DE2020814A1 - Photographic recording material - Google Patents

Description

Photographic recording material

The invention relates to a photographic recording material, consisting of a layer support, at least one silver halide emulsion layer applied thereon, and optionally Intermediate and / or outer layers, which in at least one of the layers has an anti-fogging agent and / or Contains non-forming additives.

There are already various types of photographic recording materials, e.g., recording materials having at least a negative type developable silver halide emulsion layer and recording materials having at least one direct "* \) positive silver halide emulsion layer of the reverse type, known, the most diverse common known photographic Additives, e.g. antifoggants, nucleating agents and / or for photographic purposes, e.g. intended for sensitization Contain dyes. Despite the large number of photographic additives already known, there is a need for additives new type, which are characterized by advantageous physical and photographic properties.

The object of the invention is to provide a photographic recording material to be indicated with improved sensitometric properties

009846/1273

BATH

20208U

The invention is based on the surprising finding, that the stated task in a particularly advantageous manner thereby solvable, the fs the photographic-n recording material a reactive β heterocyclic, N-substitute incorporated quaternary ammonium al ζ genaii defined structure will.

(e 's ;; tand of the invention is a photographic recording material consisting am- a layer support, mindep f> ns t-'Lner thereon a silver halide emulsion layer, and optionally the intermediate and / or lieokscliiohten that in ψ of at least one of the layers one as Contains antifoggant and / or additive acting as a keinbildner, which is characterized by the fact that the additive consists of a cyclic quaternary immonic salt in the form of a heterocyclinic compound with a 5- or 6-membered equatorial nitrogen atom on an iron ring whose quaternary nitrogen atom is substituted by a rent of the general formula:

- (CH ₂ ) _n -R

where mean:

η = 2, 3, 4, 5 or 6 and

alkyl. ^ R is a formyl or hydrazonoHfcXKJjÄ residue or a residue the general formula

-CH

where T ^ and T2 alone are alkoxy or alkylthio radicals, or together to complete a 5- or 6-membered cyclic oxyacetal or cyclic Thiοacetairinges represent required atoms.

009846/1273

The heterocyclic that can be used in the invention Compound present 5- to 6-membered ring contains in addition to " de:., quaternary nitrogen atom substituted in the manner indicated 4 to 5 more atoms, of which 3 to 4 atoms are carbon atoms and the remaining atoms are carbon, nitrogen, -, sulfur or selenium atoms.

Refer to the recording materials in the photographic material the invention present cyclic quaternary ammonium salt-2ΡΠ It is advantageous if it is heterocyclic Compounds of the general formula:

(= CH-CH) ^ ₁ = CI

• where mean:

For the completion of a heterocyclic compound riit ρ i no 5- or 6-membered atoms, in addition to the quaternary nitrogen atom, carbon, nitrogen, oxygen, vjchvefp ^ - egg selenium atoms necessary, ...

j = 1 or 2,

a = 2, 3 »4,? or 6, ■

I ^ an acid anion,

alkyl

R is a Pomyl or HydraccndHaCHHöÄ residue or a residue

of the general formula ^ T ₁ , wherein

-OH

T ^ and To alone are alkoxy or alkylthio radicals, or together those needed to complete a 5- or

00 9 846/1273

BATH

6-membered cyclic oxyacetal or cyclic thioacetal ringso represent required atoms and

R ^ is a hydrogen atom, an alkyl or alkylthio radical or an optionally substituted] aryl radical, for example phenyl or naphthyl radical. or an aralkyl radical.

In the formula given, for example, Z stands for the atoms that are required are to complete an indole, imidr ^ nl ---, Oxazole, thiazole, ßplenazole or quinoline ring, also from Rings of the imid'azole series, e.g. from benzimidazoles, beinpie'j.: ---

k. wise 5-chlorobenzimidazole, as well as naphthiraidazoles, also of rings of the thiazole series, for example thiazole, 4-methylthiazole, 4-phenylthiazole, 5-I'iethyltiiiazole, 5-phenyj.thiazole, 4,5-W-methylthdazole, 4,5 -Diphenylthiazole and 4- (2-thienyl) thiäsol, also from rings of the benzothiazole series, e.g. from Benzothii? Zc> l, 4-Chlorobenzothiazol, i3-Chlorotenzothia: iol, 6-Chlorbenzothi ~ azol, 7-Chlorobenzothiar.ol ^ 4- Methylbenzothiazole, ^ -Methylbenzothiazole, 6-methylbenzothiazole, 5 ~ bromobenzothiazole, 6-broiaobenzothiazole, 4-phenylbenzotliiazole, 5-hieiaylbenzothiazole, 4-methoxybenzothiazole, 5 ~ methosybenzothiazole, 5 ~ methosybenzothiazole, 5 ~ 4-iodobenzothiazole _r 6-methoxybenzothiazole, 5 ~ 4-iodo-benzothiazole, 6-methoxybenzothiazole, thoxybenzo ™ thiazole, 5 ~ ethoxybenzothiazole, tetrahydrobenzothiazole, 5j6-l) iinethoxybenzothiazole, 5 ~ hydroxybenzothi8-Kol and 6-hydroxy likewise ~

k thiazoi, also of rings of the naphthothiazole series, e.g. of Ot-Naphtho.thiazol, 8- methoxy- & -naphthöthiazole, 7- methoxy- Ok naphthothiazole and liaphtho / S, 1-d7thlazol, - "also of rings of thionaphtheno-7 ' »6 ', 4,5-thiazole series, e.g. from 4' -Hetiioxythionaphtheno ~ 7 ', 6', 4-, 5-thiazole, also from Hingen of the oxazole series, e.g. from 4-methyloxazole, 5 ~ methyloxazole, 4-phenyloxa- zol, 4,5 ~ diphenyloxazole, 4-lthyloxazcl, 4,5-dimethyloxazole imd 5-phenyloxazole, also from rings of the benzoxazole series, for example from benzoxazole, 5 ~ chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenz , 6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-I.iethoxybenzoxazole, -S-ethoxybenzozazole, 5-chlorobenzoxazole, C-methoxybenzoxazole, 5-hydroxybenzoxazole and 6-hydroxybenzoxazole, also from rings of the Naphthoxasbl-

0 0 9 8 4 6 / ^ 73 ._ _.,

BATH ORIGINAL

row, ζ. B. of a-naphthoxaol; also from rings of the selenazole series, z. B. of 4-methylselenazole and ^ -phenylselenazole, also from rings of the Benzoaelenazole series, z. B. from Benzo - selenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole and tetrahydrobenzoselenazole, furthermore of rings of the naphfchoselenazole series, e.g. B. of a-naphthoselenaaol; as well as rings of Chinollnrelhe, z. B. by Chinolln and Lepldin.

In the formula given, X ^ö can stand for the most varied of customary anions, 2, B. for a halide ion / for example a bromide, chloride or iodide ion, also for a sulfate ion, e.g. B. a sulfate, hydrosulfate or short-chain A1] $ L ~ sulfate ion, for example a methyl sulfate or ethyl sulfate ion, also for an aromatic sulfonate anion, e.g. B. a ρ-toluene sulfonate and benzenesulfonation, also for an acid anion derived from a carboxylic acid, for example for an acetate, trlfluoroacetate or propionatlon, and z. B. for a perchlorate, cyanate, thiocyanate, sulfamate or benzoate ion,

In the formula given, R stands for a radical of the general formula - ^ T .. and T ^ and T _{3 have} the meaning of -CH ■

Alkoxy or alkylthio radicals, these usually have 1 to 6 carbon atoms in the alkyl chains.

If T ₁ and T ₂ together form the atoms required to complete a 5- or 6-membered cyclic oxyacetal or thloacetairin tot, these rings can, for. B. 1,3-dithiolan-2-yl, 1 / i-dioxolan-z-yl, 1,3-dithiolan-z-yl or 1,3-dloxan-2-yl rings 3ein.

S if R is hydrazonoalkyl, e.g. B. hydrazonomethyl, Ilydrazonoäthyl-, Hydrazonopropyl- and the like. Rests, so can

0098 46/127 3

BUILDING

these may be substituted and, for example, also consist of a corresponding thiosemlcarbazonoalkyl radical. In particular, R can be, for example, a l-phenylhydrazonouthyl-; 1-phenylhydrazonopropyl-; l- (p-tolylhydrazono) ethyl-; t (2-benzothiazolylhydrazono) propyl-; 1- (N-phenylcarbamoylhydrazono) -butyl-; ! - (p-ToluolsulfonylhydrazonoJäthyl-; l- (p-Sulfophenylhydrazono) propyl- or a corresponding other 1-hydrazonoalkylreat.

Under alkyl radicals, alkoxy radicals and alkylthloro radicals are allk philic, branched or straight-chain alkyl, alkoxy or, Alley lthloreste to be understood, which are preferably 1 to 6 carbon atoms in the alkyl group, e.g. B. methyl, ethyl, propyl, isopropyl, η-butyl, tert-butyl, amyl or flexyl radicals as well as z. B, methoxy, ethoxy, propoxy, n-butoxy and

rest
tert-butoxy / as well as z. B. methylthio, kthylthlo, tert-butylthlo and hexylthlo radicals. Short-chain alkyl, alkoxy and alkylthloro radicals are those with 1 to 4 carbon atoms in the alkyl group. Such radicals can optionally be substituted.

Aralkyl radicals are alkyl radicals with preferably 1 to ß To understand carbon atoms which are preferably substituted by a phenyl or) naphthyl radical, e.g. B. benzyl, phenylethyl, 2-phenylpropyl, naphthylethyl and phenylbutyl radicals.

According to a particularly advantageous embodiment of the invention contain cyclic quaternary ammonium salts of the following structural formula:

CH ₂ X *

CH ₂

R ₂

0Ö9846 / 1273

BATH ORIGINAL

in Z ₁ the meaning given for Z, R-, the meaning given _{for R 1 and} ^{Χ θ have} the meaning already given and in which also mean:

k = 1 or 2,

g = 1, 2, 3, M or 5 and,

-7 - ■

0098A6 / 1273

a formyl radical or a radical of the general formula

T-z Sbc * in T3 and T4

»/ Those for T- | and To have the given meaning.

Typical in photographic recording materials Reactive cyclic quaternary ammonium salts which can be used in the invention are for example:

3- (2-formylethyl) -2-methylbenzothiazolium bromide, 3- (3 »3-dimethoxypropyl) -2-ethylbenzimidazolium chloride, ^ 3- (313-diet] ioxypropyl) -2-methylbenzothiazolium iodide, 1- (2-formylethyl) -4-methyl-quinolium bromide,

1- / 2- (I, 3-dithian-2-yl) ethyl7-2-ethylc] iinolium iodide, 3- (3> 3-diethoxypropyl) -2-methylbenzothiazolium perchlorate, 5-chloro-3- (2-formylethyl) -2-methylbenzoselenazolium bromide,

5,6-dichloro-1-ethyl-3- (2-formylethyl) -2-methylbenzimidazolium bromide,

1-ethyl-2-methyl-3- (2-propionylethyl) benzimidazolium drornide,

w 3- / 3 »3-di (ethylthio) propyl7-2-methylbenzothiazolium hydrosulfate,

3- / 3 *, 3-Di (ethyl thio) propyl7-2-methylbenzo thiazolium-p-toluenesulfonate,

1- (2-formylethyl) -4-methyl-quinolium bromide, 3- (3-Formylpropyl) -2-ethylbenzimidazonium hydrosulfate,

3- (6,6-Methoxy-n-hexyl) -2-methylnaphthq / 2 _i i.-d / tiii bromide, ... .. -., .. '> _;% . _...-..., _; ; -

8 4 6/1273

BAD ORlGIfML

3- / 3 ", 3-üi (methylthlo) propyl7-2-raethylbenzO'thiazolium]) odide, 3- (2-formylethyl) -2-methylbenzoselena2oliimbromid, 3- ( '? , 3-I> iäthyltiiiopropyl) -2- ethylbenzoxazolium bromide, 3- / 2 (1, 3-dithiolan-2-yl) ethyl7-2-methylbenzothiazolium bromide, 3- / 5- (1,3-dioxan-2-yl) ethyl7-2-methylbenzoselenazolium bromide, 3- ( 5-iOrniylpen.tyl) -2-ethylbenzoselenazoliimbroniid, 3- (2-pormylätl-Iyl) -2-methylnap] αtllo / 5,1-d / thiazolium bromide,

3- (3,3-diethoxypropyl) -2-ätl·lyl-thionaph tho / 5, ^ -d / thiazolium methyl sulfate, .

3- / 3- (1,3-Dioxolan-2-yl) propyl7-2-plienylbenziinidazoliuraperchlorat,

3- (2-formylethyl) -2-methylnaphtho / 5,3-d7thiazoli "umbromide, 3- / 3, 3-M (propylthio) propy] -7-2-p-tolylbenzothiazolium benzoate, 5-01iloro-3- (2-formylethyl) -2-methylbenzothiazolium "bromide, 3- (2-0yanoethyl) -2-ynethylbenzoxazolium iodide, 2-propyl-3- (2-carboxyethyl) -naphtho / 5,3-d7-serenazolium chloride, 3- (2-Formylethyl) -5-methoxy-2-methylbenzothiazolium bromide and 3- (2-Formylethyl) -5,6-dimethoxy-2-methylbenzothiazolium bromide.

For more information, see the photograph! Quaternaries which can be used in an advantageous manner according to the invention

009846/1273

20208H

--a / 6

Ammonium salts, for example, are through on the quaternary nitrogen atom a hydrazonoalkyl radical substituted heterocyclic compounds the general formula:

ι ————— Ζ—— ~~%

ΪΙ® C = CH-CH), ^ = GR ₁

ι K-Il

CH _{9 γ} θ

CII ₂

⁽ ? ^H 2> g-1

in which Z, R ₁ , X, k and g have the meaning given and

1 - alley 1

R, a hydrazonoXJeXifclfflCrest means ^ ..B. a hydrazonomethylresb.

The hydrox * azonomethyl radical represented by R 1 corresponds to e.g. a remainder of the formula:

M-HH-N = CH-,

in which M is an optionally substituted aryl radical, preferably of the phenyl or faphthyl series, which can be substituted, for example, by hydroxy, alkyl ^ or an * ¹ - jz'este, for example alkylamino, arylamino or heterocyclic aryino radicals, furthermore by Alkoxy or aryloxy radicals, also through amido radicals, for example acyloxyamido, arylcarbonamido, alkylcarbonamido, heterocyclic carbonamido, arylsulfonamido, alkylsulfonamido, or heterocyclic sulfonamido radicals.

The use of hydrazonoalkyl-substituted has proven to be particularly advantageous Quaternary salts of the given general formula proved, in which g = 1 and R., a methyl radical and R * means one of the following hydrazonomethyl radicals is:

009846/1273

2Q208U

a phenylhydrazonomethyl,

p-tolylhydrazonomethyl-,.

p-sulfophenylhydrazonomethyl-,
* - thiosemicarbazonomethyl,
2-benzothiazol-ylhydrazonomethyl-,
p-carboxyphenylhydrazonomethyl-,
p-toluenesulfonylhydrazonomethyl-,
p-chlorophenylhydrazonomethyl-,
p-nitrophenylhydrazonomethyl-,
N-phenylcarbamoylhydrazonomethyl-,
2, ^ - DKmethylsulfoOphenylhydrazonomethyl-, 2, ^ - Dinltrophenylhydrazonomethyl-,
3-Quinoly Lhy drazonome thy 1.-,
1-phenylhydrazonoethyl,
1- (p-Tolylhydrazono) ethy1-,

l- (p-sulfophenylhydrazono) propyl-,.

l-thioseraicarbazonobutyl,
1- (2-Benzothiazolylhydrazono) ethyl-, l- (p-Garboxyphenylhydrazono) pentyl-, l-ip-toluenesulfonylhydrazonoethyl-, 1- (p-chlorophenylhydrazono) propy1-,! - (p-Nitrophenylhydrazonoypropyl-,
l- (N-phenylcarbomoylhydrazono) butyl-, ^l

! - / "^, 'i-BisCraethylsulfonyDphenylhydrazono ^ y-propyl- or 1- (2,4-Dinitrophenylhyd] ^ azono) ethyl radical.

Typical ones used for making the photographic material suitable according to the invention, on the quaternary nitrogen atom quaternary substituted by a hydrazonoalkyl radical Ammonium salts are e.g. B .:

2-methyl-3 - / "3- (2-benzothiazolylhydrazono) propyl _- 7-benzothiazoliurajodid,

3 "/ *" 3- (p-.Carboxyphenylhydrazono) propyl_7-2-methylbenzoxazolium chloride,

3 - / "3- (p-Carboxyphenylhydrazono) propyl_7-2-methyl-benzothiazolium bromide,

009846/1 273

2-methyl-3 - / "3- (p-toluenesulfonylhydrazono) propyl_7naphthOT /-2,ld.7-thiazolium iodide _> maphtho-

3- / ~ 3- (p-chlorophenylhydrazono) propyl_7-2-methyl / ~ 2, l-d_7-thiazoliurabromide,

3- / ~ 3- (p-Carboxyphenylhydrazono) propyl_7-2-äthylnaphtho / ~ 2, l-d_7-thiazolium bromide,

2-methyl-3 - / "(3-p-nItrophenylhydrazono) propyl_7naphtho /" 2, l-d_7-thiazolium iodide,

l- / ~ 3- (p-Carboxyphenylhydrazono) p.ropyl_7- ⁱ l-methylquinolium _{iodide J} 3 - / "" 3- (2, ⁱ l-Dinitrophenylhydrazono) butyl_7benzothiazoliumbromid _J

2-methyl-3- / ~ 3- (N-phenylcarbamoylhydrazono) propyl ^ 7-naphtho - / "2, l-d_7thiazolium iodide,

3- / ~ 3- (2 ^,! L-Diraethylsulfonylphenylhydrazono) propyl_7-2-methylnaphtho / ~ 2, l-d_7thiazolium bromide,

3- / ~ 3- (p-Carboxyphenylhydrazono) propyl_7-2-benzylbenzoselenazolium-p-toluenesulfpnate,

Benzyl-3 - / "" (3-phenylhydrazono) propyl_7benzothlazoliumacetat,

3- / ~ (3-p-Carboxyphenylhydrazono) propyl__7-2-methylbenzothlazollumbromld,

3- / T3 - p-Carboxyphenylhydrazono) propyl_7-5-chloro-2-methylbenzothiazoliumbroraid,

2-methyl-3 - / "3- (phenylhydrazono) propyl_7benzothlazollumbenzolsulfoenat,

2-ethyl- / ~ 3-P "" sulfophenylhydrazorio) propyl_7benzothiazolium ~ Iodide,

2-methyl-3 - / * "3- (p-sulfophenylhydrazono) propyl_7benzothiazolium iodide,

2-methyl-3 ~ / "* 3-thiosemicarbazono) propyl_7benzothiazolium bromide,

2-methyl-3 - / "3 ^ra (thiosemicarbazono) propyl_7benzothiazolium ~ hydrosulfate,

2-methyl-3 - / "" 3- (phenylhydrazono) propyl_7benzothiazolium bromide,

2-methyl-3 - / "3- (phenylhydrazono) propyl_7benzothiazolium thiocyanate, "00 98 4 6V 12 7 3,,.,,.

2-I, ietliyl-3 - // 3- (p-tolylhydra3OTio) propyl7tenzothiazolluinbroniid, 2-methyl-5- / 3- (p-sulfophenylhydrazono) propyl7t> enzo bhiazolium-

bromide, - ■

2-Me triyl-3- / 3- (p-toluenesulfonylhydrazono) pen-byl7-benzothiazolium bromide,

2-methyl-3- / r3-tliiosemicarbazono) propyl7benzothiaolium perchlorate, .

2-methyl-3- _< /T3-phenylh.ydrazono) propyl7benzothiazoiiuinbenzenesulfonat,

2-methyl-3- / 3- (p-tolylhydrazono) propyl7benzothiazolium acetate,

2-methyl-3- / 3- (p-sulfoplienylhydrazono) propyl7benzothiazolium propionate,

2-I.Iethyl-3- / 3- ( ^/ benzothiazol -! - ylhydra.zono) propyl7-benzothiazoliu eibromide,

5,6 ~ dicliloro-1-ethyl-2-methyl-3- _i / 3- (p-sulfophenylhydrazono) -propyl7benzimidazolium bromide,

5,6-dichloro-3- / 3- (2-benzothiazolyl] aydrazono) propyl7-1-ethyl-2-methylbenzimidazolium bromide,

5,6-Oichloro-2-methyl-3- / 3- (3-quinolylhydrazono) -propyl7-1-ethylbenzitnidazolium bromide, ■

5-ghloro-2-methyl-3- / 3- (p-tolylhydrazono) ppopyl7-benzoselenazOlium bromide,

2-methyl-3- / 3- (p-toluenesulfonylhydrazono) propyl7-benzothiazolium bromide,

009846/127 3

bath

20208H -

/ η

2-methyl-3- / ~ 3- (p-tolylhydrazono) propyl_7benzothiazolium bromide,

3 - / "3- (2,4-Dinltrophenylhydrazono) propyl_7benzothiazoliumbromld,

5 _J 6-Dlchloro-1-ethyl-2-methyl-3 - / "3- (p-tolylhydrazono) propyl_7-benzimidazolium bromide,

5,6-dichloro-1-ethyl-2-methyl-3- / ~ 3- (p-nitrophenylhydrazono) -propyl_7benzimldazoliumbrornid,

3 - / "" 3- (p-Carboxyphenylhydrazono) propyl_7-5-methoxy-2-methylbenzothiazoliutnbromld,

3 - / "3- (p-Carboxyphenylhydrazono) propyl_7-5,6-dimethoxy-2-methylbenzothiazolium bromide,

3- / ~ 3- (p-Carboxyphenylhydrazono) propyl__7-2-methylnaphtho - / "" 2,3-d_7thiazolium bromide,

l ~ (p-Carboxyphenylhydrazono) pi'opyl-2,3,3-trimethyl-3H-yne do 1 i umb ro mi d,

2-methyl-l- / ~ 3- (p-carboxyphenylhydrazono) propyl_7-lH-benz / ~ e_7-indolium bromide,

3 - / "3- (p-Carboxyphenylhydrazono) propyl_7-5,6-dimethoxy-2-methylbenzothiazolium bromide,

3- / ~ 3- (p-Carboxyphenylhydrazono) propyl_7-2-raethylnaphtho- / ~ 2,3-d_7thiazoliumbrorald,

3- / ~ 3- (2-Benzothlazolylhydrazono) butyl_7-2-methylbenzothiazollum iodide,

3- / ~ 3- (p-Carboxyphenylhydrazono) pentyl_7-2-raethylbenzoxazollumchlorld, -

3- / ~ 3- (p-Carboxyphenylhydrazono) hexyl_7-2-methylbenzobhiazolium bromide,

2-methyl-3 - / "3- (p-toluolaulfonylhydrazono) butyl_7-naphtho /" 2, l-d_7-thlazolium iodide,

3- / ~ 3- (p-chlorophenylhydrazono) heptyl_7-2-raethylnaphtho- / ~ 2, l-d_7thiazolium bromide,

009846/1273

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3- / ~ 3- (p-Carboxyphenylhydrazono) butyl_7-2-ethylnaphtho- / ~ 2, l-d_7thiazolium bromide,

2-methyl-3- / ~ 3- (p-nitrophenylhydrazono) propyl_7naphtho- / ~ 2 , l-d_7thiazolium iodide,

2-methyl-3 - / "3- (N-phenylcarbamoylhydrazono) pentyl_7naphtho - /" ■ 2, l-d_7thiazolium iodide, ■

3- / ~ 3- / 3 ² » ²ⁱ - ^B i ^s (niethylsulfonyl) phenylhydrazono_7hexyl _- 7-2-methylnaphtho / ~ 2 _i ld _- 7thiazollumbrorald,

3- / ~ 3- (p-Carboxyphenylhydrazono) heptyl_7-2-benzylbenzoselenazolium-p-toluenesulfonate,

2-Wethy1-3 - / "(3-phenylhydrazono) butyl_7benzothiazolium acetate,

3- / ~ 3- (p-Carboxyphenylhydrazono) pentyl_7-2-methylbenzothlazolium bromide,

3- / ~ 3- (p-Carboxyphenylhydrazono) butyl_7-5-chloTO-2 ~ methylbenzothiazole umbromide,

3- / ~ 3- (Phenylhydrazono) hexyl_7benzothiazoliumbenzenesulfonate,

2-ethyl- / ~ 3- (p-sulfophenylhydrazono) butyl_7benzothiazolium iodide,

2-methyl-3 - / "3-p-sulfophenylhydrazono) pentyl_7benzotHiazoliumjodid,

2-methyl-3- / ~ 3- (thlo3emicarbazQno) heptyl_ _> 7benzothlazoliumbronild,

2-methyl-3 ~ / ~ 3- (thioseraicarbazono) hexyl_7benzothiazollum hydrosulfate, ,

2-methyl-3 ~ / '"3- (phenylhydrazono) butyl_7benzothiazolIumIodid _}

2-methyl-3- / ~ 3- (phenylhydrazono) pentyl_7benzothiazolium thlocyanate, '

2-methyl-3 ~ / ~ 3- (p-tolylhydrazono) heptyl_7benzothiazoliuni _t iodide,

009846/1273

2-methyl-3- / ~ 3- (p-sulfophenylhydrazono) butyl_7benzothiazolium chloride,

2-Methy1-3- / ~ 3- (thiosemicarbazone) pentyl_7benzothiazolium perchlorate,

2-methyl-3- / ~ 3- (phenylhydrazono) butyl _ / benzothiazoliumbenzenesulfonatej

2-methyl-3- / ~ 3- (p-tolylhydrazono) pentyl_7benzothiazolium acetate,

2-Methy 1-3 - / "* 3- (p-sulfophenylhydrazono) butyl _7benzothiazoll umpropionat,

2-methyl-3- / ~ 3- (2-benzothiazolylhydrazono) butyl_7benzothiazolium cyanate,

5,6-dichloro-1-ethyl-2-methyl-3- / ~ 3- (p-sulfophenylhydrazono) -pentyl_7benzimidazolium bromide,

5,6-dichloro-3- / ~ 3- (2-benzothiazolylhydrazono) butyl_7-ethyl-2-methylbenzimidazolium bromide,

5,6-dichloro-2-methyl-3 - / "* 3- (3-quinolylhydrazono) propyl_7-1-ethylbenzimidazolium bromide,

5-chloro-2-raethyl-3 - / "3- (p-tolylhydrazono) hexyl_7benzoselenazolium bromide,

2-methyl-3 - / "'3- (p'-toluenesulfonylhydrazono) butyl _7benzothiazollurabromld,

2-methyl-3 - / "" 3- (p-tolylhydrazono) pentyl_7benzothiazolium bromide,

3- / ~ 3- (2, ¹ I-DInIt rophenylhy drazono) hexyl _7benzot hiazoliumbromld,

5,6-dichloro-l-ethyl-2-methyl-3- / ~ 3- (p-to ^ rlhydrazono) butyl_ ^ 7-benzimidazolium bromide,

5,6-dichloro-1-ethyl-2-methyl-3- / ~ 3- (p-nltrophenylhydrazono) -pentyl_7benzlmldazoliumbroraid,

3- / ~ 3- (p-Carboxyphenylhydrazono) butyl_7-5-methoxy-2-methylbenzothiazoliurabromide,

00 98 4 67.127 3

3- / ~ 3- (p-Carboxyphenylhydrazono) pentyl_7-5,6-dimethoxy-2-methylbenzothlazollumbromid,

3 - / "3- (p-Carboxyphenylhydrazono) hexyl_7-2-ynethylnaphtho- / ~ 2,3-d__7thiazolium bromide and

1- / ~ 3- (p-Carboxyphenylhydrazono) propyl_7-2-niethylquinolum iodide.

For the manufacture of those used in photographic recording materials cyclic quaternary ammonium salts which can be used according to the invention are advantageously a hydro salt of a corresponding one cyclic ammonium compound reacted with an aliphatic compound between the first and second carbon atom an active double bond, z / -B, eirie ethylenic unsaturated bond, has »

The reaction is expediently carried out in an inert organic solvent of moderate polarity, which both reactants dissolves, but is not a solvent for the reaction product formed, consisting of the quaternary salt. as advantageous such solvents have organic solvents with moderate polarity, z. B. acetonitrile and Dimethylacetamide. The use of reaction catalysts is generally necessary for the conversion. The implementation is expediently at the reaction temperature

- 14 -

00 9 8 467 1273 _B AD ORIGINAL

Renes of about 20 to 30 G are carried out, but can also be higher or lower temperatures are used as long as the Roaction components remain in solution and are not heated to temperatures above their decomposition temperature // ground. The reaction products formed fall out of the reaction solution and after isolation can be cleaned in the customary known manner, e.g. by washing with solvents or one or more recrystallization is fit ion.

JJiü preparation of hydrazonoalkylsubstibuierten quaternüren Ammoriijmsalze can in a corresponding manner and under comparable reaction conditions ψ parable take place, but under encryption -. '/ ^ ^ Nrian a two s tuf enreaktion, v / obei al ζ in the first stage hydrocracking £ 3 a Cycloammonimnbase is implemented with a compound containing an activated double bond, which preferably corresponds to the following structural formula:

where m = 1, 2, 3> 4 or 5 and T ₁ - is a pormyl, acetyl or propionyl radical, whereupon the intermediate product obtained is converted into the desired hydrazonoalkyl-substituted quaternary salt in a second process step with hydrazine to give the desired hydrazonoalkyl-substituted quaternary salt.

Typical hydrazines suitable for carrying out the specified process are, for example, phenylhydrazine, p-tolylhydrazine, p-sulfophenylhydrazine, Tüiosemicarbaaid, Benzothiazol-2-ylhydrazine, p-Garboxyphenylhydrazine, p-Tolylsulfohydrazine, p-Ghlorophenylhydrazine, p-llitrophenylhydrazine, N-phenylcarbamoylhydrazine, 2, + - Di (methylsulfο) phenylhydrazine, p-Garboxyphenylhydrazine and p-sulfophenylhydrazine,

Process for the production of the photographic images Cyclic quaternary salts which can be used according to the invention are described in the German patent specification (Patent application filed by the same applicant

009 aA6 / 1273

20208U

- 4 $ -. '■■■■.' ■■ '

on the same day under the internal registration no. 122 357 submitted was described.

Lie in the photographic recording materials according to the Reactive cyclic quaternary ammonium salts which can be used in the invention are advantageously the photographic salts Silver halide emulsion layers, especially the Gelatin silver halide emulsions, for example as ■ Anti-fogging agents incorporated. You can develop from both Oilberhnlo ^ enidemulsion layers of the negative type as well as direct positive silver halide emulsion layers be incorporated.

specified cyclic quaternary ammonium salts are suitable furthermore for the production of dyes, / in particular of dyes suitable for photographic purposes. A typical condensation process for making such symmetric photographic sensitizing dyes consists, for example, in using a quaternary ammonium salt of the specified type with an excess of reactants, calculated on the stoichiometric molar amount, e.g. with diethoxymethyl acetate, 1,3,3-trimethoxypropene or the like, is implemented.

Leaving such photographic dyes unsymmetrical can be prepared, for example, by reacting a quaternary ammonium salt of the specified type with a dye intermediate, e.g. p-dimethylaminobenzaldehyde, 5-acetanilidomethylene-3-ethylrhodanine or 3-ethyl mercaptobenzothiazolium ethyl sulfate.

Dyes prepared in this way can be used, for example, in photographic recording materials as spectral sensitizers for light-sensitive compounds, for example silver halide, or for other uses for which organic dyes are advantageously suitable. _C

009846/1273

The photographic recording materials according to the invention contained in the silver halide emulsion layers in addition to the specified cyclic quaternary ammonium salts in the Usually other common known chemical additives, e.g. carriers, spectral sensitizing dyes, coating auxiliaries, Lightening Agents, Hardening Agents, Developing ! 'Connections and the like.

Typical suitable carriers are, for example, the most varied known, for this purpose commonly used hydrophilic, water-permeable binders, for example gelatin, colloidal albumin, polyvinyl compounds, cellulose derivatives, Acrylamide polymers and the like, both for themselves alone as well as in combination with one another and in the form of mixtures are usable. Those in the emulsion layers of the photographic recording materials according to the invention existing binders can optionally be polymerized Contain vinyl compounds in the form of dispersions. Typical suitable vinyl polymers of this type, as they are, for example, in the U.S. Patents 3,142,568, 3,193,386, 3,062,672 and 3,220,844 are, for example, water-insoluble polymers and latex copolymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates and the like.

Typical for use in the silver halide emulsion glass Spectral sensitizing dyes which can be used for the photographic recording materials according to the invention, as described, for example, in U.S. Patents 2,526,632 and 2,503,776, are e.g. cyanines, merocyanines, complex trinuclear cyanines, complex trinuclear merocyanines, styryls and hemicyanines.

In the case of the production of photographic recording materials Coating auxiliaries which can be used according to the invention it can be nonionic, anionic and / or

009846/1273

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20208H

act amphoteric compounds. Typical suitable such Coating auxiliaries are e.g. saponin, alkyl-substituted ones Aryloxyalkylenäthylaulfonate des in the USA patent

2 6ΌΟ 831 described type, also Maleopimarate des. In the US Pat. No. 2,823,123, as well as taurine derivatives that described in U.S. Patent 2,739,891 Type as well as alkylaminopropionates of the US patent

3 133 816 of the type described. Further typical suitable coating aids and surfactants are e.g. alkylphenoxy poly (hydroxyalkylene oxides) e.g. alkylphenoxy poly (glycidols) with about 5 to 12 glycidol units, such as those described in British Patent 1,022,878.

Those which can be used in the photographic recording materials according to the invention in a particularly advantageous manner Brighteners are usually compounds that have at least one 5- or 6-membered heterocyclic ring contain. Typical suitable such brightening agents are e.g. stilbene, stilbene triazole, triazinetilbene, coumarin, Triazinylaminocoumarin, oxazole, benzidene, benzimidazole, Benzothiazole, benzoxazole, pyrazoline and naphthalenimide derivatives. Typical suitable brightening agents are described, for example, in U.S. Patents 2,933,390 and 3,406,070.

The silver halide emulsion layers of the photographic recording materials According to the invention, in addition to the specified additives, hardeners and hardener combinations can also be used .. Typical suitable hardeners are e.g. formaldehyde, mucochloric acid, glutaraldehyde, maleic acid dialdehyde, Aldehyde hardeners, aziridine hardeners, hardeners based on dioxane derivatives, vinyl sulfones, Oxypolysaccharides, z, B, oxidized starch and oxidized vegetable gums, inorganic hardening agents such as chromium salts and like that. ·

009846/1273

BAD ORiQiNAL

Further suitable additives are e.g. developer compounds of the type described below.

In particular for performing photοgraphischen reversal process recording material! S according to the invention, NEN the photosensitive layers of Silberhalogenidurakehremulsio- or have direktpoßitiven emulsions and the direct production of positive photographic images without intermediate production and development of negative images allow, has the use of quaternary Ammonium salts, the quaternary nitrogen atom of which is substituted by a hydrazonoalkyl radical, have proven particularly advantageous as nucleating agents or fogging agents. The specified direct-positive emulsion layers are generally those in which the latent images are predominantly produced in the interior of the silver halide grains.

The photographic emulsions "which are usually used in reversal processes are (jelatine silver halide emulsions, e.g. silver bromide, silver bromoiodide or silver chlorobromide emulsions") To widen the spectral sensitization range. Such sensitizing dyes which can be used advantageously are described, for example, in the tISA patent document 2,497,876, in particular in column 2, line 15 and column 4, line 20. The latent image predominantly in the interior the silver halide grains forming emulsions are not digested in general or, if they are digested _p done the digestion without the use of chemical Oberfläohensensibilisatoren. An emulsion of the specified type ₉ which is known as so-called "BurtonVs emulsion" sB is, in de "Bucfc by Wall "Pho graphic emulsions «1927, pages 52 and 53, described. Another advantageous type of reverse emulsions is described, for example, in US Pat. No. 2,592,250.

009846/1273

Si

The production of such a reverse emulsion in which the latent image predominantly in the interior of the silver halide grains is formed, for example, can be done in such a way that silver salt grains, which at least partly from silver salts with greater water solubility exist as that of silver bromide, then at least some of the silver salt grains obtained are converted into silver bromide or silver bromoiodide and then, preferably in the absence of ammonia, a ripening process is carried out, whereupon the soluble salts either partially or completely washed out and finally soluble salts, e.g. soluble chloride, bromide or iodide, can be added in order to make a ready-to-use solution in this way Silver chlorobromide, silver bromoiodide, or silver chlorobromoiodide reverse emulsion to get. Suitable silver chlorobromide emulsions in which the latent image is predominantly inside the Silver halide grains can also be formed in the manner prepared v / ground that an aqueous gelatin solution under Stirring simultaneously with an aqueous solution of silver nitrate and an aqueous solution containing potassium chloride and potassium bromide is added, as described, for example, in Example 4 of U.S. Patent 2,996,382.

Sine "the latent image predominantly inside the silver halide grains constituting the emulsion" may be defined as an emulsion which is up au one second long exposure to light graduated intensity and subsequent four minutes of development at 2O ⁰ C in a conventional well-known "surface" - Ent'.vickler the below definition provides an image having a maximum density that is not more than 1/5 of the maximum density obtained when the same sample under the same emulsion Beliehtungsbedingungen for 3 minutes at 2O ⁰ C in a so-called ""InnerGrain" developer of the definition given below is developed.

The term "surface developer" refers to developers who in a "the latent image predominantly in the interior of the silver

009846/1273

BATH ORIGINAL

Halide grain-forming emulsion "images only on the surface of the silver halide grains develop. For example, a typical developer of the specified type has the following composition on:

p-hydroxyphenylglycine 10 g

Sodium carbonate (crystals) 100 g made up to 1 liter with water

"Inner grain developer" refers to developers who in an "emulsion forming the latent image predominantly inside the silver halide grains", images inside the silver halide grains to develop. A typical developer of the specified type has, for example, the following composition:

Hydroquinone x 15 g

Monomethyl p-aminophenol sulfate 15 g

Sodium sulfate (anhydrous) 50 g

Potassium bromide 10 g

Sodium hydroxide 25 g

sodium thiosulphate (crystals) 20 g

made up to 1 liter with water

The "surface" developer is preferably used with the aid of the specified "surface" developer obtained maximum density not more than 1/10 of the maximum density obtained with the help of the specified "Inner grain" developer is obtained. Expressed the other way around thus provides a "the latent image predominantly inside the Silver halide grain-forming emulsion "when developed in an" internal grain developer "images with a maximum density, which is at least 5 times, preferably at least 10 times greater than the maximum density obtained when exposed the same emulsion sample in exactly the same way and then developed it in a so-called "surface" developer will.

009846/1273

The cyclic quaternary ammonium salts found in reverse emulsions, which form the latent image mainly in the interior of the silver halide grains, act as nucleating agents or fogging agents, the silver halide reversal emulsions, e.g. B. sol-. Chen des from US Patents 2,566,180 and 592,250 known type, incorporated in such quantities that a carefully dosed veil in the form of tiny surface development centers, the generation of direct positive images in the Promote development, is generated. Those acting as nucleating agents cyclic quaternary ammonium salts become evident more firmly adsorbed by the silver halide grain surface conventionally known fogging agents, e.g. B. the hydrazine compounds known from US Pat. No. 2,558,982, there to achieve an equally advantageous effect of the fogging agents which can be used according to the invention, smaller amounts evade. This means a significant advantage over the prior art, since when using comparatively small amounts of fogging agents with comparatively high effectiveness, advantageously correspondingly smaller amounts of fogging agents are released into the developer solutions without the advantageous sensitometric properties to be achieved Properties are impaired as a result.

The photographic recording materials according to the invention contain the cyclic quaternary ammonium salts, which act as fogging agents, expediently in concentrations of from about 75 to 1500 mg, preferably from about 90 to 1200 mg, per mole of silver of the silver halide emulsion layers. However, depending on the type of reverse emulsion, on the chemical activity of the fogging agent used and depending on the developing conditions used, the quaternary ammonium salts which can be used according to the invention and which act as fogging agents are

009846/1273

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5t

also outside the specified concentration range in more advantageous Way usable.

For the production of direct positive photographic recording materials, which can be developed with the help of reversal processes are expediently the latent image predominantly in the Reversal emulsions of the inside of the silver halide grains specified type, which contain a nucleating agent cyclic quaternary ammonium salt of the specified type on known, for photographic purposes usually used support coated, 'whereupon the recording materials obtained are dried. A distinction must be made between the specified reversal or direct positive silver halide emulsions, as usable in the photographic or light-sensitive recording materials according to the invention, and emulsions with silver halide grains, the predominantly surface sensitivity and, upon exposure, the latent image on the silver grain surface form.

The photographic recording materials according to the invention may have a wide variety of conventionally known substrate such as film base of Celluloseesterfolien, for example, cellulose acetate * or Celluloseacetatbutyratfolien, olefins further from sheets of poly U, for example polyethylene and polypropylene, polycarbonates or polyesters, eg polyethylene terephthalate. Also suitable are layer supports made of metals, for example zinc and aluminum, also made of paper and made of papers coated with polyethylene "or polypropylene.

The photographic recording materials according to the invention containing the specified nucleating agents can be either those with color reversal emulsion layers or with black-and-white-silver halide emulsion layers. For the production of photographic color reversal materials, for example, couplers forming cyan, magenta and yellow dyes can be used adjacent to the silver halide emulsion layers which are used for

009846/1273

- 33 -

if

drawing of light, the color of which is practically the complementary color of the color development with the help of the corresponding Color couplers corresponding to dyes formed, are capable of being incorporated, as is the case, for example, in the USA patents 3,227,550 and 3,227,552. Furthermore, spectral Sensitizing dyes are used to make the existing To sensitize silver halide in a conventional manner.

For example, a multilayer, intended for color photography, can be used Recording material in the red-recording emulsion layer a coupler such as 5- (p-amylphehoxybenzenesulfonamino) -1-naphthol, in the green recording emulsion layer a coupler such as 2-cyanoeetyl-5 -, (p-sec-arayl ^ benzoylamino) coumarone, as well as in the blue-paint emulsion layer a coupler such as H-amyl-p-benzoylacetaminobenzenesulfonate contain. Further suitable couplers are known to the person skilled in the art. If necessary, the color couplers can also incorporated into the developer solutions described, for example, in U.S. Patents 2,252,718 and 2,507-154, however, such a procedure requires several exposure and color development stages «

After the imagewise exposure, the specified Direct-positive photographic imaging materials containing nucleating agents according to the invention in a customary known Surface developer solution, which has a comparatively low dissolving effect on the silver halide present exerts, immersed to produce a positive photographic image, surface developer of the specified type advantageously contain image-improving compounds which increase the maximum density of the images produced and which lower the minimum density thereof, e.g. that of the USA patent 2,497,917 known benzotriazoles *

009846/127

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8th*

Developer solutions are generally used to generate color images used, which is a p-phenylenediamine color developing compound, e.g., a 4-amino-N-dialkylaniline in the book by Mees "The Theory of the Photographic Process", 3rd Edition (1966), pages 294-295, of the type described. With A color developer is used, depending on the structure of the photographic recording material used, one or more Color images can be produced. When using polychromatic color films, blue-green images are usually produced in the red-sensitive layers, and purple images in the green-sensitive layers Layers and yellow images generated in the blue-sensitive layers. The silver still present after the development becomes ™ first converted into a soluble silver salt and then in the usual known manner from the photographic recording material removed, e.g. by treatment with a Fixatives, for example sodium thiosulfate.

The following examples are intended to explain the invention in more detail.

example 1

The cyclic quaternary ammonium salt 3- (2-formylethyl) -2-methylbenzothiazolium bromide was added to a conventional, known developable gelatin-silver bromoiodide emulsion of the negative type at a concentration of 0.6 g per mole of silver halide. The emulsion obtained was then applied to a base layer made of a polyethylene terephthalate film, and the photographic recording material obtained was dried in a conventional manner.

A photographic material was used for comparison prepared in a corresponding manner, with the exception that the emulsion does not contain a cyclic quaternary ammonium salt was added.

009846/1273

BAD ORSQjiMAL

Samples of the recording materials obtained were exposed in a conventional seneitometer known under the name "Eastman Model TB" through a step wedge with neutral density. The exposed film samples were then developed for about 2 minutes at 2O ⁰ O in a developer solution of the following composition :

p-methylaminophenol 3g

Sodium sulfite (anhydrous) 45 g

Hydroquinone 12g

Sodium carbonate, monohydrate 80 g potassium bromide 2g

made up to 2 liters with water

The processed film samples were then fixed for 3 minutes at about 2O ⁰ G in a fixing bath having the following composition:

Sodium thiosulphate 240 g Sodium sulphate (anhydrous) 15 g

Acetic acid (28 $ ig) 48 ml

Boric acid crystals 7.5 g potassium alum 15g

made up to 1 liter with water

Finally, the residual haze of the fixed film samples became certainly. The following results were obtained:

veil

initially after 2 weeks longer

Incubation

Comparative sample 0.19 1.08

Recording material

according to the invention 0.29 0.81

⁺ at 15 ° C and 85 ° C relative humidity

00 9 846/127 3

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The results show that the photographic recording material according to the invention, the specified cyclic qua contains ternary ammonium salt, which is characterized by beneficial anti-odor properties.

Seven further photographic recording materials were prepared in a similar manner! with the exception that the following cyclic quaternary ammonium salts were used instead of 3 ~ (2-iormylethyl) -2-methylbenzothiazolium bromide:

tk 3- (3,3-diethoxypropyl) -2-methylbenzothiazolium iodide, Ί- / 2-0,3-dithian-2-yl) ä-fchyl7-2-ethylquinolium iodide, 5-0hloro-3- (2-formylethyl) - 2-methylbenzoselenazolium bromide, 3- / 3,3-di (ethylthio) propyl7-2-methylbenzothiazolium iodide, 3- / 2- (I, 3-dithiolan-2-yl) ethyl7-2-methylbenzothiazolium iodide,

3- / 5- (1,3-Dioxan-2-yl) ethyl 7-2-methylbenzoselenazolium bromide and

-1-ethyl 3- / 3- (1,3-dioxolan-2-yl) propyl / ^ - 2-phenylbenziniidazolium broinide.

The exposure, development and testing of the obtained photographic Recording material was carried out in the manner described White. Accordingly, favorable results have been obtained.

It was found to be the specified, as an anti-fogging agent acting quaternary ammonium salts in concentrations of about 0.001 to 10 g per mole of silver halide can be used.

00 9-8 46/1273

Example 2

For the preparation of a photographic recording material serving as a comparative sample, a gelatin silver bromoiodide reversal emulsion, the preparation of which was carried out according to the process described in US Pat. No. 2,592,250, was applied to a layer support consisting of a cellulose acetate film. After drying, the recording material obtained was exposed to light in a sensitometer of the type indicated. The exposed film sample was then developed for about 3 minutes at 20 ^° C. in a developer solution of the composition described in Example 1. The positive image obtained by the development was then stabilized in such a way that it was about 3 minutes fixed at 2O ⁰ C in a fixer having the composition described in Example. 1

Further, one hereinafter referred to as "Film Sample 2" was used photographic recording material in the manner indicated produced, exposed, developed and fixed, with the exception that the emulsion used as a fogging agent acting quaternary ammonium salt 2-Methyi-3- / r3-phenylhydrazono) prox) yl7benzothiazoliumbromid was incorporated at a concentration of 200 mg / mol of silver. With the help of the received Photographic material gave a favorable reversal image with those listed in the following table obtained sensitometric properties. ■> -

Relative
Sensitivity Dmax Dmin gamma Comparative sample 100 0.10 0.04 0.05 Film sample 2 3720 1.44 0.15 1.57

The results show that the added to the university emulsion, quaternary ammonium salt substituted with a hydrazonomethyl radical in an advantageous manner as an effective nucleating agent works.

00 9 8 U 6/127 3

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2Ό208Κ

'ML

^ G.KJ ^

Example 3 ■ '

There were three, designated A, B and C in the following Direct positive photographic recording materials produced by using polyethylene-coated paper supports Photosensitive coating compositions of the following composition were applied in the following concentrations: ·

Film sample A p concentration

mg / m carrier fl. (mg / sq.ft.)

Gelatin-silver chlorobromoiodide emulsion that described in U.S. Patent 2,592,250 Type 323 (30), referring to silver

Gelatine 2150 (200)

Dye-Forming Coupler:
2 - // K - (4'-tert-amylphenoxy)
n-butyrylamino7-5-methyl-1-phenol 323 (30)

Formyl-4-phenylhydrazine 209 (19.4)

Film sample B

like film sample A, however
instead of formyl-4-phenylhydrazine, 2-methyl * -3- / 3- (phenylhydrazono) propyl7-benzothiazolium bromide
used 0.29 (0.027)

00 98 A 6/1273

Jilroprolae C

like film sample A, but was on
Place of formyl-4-phenylhydrazine
2-methyl-3- / 3- (p-tolylhydrazono) -

uses 0.29 (0.027) '

The film samples A, B and 0 obtained were dried, whereupon they were exposed in a densitometer of the specified type through a step wedge with neutral density. Die.belichteten film samples were then developed about 2 minutes at a temperature of 20 ⁰ C in a developer solution of the following composition;

distilled water 1 liter

Benzyl alcohol '12 ml

Sodium sulfite 1.5g

Potassium bromide 1.0g.

Potassium carbonate 55g

5-nitrobenzimidazole 0.005 g 4-Aiuino-3-methyl-IT-ethylß- (methanesulfonamide) -

ethylaniline sesquisulfate hydrate 7 g

pH adjusted to 11.3 with sodium hydroxide

The processed film samples were treated finally to remove the developed silver and the remaining silver salts for about 3 minutes at a temperature of 20 ⁰ C at a as "Biix" solution designated combined bleaching and fixing solution of the following composition:

■ 0 09846/1273

Potassium ferricyanide 35 g

Nfttrium acetate 20 g

1, e-dihydroxy-3,6-d ± ihiaootan 25 g

Bieesaig 3 ml old water made up to 1 liter

pH adjusted to 5.0 with acetic acid

The film samples treated with the indicated ^H Blix ^M solution were then washed and dried and found to have produced positive color images.

In a second and third experimental set-up, film samples A and C were produced in the manner indicated, exposed, developed and worked up, but with the exception that the pH of the developer solution used in the second Trial set to 11.15 and in the third trial set to 10.0.

The photographic densities of all the images obtained were determined. The results obtained are as follows Table listed.

pH value of the developer solution 11.3 11.15 10.0 Dmax Dmin Dmax. Dmax

Film rehearsal A. 2 , 36 0 , 18 2, 29 0 , 44 Film rehearsal B. • 2 .32 0 , 25 Film rehearsal C. 2 , 28 0 , 24 2, 30th 2 , 02

The results show that the addition of liydrazonomethylsubstituierten quaternary ammonium salts leads to the silver halide emulsions for photographic recording materials (cf. film samples B and C), with the help of which positive color images are advantageously also used with the use of developer solutions with a comparatively low pH value, without impairing the color density of the images obtained.

009846/1273

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are adjustable. In contrast, the emulsions are conventionally known Added nucleating agent (cf. film sample A), so when using developer solutions with a comparatively low pH-value the color density of the images obtained very strongly.

Further tests showed that the invention to be achieved Obtain benefits even when using reverse emulsions, couplers and developer and treatment solutions of other types if the cyclic quaternary ammonium salts of the specified type are incorporated into the silver halide emulsions will.

Example 4

According to the procedures described in Example 3 for the production of film sample A written procedure became a direct positive.s photograph! - such recording material is produced, with the exception that (a) no dye-forming coupler was used, (b) at Place of formyl-4-phenylhydrazine 2-methyl-3 * - / 3- (p-sulfophenylhydrazono) propyl7benzothiazolium bromide in such a con-

"" 2 ■ ■ ■

centering was used, as the number of feet per square meter of support area 0.29 mg (0.027 mg / sq.ft.) Was omitted, as well as (c) the spectral sensitizing dye

3,3'-di (3-eulfopropylJoxacarbocyaninhydroxyd-sodiumBalz in such concentration was added before 323 mg (30 mg / eq.ft.) were omitted.

2 was added in such a concentration that per m

After the trocia, the photographic recording material obtained became exposed and developed according to the method described in Example 2, with a silver image which qualitatively corresponded to the image obtained with the aid of the film sample 2 of Example 2.

Example 5

Following the procedure described in Example 4, a direct positive photographic recording material produced, with the exception that as a nucleating agent in place of

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2-methyl-3- / ~ 3 "- (p-sulfophenylhydrazono) propyl_7benzothiazolium bromide 1- (p-carboxyphenylhydrazono) propy1-2, 3,3-trimethyl-3H-indolium bromide was used in the same concentration. During exposure, development and work-up of the photographic obtained On the recording material, a silver reversal image was obtained which was qualitatively the same as that described in Example 4 The image obtained corresponded to the recording material.

Example 6

Two further direct-positive recording materials were produced according to the method described in Example 4, with the exception, however, that instead of 2-methyl-3- / ~ 3- (p-sulfophenylhydrazono) propyl_7benzothiazolium bromide, equal amounts of 2-methyl-3- / ~ 3- (p-toluenesulfonylhydrazono) pentyl _- 7-naphtho / ~ 2, l-d_7thiazolium iodide and 2-methyl-3- / ~ 3- (p-sulfophenylhydrazono) pentyl_7benzothiazolium iodide were used. After exposure and development as described in Example 4, silver reversal images of excellent quality were obtained «

009846/1273

Claims (17)

Patent claims Photographic recording material "consisting of a Layer support, at least one silver halide emulsion layer applied thereon, and optionally intermediate and / or top layers in at least one of the layers contains an additive acting as an anti-fogging agent and / or as a nucleating agent, characterized in that the additive of a cyclic quaternary ammonium salt in the form of a heterocyclic compound with a 5- or 6-membered ring containing the quaternary nitrogen atom, the quaternary nitrogen atom of which is substituted is by a remainder of the general formula: - - (CH ₂ ) _n -R where mean:. η = 2, 3, 4-, 5 or 6 and alkyl
R is a formyl or hydrazonoJü36Xli8rir radical or a radical of the general formula ^ * ^T 1 » -GH where T-j and Tp alone are alkoxy or alkylthio radicals, or together to complete a 5- or 6-membered cyclic oxyacetal or cyclic Thioacetal ringes represent required atoms. 2. Photographic recording material according to claim 1, characterized in that the additive consists of a cyclic quaternary ammonium salt of the following Formula consists of:. 009 8A 6/127 3 20208U Γ " t
• ι where mean: Z to complete a heterocyclic compound with a 5- or 6-membered, the quaternary ■ Nitrogen atom-containing ring required, made of carbon, nitrogen, oxygen, sulfur or Atoms consisting of selenium atoms, j = 1 or 2, a - 2, 3 »4, 5 or 6, X is an acid anion,
R is a remainder of the meaning given as well R _{1 is} a hydrogen atom or a short-chain alkyl, an alkylthio or aryl radical. _O the aralkyl radical. 3. Photographic recording material according to claim 2, characterized characterized in that the additive consists of a cyclic quaternary ammonium salt of the formula given, in the R, a methyl radical and X a halide anion, consistso 4. Photographic recording material according to claim 2, characterized characterized in that the additive consists of a cyclic quaternary ammonium salt of the formula given, in which is a = 2 consists. 5. Photographer's recording material according to claim 1, characterized in that characterized in that the additive consists of a cyclic quaternary ammonium salt of the following formula consists: 0098 4 6/1273 20208U Γ
ι (= CH-CH) ._ ι ir®
N-
I. 2 I. 2 CH
ι where Z, j ,. X and H _{1 have} the meaning given and in which also mean: g = 1, 2, 3f 4 or 5 and E ₀ . a formyl radical or a radical of the general formula -CH ι in the T ₁ and T ₂ the meaning given to have. 6. "Photograph! Β before s recording material according to claim -1, characterized in that the additive consists of a cyclic quaternary ammonium salt of the following formula: -. «—.— 2 —————— J- ' CH ₉ "■ ^: ö ■ ''"'' ■■■ ■. . ■ in which Z, J and X have the meaning given and R _{2 is} a monovalent formyl radical or a radical of the general formula ^>% γ , in which T ₁ and T «are for themselves 2 ■■■■: ■ ■. ^_■: - - ■ * alone alkoxy or alkylthio radicals having 1 to 4 carbon atoms, or together, to complete a 0 9 8 4 6/1273 BATH ORIGINAL, 20208H 1,3-Dithiolan-2-yl-, 1, ^ - Dioxolan-E-yl-, 1,3-Μ thian-2-yl- or 1, ^ - dioxane - ^ - yl-restes represent required atoms, 7. Photographic recording material according to claim 1, characterized in that the additive consists of a cyclic quaternary ammonium salt of the following formula consists: OH _{2 χ} θ CH, <? ^H 2> g-1 wherein Z, j, g and R _{1 have} the meaning given and represents a hydrazonomethyl radical. 8. Photographic recording material according to claim 1, characterized in that the additive consists of a cyclic quaternary ammonium salt of the following formula consists: Η® (^ CH-CH) ₄ ^ = C-GH, »Ι J ~ '■> CH ₉ Χ ^{θ R} 4 where Z, j _r and R. have the meaning given. 9. Photographic recording material according to claim 8, characterized in that the additive consists of a cyclic quaternary ammonium salt of the formula given, in which X is a halide anion and the by R. symbolized hydrazonomethyl radical means one of the following radicals: a phenylhydrazonomethyl, p-folylhydrazonomethyl-, 009846/1273 ρ -S ulf ophenylhy draz onome t hyl- » Thiosemicarbazonomethyl, Benzothiazol ^ -ylhydrazonomethyl-, p-Carboxyphenylhydrazonomethyl—,.: p-Tolylsulfohydrazonomethyl-,. ... p-Ohlorophenylhydrazonomethy1-, p-Wi-tr ophenylhydrazonome thyl-, li-phenylqarbamoylhydrazonomethyl, 2,4-di (methylsulfο) phenylhydrazonomethyl, 2 _f 4-dinitrophenylhydrazonomethyl or a * 3-quinolylhydrazonomethyl radical. 10. Photographic recording material according to claim 1, characterized in that the cyclic quaternary am- . monium salt 3- (2-iOrmylethyl) -2-methylbenzothiazolium bromide, 3- (3,3-diethoxypropyl) -2-methylbenzothiazolium iodide _l 3- (3f 3-diethylthiopropyl) -2-; methylbenzothiazolium iodide, 3- (2-formylethyl) -2-methyllepidinium bromide, 3- / 2 (1,3-dithiolan-2-yl) ethyl7-2-methylbenzothiazolium iodide, 3- / 2- (1,3-dithian-2-yl) ethyl7-2-ethylquinolium iodide, 3- / 2- (1,3-dioxan-2-yl) ethyl7-2-methylbenzoselenazolium bromide, 2-Methy1-3- / 3- (thiosemiearbazono) propyl7benzothiazolium bromide, 2-methyl-3- / T3-phenylhydrazono) propyl7benzothiazoliumbron ^ id, 2-methyl-3- / 3- (p-tolylhydrazono) propyl7benzothiazolium bromide, , -2-Methy 1-3- / 3- (p-sulfophenylhydrfe, zono) propyl7benzQ-, thiazο1iumbοrmid, 009846/1273 20208H 2-methyl-3- / 3- (benzothiazol-2-ylhydrazono) propyl7benzothlazolium iodide, ^ • 3- (4-Carboxyphenylhydrazono) propyl7benzothiazolium bromide, 2-ethyl-3 - /? - eulfophenylhydrazono) propyl7benzothiazolium chloride, . 3- (4-Garboxyphenylhydrazono) propyl7benzothiazolium bromide or 1- / 5- (p-Carboxyphenylhydrazono) propyl7-4-methylquinolium iodide consists. 11. Photographic recording material according to claim 7, characterized in that the silver halide emulsion layer a direct positive emulsion layer forming the latent image predominantly inside the silver halide grains consists. 12. Photographic recording material according to claim 11, characterized in that adjacent to the emulsion layer a dye forming coupler is arranged. 13. Photographic recording material according to claim 11, characterized in that in the silver halide emulsion layer the cyclic quaternary ammonium salt is present at a concentration of about 75 to 250 mg per mole of silver. 14 · PhotograpMe.ches recording material according to claim 13, characterized in that the silver halide emulsion is made aue of a gelatin-silver halide emulsion layer ^besiehtο:; ' 46/1273 - 20208H 15. Photographic recording material according to claims 7, 8 and 9f characterized in that the silver halide emulsion layer from one the latent image predominantly in the Direct positives forming the inside of the silver halide grains Emulsion layer consists, 16. Photographic recording material according to claim T, characterized in that the syllable halide component the silver halide emulsion layer consists of silver bromoiodide 17. Photographic recording material according to claim 1, characterized in that the silver halide emulsion layer a direct positive silver halide emulsion layer which forms the latent image predominantly in the interior of the silver halide grains and that the cyclic quaternary ammonium salt is made from one of the following heterocyclic compounds be ι 2-Hethyl-3- (3-thiosemicarbazonopropyl) benzothiazolium bromide _f 2- ^ Äethyl-3K3-phenylhydrazonopropyl) benzothiazolium ^ odide,, 2-methyl-3- (p-tolylhydrazonopropyl) benzothiaeoliurajodid, 2-methyl-2- (p-sulfophenylhydrazonopropyl) - * benzothiazolium bromide, 2-methyl-3- (benzothiazol-2-ylhydrazonopropyl) benzothiazoliuia iodide, ..v— 3 -. ^ 5_ (4_Carboxyphenylhydrazono) propyl7-2-ethylbenzothiazolium bromide or 2-Benzyl-3- / 5- (4-sulfophenylhydrazono) propylTbenzothiazolium chloride. 003846/1273