DE2353864A1 - SPECTRALLY SENSITIZED PHOTOGRAPHIC SILVER HALOGENIDE EMULSION AND THEIR USE - Google Patents

Description

The invention relates to a photographic silver halide emulsion, which is spectrally sensitized in such a way that its maximum sensitivity in the wavelength range of at least 580-640 nm, as well as their use.

The invention thus particularly relates to a photographic one Silver halide emulsion obtained by using a supersensitization combination in a specific Spectral wavelength range extraordinarily strong has been sensitized.

Those normally used in the field of photography • Photosensitive materials have a spectral ver ~

409819/0862

division of the sensitization, which is as evenly as possible extends over the entire optical range. Around however, a better and more desirable color image achieve is a differentiated specific spectral distribution of the sensitization or the sensitivity of the photographic material required. For this purpose, combinations of two or more sensitizers are used which have been used as supersensitization agents. To achieve brilliant. Color rendering is a broad range of spectral sensitivity for a given photographic material not at all recommendable. This is how it is, for example neither desirable, a sensitization up to ranges above 66O nm (wavelength of the maximum sensitization) nor is it particularly useful to provide a noticeable Sensitivity only in the range of longer wavelengths, for example in the range below 530 nm (wavelength of maximum sensitization).

In practice, the attempt prepares a selective spectral sensitization in the range between 58O and 64O nm again and again almost insurmountable difficulties. Photographic Sensitizing material selectively in this wavelength range is always one of the main tasks of the relevant technology.

The invention is accordingly based on the object a new method for enhanced selective supersensitization of photographic silver halide emulsions create zxi in the wavelength range of about 58O - 640 nm and at the same time the inevitable color staining that usually occurs after development

409819/0862

., If Άη £ there were the invention is = ,, to find a sensitiser, which does not, in .the. adjacent pnotoeropfinallchen layers diffuse and thereby the adjacent layer is sensitized, although only one layer is selectively spectrally sensitized with a photographic menstrual layer material; target. - '.' ■ - ''

Two Lösting this object it is proposed erfindiingsgeiaäss emulsion photograpliische a silver halide of the aforementioned type, characterized by & suitable for in & in supersensitization amounts present combination of at least one of the Garbbcyanin allgemeiBen

formula

in the Z, one for education; a ß-naphthoid toxazole ring or a ß-naphthoidazole ring _; The required group of atoms means, whereby the benzene nuclei of these rings can be substituted in such a way that they do not adversely affect the sensitivity of the silver halide emulsion. S-Pü ^ ydronäphtho ^ Cl / ^ dJ'-tiriazcil-ringes are required; A ^ a hydrogen atom _r an alkyl group, - namely a unisubstituted alkyl group with preferably Ms zn 4 carbon atoms, in particular [

up to 3 carbon atoms, or a substituted alkyl group in which the alkyl radical can preferably have up to 4 carbon atoms, in particular up to 3 carbon atoms, or represents an aryl group, preferably a mononuclear aryl group; R ₁ and R ₀ each represent an aliphatic group, namely a saturated aliphatic group or an unsaturated aliphatic group, for example an alkyl group or an aralkyl group, which are substituted; can, with up to 8 carbon atoms in the alkyl part, preferably if at least one of the radicals R- or * R_ are either a hydroxyalkyl, a carböJiyälkyl or an alkyl containing sulfo groups, with up to four carbon atoms in the alkyl part ;? X-, is a satire anion group; and 1 is 1 or 2, where, when 1 is equal to 1, the carbocyanine is an intramolecular salt with a betaine-like structure of at least one dye of the general formula ■

in which Z ' denotes a group of atoms which is required for the formation of a benzothiazole ring, a β-ITaphthothiazole ring, a benzoselenazole ring or a 4,5-dihydrörtaphtho- (1,2-d) -thiazölringes, and Z ^ denotes a group of atoms, which are required to form a benzoxazole ring or a benzimidazole ring; A_ a hydrogen atom, an alkyl group,. namely an .unsubstituted .alkyl group with preferably up to 4 carbon atoms, in particular up to 3 carbon atoms, or ¹ | a substituted alkyl group in which the alkyl part i _f preferably has up to 4 carbon atoms, in particular up to

409819/0862

to 3 carbon atoms, or an aryl group, preferably a mononuclear aryl group; R ₃ . and R ^, each, an aliphatic. Group inclusive. a saturated one. aliphatic group and an unsaturated aliphatic. Group mean, for example, an alkyl group and an aralkyl group, these. Groups can be substituted with up to zxl S carbon atoms in the alkyl part, preferably with up to ZM-A carbon atoms in the alkyl part, ... where, at least one of the radicals R_ or. R _{4 is} a hydroxyalkyl, a carboxyalkyl, or; a one. jSulfo group-containing alkyl is τ Χ- ·.-is an acid anion group ·; ml or, 2, isjt ,. whereby . for the case · m - equals 1, the dye in the form of an.intra-. molecular salt is present; or "one of the dyes of the general formula ■ ... .-. ..-- -.;." .__, .., ..

I ³ J? \

C = CH-C = OH-G /; ^,

in which Z ₅ and Z _& each denote a group of atoms which are required for the formation of a benzothiazole ring, a benzoselenazole ring, a β-naphthothiazole ring or a β-napiithoselenazole ring; A_ a hydrogen atom, * an alkyl group, and -war an unsubstituted alkyl group with preferably up to 4 carbon atoms, in particular

up to 3 carbon atoms, or a substituted alkyl group with preferably up to 4 carbon atoms in the ^r · alkyl radical, in particular up to 3 carbon atoms in the alkyl radical, or / an * aryl group; R ₅ 'and R, each denote an aliphatic group, including a saturated aliphatic group and an unsaturated aliphatic group, for example an alkyl group and

.an aralkyl group, which groups can be substituted with up to 8 carbon atoms in the alkyl radical, preferably up to 4 Kolilenstoffatomen in the alkyl radical, v / obei at least one of the radicals R ^ or R ^ either a hydroxyalkyl, a carboxyalkyl or a are alkyl containing a sulfo group; X _{3 is} an acid anion group and η is 1 or 2, the dye being in the form of an intramolecular salt when η is 1.

The invention 'is based on Äusführungs- ■ examples are described in more detail in conjunction with the drawings. Show it: ' '

Figures 1 to 19 spectrograms of the selective ■

supersensitizing dye combinations according to the invention and by .other serving for comparison purposes Dyes and ■

Fig. 20 '- in a graphical representation the

Transmission characteristics • of the filters Sp-I, Sc-50 and

Sc-56. ■■■ - ■ "■ ·

Typical examples of the heterocyclic rings of the sensitizer with the general formula (I) falling under the symbol Z ~ are, for example, the following, where both rings can be unsubstituted or substituted with substituents such as halogen atoms. Alkyl groups, acyl groups, aryl groups, cyano groups, hydroxyl groups, alcoholate groups or amino groups: bensothiazole, 5-chlorobenzothiazole, 5-bromobenzothiazole, 5-pluobenzothiazole, 5-methylbenzothiazole , 5-metlioxybenzothiazole,

5-Methylcarbonylbenzothiazol, 5-Carboxybenzotbiazol, 5-MetliOxycarbpnylbenzothiazol, 5-Plienylbenzothiazol, 5-Cyanobenzöthiazol-, 5-TrifluormethylbenzQthiazol, _5-f 5-HydrOx.yberizothiazol Aminobenzqthiazol, 5, ö-Dichlorbenzothiazöl, 5-methyl-6-methoxybenzothiazole, 5 , 6-pimethylbenzothiazol, 5 x, 6-Bitnethöxybenzothiazol ·, 5,6-Diäthöxybenzqthiaz.ol, Benzöselenazol, 5-Chlorbenzpselenazol, 5-Brombenzoselenazoi, ■ - 5-Metliylbenzoselenazole 5-Met; lioxybenzoselenazol, 4,5-DllSydrönaphtTio- ° ~ (J- _t 2-cl) ~ tlaiazole / 6-cyano-4, 5-dihydronaplitiio- (1,2-d) -thiazole ₍ .6-ethylr4. _/ S-diydronaphtlio- (1,2-d) -tliiazole ,. Q- ' chloro-4 _r 5-diliydEonaphtIio- (1 _l 2-d) -t \ hiazole and other hinge. The length of the carbon chain of the alkyl part for the y substituents on the aforementioned heterocyclic groups is preferably up to 4 Carbon atoms / especially up to 2 carbon atoms * -, ■ ·

The heterocyclic rings falling under the symbol Z_ can also be substituted, namely with the same substituents, me.sie above in connection with Z _? are mentioned. Examples for the heterocyclic rings that come under the symbol Z_ in the general formula. (II) are the following: Benzothiazoi, 5-chlorobenzothiazole, S-chlorobenzothiazole, 5-broinbenzothiazole, 5-methylbenzothiazole, S-methoxybenzothiazole, 5,6-diinethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5-athoxybenzothiazole -e-methoxybenzothiazole ,. 5-methyl-6-ethoxy-. benzothiazoi, S-ethoxy-e-methylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, 5-phenylbenzothiazole, 5-hydroxybenzothiazole, 5-cyanobenzothiazole, 4,5-dihydr: -onaphtho- (1,2-d) -thiazole, " 6-ethyl-4 _l 5-dihydronaphtho- ^ (1, 2-d) -thiazole, 8-chloro-4,5-dihydronaphtho- (1,2-d) -thiazole, benzoselenazole, -5-chlorobenzeneselenate, 5- Methylbenzoselenazole, 5-methoxybenzoselenazole, 5,6-dimethylbenzoselenazole, 5,6-dimethoxy-benzoselertazole, "5-phenylbenzoselenazole, β1-haphthobenzothiazole et al. ,.

Λ09819 / 0862

Also falling within the general formula (II) under the symbol Z ₄ can heterocyclic rings in which in connection with Z ^ manner described be substituted * Typical representatives of heterocyclische.Ringe under Z ₄ in of the general, formula (II) fall, the folgendenr benzoxazole, 5-Methyl-benzoxazole, 5-Methoxybensoxazol, 5,6-Dinaethylbenzoxäzol, -5, 6 ~ Diinethoxybenzoxazol, 5-phenylbenzoxazole _r Benziraidazol, 5-chlorobenzimidazole, 5,6-Dichiorbenziinidazol, 5-Trifluormethylbenziraidazpl inter alia

Examples of the heterocyclic rings formed by the symbols Z ~ and 2> - in the general formula (III), which can also be substituted with substituents, as they are in connection with Z _? are the following: Benzothiazole, 5-chlorobenzothiazole, 5-bromobenzothiazole, 5-iiethylbenzothiazole, 5-methoxybeiizothiazole, S-AcSetyllDenzotliiazole, S-metlioxycarbonylbenzothiazole, 5-athoxycarbonylbenzothiazole, 5-athoxycarbonylbenzothiazole, 5-phenobenaylbenzothiazole, 5-phenolycarbonylbenzothiazole, 5-phenylbenzothiazole, 5-phenoxybenzothiazole, 5-phenoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenylbenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenylbenzothiazole, 5-ethoxycarbonylbenzothiazole , 5-chlorobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5-phenylbenzoselenazole, ß-naphthothiazole, ß-naphthoselenazole and others

A ,, Ä _? and Ä “, in the general formulas {I), (II) and (Hl) can each be a hydrogen atom, a methyl group , an ethyl group, a propyl group, a phenyl group, a phenylethyl group and others.

R ,, R-, R ,, R ^, R, - and -Rg each mean, for example, one Methyl group, an ethyl group, a propyl group, an allyl group, a hydroxyalkyl group, for example 2 ~ Hydroxyäthyi, or 3-Hydroxyäthyl, a carboxyl group,

for example 2-carboxyethyl / 3-carboxypropyl or

4-carboxybutyl, an alkoxyalkyl group, for example /

409819 / 0ÖS2 '

2-methoxyethyl, an alkyl containing a sulfo group group, for example 3-sulfopropyl, 3-sulfobutyl, 2- (3-sulfopropoxy) ethyl, 2-hydroxy-3-sulfopropyl or 3-sulfopropoxyethoxyethyl, a halogenated alkyl group, for example 2-bromoethyl, an aminoalkyl group, for example morpholine alkyl, a cyanoalkyl group or a SuIfoaralkylgruppe, such as p-SuJ-fophenyläthyl. . "■,." -

X ,, X »and X ^ each mean, for example, an iodide, bromide, Chloride, a p-toluenesulfonic acid anion, a benzenesulfon * - acid anion, .an ethylsulfuric acid anion, a perchlorate, a khodanate and other similar anions commonly used can be used in conjunction with cyanine salts.

The chemical structure of the sensitizing dye given by the general formula (I) _f can be characterized as a nonsymmetrical carbocyanine dye which is substituted on the nitrogen atom of the nitrogen-containing heterocyclic ring with at least one alkyl group, namely with hydroxyalkyl, carboxyalkyl or with a Alkyl containing sulfo groups, and whose sensitivity maximum is preferably in the wavelength range from 580 to 625 im. The sensitizing dye is furthermore characterized by the tendency to: Formation of J-aggregates. ■ ·

Furthermore, the dye of the general formula (I) is characterized by the ability, when combined Use with a dye of the general formula (II) or the general formula (III) the spectral sensitivity of a silver halide emulsion without its input maximum in a wavelength range

409819/0862

is shifted longer than 640 nm.

The chemical structures of the sensitizing dyes of the general formulas (II) and (III) are represented by one or more of the following substituents Hydroxyalkyl, carboxyalkyl or containing a sulfo group Alkyl characterized, these substituents only on one of the nitrogen atoms, but preferably on both nitrogen atoms of the one containing the nitrogen atoms heterocyclic ring.

By using these special dyes it has become possible to produce a high, practically pure red— to generate sensitivity with minimal additional sensitization, without the maximum sensitivity to shift too far into the long-wave range and at the same time the color staining that occurs after development suppress even when using very large amounts of dye.

The combination of the special dyes mentioned caused supersensitization according to the invention is surprisingly extremely resistant to sensitization poisoning, such as that in the presence of Color couplers are otherwise often observed.

For example, the combination of the invention increases used color sensitizers not the fogging tendency and. also does not lead to diffusion of the dye into the adjoining emulsion layer and is therefore not able to remove this layer (silver halide) to raise awareness in an uncontrolled and undesirable manner, when the color sensitization combination according to the invention in a layer of a photosensitive "

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1353864

Multi-class structure with different emulsions. is used"

The supers e ^ sibilisierüng according to the invention is suitable sieve, especially for the production of photοempfindlichen "Eiflul ^ ■ sioiieh vöifi 'örtliöpän Ti'p ^ · V for producing multilayer pliötoempf indliehen PärbeTnulsiönsStrulituiren Slit. Eingemisöhteiti Kupper- in the emulsion, such as B ± & For example "iiiMertrS ^ PS 3 40a 43'4 and in GB-PS 1 2S2 0S6 '. Described aind _# especially for the creation of effttllsiöneri for reversal or negative films - for the color photographe ₄ "". -

Population examples of the serisibilisiercönden colors that he findings gerriäs s uses Four den-> are described in the following examples, although the invention is not limited to the only " examples: expressly" mentioned sensitizers * -.

Examples of compounds falling under the general formula (Ϊ) fall / are the following:

40 9819/086 2

C-CH = C-CH = C

IV

CH.

C-CH = C-CH = C

CH

. G-CH = C-CIJ = C

OCH-

-CH = C-CH = O "

Cl

98 1 9/086

D>

-N

J-CH = C-CH = '

Γ ■ ■

-CH = C-CH = C '

Cl

(CH ₂ ) ₃ S0

-j 3

? 2 ^H 5 / Se.

C-CH = C-CH = C

• IK .. ^ "CH-

H ^H 5

C = CH-CH = CH-C.

409819/0862

(i-i)

C = CH-CH = CH-C

3SO ₃ HNCC

COOCH,

^C 2 ^H 5

-CH = C-CH =

,H,

Examples of compounds falling under the general formal (II) fall are the following:

(HA)

r ² 5 / -

= CH-C = CH-C ₊

(H-B)

Cl

C-CH = C-CH = C

) ₃ so ₃

409819/0

-is

-c)

GsGH-G = Gii-.G.

G = CH-G = GH-G +

(H-E)

CH-

CH

■ G = GH-CH ^ CH-C

ORIGINAL INSPECTEP

C = CH-CH = CH-C-

Cl

Cl

NaO

(CH ₂ ), SO, Na- (CH ₂ ), SO

(H-H)

C = CH-CH = CH-C

Cl

CH ₂ CH ₂ COOH (CH ₂ ) , SOZ

( HI )

C = CH-CH = CHrC +

Cl

Cl

CH ₃ CHpCHCB ■ 2 2,

H.

C-CH = C-CH = C

409819/0862

C 3QWK D

-Euir

Porirrel i

iiäi * e '

ίΙΙΙ-Β)

Cl

■ ίΐΐΐ-Ο-

C-GH-C-CH-G ψ

"S"

4098 1 9 / 08.62

! 353864

(HI-F)

(HI-G)

\ * - ίτΟ.γί C.

^ = GB-C = CH-C ₊

C = CH-C = CH-C

409819/0862

ORIGtNAL INSPECTED

(HI-H)

C = CH-C = CH-C

Eq

(CH ₂ ) ₂ OH

Cl

(CH ₂ ).

Br

For comparison, the following would also be included sensitizing dyes used:

C-CH = C-CH = C

C = CH-C = CH-C ₊

H ^.

= CH-C = CH ^ C

C ₂ Hj

a ^H 5

Cl

CH

SO-

409819/0862

ORIGINAL INSPECTED

C = CH-C = CH-C

Br

The silver halide photographic emulsion used in the invention can be made according to any of the following known processes and contains fine particles of silver chloride, silver bromide, silver iodide and of mixtures' of these halides obtained 'by precipitation by one of the processes known per se' have been, for example by single-jet precipitation, double-jet precipitation or a combination of these methods with subsequent maturation. . '·

Suitable processes for the preparation of such emulsions are described, for example, by Trivelli Smith, "The Photographic Journal", Vol. 79, pp. 330-338, CE.K. ' Mees, "The Theory of Photographic Process", Macmillan and Gfafkides, "Photographic Chemistry", Vol. 1, pp. 327-336, Pauntain Press .. The silver halide used in the context of the invention preferably contains at least 90 M0I- / 6 silver bromide and less than 7 mole percent silver iodide. 'A preferred silver halide composition contains not more than ^r IO mol%, for example 2-7 mol%' iodide. ■ '

In particular, the use of silver is iodide bromide or silver iodine chloride preferred

. The mean grain size of the particles used is

W % J% ß O V ** J ti UOÖiii

2353S64

preferably ixa "range of 0.04-2 .mu.m, measured by the area projection method using the numerical mean. '. -'

The photographic silver halide emulsion straightforward Invention can be accomplished by any of the conventional methods of sensitization sensitized, for example by gold sensitization, as in US Pat. No. 2,540,085, 2,597,856, 2,597,915 or 2,399,083 Sensitization with metal ions of the 8th subgroup of PSE, by sulfur sensitization, as in the US P3s 1 574 944, 2 278 947, 2'44O206, 2 410 689, 3 1S9 458 or 3 415 649, by reduction sensitization, as described, for example, in U.S. Patents 2,518,698, 2,419, or 2,983,610,1 and by various combinations of two or more of the aforementioned sensitization methods. , '.

As a typical representative for the traditional chemical Sensitizers that can be used are the following called: thiourea, sodium thiosulphate ,. Cystine and other sulfur-containing sensitizers Potassium chloroaurate gold (I) thiosulphate, potassium chloropailadate and other precious metal sensitizers or tin chloride, Phenylhydrazine, Seducton or other reducing sensitizers. - ι. '.- ■.

Other sensitizers, such as, for example, can also be used. Polyoxyethylene compounds as in U.S. Patent 2,716 described, 'polyoxypropylene compounds having an oxonium group or an ammonium group, as described, for example, in U.S. Patents 2,271,623, 2,288,226 or 2,334,864, are incorporated »'" ■' ·. ·

4 0.9 8 1 9/0882

" ²² ~ 7353864

Furthermore, auxiliary substances known per se can also be added to the emulsion according to the invention, for example additives to suppress the formation of fog, such as, for example, nitrobenzazoles, such as nitrobenzimidazo! (GB-PS 403 789), platinum salts such as ammonium chloroplatinate. (US Pat. No. 2,566,263 or 2-566 245), stabilizers such as, for example, 4-hydroxy-6-methyl-1,3,3a _t 7-tetrazaindene, thiazolium salts (US Pat. No. 2,131,038 or 2,716), Azaindenes such as 4-hydroxy-6-methyll, 3,3a, 7-tetrazairiden (US Pat. No. 2,886,437 or 2,444,6O5), urazoles (US Pat. No. 3,287,135), sulfate catechols (US Pat. No. 3,236,652 ), Oximes, mercaptotetrazoles (US Pat. 2,403,927, 3,266,897 or 3,397,987), nitrogen-containing salts of polyvalent metals (US Pat. No. 2,839,405), thiuronium salts (US Pat. No. 3,220,839), salts of metals , such as, for example, Palladiura, platinum or gold (US Pat Dichloroacrolein, coating aids, such as, for example, saponin, alkylaryl sulfonates, such as, for example, sodium alkylbenzenesulfonates (US Pat. No. 2,600,831), and finally amphoteric compounds, as described in US Pat. No. 3,133,816 ben.

The photographic silver halide emulsions according to of the invention can also be combined with others Sensitizing dyes and heterocyclic compounds are supersensitized in such a way that the maximum of the sensitization remains in the range of about 530 - 640 nm. '·'. ■

For example, it is possible to have such a supersensitization through.the use of dyes from one of the following groups to "effect": Irnidazole carbocyanine

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dyes, Iiaidazoloxacarbocyanin dyes, -imidazo 1-. indocarbocyanine dyes, 2,2'-quinocyanine dyes, pseudocyanine dyes, simple merocyanine dyes, dimethine merocyanine dyes, styryl dyes, including styryl bases; ¹ and compounds such as imidazoles, imidazolinium compounds, pyrazolones, naphthothiazoles., Benzothiazoles, triazoles or tetrazoles, such as _: for example in CEK Mees, "The Theory of the Photographic. Process", MacMillan. And in FM ^V. Hamer, "The Cyanine Dyes and Related. Compounds" Interscience Publishers. These dyes include, for example, also polymethine dyes with one or more alicyl groups which are substituted with a sulfo group or a carboxyl group; as a l 7 'substituent on the basic heterocyclic nucleus "'

By using the dyes listed above and connections will also obscure the material and its storage capability improved. .

The silver halide emulsion according to the invention Tcann also contain color couplers, such as those described, for example, in US Pat. Nos. 3,476,563, 3,516,831, 3,515,557 or 3,582 are described, as well as dispersants for these couplers, when used in the context of color photographic material will. Of the various color couplers available, the cyan couplers are special preferred »These couplers become in turn. ' in particular the phenolic couplers / v / ie them in the U5-PS 2,698,794 and a naphthol coupler preferred «■ ~" .. '., -',. -

Furthermore, the silver halide photographic emulsions

.- '. "■ - ■'.." ■ "4ö9Si9 / Öi8t .-. ■■" ■ '. ··' ■■■ "" ■■■.

according to the invention as protective colloid gelatin or acylated gelatine, for example phthalated gelatine / malonated gelatine or succinated gelatine, cellulose compounds, väe, for example, hydroxyethyl cellulose or carboxymethyl cellulose, dextrin and other soluble ones Starches, hydropilic polymers such as polyvinyl alcohol, Contain polyvinylpyrrolidone, polyacrylamide or polystyrene sulfonic acid.

Other additives such as plasticizers, Dimensional stabilizers, latex polymers or Matting agent added.

The finished emulsion can be applied to a suitable tracer be given, for example on a .barite paper, on a resin-coated paper, on a synthetic paper, on a triacetate film, on a polyethylene terephthalate film, on a glass plate or on other plastic supports.

The sensitizing dyes according to the invention are added to the emulsion as a solution in a water-miscible solvent, for example as Solution in methanol, .atlian oil, methyl cellosolve or Pyridine. :

Each of the three general sifcnsibilizing dyes Formula (I), (· ΙΙ) and (III). is used in amounts customary for color supersensitization are, i.e. in amounts of 5 χ IO to 1 χ IO mol every compound per mole of silver. . ■

The molar ratio of the dyes of the general formula (II)

/ 09819/086 2

ORIGINAL INSPECTED

or the dyes of the general formula (HL) to then Dye of the general formula (I) can be used in wide - ■ Areas necessary for 'supersensitization Quantities be determined: and fluctuate, but is preferred in the range from 100: 1 to 1: 5.

In particular, it is recommended - that the molar proportion of the dye of the general compound (I) is higher than that of the compound of the general formula (III).

The dyes used according to the invention can just as well be used for spectral sensitization, as they are described in DT-OS 2,104,283 and in US Pat. No. 3,649,286. _; ; . '

The invention is illustrated below with the aid of specific examples described in DejLa.il. Unless expressly stated otherwise, all of the items are given in parts and percentages to be understood as parts by weight or percentages by weight. .

example 1

After the two-beam process, silver halide grains became. precipitated, physically using a method known per se matured, desalinated and then chemically matured and in this way produced a silver iodide formomide mu-sion with an iodide content of 7 mol - '/ έ. The middle grain grinder the silver halide grains affected in the obtained F. emulsion 0.42 / um. The emulsion contained 0.52 mol of silver · halide per leg emulsion «1 kg of this emulsion would be weighed out and filled into a vessel that is in a thermostat was kept at 50 C for the solution »D'aneben ywrden

''. ' '. . '. ■■ - 4098 19 / 08B2' - - .. -

methanolic solutions of the dyes according to the invention Solutions of known sensitizers were also prepared in the same way for comparison purposes. The solutions prepared in this way were der.tempera turkonstant held emulsion in certain Kengen added and mixed with this emulsion with stirring at a temperature of 40 C. The ones received in this way Emulsions with 10> nl of a 0.1% aqueous Solution of 4-hydroxy-6-raethyl-1,3, 3a, 7-tetrazairiden, with 10 ml of a 10% aqueous solution of 1-hydroxy-3,5-dichlorotriazine in Forra des Natriura Salt and with ' 10 ml of a 1% aqueous. Solution of sodium cloecylbenzenesulfonate added with stirring.

The finished emulsions finally obtained viurden on a carrier from a. Cellulose triacetate filra applied and dried, using a photosensitive material having a thickness of the photosensitive layer from 5 to get vnirde.

Each of the filrae thus obtained was cut into strips. The strips thus obtained were with the interposition of a photographic wedge with a Sensitoraeter exposed, which was equipped with a light source with a color temperature of 5400 K. To the Different filters were used for the exposure, including a blue filter (Sp-I), a yellow filter (Sc-50) and a red filter (Sc-56) (Fuji Photo Film Co. Ltd.) »

Next to it .v.nir de for recording a spectrogram Further exposure using a grating spectrograph. with a wolf ramlampa from a Parbteraperatur carried out by 2666 K »

409.8.Τ9- / Ό8-6-2- '"'

The samples exposed in this way were for 2 minutes at 20 C in a developer liquid (D-rl9) der the composition below

water 500 ml Metol ..-.-. 2 G water-free sodium
sulfite 90 G Hydroquinone
Sodium carbonate nioiio-
hydrate - ■ ■
Potassium bromide 3
52,
5 G
5 g
G Water on 1 1

After removal from the developer bath, the development * stopped, fixed and rinsed with water so as to obtain the black and white images.

On the samples obtained, densitoxnetric density measurements (S-Dervsitometer from Fuji Photo Film Co, Ltd.) to determine the blue filter sensitivity, - (S- "), the yellow filter sensitivity (3 _γ ) and the red filter sensitivity (S-) or ^. the obfuscation made.

ix - ⁼

As a standard of the; .optical density against which the sensitivity was determined, the level served (veil + O, 20).

The results of these measurements are shown in! Table 1 given in the form of relative words. The one under the digits 11, 13 and 15 are the results of comparative experiments *

The spectral transmission of the filters Sp-I used, Sc-50 and Sc-56 are shown in Fig. 20,

. 40981970862

The spectral measurements obtained for the various samples are shown in Figures 1-19.

The shown in Figures 1 - 19 and in Table I, experimental results is associated with. the comparative results the surprisingly clear superiority the according to the invention - supersensitized Filrft to be taken .. - -

408118/0882

BAD OWGtNAL

■ Table I ■ - (HI-A) 1 , ,
■■ £,. * SR
rela
tiver
value SB
rela
tiver,
value veil Spectro
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The combination of sensitizing dyes according to of the invention have a supersensitizing effect and can advantageously for the spectral sensitization of photographic Siiberlialogenidenuilsxonen for the red sensitive Layer of far fopnotograjäiis brazen material, for example of color negative films, color uni-color films or similar Films serve »Furthermore, the combination according to the invention can be used for the spectral sensitization of silver halide emulsions for photographic black and white sfilrac-, for the spectral sensitization of silver halide emulsions, which are used in plio-hardening substances, and can eventually go for spectral awareness for silver halide special emulsions which are used for Manufacture of photo-sensitive material for lighting serve in the microsecond area and. for example for cathode ray recordings, holographic recordings, or facsimile systems.

When used in color photographic material, it is advisable to connect an external magenta or red filter on or in front of the red-sensitive silver halide layer according to the invention so that the green sensitivity of the photosensitive material is significantly reduced relative to the red sensitivity a series of suitable colored materials of this type are described in a number of patents, for example in Japanese Patent Applications 13459/1966, 3504/1960 _# 13163/1968, 22059/1964, in Japanese Patent Applications "98474 / 3.9.71, 42668/1971 and 42667/1971, in U.S. Patents 3,440,051, 3,468,883, 3,294,539, 3,379 533 _ä 3,352,680, 3,379,533, 3,389,994, 3,384,437, 3,473,207, 3,493,375, 3 486 397, 3 431 927, 3 497 502, 3 "573.209, 3 56O 214, 3 615 432 and 3, 232 699 as well as in GB-PS 5O6 3S5 _O

Substances that are selective are particularly preferred absorb in the wavelength range of less than 570 ran.

Furthermore, the methods used in DT-OS 2 008 832, in US Pat. Nos. 3,425,834 and 3 2S2 699, in HE Patents 682 413, 6S5 292, 703 939 and 627 3OS ₄ in the Japanese Äuslegeschriften 21766/1965, 13493/1968 15896/1970 and 10254/1968 _t are described.

The substances mentioned in these publications can to "suppress radiation and overexposure sqwolxl can be incorporated into the emulsion layer.

as well as in the form of a separate anti-glare protection

to be provided "

Claims (1)

; l./ Photographic silver halide emulsion * those in eggs This sensitivity is spectrally sensitized smaxi-num in the wavelength range of at least 58Ο to 64Ο ma, marked by one in quantities required for supersensitization Coordination of at least one carbocyanine of the general formula C = CH-C = CH-C in the Z, means a group of atoms leading to Formation of a ß-naphthoxazole ring or a ß-naphthoimidazole ring is required; Z "a group of atoms means that contribute to the formation of a benzo. thiazole ring, a bensoselenazole ring or one 4, S-Düiydroriapatiio-Cl, 2-d) -tniazolringes required are: A, a hydrogen atom, a substituted one or unsubstituted alky group or an aryl group is; R- and R "are each a substituted or unsubstituted one mean aliphatic group, where at least one of the radicals R, or R_ is a hydroxyalkyl group,. a carboxyalky group, or an alkyl group with a Sulpho group is X, is an acid anion. and 1 1 or 2 40 98T9 / igt2 1353864 1 ipt, : feetp # ia: r1 ^ ig @ 2: structure in front of © ine ?? Connection of ail ** riigipe γοη lktoinen means that. giif BIl- * it or one are an i s? Q? i Ä4 © iP-en means * of one BeniiöiS ^ Glringes © der one '. These are all hydrogen, a substituted or substituted alkyl group Q which is an aryl group! R-3 and 1 ^ - one each the MA,§ does one diminish- the agitation Ά? Q && Z Ra a liYärox p © ine "QarfeQjsyalkylgruppe od, he is one of a §ulf © group ' ; ^' ^ ' ^Q acid ^ nlop · is and in X © de, ?? 2: ipt« wa.b ^ I _f if m g ^ eicrih, X is, 'di connection as intreimolecular ^; ^ s S ^ Ig Tnit ■ structure, ■ ^ © r lies * CK ^ er e. | n, ei;' ^: ¥ erbindiing Fprmel ■. " Ν ' Atf "V / obei Zp. And Z, - each denote a group of atoms which are required for the formation of a benzothiazole length, a benzoselenazole ring / a B-l-taphthotliiazole ring or a β-IIaphthoseleriazole ring, a hydrogen , an optionally substituted alkyl group or a R ₁ - and R _ß each mean an optionally substituted aliphatic group with the proviso that at least one of the "radicals R _g or R> is a hydroxyalkyl group, a carboxyalkyl group or an alkyl group with a sulfo group. . ti is a XZ Säureanionengruppe and η gleirfi I barren, wherein, werm η is 1, the compound in vorliegt.- 'form an intramolecular salt with betainartiger structure ^·: "■ IF emulsion na'ah steps things ^ I. · 1, because the heterocyclic ring formed with Zt is a ß-haphthoxazoiringifer itiit'Z ^ formed heterocyclic ring a * '4 _# 5-öihydröhaj5htho - (1, 2'-d) -thiazole ring, a benzo ; Thiazolrilig or a benzoselenazole ring in which the 5- »position is unsubstituted or substituted with a chloratoiri, a trifluoromethyl group, an alkoxycarbonyl group, a methyl group, a mathoxy group or a. Phenyl group, - and that A is an ethyl group. ^v - ' ^: " ^: ' 3. Emulsion according to claim 1, characterized in that the iuit E ₁ formed hete ^ ocYclic ring. ß-lTaplathoimidazblring ₇ the with % ₂ g @ Mläete lieterqcyclische ring a benzo thiazole ring oca ^ r a. Bensoselenaziolriiig, in which the 5-Stellun.g eatwecaer is unsubstituted or substituted with chlorine, ϊ-rifluoriiiethyl, alkoxycarbonyl, methyl, methoxy or phenyl and A-. Is hydrogen. 4. Emulsion according to any one of claims 1 to 3 _r, characterized in that A ^ is hydrogen or-ethyl, and that. R ,, and R. each have a Methyligruppe a. Ethyl group, a propyl group, an allyl group, a carboxyalkyl group, or a suIfoalkyl group. 5. Emulsion according to one of the. Claims 1 to 3, characterized marked; that A_ hydrogen, methyl, ethyl, Propyl or phenyl and that'R- and R ^ are each one ethyl group, an ethyl group, a propy group, an allyl group, a carboxyalkyl group or a Mean SuIfoalkylgruppe. , · ... -,, .-, - 6. Emulsion according to claim 1, characterized in that A, "A ~ and .Aj are each hydrogen, an alkyl group, an aryl group or an aralkyl group, and that R ₁ , R ₇ ,, R ₀ , R.-, R _c and R- each represent an alkyl group, an allyl group ,. a Hydroxyallsylgruppe, a CarbpxyalkylgrupiDe ,. one. Allcoxyalkylgruppe mean, one _egg sulfoalkyl, a Haiogenalkylgruppe a Aniinoalkylgruppe, a cyanoalkyl or Sulfoaralkylginippe. ... .... ", _{.. · F5} . ~ _Ren ., -, -. ■. · _; · .... ■ ^: -. ·. ■", · 7. Emulsion according to claim 6, .. characterized / that A ,, A_ and A "each have a hydrogen atom, είςε-methyl group, an ethyl group, a propyl group _f . one. Phenylgrupp.e, or a phenylethyl group. and -.._...: ■ · R ₁ , R ₉ , R-. _t , R _a , .R ,. and. iL .. je., alkyl, ÄJLlyl., hydroxy- , 'alkyl, .. carboxyalkyl, -Älkpxyaikyl _r an «.a sulfo group .containing an alkyl group. t, halo-alkyl, amino- 'alkyl, cyanoalkyl or suIfpacalkyl. 8. Emulsion according to one of claims ^ i to 5, characterized marked that those formed with 2 ". Rings substituted Are rings, with halogen as substituents, Alkyl ,. Trifluoromethyl, alkoxy, alkylcarbonyl #carboxy, Alcoxycarbonyl, "acyl, aryl, cyano, hydroxyl, alcoholate or amino groups occur. . 9.! Trails ion- according to any one of claims 1 to 5, characterized in that the _{ring formed with S 9 is} benzothiazole, 5 ~ chlorobenzotli4.az.ol, 5-bronibensothiazole, 5-fluorobenzothiazole, 5-methylbenzothiazole, 5-methoxy -'benzothiazole, 5-methylcarbonylbenzothiazole, 5-carboxybenzothiazole, 5-ilethojiycarbonylbenzotliiazole, 5-phenylbenzotlaiazole, 5-cyanobenzothiazole, 5-trifluoromethylbenzotliiazole, 5-hydroxybenzo- zothiazole, 5-methyl-6-dichlorobenzothiazole, 5-methyl-6-dichlorobenzothiazole, 5-methyl-6-dichlorobenzothiazole, 5-e-methylbenzothiazole, 5-methyl-6-dichlorobenzothiazole, 5-methyl-6-dichlorobenzothiazole metnoxybenzothiazole, 5, 6-diiriethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-diethoxybenzothiazole, eenzoselenazole, 5-chlorobenzoselenazole, 5-bromobenzoselenazole, 5-methylbenzoselenazole, 5-14ethronaphthoxybenzoselenazole, 5-14ethronaphthoxybenzoselenazole, -d) -thiazole, 6-cyano-4,5-dxhydronaphtho- (1,2-d) -tMasol, 6-ethyl-4,5-dihydronaphthio- (1,2-d) -, thiazole or S-chlorine -4,5-dihydronaphtho- (1,2-d) -thiazole. - 10. Emulsion according to one of claims 1 to 5, characterized in that the with Z_, Z., Z ₁ - or Z _fi formed heterocyclic rings are substituted, namely with halogen, alkyl, trifluoromethyl, alkoxy, Alkylcarbonyl; Carboxy, alkoxycarbonyl, acyl, aryl, ■ ~. "'■ Cyano, hydroxyl, alcoholate or with amino groups. 11. Emulsion according to one of claims 1 to 5, characterized 409819/0882 ■ ". ■■■; ■ '- 4i - ■ ■. ■■ · ■ characterized in that the heterocyclic ring formed with S. benzothiazole, 5-chlorobenzothiazole, 5-brobeilzothiazole, '5-methylbenzothiazole, 5-methoxybenzothiazole, 5, 6-dimetliylbsnzothiazol, 5, 6-dirnethoxybenzothiazole, 5-ethoxybenzothiazole , "5-methylbenzothiazole," 6--. Methoxybenzothiazole, 5-methyl-6-ethoxybenzothiazole, S-ethoxy-o-raethylbenzothiazole, 5-hydroxy-6-raethylbenzothiazole, 5-phenylbenzotliiazole ", 5-hydroxybenzothiazole, 5-T-cyanobenzothiazole,. 4,5-dihydronapntho- (1, 2-d) -thiazole _# 6-iithyl-4, 5-dihydronap] itho- (1, 2-'d) -thiazole, / S-chloro-4,5-dihydronaphtho- (1,2 ~ d) -thiazole, benzoselenazole, 5-chlorobenzoselenazole, 5-methylbenzoselenazole, 5-MetliDxybenzoseleriazol, 5, 6-dimethylbenzoselenazole, 5, e-dimethoxyberisoselenazole, 5-phenylbenzoselenazole, or J3-zothiazylbenzoselenazole. Ring benzoxazole, 5-methylbenzoxazole, 5-methoxybenzoxazole, 5,6-diiuethylbenzoxazole, 5/6-diinethoxybenzoxazole, 5-phenylbenzoxazole, benziraidazole, 5-chlorobenzimidazole, 5,6-dicilobbene ziinidazole or 5-trifluoromethylbe'iiziiiiidazole, and that the heterocyolic rings formed with Z- and Z _x - are each benzothiazole, 5-chlorobenzothiazole ,. 5-bronibenzothiazole, 5-methylbenzothiazole, 5-methoxybenzothiazole, ■ 5-acetylbenzothiasol, 5-metho:> cycarbonyibenzothiazole, 5-ethoxycarbonylbenzothiazole, .5-phenylbenzothiazole, 5-cyanobenzothiasol, 5-hydroxybenzothiazole -ChlorbenKoselenazol, S-Methylbenzoselenazpl, '5-Methoxybenzoselenazol, S-PhenyllDenzoselenazbl, ß-Naphthothiazol or ß-Haphthoselenazol are «, 12. Emulsion according to one of claims 1 to 11, characterized characterized that the silver halide S used in the emulsion is above chloride, silver bromide, silver iodide 98T9 / 0862 or Gerais before this one. Salts or mixed salts of these Silver halides are * 13 ". Emulsion according to one of claims 1 to 12, characterized characterized in that the silver halide is at least 90 mole percent silver bromide and less than 7 mole percent silver iodide contains. 14. Emulsion according to one of claims 1 to 13, characterized gelcennzeich.net that d5.e mean grain size of the Silver halide particles ranging from 0.04 to 2 to lies. "'" ". 15. Emulsion according to one of claims 1 to 14, characterized in that each of the sensitizing Colorants of the general formulas (I) and '(II) or (TII) irt the emulsion is present in a concentration of · 5 lo "" ^J to 1 χ 10 ~ mol per mol of silver. 16 "Eraulsion according to any one of claims 1 to 15, characterized characterized in that the molar ratio of the compounds of the general formula (II) or (III) to the compound of the general formula (I) in the range from 100: 1 to 1: 5. 17. Emulsion according to claim. 1, characterized in that that the sensitizer of the general formula (I) ■ is one of the following compounds: 9819/08 62 -'43 Cl-A-) (T + ^; ^ G-CH = G ~ CIl = cf • Ν '2 ^ 5 ■■ (I-B). P _x fa% +. C-CH = C-CH = C ι \ CH ₃ C-CH = C ^ -GH = C (i-P) G-CH = C-CH = C .. Cl 19/0862 C-CH = C-CH = C (CH ₂ ) ₃ S0 ₃ (I-F) οχ ί CCHC C-CH = C-CH = C Cl C ₂ H ₅ (I-G) \ I ²⁵ ■ C-CH = C-CH = C CH, SO (-I-H) C = CH-CH = CH-C -s- (C. 19/0862 C = CH-CH = CHtC (CRp) ₃ SO ₃ HN (C ₂ H) COOCH- (i-J) ^C 2? 5 _X S ^ ² i ^H 2 + C-CH = C-CH = C that the sensitizer of the general formula is one of the following: CII-A) C = CH-C = CH-G ₊ C ₂ H ₅ - 4098 19/0862 (H-C) C = G Η— C = CH-G -j- CH, CH CH ₃ 0Ν ^^ ^υΒ 3 ιΛΛ CH- CH, C = CH-O = OH-O CH ₃ O OCH, N ^ ^ \ / Cl C = CH-CH = CH-C + Cl 19/0862: <n-G) C = CH-CH = CH-C I --- ^ Cl N ^ MaO (HH)? 2 ^H 5 C = CH-CH = CH-C Cl CH ₂ CH ₂ COOH CH-I) .: C = CH-CH = CH-C Cl Cl (H-J) H-. ;. C-CH = C-CH = C 4 09819/08 )the (ΙΙ-Κ) ΈΛ C = CH-CH = CH-G "^ N Cl Cl and that the sensitizer of the general formula (IXI), is one of the following: (III-A) C ₀ H C = CH-C = CH-C + (HI-B) '"CIII-C) CHi = CH-C = CH-C ^ + CH ^
Γ = νΐί — 0 = 01ι — 0 '.j. CH- (CH ₂ J ₇ SO ₃ " 409819/0862 (iii-a » ο: C = CH-C = CH-G If C ₂ H ₅ COOGH ₃ (CH ₂ ) (IU-E) CX I ³⁷ C = CH-C = CH-C ₊ [
(CH ₂ O ₂ COOH | ^a ^ / ^S I = CH-C = CH-C. ■ + CH ₂ ) (HI-G) C = CH-C = CH, -C C ₂ H ₅ 409819/0862 osier (HI-H) C = CH-C = CH-C Cl (CH ₂ ) ₂ OH (CH ₂ ) ₂ OH Br IS. Use of the emulsion according to one of the claims 1 to 17 for the production of light-sensitive ingredients, especially color photographic material on one known carrier. 4098 19/0862 Lee rs hurry