DE2046672B2 - LIGHT SENSITIVE, SPECTRALLY SENSITIZED PHOTOGRAPHIC SILVER HALOGENIDE EMULSION - Google Patents

Description

/ \ S X ©

R ₁ - N (- CH = CH) _m _rc = CH-CH = C C-CH-CH Q-CH-CHUN-R ₂ X

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 ° an acid anion; Z and Z ^{1 are} the atoms required to complete heterocyclic rings typical of cyanine dyes, and m and «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 benzothiazole, benzoxazole or naphthothiazole rings and in which Q, Χ ^Θ , 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-II- (4-methyl-1-piperazinyl) oxatricarbocyanine-; 3,3'-diethy 1-10,12-ethylene -11 - (4 - methyl -1 - piperazinyl) - thiatricarbocyanine-; 3,3'-diethyl-10,12-ethylene-II- (4-phenyl-

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

II - (4 - ethyl - 1 - piperazinyl thiatricarbocyanine-; 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 '- sll (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.

30 The invention relates to a light-sensitive silver halide photographic emulsion containing a silver halide spectral sensitizing tricarbocyanine.

It is known e.g. B. from the USA patents 2,705,234 and 2,735,770 that carbocyanine dyes whose mesocarbon atom is replaced by an amino radical is substituted as filter dyes and sensitizers for photographic sensitization Silver halide emulsions are suitable. The known carbocyanine dyes sensitize the usual ones Silver halide emulsions down to a range of about 530 to 685 nm. This sensitization has occurred proven to be sufficient in some cases. she is

however z. B. inadequate when it comes to a

good red and infrared sensitivity of the emulsion is important

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. 3,3'-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 larger amounts of long chain tricarbocyanine sensitizing dyes not only result in a more effective one 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

concluded with regard to the amount of dye used and the optimal sensitivity that can be achieved. Only comparatively small amounts of the known tricarbocyanines can therefore be used and consequently only comparatively small infrared sensitization effects are expected in order to reduce the loss of sensitivity in the natural sensitivity range of photographic silver halide emulsions to be kept within reasonable limits. This disadvantage of known infrared sensitizers is particularly evident then strongly noticeable when the silver halide emulsion to be sensitized further, the sensitization favorably influencing substances, e.g. B. Contains supersensitizers.

It is the object of the invention. to indicate 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 mn, spectrally are sensitized without even in the presence of Supersensitizers their natural sensitivity to blue suffers too much and without affecting their sensitivity in the infrared range of the spectrum decreases too much after longer storage.

The invention is based on the knowledge that the stated object can be achieved in that carbocyanine 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 marked. that it contains a tricarbocyanine dye of the following formula:

/ \ H ₂ C CH ₂

H ₂ C CH ₂

I c

N (- CH = CH) ₁ ^ C = CH - CH = C C - CH = CH - Q = CH - CH) = N - R 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 ^{e is} an acid anion; Z and Z ^{1 are} the atoms required to complete heterocyclic rings typical of cyanine dyes, and m and n 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 with dyes in which the carbon atoms of the two methine residues, those of the meso carbon 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.

The invention achieves that silver halide emulsions are available which are 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 a 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 are short-chain alkyl radicals having 1 to 4 carbon atoms or substituted alkyl radicals, for example hydroxyalkyl radicals, e.g. B. / i-hydroxyethyl, γ-hydroxypropyl, f / -hydroxypropyl, γ-hydroxybutyl or ω-hydroxybutyl radicals or alkoxyalkyl radicals, e.g. B. / 7-methoxyäthyl, (t-Aih oxyäthyl-, β - butoxyäthyl-, γ - methoxypropyl, (,) - ethoxypropyl, ω-methoxybutyl, w-ethoxybutyl or y-butoxybutyl or carboxyalkyl, z. B. carboxymethyl, ß-carboxyethyl, y-carboxypropyl or ω-carboxybutyl radicals or sulfoalkyl

leftovers, ζ. B, / ϊ-sulfoethyl, y-sulfopropyl,; .'- sulfobutyl or ω-sulfobutyl or sulfatoalkyl, z. B. / S-sulfatoethyl, j-sulfatopropyl y-sulfatobutyl or io-sulfatobutyl or alkanoyloxyalkyl, z. B. / 3-acetoxyethyl, / I-propionyloxyethyl, 0-butyryloxyethyl, ^ acetoxypropyl. y-Fiopionyloxypropyl, ω-acetoxybutyl, ω-propionyloxybutyl or ω-butyryloxybutyl or alkoxycarbonylalkyl, e.g. B. Methoxycarbonylmethyl-, / i-Methoxycarbonyläthyl-, β - Äthoxycarbonyläthyl-, γ - Meth- ίο oxycarbonylpropyl-, y-Äthoxycarbonylpropyl-,

ω-methoxycarbonylbutyl or (»-ethoxycarbonylbutyl radicals or aralkyl radicals, e.g. B. benzyl or phenethyl radicals.

If R ₁ and R ₂ are alkenyl radicals, these can consist, for example, 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-. Ethylphenyl, xylyl, methoxyphenyl, chlorophenyl, sulfophenyl or carboxyphenyl radicals.

If R _{3 has} the meaning of an optionally substituted alkyl or aryl radical. so this can be a remainder of the door R ₁ and R ₂ given meaning.

_{R 3} is preferably an alkoxycarbonyl radical. iü which the alkoxy group has 1 to 12 carbon atoms, for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl. Decyloxycarbonyl or dodecyioxycarbonyl 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-methylihiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole or a 4- (2-thienylthiazole);
a benzothiazole ring, e.g. B. a benzothiazole, 4 - chlorobenzothiazole, 5 - chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole , 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybsnzothiazole, 5-ethoxybenzothiazole, 5-ethoxybenzothiazole , 6-dimethoxybenzothiazole, 5,6-dioxymethylene benzothiazole, 5-hydroxybenzothiazole or a 6-hydroxybenzothiazole ring;

a naphthothiazole ring, for example a naphtho- [2, ld] thiazole, naphtho [1,2-d] thiazole, 5-methoxynaphtho [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-T '^' AS-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-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole or a 6-hydroxybenzoxazole ring;
a naphthoxazole ring, e.g. B. an n-naphthoxazole or / y-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. an α-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 one 5-methyl-2-pyridine ring;

a 4-pyridine ring, e.g. B. a 4-pyridine or 3-methyl 1-4 pyridine ring;

a 2-quinoline ring, e.g. B. a 2-quinoline, 6-chloro-2-quinoline, 8-chloro-2-quinoline, 6-methoxy-2-quinoline, S-ethoxy ^ -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-dialkylindolenin ring, e.g. B. a 3,3-dimethylindolenine, 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-dimethylimidazole ring;

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

a naphthimidazole ring, e.g. B. a 1-methyl <i-naphthimidazole, l-ethyl - «- naphthimidazole, 1-butyl-a-naphthimidazole, 1-phenyl-a-naphthimidazole-,

Ιδεί 3

> thi- I l-phenyl '/ i-naphthimidazole or a 1-methyl : o \ -, I 5-methoxy-a-naphthimidazole ring, or Uh- s of a benzindole ring, z. B. a 1 H-Benz [e] indole, Di- I 3H-Benz [f] indole or a 3 H-Benz [g] indole ring. thi- 1 If R _{3 has} the meaning of an alkyl radical, then has

-Iy- j this radical preferably has 1 to 12, in particular 1 to 4 carbon atoms and consists, for example, of 10; from a methyl, ethyl, propyl, isopropyl or> cy- ] butyl radical.

hi- if R _{3 has} the meaning of an alkoxycarbonyl

As the remainder, this remainder preferably has 2 to 5 carbon atoms and consists for example of one; it; Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, Isopropoxycarbonyl or butoxycarbonyl radical. x- The tricarbocyanine used according to the invention

e-dyes can be made from symmetrical as well as from

er ^: unsymmetrical tricarbocyanine dyes exist. Tricarbocyanine dyes which have proven to be particularly advantageous are those in which R _{3 is} an alkoxycarbonyl radical. These dyes have proven to be particularly advantageous spectrally sensitive

Sizing dyes with a particularly low fog level have been shown.

Typical advantageous, used according to the invention; bare symmetrical tricarbocyanine except '■ the dyes described later are:

3,3'-dimethyl-10.12-ethylene-l l- (4-ethoxycarbonyl-1 piperazinyl V-oxatricarbocyanine perchlorate;

3,3'-dibutyl-10,12-ethylene-l l- (4-ethoxycarbonyl-

I -piperazinylj-oxatricarbocyanine perchlorate; \ 3,3'-Diethyl-10,12-ethylene-l- <4-butoxycarbonyl-

ί 1 -piperazinylj-oxatricarbocyanine perchlorate;

\ 3,3'-Diethyl-10,12-ethylene-1 H4-propyl-1-piper-

'■ aziny ooxatricarbocyanine perchlorate;

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

azinyl) oxatricarbocyanine perchlorate; 3,3'-diethyl-10,12-ethylene-l l- (4-phenyl-l-piper- ; azinyl joxatricarbocyanine perchlorate;

3,3 '-Diethyl-10,12-ethylene-11 - {4-propyl-1 -piper-

azinyl thiatricarbocyanine perchlorate; 3,3'-piäthyl-iq, 12-ethylene-ll- (4-butyl-l-piper-

azinyl thiatricarbocyanine perchlorate; 3,3'-dimethyl-10,12-ethylene-11 - {4-ethoxycarbonyl-1 -piperazinylj-thiatricarbocyanine perchlorate;

3,3'-Dipropyl-10,12-ethylene-11- <4-ethoxycarbonyl-piperaziiyl-thiatricarbocyano-perchlorate;

3-ethyl-3'-butyl-10,12-ethylene-11 - (4-methyl-

1 -piperazinyl ioxatricarbocyanine perchlorate; 3-A thy 1-3'-butyl-10,12-ethylene-11 - (4-methy 1-1 -piperaziny l) thiatricarbocyanine 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 ioxathiatricarbocyanine perchlorate; 3,3'-diethyl-10,12-ethylene-11 - (4-ethoxycarbony 1-l-piperazinyl j-oxathiatricarbocyanine per-

chlorate;
3,3'-dibutyl-10,12-ethylene-11 - (4-ethoxycarbonyl-1-piperazinyl) oxathiatricarbocyanine perchlorate;
3,3'-Diethyl-10,12-ethylene-l l- (4-methoxycarbonyl-1 -piperazinyO-oxathiatricarbocyanine-

perchlorate;
3,3'-diethyl-10,12-ethylene-11 - (4-butoxycarbonyl-1-piperazinyty-oxathiatricarbocyanine perchlorate;

3,3'-diethyl-10,12-ethylene-11 - (4-methy 1-l-piperazinyooxaselenatricarbocyanine- perchlorate;

3,3'-diethyl-10,12-ethylene-II- (4-butyl-1-piperazinylioxase selenate tricarbocyanine perchlorate; 3,3'-diethyl-10,12-ethylene-1 l- (4-methyl-1 -piper-

azinyoselenathiatricarbocyanine perchlorate; 3,3'-Diethyl-10,12-ethylene-II- (4-ethoxycarbonyl-1 -piperazinylj-oxaselenatricarbocyanine perchlorate;

3,3 '-Diethyl-10,12-ethylene-11 - (4-ethoxycarbony 1-l-piperazinyl ^ 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 —...

40 R ₁ - N (= CH

- CH = CH - NR ₄ R ₅

45

X ° (II)

wherein m, R _1, 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:

nyl-1 -piperazinylj-thiatricarbocyanine per-

chlorate;
3,3'-diethyl-10,12-ethylene-II- <4-methyl-I-piper-

azinyl selenium tricarbocyanine perchlorate; 3,3 ^f -diethyl-10,12-ethylene-l- (4-ethoxy-

carbonyl- l-piperazinylj-selenate tricarbocyanine-

perchlorate

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

3 ^ '- diethyl-10,12-ethylene-II- (4-ynethyl-

l-piperazinyljoxathiatricarbocyanine per-

chlorate;

H ₂ C

H ₂ C

CH ₂
CH ₂

Xf

(III)

H ₂ C

CH ₂

^ y.yHyp azinyl ioxathiatricarbocyanine pentchlorate; where R ₃ and Q have the meanings already given, and X _{1 is} an acid anion

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 distributed herein thoroughly. The addition of 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

j 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

s '' * ^v x / \ halide emulsions that are

R.-N (= CH-CH) = fC-CH = CH-CH CH ₂ 20 turn of common known hydrophilic colloids

'1' as a dispersant for the silver halide

χβ ^ Q 'have been placed, e.g. B. using natural Substances, e.g. B. gelatin, albumin, agar-agar,

(IV) gum arabic, alginic acid, or hydrophilic syn-

25 thetic binder, e.g. B. polyvinyl alcohol. Polyvinylpyrrolidone, Cellulose ethers, partly hydrolyzed

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

The concentration of the compound of the formula II used according to the invention, which, however, differs from the compound of the required new dyes in the emulsion, can be very different from the compound II used for the preparation of the compound of the formula II. Appropriately, the dyes formula IV was used differentiates. An unsymmetrical tricarbocyanine liter of flowable emulsion is used in this manner in concentrations of from about 5 to about 100 mg each. The obtained in the single dye. In formula IV, R ₁ , R ₃ , Q have the most favorable concentration depending on the type and X and Z have the meanings already given. the light-sensitive emulsion used and the condensation effects will advantageously be achieved. The reactions in the individual case for the production of both the most favorable symmetrical concentration can easily be determined in the usual way and also with the asymmetrical dyes in one series of tests. The emulsions inert solvent medium, for example Ν, Ν-Di- can then be applied to conventional known substrates methylacetamide, ethanol or acetic anhydride, z. B. made of paper, glass, cellulose. The condensation is preferably carried out using acetate-cellulose acetate propionate, cellulose nitrate. Polyamide, a polyester, a polyamide and the like in the presence of a conventional basic condensate.
sation means, e.g. B. a trialkylamine, for example. In an advantageous manner, gelatin silver, triethylamine, tripropylamine, triisopropylamine halide emulsions, for example as follows, mil and the like, or an N, N-dialkylaniline, e.g. B. Ν, Ν-Di- one of the dyes used according to the invention methylaniline, N, N-Diäihyianiiin or an N-alkyl 45 sensitive:

piperidines, e.g. B. N-methylpiperidine or N-ethyl- A certain amount of the dye is ir

piperidine. The condensation is preferably carried out dissolved in a suitable solvent, whereupon eir

furthermore at elevated temperatures, in particular a certain volume of the solution obtained mi

special at the reflux temperature of the reaction mixture about 5 to 100 mg of dye slowly to about 1000 m

schung. 5 ° of the gelatin silver halide to be sensitized

When the reaction mixture cools, emulsion is added. In most cases

the dyes from the reaction mixtures suffice from 10 to about 23 mg of dye per liter of emul

and can be sioned one or more times to achieve maximum awareness

Extract or recrystallize using effects using conventional gelatin silver

Prepare a suitable solvent in pure form. 55 halide emulsions, the silver halide of which, for example

In the case of the production of symmetrical dyes from silver chloride, silver bromide, silver bromo

can optionally one reaction component iodide, silver chlorobromide or silver chlorobromo

may exist in a slight excess over the other iodide.

Reaction components are used, d. b, in the case of fine-form emulsions, to denei

a concentration above the calculated stoichiometric amount of most common gelatin-silver chloride emulsions

metric concentration is preferably to belong to, slightly higher concentrations ai

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

To achieve heterocyclic compound of the formula Π with a büisierangseffekt. The stated information

Moles of an enamine salt of the formula ΠΙ are of course not converted to the use of voi

In the case of the production of asymmetrical dyes 65 Gclatme-Sfloerhalogenidemulsionen limited son

are the reaction components in molar equidents also apply to emulsions in which there

valenten used The heterocyclic starting binders are not or only partially made of gelatin

Compounds of the formula II are known compounds

V ₁ ,

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 production of such photographic recording materials used, they are particularly suitable for the production of such false color films which contain an infrared-sensitive layer.

The light-sensitive photographic silver halide emulsions according to the invention, which can be coarse-grained, medium-grained or fine-grained emulsions or emulsions from mixtures of such emulsions, can be prepared by conventionally known methods. B. so-called single enema emulsions or so-called double enema emulsions. The emulsions may further so-called ^T ippmann emulsions be or consist of ammoniacal emulsions or ripened in the presence of a thiocyanate or thioether emulsions, such as are known for example from the USA. Patents 2222264, 3 320,069 and 3 271 157, or Silver halide emulsions with cubic silver halide grains as described, for example, in Journal of Photographic Science, Vol. 12, 1964, pp. 242 et seq. And Journal of Photographic Science, Vol. 13, 1965, pp. 85-89.

Furthermore, the photosensitive silver halide emulsions of the present invention can be so-called Be outer grain and inner grain emulsions, such as those from 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 components or surface grain and inner grain emulsions, such as those described in the United States patent 2996 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 the USA patents 2 184013, 2541472, 3 367 778, 2456953 and 2 861885 and British patent 723 019 and French patent 1520821.

The silver halide photographic light-sensitive emulsions of the present invention may be unwashed or washed for the purpose of removing soluble salts. For example, the soluble salts may have been removed by quenching and leaching the emulsion, or by washing the coagulated emulsion, & h. for example, by methods as are known from the USA. Patents 2618 556, 2 614928, 2565418, 3 241969 and 2489 341st

The silver halide photographic emulsions of the present invention can further by adding 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 which can be used are, for example, from the USA patents 1 623 499, 2 399 083, 3 297 447 and 3 297 446 are known.

The light-sensitive photographic silver halide 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, their use, for example from U.S. Patents 2,886,437, 3,046,134, 2,944,900 and 3,294,540.

The silver halide 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 known azaindenes, those known from U.S. Patent 2,728,663 Mercury Salts Obtained from the U.S. Patent

3,287,135 urazoles known, the sulfobrenzcatechols known from US Pat. No. 3,236,652; the oximes known from British patent specification 623 448, and also those from the USA patents 2,403,927, 3,266,897 and 3,397,987 known nitroindazoles as well as mercaptotetrazoles and nitrone; the polyvalent metal salts known from US Pat. No. 2,839,405; that from the USA patent 3,220,839 known thiuronium salts and finally those from the USA patents 2 56> 263 and 2,597,915 known palladium, platinum and gold salts.

Optionally, the light-sensitive photographic Süberhalugenidernulsione Ti after 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 US Pat. No. 2,592,368 and de French patent 1505 778 is known in the emulsions are incorporated.

The photographic silver halide emulsions according to the invention can be further durcl harden the usual known organic and inorganic hardening agents such. B. using of hardening agents from aldehydes, so-called blocked aldehydes, ketones, carboxylic acids Carboxylic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfones, compounds with active Halogen atoms, epoxy compounds, aziridines, al

Ö14

tive olefins, isocyanates, carbodiimides, hardeners 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 has already been explained, the most varied Colloids are 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 that increase the dimensional stability of the product to be produced contribute to photographic recording material. Synthetic polymers suitable as binders are, for example, from U.S. Patents 3,142,568, 3,193,386, 3,062,674, 3,220,844, 3,287,289 and 3 411911 known. The water-insoluble polymers have proven to be particularly effective Polymers of alkyl acrylates and alkyl methacrylates, acrylic acid, sulfoalkyl acrylates and sulfoalkyl methacrylates proven, which are suitable for cross-linking, which facilitates the hardening of the emulsions, and also those polymers with repeating sulfobetaines, such as those for example from Canadian patent 774 054 are known.

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, etc., 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 of the present invention Finally, silver halide emulsions can be based on a wide variety of conventionally known Supports are applied, e.g. B. those made of cellulose nitrate, cellulose esters, Polyvinylaceiaien, Polystyrene, polyalkylene terephthalate, polycarbonates and the like, and also made of glass, paper, metal and the like. For example, the emulsions can be applied to flexible substrates, in particular made from paper, which may be is partially acetylated, applied or on paper backing with a baryta layer and / or a layer of an α-olefin polymer, in particular a polymer of an α-olefin having 2 to 10 carbon atoms, e.g. B. polyethylene, Polypropylene, an ethylene-butene copolymer or the like.

Optionally, the photosensitive silver halide photographic emulsions of the present invention can be used also plasticizers or plasticizers and lubricants, e.g. B. polyalcohols, e.g. B. Glycerine and diols, such as are known, for example, from US Pat. No. 2,960,404, or fatty acids or fatty acid esters such as those disclosed in U.S. Patents 2,588,765 and 3,121,060 are known, and also silicone resins, such as, for example from British patent specification 955 061 are included.

Finally, the light-sensitive silver halide photographic emulsions of the present invention can be used 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 known, for example, from US Pat. No. 3,133,816.

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 contain an optical brightener, z. B. a brightener consisting of a stilbene, triazine, oxazole or coumarin compound, contain. For the production of such recording materials, for example, the water-soluble optical brighteners are used, which are from the German patent specification 972 067 and the USA patent specification 2 933 390 are known, as well as brightener dispersions, such as those in German U.S. Patent 1,150,274 and U.S. Patent 3,406,070.

The light-sensitive photographic silver halide emulsions of the present invention can be can also be used for the production of photographic recording materials which use light contain absorbent substances or filter dyes, such as those from the USA patents 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.

Those for making a photosensitive photograph The silver halide emulsion of the invention used sensitizing dyes as well optionally other emulsion approaches can be used with the emulsion from aqueous solutions or solutions organic solvents are added, whereby, for example, processes can be used, as known from U.S. Patents 2,912,343, 3,342,605, 2,996,287, and 3,425,835. the Dyes can be dissolved separately from one another or together in a solvent, with the optionally combined solutions can be incorporated into the silver halide emulsion or whereupon an emulsion applied to a layer support, optionally with such a solution can be bathed.

The silver halide photographic emulsions of the present invention can be prepared according to conventionally known ones Procedure, 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 that disclosed in U.S. Patent 2,681,294 is known, and the like, on conventional known substrate be applied. If necessary, you can do this

046 672

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 silver halide photographic light-sensitive emulsions of the present invention are useful excellent for the production of photographic materials for the KoHoid transfer process, such as it is known, for example, from US Pat. No. 2,716,059, or for the production of recording materials for the silver salt diffusion transfer process such as that disclosed in U.S. patents 2,352,014, 2,543,181, 3,020,155 and 2,861,885 is known, as well as for the production of recording materials for color image transfer processes such as those found in U.S. patents 3 087 817, 3 185 567, 2 983 606, 3 253 915 3 227 550, 3 227 551, 3 227 552, 3 415 644, 3 415 645 and 3,415,646 are known, as well as for the production of recording media 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 known, for example, from U.S. Patents 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 of 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 1,110,046. Finally, are suitable The emulsions are also used to produce recording materials through physical development should be developed, as for example from British patent specification 920 277 and 1 131 238 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, 7.801171, 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 Color couplers, such as those disclosed in U.S. Patents 2,252,718, 2,592,243 and 2 950 970 is known.

Exposed silver halide photographic emulsions according to the invention can be developed by conventionally known methods, for example using alkaline developing solutions with conventional developing agents, e.g. B. hydroquinones, pyrocatechols, aminophenols, 3-pyrazolidones, phenylenediamines, ascorbic acid derivatives, hydroxylamines, hydrazines and the like a so-called stabilization development, as it is known, for example, from the PSA-Journal, Vol. 16 B, August 1950 . B. in the journal Phot Sei. and Eng., Vol. 2, No. 3, October 1958, and U.S. Patent 3,392,019 can be used. Optionally, the photographic silver halide emulsions according to the invention can also be developed using developers containing hardeners, as are known, for example, from U.S. Pat. No. 3,232,761, and in developing devices having transport rollers, as described, for example, in U.S. Pat. No. 3,025,779 or by surface development, as is known, for example, from Example 3 of US Pat. No. 3418132.

The light-sensitive photographic silver halide emulsions of the present invention are also excellent for making lithographic printing plates, e.g. By colloid transfer of the undeveloped and uncured areas of an exposed and developed emulsion layer onto a suitable substrate, e.g. B. of the type known from US Pat. No. 2,763,553, in which relief images are obtained (cf. US Pat 271 150 is known.
If necessary, the tricarbocyanine dyes used according to the invention can also be used together with other known sensitizing dyes. For example, additional spectral sensitization can be achieved by treating the emulsion with a solution of another sensitizing dye in an organic solvent or with a dispersion of another dye, as is known, for example, from French patent 1,482,774. It is of course also possible to use solutions of the tricarbocyanine dyes used according to the invention which also contain a further dye. The dyes used in addition to the tricarbocyanine dyes used according to the invention can likewise be added to the finished emulsion or else in an earlier phase of the emulsion preparation. Typical suitable dyes which can be used in addition to the tricarbocyanine dyes used according to the invention are described, for example, in U.S. Patents 2,526,632, 2,503,776, 2,493,748 and 3,384,486. The additionally used sensitizing dyes can for example consist of cyanine, merocyanine, complex tri- or tetranuclear merocyanine, complex tri- or tetranuclear cyanine, holopolar cyanine, styryl, hemicyanine, enaminehemicyanine, oxonol and hemioxonol dyes.

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, Substituted alkyl, haloalkyl, cyano or alkoxy radicals could be. The dyes can also be symmetrical or asymmetrical dyes be, whose methine radical or polymethine chain is optionally replaced by alkyl, phenyl, enamine or heterocyclic radicals can be substituted.

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

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

Finally, in addition to the tricarbocyanine dyes, the emulsions can also be used in an advantageous manner supersensitizing additives are incorporated, which do not absorb visible light, for example ascorbic acid derivatives, azaindenes, cadmium salts and organic sulfonic acid as described, for example, in U.S. Patents 2,933,390 and 2,937,089 will. As a particularly advantageous supersensitizing agent for those used according to the invention Dyes have sulfonated polynuclear aromatic compounds, silver halide reducing compounds, azaindenes and combinations of these compounds have been shown, for example from the German Offenlegungsschrift 2046 687 is known.

Preparation of the tricarbocyanine dyes used according to the invention A. 3,3'-Diethyl-10,12-ethylene-II- (4-methyl-1-piperazinyl) oxatricarbocyanine perchlorate

C-CH = CH-C

ClOP

1.3 g of 1-cyclopentylidene-4-methylpiperazinium perchlorate and 4.8 g of 2- (2-acetanilidovinyi) -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 with stirring for 10 minutes. The reaction mixture was then placed in a beaker and allowed to stand for 5 minutes at room temperature. The one with it precipitated crude dye was filtered off and washed with ethanol. After two recrystallizations 0.2 g of dye, corresponding to 6% of theory, were obtained from a cresol-methanol mixture obtained with a melting point of 267 to 268 ° C with decomposition.

B. 3,3'-Diethyl-10,12-ethylene-II- (4-methyl-1-piperazinyl) thiatricarbocyanine perchlorate

1.3 g of l-Cydopentyliden ^ -methylpiperaziniumperhlorat, 5.0 g of 2- (2-acetanilidovinyl) -3-ethylbenzothiizolium iodide and 1.5 ml of triethylamine were dissolved in 10 ml of ethanol, whereupon the solution was 10 minutes ang was heated to reflux temperature. After cooling to room temperature, the lower

filtered off, washed with methanol and dried After two recrystallizations from a cresol-methanol mixture, 1.0 g became more pure Dye, corresponding to 31% of theory, with a melting point of 261 to 262 ° C. with decomposition obtain.

C. 3,3'-Diethyl-10,12-ethylene-1 H 1, phenyl-1-piperaanyl thiatricarbocyanine perchlorate

QH ₅

CH = C C - CH = CH

ClOI

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-l l- (4-ethy! -L-piperazinyl) oxatricarbocyanine perchlorate

C ₂ H ₅

/ \ H ₂ C CH ₂

H ₂ C CH ₂

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, with a melting point of 250 to 251 ^° C. were obtained with decomposition.

21 ²²

E. 3,3'-Diethyl-10,12-Ethylene-II- (4-Ethyl-1-piperazinyl) thiatricarbocyanine perchlorate

H ₂ C
H ₂ C

C ₂ H ₅

CH ₂

CH ₂

SC ^s

C = CrI-CH = C C-CH = CH-C NH ₂ C CH ₂

αο ₄ ^Θ

CH,

N
C ₂ H ₅

1.4 g of 1 - cyclopentylidene - 4 - ethylpiperazinium 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. After cooling to room temperature for 5 minutes, it was precipitated! The raw dye is nitrided off, washed with methanol and dried. After a one-time re-installation 0.7 g of pure dye, corresponding to 21% of theory, with a melting point were obtained from methanol obtained from 243 to 244 ° C with decomposition.

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

O OC ₂ H ₅ C

H ₂ C CH ₂ H ₂ C CH ₂

oco

/ V

C = CH-CH = C C-CH = CH-C H ₇ C CH ₂

ClOi

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 N, N-dimethylacetamide, whereupon the solution for 10 minutes was heated with stirring so vigorously that a gentle reflux took place. 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 rol dye was filtered off, washed with methanol and dried. After a single recrystallization ai methanol 0.8 g of pure dye entsprecher 24% of theory were obtained with a melting point of <! ■ up to 248 ⁰ C with decomposition.

23 24

G. ll- (4-Ethoxycarbonyl-1-piperazinyl) -3,3'-diethyl-10,12-ethylthiatricarbocyanine perchlorate

OC ₂ H ₅

C-CH = CH-C

1.6 g of 1 - cyclopentylidene - 4 - ethoxycarbonylpiperazinium perchlorate, 5.0 g 2- (2-acetanilidovinylV 3-ethylbenzothiazolium iodide and 1.5 ml triethylamine were dissolved in 15 ml Ν, Ν-dimethylacetamide, whereupon the solution was brought to a gentle boil with stirring for 10 minutes under reflux conditions became. 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 cooling down for 10 minutes the precipitate was filtered off to room temperature, washed with methanol and ge dries after a single recrystallization from a mixture of Ν, Ν-dimethylacetamide and methano were 1.9 g of pure dye, corresponding to 54 ° / theory, with a melting point of 266 bi 267 ° C obtained with decomposition.

H. Anhydro-1 l- (4-ethoxycarbonylpiperazin-l-yl) -10,12-ethylene-S ^ '- diO-sulfopropyO-thiatricarbocyanine hydroxide, Triethylamine salt

\ = CH-CH = ^ y

HN (C ₂ Hs) ₃

1.6 g of 1-cyclopentylidene -4- ethoxycarbonylpiperazinium perchlorate, 4.0 g of anhydro-2- (2-anilinovinyl) -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 a further 2-3 minutes. Thereupon the Res The mixture was filtered while it was still hot. The precipitated dye was filtered off and once from metha: The pure dye was recrystallized in a yield of 1.6 g, corresponding to 36% of the Theo obtained with a melting point of 235 to 236 ° C and decay.

309 52C

26th

Anhydro-II- (4-ethoxycarbonylpiperazin-l-yl) -10,12-ethylene-3,3'-bis (3-sulfopropyl) -S.o ^ '. O'-dibenzothiatricarbocyanine hydroxide, Triethylamine salt

O _{> /} OQH _S C

C-CH

= CH - = CH - CH =

I I

2.16 g of l- (5-aniIinomethylene-2-phenyliminomethyl-1-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 heated for 2 minutes in a reaction vessel with a reflux condenser so that a gentle reflux began. After the reaction mixture had cooled, the dyestuff which had precipitated out was filtered off and recrystallized once from methanol which contained some triethylamine. In this way, 0.9 g of pure dye, corresponding to 19% of theory, with a melting point of 263 to 264 ^° C. was obtained with decomposition.

II.

Production of starting compounds
for the production of the dyes

J. 1-Cyclopentylidene-4-methylpiperazinium perchlorate

CH ₃

H ₇ C

CH ₂

H ₂ C CH ₂

\ β '

ClQf

H ₂ C

CH ₂

K. 1-Cyclopentylidene-4-phenylpiperazinium perchlorate

QH ₅

H ₂ C
H ₂ C

V.

CH ₂
CH ₂

ClO ₄ ⁶

H ₅ C

H ₂ C-

CH ₂
-CH,

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

The reaction product was heated by Z ^ isat; precipitated from ethanol and, after cooling, the reaction mixture is filtered off and dried. E; were 28.7 g of reaction product, corresponding to 87 ° / < of theory, with a melting point of 185 to 186 ° C.

L l-ethoxycarbonyl-4-ethylpiperazine

55

I I

H ₂ C CH ₂

20.1 g of 1-methylpiperazmyl hydroperchlorate and 10.1 g of cyclopentanone were dissolved in 75 ml of ethanol, whereupon the solution was refluxed for 30 minutes. After cooling it was the deposited precipitate is 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.

OC ₂ H ₅

H ₂ C
H ₂ C

CH ₂

^ H ₂

N
QH ₅

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

M. 1-Ethylpiperazine
H

O. 1-Cyclopentylidene-4-ethoxycarbonylpiperazinium perchlorate

H ₂ C
H, C

CH ₂

H ₂ C

CH,

H ₁ C

CH ₂

CH,

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 4O ⁰ C.

N. 1-Cyclopentylidene-4-ethylpiperazinium perchlorate

i!

H ₂ C
H ₁ C-

CH ₂

-CH,

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, woraul the solution to reflux temperature for 30 minutes was heated. After the reaction mixture was cooled, the precipitated reaction product became filtered off, 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 141 ° C.

I.
N
/ > H ₅ \ H; \ e \
CH ₂ H; CH ₂
/ /
.c , C

/ \
H ₂ C CH ₂

40

45

50

H, C-

CH ₂

To a cold solution of 2.0 1-ethylpiperazine 3.0 ml of 72% perchloric acid were slowly added to 200 ml of ether. After decanting the Ether and the excess perchloric acid the residue dissolved in 25 ml of ethanol. The solution was then heated to reflux temperature, whereupon 2.0 g of cyclopentanone were added. This was followed by a further 2 minutes at reflux temperature heated. 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 one-off Recrystallization from Ν, Ν-dimethylacetamide-methanol a product having a melting point of 240 to 241 ° C. was obtained with decomposition.

III.

Preparation of photosensitive silver halide photographic emulsions

example 1

Dyes A through I were added to various proportions of a gelatin silver bromoiodide emulsion containing 0.77 mole percent iodide and prepared according to the method described in Phot Journal, 79, 330 (1939). The dyes were first dissolved in suitable solvents and, in the form of these solutions, separate portions of the emulsion were added 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 exposed in a conventional sensitometer and also exposed to a step wedge spectrographer, whereupon the test specimens ir 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

Filled up with water to 1.01

The test specimens were then fixed, washed and dried in the usual way The sensitization values maintained are contained in Table 1 below.

Table 1

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

FarbslofT-
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
I. 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

C ₂ H ₅

(II) 3,3'-diethyloxatricarbocyanine (prior art) α;

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

J ^e

QH ₅

(III) II- (4-ethoxycarbonyl-l-piperazinyi) -3,3'-diethyl-10,12-ethylthiatricarbocyanine perchlorate (dye G which can be used according to the invention)
HX-CH ₂

CH-CH

CH = CH ClOi

COOC ₂ H ₅

(IV) II- (4-ethoxycarbonyl-1-piperazinyl) -3,3'-diethyl-10,12-ethylene oxatricarbocyanine perchlorate (according to the invention usable dye F)

H ₂ C-CH ₂ ) = CH-

CH

H ₂ C CH ₂

H ₂ C CH ₂

COOC ₂ H ₅

A Ο ^ -μΜ-sulfur and served as a test emulsion gold sensitized gelatin - silver bromoiodide emulsion with an iodide content of 2.5 mole percent and cubic silver halide grains.

The following supersensitizers were also added to the emulsion added:

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

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

(I ₅ O g / mol 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, after which the emulsion obtained was applied in an amount of 11 mg / dm ² to a cellulose acetate layer support. Each of the film samples obtained 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 in a roller transport developer device for 80 seconds at 23 ° C in an N-methyl p-aminophenol sulfate and developers containing hydroquinone are developed and fixed, washed and dried The results obtained are shown in the table below.

dye

III

II

IV

Dye concentration)

mmol / mol
Ag! (Γ ⁴

0.5
1.5
0.5

3.0

Relative
sensitivity
(Minus blue)

100
346
302
813

veil

0.05
0.06
0.04
0.07

Awareness

Max.

820
800
730

area
(nm)

710 to 870 640 to 880 590 to 780

730 | 580 to 820

*) The indicated concentrations led to a maximum sensitivity, as with the help of 0.5 to 10 mmol / mol Ag Reaching concentration series was determined.

The results clearly show the advantages that can be achieved according to the invention with regard to the sensitization range and minus blue sensitivity.

109 520/381

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 C CH ₂ H ₂ C CH ₂