage can be added to the preparation of the emulsion. Typical suitable dyes, in addition to those according to the invention Tricarbocyanine dyes used can be used, for example, in the USA patents 2526 632, 2 503 776, 2493 748 and 3 384486. The additionally used Sensitizing dyes can, for example, from cyanine, merocyanine, tri- or tetranuclear complexes Merocyanine, complex tri- or tetranuclear cyanine, holopolar cyanine, styryl, Hemicyanine, enamine hemicyanine, oxonol and hemioxonol dyes exist.

Particularly suitable dyes of the cyanine classes, which together with the tricarbocyanine dyes can be used contain such basic rings as thiazoline, oxazoline, pyrroline, Pyridine, oxazole, thiazole, selenazole and imidazole rings. These rings can optionally be substituted, e.g. B. by alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine residues. These rings can optionally also be substituted on Carbocyclic or heterocyclic ring systems

be condensed, these ring systems optionally, for example by halogen atoms, phenyl, Alkyl, haloalkyl, cyano or alkoxy radicals can be substituted. The dyes can thereby also be symmetrical or asymmetrical dyes, their methia radical or polymethine chain may optionally be substituted by alkyl, phenyl, enamine or heterocyclic radicals.

Those which can be used together with the tricarbocyanine dyes used according to the invention Merocyanine dyes can advantageously contain basic rings, as described in US Pat Cyanine dyes are included, as well as acidic rings and residues, e.g. B. thiohydantoin, rhodanine, Oxazolidendione, thiazolidendione, barbituric acid, thiazolidione and malononitrile rings and radicals. Possibly these rings and radicals can also be substituted, e.g. B. by alkyl, alkylene, phenyl, Carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxy

1. alkyl or alkylamino radicals or heterocyclic radicals. If necessary, combinations can also be used these dyes can be used

Finally, in addition to the tricarbocyanide substances, supersensitizing additives can also advantageously be added to the emulsions, which do not absorb any visible light, for example ascorbic acid derivatives, azaindenes, cadmium salts and organic sulphonic acids, as they are, for example, in the US ^Pat . be written. Sultonated polynuclear aromatic compounds, bilDernalogenide-reducing compounds, azamdenes and combinations of these compounds, as is known, for example, from German Onenlegungsschrift 2,046,687, have proven to be particularly advantageous super-sensitizers for the dyes used according to the invention.

Preparation of the tricarbocyanine dyes used according to the invention A. 3,3'-Diethyl-10,12-ethylene-l 1 - ^ - methyl-l-piperazinyl joxatricarbocyanine perchlorate

CH,

H ₂ C
H ₂ C

\
CH ₂

CH ₂

C-CH = CH-C Jl J

ClQF

1.3 g of 1-cyclopentylidene-4-methylpiperazinium perchlorate and 4.8 g of 2- (2-acetanilidovinylj-3-ethylbenzoxazolium iodide and 1.5 ml of triethylamine were dissolved in 15 ml of acetic anhydride, whereupon the solution was heated to reflux temperature for 10 minutes while stirring The reaction mixture was then placed in a beaker and C ₂ H _{5 therein for 5 minutes}

left to stand for a long time at room temperature. The crude dye which had precipitated out was filtered off and washed with Washed ethanol. After two recrystallization from a cresol-methanol mixture were 0.2 g of dye, corresponding to 6% of theory, with a melting point of 267 to 268 ° C. with disintegration receive.

B. 3,3'-Diethyl-10,12-ethylene-11 - (4-methyl-1-piperazinyl jthiatricarbocyanine perchlorate

CH ₃

H ₂ C
H ₂ C

CH ₂

CH ₂

'n

C-CH = CH

C ₂ H ₅

1.3 g of l-cyclopentylidene-4-methylpiperaziniumperchlorar, 5.0 g of 2- (2-acetanilidovinyl) -3-äthylbenzothiazoliumjodid and 1.5 ml of triethylamine were in Dissolved 30 ml of ethanol, whereupon the solution was heated to reflux temperature for 10 minutes. After Cooling down to room temperature, the lower

filtered off, washed with methanol and dried. After two recrystallizations a cresol-methanol mixture was 1.0 g of pure dye, corresponding to 31% of theory, with a Melting point of 261 to 262 ° C obtained with decomposition.

C. 3,3'-Diethyl-10,12-ethylene-11 - (4-phenyl-1-piperazinyl (thiatricarbocyanine perchlorate

IN

H ₂ C

H ₂ C CH ₂
CH ₂

i C

/ \
C = CH - CH = CC - CH = CH - C

/ Il V

NH ₂ C CH ₂ N

ClOi ³

C ₂ H ₅

C ₂ H ₅

1.6 g of l-cyclopentylidene-4-phenylpiperazinium perchlorate, 5.0 g of 2- (2-acetanilidovinyl) -3-äthylbenzothiazoliumjodid and 1.5 ml of triethylamine were in 15 ml of acetic anhydride dissolved, whereupon the solution was refluxed for 10 minutes with stirring was heated. The reaction mixture was then allowed to stand at room temperature for an additional 10 minutes stirred, whereupon the deposited precipitate was filtered off. The raw dye was used first extracted with hot methanol and then once from a mixture of N, N-dimethylacetamide and Recrystallized methanol. There were 1.5 g of pure dye, corresponding to 43% of theory, with a Melting point of 266 to 267 ° C obtained with decomposition.

D. 3,3'-Diethyl-10,12-ethylene-11- (4-ethyl-1-piperazinyl joxatricarbocyanine perchlorate

QH ₅

/ \ H ₂ C CH ₂

H ₂ C CH ₂

OCO

J C = CH-CH = C C-CH = CH-C II

NH ₂ C CH ₂ N

C1OJ>

C ₂ H ₅

QH ₅

1.4 g of 1 - cyclopentylidene - 4 - äthylpiperaziniumperchlorat, 4.8 g of 2- (2-acetanilidovinyl) -3-ethylbenzoxazolium iodide and 1.5 ml of triethylamine were dissolved in 15 ml of ethanol, whereupon the solution was stirred for 10 minutes at reflux temperature was heated. After cooling to room temperature, the precipitated dye was filtered off, washed with methanol and dried. After a single recrystallization from methanol, 1.2 g of pure dye, corresponding to 39% of theory were obtained with a melting point of 250-251 ⁰ C under Zerfaii.

/ I'L

21 22

E. 3,3'-Diethyl-10,12-ethylene-l l- (4-ethyl-l-piperazinyl thiatricarbocyanine perchlorate

C ₂ H ₅

/ \ H ₂ C CH ₂

i I

H ₂ C CH ₂

N C

/ V

C = CH - CH = C C CH = CH - C

H ₂ C-

-CH,

ClOi

1.4 g of 1-cyclopentylidene-4-ethylpiperazinium perchlorate, 5.0 g of 2- (2-acetanilidovinyl) -3-ethylbenzothiazolium iodide and 1.5 ml of triethylamine were dissolved in 15 ml of acetic anhydride, whereupon the solution was refluxed for 10 minutes with stirring was heated. After cooling to room temperature for 5 minutes, the precipitated crude dye was filtered off, washed with methanol and dried. After a single recrystallization from methanol, 0.7 g of pure dye, corresponding to 21% of theory, with a melting point of 243 to 244 ^° C. was obtained with decomposition.

F. II- (4-Ethoxycarbonyl-1-piperazinyl) -3,3'-diethyl-10,12-ethylene oxatricarbocyanine perchlorate

C-CH = CH-C

1.6 g of l-cyclopentylidene-4-ethoxycarbonylpiperazinium perchlorate, 4.8 g of 2- (2-acetanilidovinyl) -3-ethylbenzoxazolium iodide and 1.5 ml of triethylamine were dissolved in 10 ml of Ν, Ν-dimethylacetamide, whereupon the solution was so strong for 10 minutes while stirring heated to a gentle reflux. The reaction mixture was then transferred to a beaker and diluted therein to a volume of 350 ml by adding hot methanol After cooling, the precipitated crude dye was filtered off, washed with methanol and unc dried. After a single recrystallization from methanol, 0.8 g of pure dye, corresponding ™ 24% of theory, with a melting point of 24 to 248 ° C., with disintegration.

23 24

G. 1 l- (4-ethoxycarbonyl-l-piperazinyl) -3,3'-diethyl-10,12-ethylenethiatricarbocyanine perchlorate

O
\ C. OC ₂ H ₅ / N
N /
H ₂ C \
CH ₂ H ₂ C /
N CH,
/

/ V /

C = CH - CH - C C - CH = CH - C

/ i I \ _ffl / \ /

NH ₂ C-CH ₂ N

ClO ₄ ⁰

C ₂ H ₅

C ₂ H ₅

1.6 g of 1 - cyclopentylidene - 4 - ethoxycarbonylpiperazinium perchlorate, 5.0 g of 2- (2-acetanilidovinyl) -3-ethylbenzothiazolium iodide and 1.5 ml of triethylamine were dissolved in 15 ml of Ν, Ν-dimethylacetamide, whereupon the solution was brought to a gentle boil with stirring for 10 minutes under reflux conditions would. The reaction mixture was then transferred to a beaker, whereupon so much hot Methanol was added so that the total volume was 350 ml. After 10 minutes of cooling the deposited precipitate was filtered off to room temperature, washed with methanol and dried. After a single recrystallization from a mixture of Ν, Ν-dimethylacetamide and methanol were 1.9 g of pure dye, corresponding to 54% of theory, with a melting point of 266 to 267 ° C obtained with decomposition.

35

H. Anhydro-II- ^ ethoxycarbonylpiperazin-l-ylJ-lO.n-ethylene-S.S'-diO-sulfopropyO-thiatricarbocyanine hydroxide, Triethylamine salt

O OC ₂ H ₅

CH - CH = / \ - CH = CH

HN (C ₂ Hs) ₃

1.6 g of 1 - cyclopentylidene - 4 - ethoxycarbonylpiperazinium perchlorate, 4.0 g of anhydro-2- (2-anilmovinyI) -3 - (3 - sulfopropyl) benzothiazolium hydroxide, 1.0 ml of acetic anhydride and 4.2 ml of triethylamine were dissolved in 15 ml of Ν, Ν-dimethylacetamide, whereupon the solution is stirred on a hot plate up to Reflux temperature was heated. After reaching the reflux temperature, the heating plate was switched off, however, the reaction mixture was stirred for another 2 to 3 minutes. The reaction mixture was then stirred nitrated while hot. The precipitated dye was filtered off and once from methanol recrystallized The pure dye was in a yield of 1.6 g, corresponding to 36% of theory, obtained with a melting point of 235 to 236 ° C with disintegration.

309648 / 3Ä

<* ■> ■■ · '■ w

/ ff

Anhydro-II- (4-ethoxycarbonylpiperazin-I-yl) -10,12-ethylene-3,3'-bis (3-sulfopropyl) -5,6 ^ ', o'-dibenzothiatricarbocyanine hydroxide, Triethylamine salt

OC ₂ H ₅

I I

HN (C ₂ H ₅ J ₃

2.16 g of l- (5-anilinomethylene-2-phenyliminomethyll-cyclopentenyl) -4-ethoxycarbonylpiperazine, 3.31 g of anhydro-2-methyl-3- (3-sulfopropyl) naphtho [2,3-d] -thiazolium hydroxide, 1.0 ml of acetic anhydride and 1.0 ml of triethylamine were dissolved in 15 ml of N, N-dimethylacetamide, whereupon the resulting solution was 2 minutes long in a reaction vessel with a reflux condenser was heated so far that a weak Reflux began. After the reaction mixture had cooled, the dyestuff which had precipitated out was filtered off and once from methanol, which contained some triethylamine, recrystallized. That way were 0.9 g of pure dye, corresponding to 19% of theory, with a melting point of 263 to 264 ° C below Get decay.

II.

Production of starting compounds
for the production of the dyes

J. 1-Cyclopentylidene-4-methylpiperazinium perchlorate

CH ₃

H ₂ C
H ₂ C

CH ₂

CH ₂

ClOf

H ₂ C
H ₂ C-

CH ₂

-CH,

K. 1-Cyclopentylidene-4-phenylpiperazinium perchlorate

C ₆ H ₅

/ \
H ₂ C CH ₂

H ₂ C CH ₂

35

40

H ₂ C

CH ₂

H ₂ C CH,

To a mixture of 17.0 g of 1-phenylpiperazine and 16.8 g of cyclopentanone, 14.0 g of 72% perchloric acid were added with cooling. The mixture was then on a steam bath for 15 minutes

heated. The reaction product was precipitated by adding ethanol and, after cooling, the The reaction mixture is filtered off and dried. There were 28.7 g of reaction product, corresponding to 87% of theory, with a melting point of 185 to

50 186 ° C obtained. l-ethoxycarbonyl-4-ethylpiperazine

55

20.1 g of l-methylpiperazinyl hydroperchlorate and 10.1 g of cyclopentanone were dissolved in 75 ml of ethanol, whereupon the solution was refluxed for 30 minutes was heated. After cooling, the deposited precipitate was filtered off with ethanol washed and dried. The yield of reaction product was 16.1 g, corresponding to 60% of the Theory. The melting point of the compound obtained was 155 to 158 ° C

H ₂ C CH ₂

H ₂ C CH ₂ NC ₂ H ₅

The compound was prepared as described in J. Chem. Soc, 1929, p. 39.

M. 1-Ethylpiperazine
H

/ \
H ₂ C CH ₂

H ₂ C CH ₂
N
C ₂ H ₅

22.7 g of 1-ethoxycarbonyl-4-ethylpiperazine were dissolved in 100 ml of 5N NaOH, whereupon the solution was heated to reflux temperature for 4 hours with stirring. After cooling, the reaction mixture was added with concentrated hydrochloric acid until it was just acidic. Finally, the reaction mixture was _{neutralized by adding Na 2} CO ₃ and made basic by adding 50% NaOH. Then it was continuously extracted with benzene for several days. From the benzene extract, the benzene was distilled off under reduced pressure, whereupon the residue was distilled. The yield of reaction product was 2.0 g, corresponding to 14% of theory. The boiling point of the reaction product was at a pressure of 7 mm at 40 ° C.

N. 1-Cyclopentylidene-4-ethylpiperazinium perchlorate

QH ₅
N
H ₂ C CH ₂

H ₂ C CH ₂

ClOI

H ₂ C

HX-

CH ₇

-CH,

O. 1-Cyclopentylidene-4-ethoxycarbonylpiperazinium perchlorate

O OC ₂ H ₅

/ \
H ₂ C CH ₂

H ₂ C

CH,

N
C.

HX

H ₂ C-

-CH,

25th

30th

35

40

45

3.0 ml of 72% perchloric acid were slowly added to a cold solution of 2.0 1-ethylpiperazine in 200 ml of ether. After decanting off the ether and the excess perchloric acid, the residue was dissolved in 25 ml of ethanol. The solution was then heated to reflux temperature, whereupon 2.0 g of cyclopentanone were added. The mixture was then refluxed for a further 2 minutes. After cooling, the precipitated solid reaction product was filtered off and dried. The yield of reaction product was 4.7 g, corresponding to 96% of theory. After a single recrystallization from Ν, Ν-dimethylacetamide-methanol, a product with a melting point of 240 to 241 ^° C. was obtained with decomposition.

25.9 g of 1-ethoxycarbonylpiperazine hydroperchlorate, 10.1 g of cyclopentanone and 4 drops of 1-ethoxycarbonylpiperazine were dissolved in 50 ml of ethanol, whereupon the solution was refluxed for 30 minutes was heated. After the reaction mixture was cooled, the precipitated reaction product became filtered, washed with ethanol and dried. The reaction product was in a yield of 21.3 g, corresponding to 65% of theory, were obtained. It had a melting point of 139 to 14TC.

III.

Manufacture of photosensitive photographic
Silver halide emulsions

example 1

The dyes A to I were added to various proportions of a gelatin silver bromoiodide emulsion containing 0.77 mole percent iodide and after the in Phot. Journal, 79, 330 (1939). The dyes were first dissolved in suitable solvents and, in the form of these solutions, added to separate portions of the emulsion in the concentrations given in Table 1 below. After digestion for 10 minutes at 52 ° C., the emulsions were applied to cellulose acetate film layers in a layer thickness corresponding to 432 mg of silver per 0.0929 m ^{2 of support surface.}

Samples of the recording materials obtained were then wetted in a conventional sensitometer and also exposed to a step wedge spectrograph whereupon the test specimens for 3 minutes in a developer of the following composition:

N-methyl-p-aminophenol sulfate 2.0 g

Sodium sulfite (anhydrous) 90.0 g

Hydroquinone 8.0 g

Sodium Carbohydrate (Monohydrate) 52.5 g

Potassium bromide 5.0 g

Made up to 1.01 with water

The specimens were then fixed, washed and dried in the usual way Sensitization values are given in Table 1 below.

29

Dye-
concentration
in g / mol
silver Table 1 Sensitive
ization area
(nm) Sensitive
ization
maximuni
(nm) Color
material 0.02
0.02
0.02
0.02
0.02
0.02
0.02 Type of
emulsion to 830
700 to 850
700 to 840
590 to 820
700 to 850
560 to 810
580 to 850 750
800
790
750
800
730
780 A.
B.
C.
D.
E.
F.
G Bromo-
iodide
the same
the same
the same
the same
the same
the same

Carbide
concentration
in g / mol
silver 30th Sensitive
ization area
(nm) Sensitive
ization
maximum
(nm) Color
material
5 0.024
0.025 Type of
emulsion 680 to 840
680 to 830 790
790 H
1 the same
the same

Example 2

ίο This example shows the far more advantageous Sensitization effects with tricarbocyanines which can be used according to the invention in comparison to the Tricarbocyanine dyes known from Glafkide's book "Photographic Chemistry" are achievable.

The following were used as sensitizing dyes:

(I) 3,3'-diethylthiatricarbocyanine (prior art)

= CH - CH = CH - CH = CH - CH = CH

J °

C ₂ H ₅

C ₂ H ₅

(II) 3,3'-diethyloxatricarbocyanine (state of the art)

CH - CH = CH - CH = CH - CH = CH

C ₂ H ₅ C ₂ H ₅

(III) II- (4-ethoxycarbonyl-l-piperazinyl) -3,3'-diet_v! -10,12-ethylthiatricarbocyanine perchlorate (dye G which can be used according to the invention) H ₇ C-CH ₂

CH-CH

CH = CH

COOC ₂ H ₅

(IV) II- (4-ethoxycarbonyl-l-piperazinyl) -3,3'-diethyl-10,12-ethyleneoxatricarbocyanine perchlorate (dye F which can be used according to the invention) H ₇ C-CH ₂

CH = CH

ciop

COOC ₂ H ₅

IO

A 0.2 ^ M sulfur and served as a test emulsion gold sensitized GelatiL-e - silver bromoiodide emulsion with an iodide content of 2.5 mole percent and cubic silver hciogenide grains.

The following supersensitizers were also added to the emulsion:

Disodium 4,4'-bis [4,6-bis (o-chloroanilino) -

2-triazinylamino] stilbene-2,2'-disulfonate

(1.0 g / mole silver)
4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene

(2.0 g / mole silver)
2,5-bis (1-methylundecyl hydroquinone

(6.6 g / mole silver)

The dyes to be tested were added to separate portions of the specified emulsion in the concentrations listed in the table below, whereupon the emulsion obtained was applied in an amount of 11 mg / am ² to a cellulose acetate layer support. Each of the obtained film samples was exposed to rays from a tungsten lamp in a 1B sensitometer through a step spectrograph and through a continuous step wedge using a Wratten 16 filter (minus blue). The exposed film samples were developed in a roller transport developer device for 80 seconds at 23 ° C. in a developer containing N-methyl p-aminophenol sulfate and hydroquinone, and were fixed, washed and dried. The results obtained are shown in the table below.

Color Dye-
focus Relative
Sensation veil Awareness Area material tralion *) opportunity (nm) mmol / mol (Minus MaY 710 to 870 Ag ■ 10- * blue) IVl Aa, 640 to 880 I. 0.5 100 0.05 820 590 to 780 III 1.5 346 0.06 800 580 to 820 II 0.5 302 0.04 730 IV 3.0 813 0.07 730

*) The specified concentrations led to a maximum Sensitivity as determined by a concentration series ranging from 0.5 to 10 mmol / mol Ag.

The results clearly show the concept of the invention achievable advantages in relation to the area of awareness and minus blue sensitivity.

Claims (1)

Patent claims: 1. A light-sensitive silver halide photographic emulsion containing a silver halide spectral sensitizing tricarbocyanine dye, characterized in that it contains a tricarbocyanine dye represented by the following formula H ₂ CH ₂ C CH ₂