DE2008114A1 - Spectrally sensitive, highly sensitive material - Google Patents

Description

20081IA

AGFA-GEVAERTAG

Hs / Od.

Spectrally sensitized light-sensitive fleece Material.

The invention relates to a photosensitive photographic Material, in particular one with silver halide emulsion layers preferably containing color couplers, which is spectrally sensitized by means of a new sensitizing dye © are.

Increasing the sensitivity of light-sensitive layers, in particular of silver halide emulsion layers by addition of substances that expand the spectral sensitivity range of photosensitive substances has long been known. For the sensitization of silver halide emulsion messages numerous substances have been described which essentially belong to the class of the cyanine dyes. However, these known substances often have compartments, which consist, for example, in that their sensitizing effect is unsatisfactory, that they give the layer a disturbing color lend or that they the photographic process in itself adversely affect. This is especially true for special photographic materials too. The adsorption on the silver halide should be so strong that the sensitization effect is as possible little by other necessary additives such as wetting agents and Emulsifiers, stabilizers, color couplers, bleachable dyes, whiteners, etc. is disturbed. The awareness must also be guaranteed under extreme conditions such as increased temperature and humidity. The sensitizing dyes are also allowed no additional reinforcement of the

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haadenen Grundachieiera, as with the basic ones Cyanine dyes is occasionally the case. Of the Sensitizing dyes will also have certain sensitizing properties desired, but in addition to a sufficient sensitization intensity in the senibilization range Above all, the steepest possible drop in Semaibiliaiertimg at the transition to larger wavelengths of light is to be mentioned, For the reasons mentioned there is a considerable interease in the discovery of new Sensibiliaierungafarbatoffe which do not have the disadvantages given.

2,4'-Trimethinecyanine are trimethine dye ^ in which the one end of the trimethine chain with the 4-position of a quinoline ring and the other end with the 2-position one of the usual nitrogen-containing heterocyclic rings is linked. The basic bodies of this class of dyes are known. A «summary The position can be found in P. M. Hamer, The Cyanine Byes and related Compounds, 19641 Interscience Publishers. It is also known to have sensitizing properties to have. However, they generally do not meet the requirements and requirements placed on them in photographic practice presumably have therefore found practically no use in awareness-raising technology. A particular disadvantage is that the sensitization brought about by them is not stable on storage, which manifests itself in a decrease in sensitivity and a tendency to fog.

It is known that the sensitizing properties of the Base bodies of the various classes of dyes can be changed by introducing substituents. As substituents are for example alkyl, alkoxy, aryl, hydroxyl, carboxyl and optionally substituted amino groups have been proposed, also halogen atoms or fused-on benzene rings. In American patents 2,066,047 and 2,126,078, the substituent is for carbocyanines, i.e. also for 2,2'-trimethine cyanines called the methylthio group. All of these substituents can depending on the dye grits in which they are introduced, not only influence the position and intensity of the maximum sensitization,

AG 609 - 2 -

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but also change other properties of the sensitizing dyes, for example fog or compatibility with other emulsion additives such as wetting agents, stabilizers, color couplers, bleachable dyes, whiteners or hardeners. However, these changes due to substitution do not always work out in the best possible way. Substitution possibilities are basically in two heterocyclic groups at 2.4 ^I -Trimethincyaninen. Little is known about 2,4'-trimethine cyanines old substituents in the quinoline group.

The invention is based on the object of providing sensitizing dyes for the sensitization of light-sensitive layers, in particular to find silver halide emulsion layers which do not have the disadvantages mentioned at the outset and which moreover have advantageous properties, especially when used in color photographic materials.

It has now been found that by introducing a methylthio group in the 6-, 7- or 8-position of the quinoline ring of 2,4'-Trimethinecyaninen the sensitizing properties these dyes are changed so favorably that these Dye class can be used to sensitize highly sensitive color photographic materials.

The invention therefore relates to a light-sensitive photographic material with at least a content of a 2,4'-trimethyl cyanine spectrally sensitized silver halide emulsion layer, which is characterized in that the quinoline ring connected to the trimethine chain via the 4-position is in 6-, 7- or 8-position carries a methylthio group. - _:.

AG 609 - 3 - "

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20081U

The methylthio-substituted 2,4'-trimethine cyanines are described by the following general formula:

SCH ₃

'Z "λ
ns ^ -CH = CH-CH =

χ Θ

where mean:

R and R ¹ = identical or different radicals, namely 1) saturated or olefinically unsaturated aliphatic groups with preferably up to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl or allyl, which can be substituted, for example with halogen atoms such as chlorine or bromine, phenyl, hydroxy, amino, mono- or dialkylamino, carboxyl, sulfo, phosphonic acid, sulfonylamino, sulfamyl, carbonamido, carbamyl, carbalkoxy, sulfato or thiosulfato, 2) cycloalkyl groups, preferably cyclohexyl, or 3) aryl groups, especially phenyl ;

X ^ "= any anion, e.g. halide, such as chloride, bromide or iodide, perchlorate, sulphate, methyl sulphate, p-toluenesulphonate and the like; the anion is omitted if R and / or R ^{1 contains} an acidic group in anionic form, so that a betaine is present; the type of anion is not critical and the anion itself is often only determined by the manufacturing method.

Z = one required to complete a heterocyclic group with 5- or 6-membered hetero ring Rest; the heterocyclic group can be a fused benzene or naphthalene ring

AG 609 - 4 -

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■ "■ ο ■ ■

and contain other substituents; come into question the heterocycles customary in cyanine chemistry like for example

those of the thiazole series (e.g. thiazole, 4-methylthiazole, 5-methylthiazole, 4,5-dimethylthiazole, 4-phenylthiazole, 5-phenylthiazole, 4-methyl-5-phenylthiazole, 4,5-diphenylthiazole, benzthiazole, 4 -Chlorobenzthiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, S-bromobenzthiazole, 6-bromobenzthiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, ^ - methylbenzthiazole, '5-methylbenzthiazole, 6-methylbenzthiazole, 6-methylbenzthiazole, 6-methylbenzthiazole, 6-methylbenzthiazole, 4-phenylbenzthiazole, 5-phenylbenzthiazole, 6-phenylbenzthiazole, 5- (2'-thieayl) benzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 4-methoxybenzthiazole, 5-methoxybenzthiazole, 6-methoxybenzthiazole, 5-Äthoxybenzthiazol, 6-Äthoxybenzthiazol , 5,6-Diinethoxybenzthiazole _f 5,6-Methylenedioxybenzthiazole, 5-Diethylaminobenzthiazole, 6-Diethylaminobenzthiazole, 5-Carboxybenzthiatol, 5-Sulfobenzthiazole, Tetrahydrobenzthiazole, 7-Oxotetrahydrobenzthiazole, Naphtholo- / "~ -d7thiazol, 5-methoxynaphtho / "" 2,1-d7thiazOl, 5-ethoxynaphtho / "2,1-d7thiazol» 7-met hoxyäaphtho ^ ~ 2,1-d7thiazole, 8-methoxynaphtho / ~ 1,2-d7thiazole etc.), those of the selenazole series (e.g. 4-methylselenazole or 4-phenylselenazoT, benzoselenazole, 5-ghlorb'enzoseienazole, 5,6-diniethylbenzoselenazole, 5-hydroxybenzoselenazole, 5-methoxybenzoselenazole, tetrahydrbbenzoselenazole, naphtho / "1,2-d7selenazole or naphtho ^""2,1-d7selenazole), those of the oxazole series (e.g. oxazole, 4-methyloxazole, 4 * -phenyloxazole diphenyloxazole, benzoxazole, 5-chlorobenzoxazole, 6-chlorobenzoxazole, 5,6-dimethylbenzoxazole, 5-phenylbenzoxazole, 5-Hydröxybenzoxazol, 5-methoxybenzoxazole, 5-ithoxybenzoxazol, 6-Dialkylaiainobenzoxazolj 5-carboxybenzoxazole, 5-Sulfobenzoxazol, 5-Sttlfonamidobenzoxazol, 5 -rß-Carboxyvinylbenzoxazole, Naphtho ^ "" 1,2-d7oxazole, Naphtho / "" 2,1 - ^ oxazole or liaphto / "* 2,3-d7-oxazole), those of the imidazole series (e.g. I-methylimidazole, 1 - Xthyl-4-phenylimidazole, 1-butyl-4,5-dinje thylimidazole, 1 -Me thy 1-

AG 609 '- 5 -

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benzimidazole, 1-butyl-4-methylbenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-methylnaphtho / "~ 1,2-d7imidazole or 1-ethylnaphtho / ~ 2,3-d7imidazole) such the 3,3-dialkylindolenine series (e.g. 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3-dimethyl-5-methoxyindolenine, etc.), those of the 2-pyridine series (e.g. pyridine, 3-methylpyridine, 4-methylpyridine, 5-methylpyridine, 6-methylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine, 3,6-dimethylpyridine, 4,5-dimethylpyridine, 4,6-diaethylpyridine, 4-chloropyridine, 5-chloropyridine, 6-chloropyridine, 3-hydroxypyridine, 4-hydroxypyridine, 5-hydroxypyridine, 6-hydroxypyridine, 3-phenylpyridine, 4-phenylpyridine, 6 ~ phenylpyridine, quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline-6-hydroxyp quinoline, 8-hydroxyquinoline, S-oxo-Siö ^ jS-tetrahydro-quinoline, Isoquinoline or 3,4-dihydroiaoquinoline), those of the thiazoline series (e.g. thiazoline, 4-methylthiazoline, etc.), as well as those the pyrroline, tetrahydropyridines thiadiazole, oxadiazole, Pyrimidine, triazine or benzothiazine series.

The heterocyclic groups can be further substituted in any desired manner, for example by further alkyl groups with preferably up to 3 carbon atoms, such as methyl or ethyl, halogen such as chlorine or bromine, hydroxyl, alkoxy with preferably up to 3 carbon atoms such as methoxy or ethoxy, hydroxyalkyl, alkylthio, aryl such as phenyl or aralkyl such as benzyl, amino, substituted Amino and the like.

Useful sensitizing dyes according to the present invention Invention are for example the following:

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dye

Sensitization maximum in mn

NS,

CÜ

-CH = CH-CH = / "Ii-GH,

W / ^K - ^{/ 3}

SCH ₅ -

-CH,

C ₂ H ₅

N
C ₂ H ₅

% -CH = CH-CH = / N-CH

Br

N '

I.
C ₂ H ₅

NS,

il I

\ -GH = CH-CH = / Ν-υ «,

ψ / ^w '

U ■ * ^Θ

690

695

685

OH- 700

A-G 609

-T-

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dye

Sensitization maximum in mn

NS,

-CH = CH-CH =

700

NS,

C ₉ H.

CH,

θ /

₆ H (O-CH ₂ -CH) ₃ -O <^^ f " j 0

.-CH = CH-CH = / N-CH

700

CH,

SÜH,

670

NS,

-OH = CH-CH = _{</ H} -CH

N '

650

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Dye sensitization maximum in do

NS

-CH = GH-GH * / N-CH

C ₂ H ₅ 720

NS,

CH,

-CH = CH-CH = / N-CR

700

NS,

ti H ₅ C ₂ -OOG

ff

V "N.-CH = CH-CH = / ^ N-CH,

⁰ V I j

CH ₃ 695

NS,

CH,

-CH = CH-CH =

660

CH,

A-G

1 09 & 36 / i278

No.

dye

20081U

Sensitization maximum in nm

N-CH,

NS,

-CH = CH-CH ₃

670

620

SC

-CH = CH-CH = / N-CH

690

AG - 10 -

10 9 836/1278

No.

Dye

Sensitivity at maximum in nm

NS,

-CH = CH-CH = / N-CH

695

* ".τ Θ

NS,

CH,

CH,

690

-CH-CH-CH = / N-CH

CH, SCH ₃

Vs

^s W C ^

^ -CH = CH-CH = / N- (CH ₅ ), -SO, V- ^; 690

NS,

-CH = CH-CH = / N- (CH ₂ ) ₃ -SO ₃

^ 5 ^ - * CH

AG - 11 -

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No.

dye

20081H

Sensitization maximum in nm

NS,

S. W 705

X-CH = CH-CH = / "N-CH ₂ -CH-CH ₂

-CH = CH-CH =

NS,

n-CH ~ -CH = CH ₅
2

685

> ^H 5

22nd

NS,

-CH = CH-CH = / ίί- (CH ₂ ) ₃ -So ₃

680

23

H ₅

, I X-CH = CH-CH = / N-CH,

NS,

690

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- 12 -

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dye

$ 1

20081U

Sensitization maximum in mn

Se

V \\ - SCH, -CH = CH-CH = / ^ NC ₂ Hc 680

-CH = CH-CH =, ClO ₄ β '

// A-SCH, _w ^CH 3 710

θ / ^M

, -CH = CH-CH = / "N-CH.

680

C ₂ H ₅

NS

-CH = CH-CH = / N-CH ₂ -CH = CH ₂ 690

Br

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dye

NS,

20081H

Sensitization maximum in nm

, ι ^ n-CH = CH-CH = / N-CH, CH ₅ ^^ W

705

CH,

NS

-CH = CH-CH =

-CH,

685

NS

N. -CH = CH-CH = / N-CH

685

The 2,4'-trimethine cyanines substituted in the quinoline ring methylthio are new. They are produced in a manner known per se, e.g. by condensation of suitable derivatives, for example the N-acetyl (or N-p-toluenesulfonyl) anilinorinyl derirates of 6-, 7- or 8-methylquinoline with 2-methylcycloammonium salts heterocyclic bases or vice versa by condensation of the 2-anilinovinyl derivatives of heterocyclic bases

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-H-

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with the quaternary salts of methylthio-substituted lepidines. '

The methylthio-Iepidines required as starting substances are known. They are expediently by condensation of the isomeric thioanisidines with methyl-ß-chloroethy! Ketone in Nitrobenzene produced.

ü-riethyrthidtepidin

50 g p-Thioanisidin-hydrochlorld, 150 ml of concentrated hydrochloric acid, 30 ml of nitrobenzene and 40 g of methyl-.beta.-chloräthylketon are heated for 10 hours at 100 G ^0. The nitrobenzene is distilled off and the back of the flask is made alkaline. The resulting dark oil is shaken out several times with ether. The ether extracts are washed with water, dried and the ether is allowed to evaporate. The residue is distilled in vacuo.
Kp 12 mm 186 - 193 ⁰ O

The isomeric lepidines are made following the same process obtain.

The three lepidine derivatives are commonly used in the Quaternary salts converted, e.g. with methyl sulfate, allyl bromide or propanaulton. The N-acetyl-amilinOTinylquinoline quaternary salts can be prepared from these salts, for example by heating with diphenylformamidine in acetic anhydride produced by condensation with 2-methylcycloammonium salts heterocyclic bases in acetic anhydride give the desired sensitizing dyes. in the The following is the preparation of dye No. 22 in detail described.

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Anhydro-3-ethy1-7'-methylthio-1'-sulfopropyl-thia-4'-quinotrimethine-cyanine hydroxide (Dye 22)

a) 2-Acetanilinovinyl-3-ethyl-benzothiazole »B; iodide

15 g of 2-methylbenzthlazolium iodide, 20 g of diphenylformamidine and 50 ml of acetic anhydride are refluxed for 1.5 hours. Pouring into water gives a smear that solidifies immediately when rubbed with a glass rod. Crude yield 17 g, pp. 215-220 ⁰ C.

b) Quaternization of the lepidine base

2.5 g of 4-methyl-7-methylthioquinoline and 1.6 g of propanesultone is heated on the oil bath until the temperature of the reaction mixture is 125 ⁰ C. After removal of the heating source, the temperature rises still further to 140 ⁰ C. The product thus obtained is treated with acetone and ether and getreekent in a desiccator. Yield 3.7g.

c) Parbetoff formation

2.7 g of the substance obtained under b) and 4.0 g of the substance obtained under a) and 125 ml of acetic anhydride are heated to 50 ^° C., 3.5 ml of triethylamine are added and the mixture is heated to the boil for 4 hours. This creates a green coating of the dye you are looking for on the bulb wall. It is left to stand in the refrigerator overnight, suctioned off and washed with water, alcohol and ether. Crude yield 1.2 g.

"After recrystallization from a mixture of 400 ml The pure dye 22 is obtained in chloroform and 100 mm of methanol.

Yield 0.8 g, melting point 268 ^° C., absorption maximum 640 nm (in methanol).

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According to the present invention in the quinoline ring with a Methylthio group sensitized 2,4 '-! Erimethinecyanine show compared to the unsubstituted basic bodies of this class of dyes Significantly improved © sengibilizing properties on. It is not caused by the introduction of the methylthio groups only the absorption maximum and thus also the sensitization maximum shifted in the desired way to larger wavelengths of the spectrum, but one also achieves one Sensitization with higher intensity and much better Storage stability. The tolerance is also excellent with other emulsion additives, especially with color couplers. This property combined with the location the absorption maximum (620 to 720 nm, depending on the type and Substitution of the azole ring) makes the invention Dyes particularly suitable for use in color photographic Materials, particularly in silver halide emulsion compositions containing color couplers.

It is particularly noteworthy that with the inventive Dyes achieved sensitivity through certain isocyclic or heterocyclic aromatic mercapto compounds Not only is it increased again, but also stabilized to an astonishing degree at the same time Stabilizers for the methylthio-substituted ^, ^ - trimethine cyanines according to the invention prove to be compounds the following general formula.

R '' -SH

R ¹¹ denotes an isocyclic or heterocyclic aromatic group which carries at least one further substituent of the following type: aryl, for example _a phenyl, halogen such as chlorine or bromine, an electron-withdrawing group such as trifluprmethyl, alkyl or arylsulfonyl, nitrile or, preferably, an acidic group such as SuIfο, carboxyl, ß-carboxyvinyl,

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2G081U 1t

Sulfajnyl, monoalkyl- or monoarylsulfamyl.

Of course, the latter acidm groups as well as the mercapto group may be in anionic form, such as alkali metal, animal Amnoniumsalz.

An isocyclic aromatic group represented by R ¹ 'is, for example, phenyl. All heterocyclic aromatic groups are, for example: benzoxazole, - naphtho- / ~ 1,2-d7oxazole, naphtho / ~ 2,3-d7oxazole, naphtho / "1,8-d« 7oxazine, benzthiazole, benzimidazole, for example ip-dimethylaminophenylbenzimldazole or Tetrazpl.

Suitable sensitivity-increasing and stabilizing mercapto compounds are, for example, the following:

NaO _x S

III

A-G 609 - 18 -

1 0 3 8 J G / 1 2 7 8

Pie according to the invention sensitizing dyes can be used in any Silver halide emulsions are used. The silver halide used is silver chloride, silver broinide or mixtures thereof, possibly with a low content of silver iodide up to 10 mol-96 is suitable.

The Silberhalqpnide can in the usual hydrophilic compounds be dispersed, for example carboxymethyl cellulose, Polyvinyl alcohol, polyvinyl pyrrolidone, alginic acid and its salts, esters or amides or, preferably, gelatin.

The sensitizing dyes to be used in the present invention are preferably added to the photographic emulsion after chemical ripening and before casting. The methods used for this are generally known to the person skilled in the art. The sensitizing dyes are im generally in the form of solutions e.g. in alcohol or alcohol / -

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Water mixtures incorporated into the emulsion. Of course the solvents must be compatible with gelatin and must not have any adverse effects on the photographic Exercise properties of the emulsion. Water, methanol or mixtures thereof are generally used as the solvent. The amount of the sensitizing dye added can be in vary within wide limits, e.g. between 10 and 1000 mg per mole of silver halide, preferably between 30 and 300 mg per mole of silver halide. The concentration of the dye can be the particular requirements, depending on the type of emulsion desired sensitization effect, etc. can be adjusted. The a-n most suitable concentration for any given emulsion can be determined without difficulty by the tests customary in photographic practice.

P The emulsions can also be chemically sensitized, e.g. by adding sulfur-containing compounds in the chemical Ripening, e.g., allyl isothiocyanate, allyl thiourea, sodium thiosulfate and the like. As chemical sensitizers you can also use reducing agents, e.g. the tin compounds described in Belgian patents 493 464 or 568 687, also polyamines such as diethylenetriamine, or aminomethylsulfinic acid derivatives, for example, according to British Patent 789,823.

Noble metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. This method of chemical \ sensitization in the article by R. Kozlovsky, Z.Wiss. Phot 46, 65-72, (1951).

It is also possible to use the emulsions with polyalkylene oxide derivatives to sensitize, e.g. with polyethylene oxide with a molecular weight between 1000 and 20,000, also with condensation products of alkylene oxides and aliphatic alcohols,

AQ 609-20-

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Glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides. The condensation products have a molecular weight of at least 700, preferably more than 1000. To achieve special Effects can of course be combined with these sensitizers as described in Belgian patent 537 278 and British patent 727 982.

The emulsions can literally amch. other spectral sensitizers contain, e.g. the usual polymethine dyes, such as Neutrocyanine, basic or acidic carbocyanine, rhodacyanine, Hemicyanines, styryl dyes, oxonols and the like. Such sensitizers are in the work of P.M. Hamer "The Cyanine Dyes and related Compounds ", (1964).

The emulsions according to the invention can contain the usual stabilizers contain, such as homopolar or saline compounds of mercury with aromatic or heterocyclic compounds Rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds. Azaindenes are also suitable as stabilizers, preferably Tetra- or Pentaazaindenes, especially those with hydroxyl or amino groups are substituted. Such connections are in the article by Birr, Z.Wiss.Phot. 47, 2-58 (1952). Other suitable stabilizers include quaternary benzothiazole derivatives, benzotriazole and the like.

The emulsions can be hardened in the usual way, for example with formaldehyde or halogen-substituted aldehydes; that contain a carboxyl group, such as mucobromic acid, diketones, Methanesulfenic acid esters, dialdehydes and the like.

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The emulsions according to the invention can be used for the most diverse fluden photographic processes. For example for Recording materials, for copy materials, for reproduction technology Films, for X-ray films, for materials used for the silver salt diffusion process are suitable, for color photographic materials, for photographic materials for silver color bleaching processes and other.

The sensitizers to be used in the manner according to the invention are also suitable for the spectral sensitization of electrophotographic layers, preferably those layers which contain photoconductive zinc oxide distributed in an insulating binder.

The advantageous properties of the 2,4'-trimethine cyanines according to the invention can be seen from the tables below.

Table 1 shows the shift in the absorption maximum (abs. Max.) Due to the substitution with methylthio groups.

Table 1

Abs.max. in methanol

630 mn U η C & // \ rJ ^J

N-CH = CH-CH = / NCH,

650 nm

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/ J

Methanol

-CH = CH-CH = / NCH, 642 nm

γ _χΘ

O ₂ H ₅

^^ N

X-CH-CH-CH = / "NCH _x 640 nm

Table 2 explains some examples, which by the Substitution with methylthio groups achievable improvement the sensitization properties, i.e. the shift in the Sensitization maximum (Sens.max.) And the increase in relative sensitivity to red light.

The relative values given in Tables 2-6 below Sensitivities (number of visible gray levels) were with TO mg of sensitizing dye and optionally the specified amount of sensitivity-increasing, stabilizing mercapto compound per kg of a silver bromide emulsion obtained per kg of 50 g of silver bromide, 90 g of gelatin and 10 g of a color coupler of the following formula:

OH

After pouring and drying it was placed behind an Agfa-Gevaert filter L622 and a gray wedge with ^ -steps and exposed in developed in the usual way. The said filter is only permeable to light with wavelengths greater than 622 nm.

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From the last two examples of Table 2 it can also be seen that the substituent on the nitrogen atom of the Quinoline ring is without influence on the sensitization.

Table 2

Paring agents

ReI.Sensitivity Sens.max. for red in steps \ 3 Γ

-CH = CH-CH = / IfCH ₃

nm

SCR

.-CH = CH-CH = / NCH

C ₂ H ₅

nm

26th

o: <

(V A-SCH, -CH = CH-CH = / NCH,

C ₂ H ₅

. NS,

nm

-CH = CH-CH = / NCH ₃ 685 nm

C ₂ H ₅

A-G 609

- 24 -

22nd

25th

109836/1278

Dyes

008114

ReI.Sensitivity Sens.max. for red in steps

^C 6 ^H 5

° 6 ^H 5

CH,

7 \ N -CH = CH-CH = / ~ NCH,

695 nm

NS,

X-CH = CH-CH = / HCEr 700 nm

27

^C 6 ^H 5

SC

X-CH = CH-CH =

N _x @

CH,

700 nm 27

Table 3 shows a further increase in some examples the susceptibility through the additional use of a sensitivity-increasing, stabilizing; Mercapto compound (Compound IV).

A-6

- 25 -

Table 3

2008TU

ReI. Sensitivity for red in steps 3, -v

Dye no. 10 mg of dye 10 mg dye + 60 mg IV 30th 24 26th 8th 20th 25th 3 24 26th 29 24 26th

In addition to the sensitivity-increasing effect of compound IV, Table 4 also shows its stabilizing effect. In A are in the following Tables 4 to 6, the relative sensitivities of the fresh material indicated that of the so-called under tropical conditions stored (4 days at 40 ⁰ C and 82 i> relative humidity) material under B. It can be seen that the sensitivity of the emulsion sensitized without the addition of stabilizers leads in some cases to a decrease in sensitivity due to storage under tropical conditions, especially when the dyes alone provide a very high sensitivity (e.g. dyes No. 2, 10 , 20 and 22), but that after the addition of the mercapto compound IV the high sensitivity achieved is retained in most cases.

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Table 4

Jf.

dye Relative sensitivity for red in stages- ^ dye 10 mg dye + B. No. 10 mg J 60 mg IV 26th B. A. 26th A. .23 27 26th 10 27 22nd 27 23 20th 26th 20th 27 .26 29 24 21st 23 25th 24 21st 24 26th 26th 2 26th 20th 25th 26th 26th 22nd 24 26th 26th 21st 24 25th 27 .27 23 26th 23 27 25th 1 26th 23 27 24 27 26th 21st 26th 23 18th 24 21st 24 27 25th 21st 21st ■ O Λ ' 9 25th 23 27 22nd 26th

Table 5 shows that the obtained with the mercajto compound IV Stabilization when using a 2,4'-trimethine cyanine of the invention is much more pronounced than in the case of sensitization with the corresponding trimethine cyanine without methyl thio group.

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Table 5

dye Relative sensitivity to ? dye 10 mg
60 mg Red in stages No. 10 mg] B. A. Dye +
IV A. 18th 26th 10
but without
-SCH ₅ 24 23 27 10 27 B. 23 26th

Table 6 shows further results, with other stabilizing ones as well Mercapto compounds can be used in varying amounts.

Table 6

Dye no. Stabilizer, amount ReI .Sensitivity to B. 10 mg Red in steps% 23 A. 25th 1 26th 24 1 IV 60 mg 27 24 1 I 60 mg 25th 23 1 I 20 mg 25th 23 1 II 60 mg 25th 22nd 1 II 120 mg 24 2 - 25th

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Table 6 (continued)

Dye no. 2 Stabilizer, amount ReI. 26th Sensitivity to B. 25th 10 - ^ mg 2 Red 24 in stages 4 Π? 23 17th A. 26th 14th 17th IV 60 mg 27 16 17th II 60 mg 27 ¹ 7 17th - 26th 17th 28 V 15 mg • 27 18th 28 V 30 mg 28 2O ₁ 28 V 60 mg 28 ■ 22 28 - 27 24 18th V 15 mg 24 .20 18th V 30 mg. 25th 23 V 60 mg VI 60 mg

A-G 609

- 29 -

109836/1278

Claims (5)

Claims: 2008 J0 p light-sensitive material having a phctügraphisches by a content of a 2,4'-trimethine au spectrally senaibilisierten Silberhaiogenidemulsionsschicht, characterized in that the 4-position associated with the trimethine quinoline ring in the 6-, 7- or 8-position carries a methylthio group at least. 2. Light-sensitive photographic material with at least one silver halide emulsion layer, characterized by a 2,4'-trimethine cyanine content of the following Formula: \ -CH = CH-CH = / ~~ N-R ' in which mean R and R ¹ = identical or different radicals, namely 1) saturated or olefinically unsaturated aliphatic groups with up to 6 carbon atoms, which can be substituted, 2) cycloalkyl groups or 3) aryl groups; X ^ = any anion that is omitted if R and / - or R ^{1 contains} an acidic group in anionic form ™, so that a betaine is present; and Z = one required to complete a heterocyclic group with 5- or 6-membered hetero ring Rest. - 30 - 109836/1278 3. Material according to claim 2, characterized in that
an aromatic mercapto compound of the following formula is also included: R ¹ '■ - SH wherein R ¹ 'denotes an isocyclic or heterocyclic aromatic group which is further substituted by aryl,
Halogen or an electron withdrawing group. 4. Material according to claim 3, characterized in that the
the aromatic group represented by R ¹ 'is substituted by an acidic group which can also be present in anionic form. 5. Material according to claim 2 to 4, characterized by a Content of a color coupler. AG 609 - 31 - €> f A 109836/1278