DE2016083A1 - Photographic process for making images - Google Patents

Description

Photographer's method of making pictures

The invention relates to a photographic method of manufacture of images, in which a photographic recording material, consisting of a layer support, at least a light-sensitive, silver halide-containing one applied to it Layer, and optionally intermediate and / or top layers, is exposed and developed in the presence of thiourazoles, and it also relates to a photographic recording material to carry out the procedure.

It is known to photographic images by exposure and development of photographic recording materials in the presence of so-called "antiplumming agents", i.e. means to prevent bluish air drying in High-gloss dry process, and / or thiourazoles acting as antifoggants, namely monothiourazole and dithiourazole compounds, e.g. i-phenyl-JjS-dithiourazole printable silver halide emulsion layers in which

009844 /! GOS

the latent image is formed predominantly inside the silver halide grains, as well as from U.S. Patent 3,396,017 photographic recording materials containing thiourazole directly copiable emulsion layers known. However, it is disadvantageous that such photographic recording materials, for example, those in which the latent image is mainly formed in the interior of the silver halide grains are not entirely satisfactory Images lead, for example, to images whose maximum density is not high enough and / or whose minimum density is not low enough and / or the stability of which is not sufficiently great when exposed to light for a long time. Same drawbacks also have known photographic recording materials of the specified type, which contain emulsion layers intended for rapid copying out. Unsatisfactory in Also with regard to antifriction action are known photographic recording materials of the specified type, the have chemically developable emulsion layers.

The object of the invention is to provide a photographic process and a photographic recording material, with the help of which images with improved properties, e.g. improved maximum and minimum density and stability, as well as reduced background fog, especially when using photographic recording materials with heat-stabilizable, copy-out silver halide emulsion layers.

The invention is based on the surprising finding that the stated object can be achieved in a particularly advantageous manner can be solved in that new addition compounds are used as a means for improving the image quality, which at the reaction of thiourazoles with organic compounds of a precisely defined structure.

The invention relates to a process for the production of images, in which a photographic recording material,

0098AA / 16Q6

consisting of a layer support, at least one light-sensitive, silver halide-containing layer applied to it Layer, and optionally intermediate and / or top layers, is exposed and developed in the presence of thiourazoles, which is characterized in that the exposed photographic Recording material in the presence of addition compounds of thiourazoles and CX jß-unsaturated organic Carbonyl compounds of the following or an equivalent tautomeric general formula:

N-

Il

Y-S-C. -G-X

in which:

X is a radical of the formula -OH, -SH, -NH ₂ or

-S-CHR ¹ -CHR ² -CR ⁵ , in which R ¹ and R ^{2 represent} hydrogen atoms or alkyl radicals with 1 to about 4 carbon atoms, and R represents an alkyl radical with 1 to 10 carbon atoms,

Y alone is a radical of the formula -CHR ¹ -CHR ² -CR ⁵ ,

1 ρ
wherein R and R have the meaning given

and R ^{5 represents} a hydrogen atom, a hydroxyl, amine, alkyl ether or alkyl radical having 1 to 10 carbon atoms, or

together with Z the necessary for the ring closure

divalent hydrocarbon radical of the formula OH

-OHR ¹ -Offi ^ -CR ⁴ "-, where R ¹ and R ² are as indicated

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Have meaning and that carry the OH group Carbon atom is intended to be bonded to the nitrogen atom, and in which R is also Represents hydrogen atom or an alkyl radical having 1 to 10 carbon atoms, as well as

Z alone represents a hydrogen atom, an alkyl radical with
1 to 8 carbon atoms or an aryl radical of
Phenyl or naphthyl series, or

together with Y the divalent hydrocarbon radical of the specified ones required for ring closure
Meaning,

where X does not represent a radical of the formula -S-CHR ¹ -CHR ² -8-R ⁵ when Y is a radical of the formula

1 2 ft 3

-CHR-OHR-C-R ^ means, optionally in the form of hydrazones, Phenylhydrazones, oximes, semicarbazones or thios emicarbazons.

The invention also relates to a photographic recording material for carrying out the process, consisting of a layer support, at least one photosensitive, silver-hlogenid-containing layer applied thereon, and optionally intermediate and / or top layers with "a content of thiourazoles in at least one of the solutes, the
is characterized by a content of addition compounds from thiourazoles and ζχ, ß-unsaturated organic carbonyl compounds of the general formula given.

The addition compounds which can be used for carrying out the process of the invention consist of bicyolic monoaddition products which are formed in the reaction of thiourazoles with ß X, ß-unsaturated aldehydes or ketones of the type indicated below, from monocyclic monoaddition products which are formed in the reaction of thiourazoles with <^, ß-unsaturated acids,
Esters, amides or ketones of the type given below enr.-

009844/1608 BAD

stand or from bicyclic diadducts, which in the Implementation of dithiourazoles with Λ, β-unsaturated ketones and / or aldehydes of the type specified in ink arise.

The addition compounds which can be used according to the invention can furthermore, since they contain free ketone or aldehyde groups, in ■ lorm of conversion products are present during the implementation of these ketone or aldehyde groups with reactive compounds, e.g. hydrazines, hydroxylamine, semicarbazides or Thiosemicarbazides are formed, e.g. in the form of hydrazones, Phönylhydrazonen, Oximes, Semicarbazonen or Thiosemi * - carbazones. -

To carry out the method of the invention it has been found as proven to be particularly advantageous, photographic recording materials with heat-stabilizable copy-out silver halide emulsion layers., their silver halide grains preferably include trivalent metal ions such as bismuth ions contain, and which the specified addition compounds are incorporated to use.

It has proven to be particularly advantageous to carry out photographs useful in the process of the invention Recording materials to incorporate the specified addition compounds in such a way that the used Addition compounds first dissolved in an alkaline solution and then in the form of the solution obtained for the Preparation of the photographic recording materials used emulsions are added, especially if it they are copiable, heat-stabilizable emulsions As a rule, the addition compounds are alkaline LÖBungen ^ elöet, the alkali metal hydroxides, alkali metal carbonates or contain organic amines. Eventually, you can the addition connection is also formed in the catfish and the Emulsions are incorporated that are intended for implementation Thlourasole or Dithlourazole with the of, 0-ungeBättig'-

• - ORIGINAL BATHROOM

ten orange compounds, e.g. aldehydes or ketones, in one alkaline medium, whereupon the resulting mixture is left to stand for at least about 1/2 hour and then is added to the emulsion used.

To prepare the addition compounds which can be used for carrying out the process of the invention, as a rule Thiourazoles of the following or a corresponding tautomeric general formula:

HN-

in which:

X is an oxygen or sulfur atom or an imino group and

R is a hydrogen atom, an alkyl radical with 1 to 8 carbon atoms, e.g. a methyl, ethyl, propyl, isopropyl, butyl or isobutyl radical, or an aryl radical of the phenyl or naphthyl series, e.g. a phenyl radical,

reacted with Oi ₁ ß-unsaturated organic carbony compounds of the following or a corresponding tautomeric general

formula _{1 o}

R ¹ R ^ ü

II It X

HC = C - 0 - R ^p

in the mean)

1 2
1 and R Waeeeretoffatome or Alkylreete with 1 to about

4- carbon atoms and R a hydrogen atom, a hydroxyl, amine,

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Alkyl ether or alkyl radical with 1 Ms 10 carbon atoms.

If thiourazoles of the given general formula are reacted with a £ K, ß-unsaturated organic aldehyde KXKX TSSäOääL of the given general formula, then bicyclic monoaddition compounds of the following or a corresponding tautomeric general formula are obtained:

12 4

in which X, R and R have the meaning given and R ^ "a Hydrogen atom or an alkyl radical having 1 to 10 carbon atoms means.

If thiourazoles of the given general formula are reacted with (X ₁ ß-unsaturated acids, esters or amides or ketones of the given general formula, then monocyelic monoaddition compounds of the following or a corresponding tautomeric general formula are obtained:

HN

1 ι ι H -χ .0 - S - G - C - 0 - R- ⁵

1 2 "5
in which X, R, R, R and R · 'have the meaning given

BATH ORIGINAL

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If dithiourazoles of the given general formula, in which R denotes a hydrogen atom, are reacted with 2 molar equivalents of CK , ß-unsaturated aldehydes and / or ketones of the given general formula, then bicyclic diaddition compounds of the following or a corresponding tautomeric general formula are obtained:

G-S-O-C-O-R

R ¹ 4

CH H JG-OH ^R

in which R, R and R have the meaning given and R · ^ represents an alkyl radical having 1 to 10 carbon atoms.

1 2 Of course, the radicals R and R can be one of the other have different meanings. R-> can also be a hydroxyl, Amino or alkyl ether residue.

The photographic recording materials useful for practicing the process of the invention contain, if it are those with chemically developable photosensitive, silver halide-containing layers, per mole of photosensitive Compound conveniently about 0.01 mg to 20 g, preferably about 0.1 mg to 10 g addition compound of the specified Type.

Is it the photographic recording materials used? around those with silver halide emulsions, thus they contain the specified addition compounds in two concentrations in such concentrations as they are for antifoggants are common, whereby in such cases preferred

0 0 9 8 k U t 1 8 0 6 BAD ORlGiNAL

wise addition compounds with an -alkyloarbonyl group be used.

It has proven to be particularly advantageous to the specified Addition compounds for photographic recording materials incorporated with silver halide emulsion solvents, the silver halide grains with incorporated therein are polyvalent en metal ions, preferably trivalent metal ions, e.g. bismuth or iridium ions. Typical suitable emulsions and emulsion layers of the specified type are e.g. in U.S. Patent 3W927.

Photographic recording materials with silver halide emulsion layers of the specified type can be exposed, heat-treated and with the aid of conventional known methods of light, e.g. according to that from the USA patent 3,418,122. Known Process. When using photographic recording materials with silver halide emulsion layers of the type indicated, it has proven to be expedient to add the indicated addition compounds to the SiI overhalide emulsion layers in concentrations of up to about 100 mol #, preferably from about 1 to 25 mol # on the existing silver. ■

Those useful in practicing the method of the invention Photographic recording materials can contain conventionally known additives, e.g. gelatine plasticizers, coating aids, Antifoggants, e.g. those based on azaindenes, as well as hardeners, e.g. aldehyde hardeners, for example formaldehyde, mucochloric acid, glutaraldehyde bis (ziatriurabisulfite), maleic acid dialdehyde, aziri dine, vinyl sulphonyl ether, dioxane derivatives and oxypolysaccharides. The silver halide muleioneso layers can also with the help Clay sensitizing dye «η, e.g. those of the USA- · Pateiitsolirift "" 2 526 632 and 2 503 776 described type, ö * h be. Typical suitable such spectral ben-

BATH

- 1D -

Sensitizers are e.g. cyanines, merocyanines, complex trinuclear ones Cyanines, complex trinuclear merocyanines, styryls and hemicyanines.

Optionally, the silver halide emulsion layers or layers adjacent to them can be used developer compounds may also be incorporated into photographic recording materials. As photosensitive compounds The most varied of customary known silver salts can be present, e.g. silver bromide, silver iodide, silver chloride or mixed silver halides, e.g., silver chlorobromide or silver bromoiodide. In the case of the silver halides used, they are those that form the latent image predominantly on the surface of the silver halide grains, or those that which form the latent image inside the silver halide crystals, such as in U.S. Patent 2,592 is described.

The photographic recording materials which can be used for carrying out the process of the invention can have silver halide emulsion layers, the binder of which consists of a wide variety of known hydrophilic, water-permeable substances commonly used for this purpose. Typical suitable binders of this type are, for example, gelatin, colloidal albumin, polyvinyl compounds, cellulose derivatives, aorylamide polymers and the like. Mixtures of the specified binders can also be used. The binders used to produce the emulsion layers can also contain dispersed polymerized vinyl compounds, 2.B. those of the type described in U.S. Patent Nos. 3,142,568, 3,193,386, 3,062,674, and 3,220,844. They can also contain water-insoluble polymers and latex polymeric polymers of alkyl acrylates and methaorylates, acrylic acid, sulfoalkyl acrylates or methaorylates and the like.

BAD ORiQJNAL

009844/1606

The photographic recording materials which can be used for carrying out the process of the invention can have a wide variety of conventionally known film supports. Typical suitable supports are, for example, supports made of. Oellulose nitrate films, Cellulose ester films, polyvinyl acetate films, polystyrene films, polyethylene terephthalate films, polycarbonate films and foils made of corresponding resinous substances, and also film supports made of glass, paper, metal and the like. It is also possible to use layer supports made of paper, which with CH-olefin polymers is coated, in particular with polymers of (^ -olefins with 2 or more carbon atoms, for example with polyethylene, polypropylene, ethylene butene copolymers and the same. "

Those useful in practicing the method of the invention Photographic recording materials can also contain jamulsion layers to increase sensitivity on customary known hydrophilic colloids, e.g. Oarboxymethyl proteins that described in U.S. Patent 3,011,890 Type ,, or polysaccharides of the type described in Canadian Patent 635,206.

Those useful in practicing the method of the invention Photographic recording materials can furthermore have light-sensitive emulsion layers which are conventionally known compounds that increase sensitivity, e.g. quaternary Ammonium compounds, polyethylene glycols or thioethers, incorporated are. It often proves to be expedient not to use such compounds which increase sensitivity to light To incorporate emulsion layers, but those used to develop the exposed emulsion layers to add photographic developer solutions.

Those useful in practicing the method of the invention photographic recording materials are in photographic

009844/1606

phic systems of the most varied types can be used, e.g. in the form of X-ray and other optically non-sensitized Systems as well as in orthochromatic, panchromatic and infrared-sensitized Systems. When using sensitizing additives can be added to these before or after the addition of the sensitizing dyes used.

The photographic recording material used to carry out the method of the invention can also be used for Color photography can be determined, i.e. it can be emulsion layers which contain the color-forming couplers or which with the aid of solutions, the couplers or other color-forming compounds contain, are developable. Furthermore, it can be photographic recording materials, to their Preparation Emulsions of the so-called miachpack type, for example of the type described in U.S. Patent 2,698,794, are used , or those that can be used for silver dye bleach systems, or those for their preparation Mixed grain type emulsions such as the type described in U.S. Patent 2,592,243 can be used.

The photographic ones which can be used for the production of the present invention Silver halide emulsions used for recording materials can be prepared according to known methods in the preparation of the emulsions methods commonly used, e.g., by treatment with naturally active gelatin or with the help of a wide variety of sensitizing sulfur, selenium or tellurium compounds and / or gold compounds. Furthermore, the emulsions can with the help of salts of noble metals of group VIII of the periodic table with be sensitized to an atomic weight of over 100.

The photographic recording materials used to carry out the process of the invention can also be used for Implementation of diffusion transfer processes are used in which this occurs in the non-image areas of the negative

009844/1606

present undeveloped silver halide in the manner for Generating a positive image is used that doesn't developed silver halide dissolved and deposited on a silver layer which was in contact with the original silver halide emulsion layer is brought into close contact, is precipitated. Methods of the specified type are described in numerous parts of the literature, e.g. in U.S. Patents 2,352 OH, 3,543,181 and • 3 020 155. The photographic recording materials used can also be used for color diffusion transfer processes be determined where the photosensitive on the exposed Layer of the recording material in an image-wise distribution present developer compounds, couplers or dyes. transferred to a second layer by diffusion while the two layers are in close contact.

To carry out the method of the invention, as already mentioned, photographic recording materials used in a particularly advantageous manner, which in one of their Layers contain the specified addition compounds. If appropriate, however, the addition compounds can also use the incorporated into photographic developers used to develop the exposed photographic recording materials as this also ensures that that the creation of the image in the presence of the antifoggant acting addition compounds takes place.

Will the specified addition compounds in silver halide emulsion layers when used, they are expediently used for the production of photographic recording materials used silver halide emulsions of the specified types incorporated during their manufacture. Is it the used phötographisehea record », materials around such With binder-free silver halide brackets, but also SiXberh ^ Logtni ^ on a suitable, Sohionttraättfgedti & pft fdLrdf so 'are the JAdi ti one connections

expediently on the vapor-deposited silver halide layers applied in the form of layers.

In the examples given below, addition compounds were used used, for the preparation of which the procedures designated in the following with A to T were used.

A) Production of 3- / B-Oarboxyäthylthio7-1,2,4-triazolin-

- 5-thion Z

3.6 g of acrylic acid were added to a suspension of 6.65 g of 1,2,4-triazolidine-3,5-dithione in 50 ml of water with stirring. After stirring for about 15 minutes at room temperature, the solids had dissolved and after stirring for about 1/2 hour a precipitate formed. The stirring was continued for a further 1/2 hour, after which the suspension obtained was cooled and the precipitate formed was collected. 11 g of crude product were obtained. The crude product obtained was recrystallized from dilute alcohol. The yield was 84 #, the melting point P β 204 to 205 ^° C.

B) Production of 3 - / # - methyl-ß-carboxyäthylthio7-1 »2,4-

triazοlin-5-thione

The process described under A) was repeated with the exception that crotonic acid was used instead of acrylic acid. The yield of Yerfahreneprodukt was 75 $, P ■ 196 to 198 ⁰ C.

C) Production of 3- / S-Carboxyäthylthio7-4-phenyl-1,2,4-

triazoline-5-thione

The procedure described under A) was repeated, with the exception that instead of 1,2,4-triazolidine-3 »5-ci- \ Jion on 1,2 _> 4-triazolidine-4-phenyl-3 _> 5 -dithion was referenced. The yield of process product was 93% S - 175 to 176 ⁰ O.

009844/1606

2016G83

D) Production of ^ - / ^ - !!, W-Dimethylcar'boxamidoätliylthio / - 4-uhenyl-i.2 _t 4-triazolin-5-thione

The procedure described under A) was repeated, with the exception that instead of 1,2,4-TrIaZoUdIh ^, 5- * dithione 1, ^^ - Triazolidin ^ -phenyl- ^ fS-dithione and instead of acrylic acid Ν, Ν -Dimethylacrylamide were used. The yield of process product was 82 #, P = 169 to 171 ^° C

E) Production of 3- / E-N, E-Dimethylearboxamidoäthylthio7-

1.2.4-triazoline-5-thione ; .

The process described under A) was repeated with the exception that N, N-dimethylacrylamide was used instead of acrylic acid. The yield of process product was 94 #, F = 190 to 192 ^° C.

F) Production of ^ - / B-Carbobutoxyäthylthioj-I »2,4-

triazoline-5-thione .. -

The process described under A) was repeated with the exception that butyl acrylate was used instead of acrylic acid. The yield of process product was 78 $> \ P = 110 to 112 ^° C.

G) Production of 3- ^ B-Carboxamidoäthylthio7-1 '»- 2» 4 ---

triazoline-5-thione _; -

The process described under A) was repeated with the exception that acrylamide was used instead of acrylic acid. The yield of process product was 82 #, F = 208 to 210 ⁰ C, "

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H) Production of 3- / B-methyl-ß-carboxamidoethylthio7- 1,2,4-triazolin-5-thione

The procedure described under A) was repeated with the exception that instead of acrylic acid methylacrylamide was used. The yield of process product was 61? S, F «202 to 205 ° C.

I) Preparation of 3- / B-carbethoxyethylthio7-1,2,4-triazoline- 5-thione

The process described under A) was repeated with the exception that ethyl acrylate was used instead of acrylic acid. The yield of process product was 73 $> ϊ ¹ = 102 to 104 ° 0.

J) Preparation of 1-phenyl-3i5-dithiourazole

This known compound was produced according to the procedure described in "Reports of the German Chemical Society" (1904), Volume 1, page 184 (37th year), described procedure.

K) Production of 3- / B-Oarboxyäthylthio7-1,2,4-triazolin-

5-on

The procedure described under A) was repeated, with the exception that 1 ^^ - Triazolidin ^ -thion-S-one was used instead of 1,2,4-triazolidine-3,5-dlthione. The yield of process product was 90 #, F * 188 to 189 ⁰ O.

L) Preparation of the monoaddition compound from dithiourazole and crotonaldehyde

A suspension of 53.2 g (0.4 mol of dithiourazole in 400 ml of a mixture consisting of 1 part alcohol and 1 part water) was obtained Mixture at room temperature with stirring

0098UM60S. BATH

28 g (0.4 mol) of crotonaldehyde were added. The suspension obtained warms up while stirring and after about 15 minutes a clear solution was obtained. It was found to be expedient to heat the reaction solution obtained to 60 to 70 ° C. and then, if necessary, to filter it. The mixture was stirred for a further hour, after which the reaction solution was cooled. A precipitate formed which was filtered off and washed on the filter funnel twice with 50 ml of an acidic mixture of 1 part alcohol and 1 part water. The washed precipitate was added at 75 ⁰ C in a vacuum oven dried. A 1st fraction was obtained in a yield of 47 to 49 g »F = 190 to 192 ^° C.

The filtrates obtained on filtration of the precipitate were combined and concentrated to about 2/3 of the original volume, whereupon the concentrate obtained was cooled and inoculated with a crystal of the indicated 1st fraction. In this manner, a 2nd fraction in a yield of 12 to 13g, was F = 189-191 ⁰ C is obtained, so that the overall yield of process product is 59 to 62 g, corresponding to 73 to 77 was fif ·

The addition compound obtained could be recrystallized from 50% alcohol in yields of over 90%. The recrystallized product had a melting point of. P = 191 to 192 ⁰ C. on.

M) Preparation of 3- (ß-acetylethylthio) -1,2,4-triazoline · * · -5 -thione ; ,

6.7 g of dithiourazole were added to 3.5 g of methyl vinyl ketone in 50 ml of an aqueous 50% ethyl alcohol solution added Eb there was an immediate reaction, with stirring

Allowed to progress for a long time at Zimjserteiaperatur Pai obtained mixture was absitsengelaeaen and on

then filtered. The process product obtained in a yield of 10 g was crystallized from ethyl alcohol and then dried. The yield was 8.5 g, P = 146.8 ⁰ C. After Umkristaliisation had the Yerfahrensprodukt a melting point of 152.4 F = ⁰ C.

Analysis: Calculated: C, 35.5; H 4.4; N 20.7; S $ 31.5> found: C 35.8; H 4.2; N 20.7; S £ 31.2

N) Preparation of the diaddition compound from dithiourazole and methyl vinyl ketone, or methyl vinyl ketone in combination with acrolein

Method A:

A suspension of 9.5 g of the monoaddition compound according to the method described under M) and 3.5 g of methyl vinyl ketone in 100 ml of 50% aqueous ethanol was stirred for 18 hours at room temperature. After about 1/2 hour the pests dissolved and after about 6 hours a precipitate began to form. The resulting suspension was cooled, whereupon the precipitate formed was collected and recrystallized from ethanol. The yield of process product was 10.2 g, P = 126 to 127 ^° C

Analysis! For C ₉ H ₁₃ N ₅ O ₂ S ₂ : calculated: N 16.2 %

found: N $ 16.5>

Method Bi

Ee became a suspension of 5.1 g of the monoaddition compound according to the procedure described under M) in 40 ml • a mixture of 2 parts water and 1 part ethanol, which also contained 1.5 g of acrolein, stirred for 1/2 hour at room temperature. The solids dissolved within 1/2 hour with development of heat and on cooling the reaction mixture formed a precipitate

00984W1606

blow. The precipitate formed was collected and then crystallized from ethanol. The yield of process product was 5.3 g, F = 124 to 126 ^° C. The process product obtained had the same melting point, the same mixed melting point and the same IR spectrum as the process product produced using method A. - "χ

0) Preparation of the addition compound from monothiourazole and acrolein -

A suspension of 11.7 g of monothiourazole and 5.6 g of acrolein in 50 ml of 50% aqueous ethanol was stirred at room temperature. After 1 hour the solids dissolved and stirring was continued for an additional 2 hours. The reaction solution obtained was then cooled, and 15 g of the crude product were obtained. After recrystallization from 50% aqueous ethanol, 10 g of process product, F = 209 to 210 ^° C., were obtained. . ·

Analysis, for C ₅ H ₇ N ₅ O ₂ S: Calculated: N 24.3 #

found: N $ 24.5>,

P) Preparation of the addition compound from monothiourazole and orotonaldehyde - '

A mixture of 3.0 / monothiourazole and 1.8 g of crotonaldehyde in 20 ml of 50% aqueous ethanol was stirred for 2 hours at room temperature. After cooling, 3.3 g of precipitate were obtained, which was crystallized from ethanol. The process product obtained had a melting point of F = 217 to 218 ^° C.

Analysis for C ₆ H ₉ NjO ₂ Ss -

calculated: G 38.7? H 4.8; N 24.8; S 16.1 # found: C, 38.3; H 5.2; N 24.5; S 16.5 ^

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Q) Preparation of the mono- and diaddition compound from dithiourazole and methyl vinyl ketone

Dithiourazole was allowed to react with 2 moles of methyl vinyl ketone in water while cooling with ice. The monoaddition compound was formed in the form of a precipitate in an almost quantitative yield within a short time. The melting point of the monoaddition compound was P = 152 to 154 ⁰ O.

The obtained monoaddition compound was allowed to react in water for further 18 hours at room temperature with stirring, whereby it gradually dissolved to give the diaddition compound, which precipitated in high yield when the reaction mixture was cooled. The melting point of Diadditionsverbindung was P = 82 to 84 ⁰ C.

R) Preparation of the oxime of 3- / "- ketobutylthio-1,2,4- triazoline-5-thione

10.15 g of the addition compound described under M) were dissolved in 100 ml of 50% aqueous ethyl alcohol. The solution obtained was admixed with 3.5 g of hydroxylamine hydrochloride and 4.1 g of anhydrous sodium acetate, yellow in 50 ml of water. A reaction set in immediately upon mixing. After the completion of the same, the reaction product formed was allowed to settle and, after the reaction mixture was cooled, collected. The yield of product of the process was 10 g, F = 194.5 ⁰ O.

N analysis for OgH ₁₀ ON.S ₂ : calculated: / 25.7 Jd

found »N 25.7 96

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S) Preparation of the 4-methyl-3-thiosemicarbazone of 3 - ^ - ketobutylthio-1, 2 _> 4-triazolin-5-thione

10.15 g of the addition compound described under M) were dissolved in 50 ml of 50% aqueous ethyl alcohol. The resulting solution was mixed with 5 »25 g of 4-methyl-3-thiosemicarbazide in 50 ml of 50% aqueous ethyl alcohol. After the reaction had ended, the reaction product formed was allowed to settle, cooled and filtered. The yield was 15 g, Ϊ = 187.9 ⁰ C

Analysis for C ₈ H ₁ -U ₆ S ,: Calculated: .If 29.0 56

found: N 28.6 %

T) Preparation of the phenylhydrazone of 3 - ^ - ketobutylthio-1,2,4-triazolin-5-thione

For example, 10.1 g of the addition compound described above about M) were dissolved in 100 ml of 50% aqueous ethyl alcohol, whereupon the resulting solution was at the boiling point for 1/4 hour
was reacted with phenylhydrazine for a long time. 8 g of reaction product were obtained in the form of a precipitate, P = 155 ^° C.

Analysis ^{calculated for c} i2 ^H 15% ^S 2 ': N 23.9 °

found N 23.7 #

The following examples are intended to explain the invention in more detail. 1

froben der ünte3? A) Ms * T) the addition compounds described above can be mixed up in a highly sensitive, with
Help eii & ee CJyi & niiafarisstoffeö panöhromatisoh sfinsibilized

eye emtzt * The received liaul

Sion samples were made on cellulose acetate films

ρ layer carrier applied in such a way that per m carrier area It accounted for 4.95 g of silver (459 mg / sq. Ft.) And 11.2 g of gelatin (1040 mg / sq. Ft.). Samples of the obtained photographic Recording materials were then exposed on a so-called "Eastman 1B" sensitometer, whereupon they Developed for 5 minutes in a developer of the following composition:

N-methyl-p-aminophenol sulfate 2.5 g

Sodium sulfite, anhydrous 30.0 g

Hydroquinone 2.5 g

Sodium metaborate 10.0 g

Potassium bromide 0.5 g

made up to 1 liter with water

The developed film samples were fixed, washed and dried, whereupon they were subjected to the usual known sensitometric tests. The results were as follows obtain:

009144/1606

Additions L) ' ReI. fresh veil at ReI. 2 weeks incubation. ■■ ·; ^; rel. · ■ -. ■ link Sensation Sensation 49 ⁰ C and 50 <fo (g / mol lichk. lichk. humidity 0.15 veil 100 y value 0.11 34 /"-Value (-) 65 0.09 43 Compare (0.09) 57 0.12 36 0.66 O sample (0.09) 85 1.29 0.13 69 . 0.96 0.13 O
(O A. ('0.009) 76 1.03 0.11 58 0.98 0.10 00 B. (0.09) 67 0.87 0.12 47. 0.80 0.22 Q (0.09) 74 1.22 0.11 48 1.20 0.17 I) (0.09) 58 1.17 .0.10 34 1.10 0.15 O) B. (0.09) 62 1.15 0.12 49 1.10 0.20 en F. (0.09) 55 1.17 0.14 44 1.08 0.15 G (0.09) 83 1.07 60 0.87 0.16 H (0.09) 1.15 1.20 0.19 I. 1.20 1.12 0.28 J 1.43 1.13

CD O OO

The results show that the usable according to the invention Addition compounds, the preparation of which was carried out according to the procedures described under A) I), in photographic Emulsions act as better antifoggants than known antifoggants, namely that described under J) 1-phenyl-dithiourazole.

Example 2

A sample of the addition compound described under K) became a highly sensitive, panchromatically sensitized Incorporated silver bromoiodide emulsion, followed by the obtained Emulsion applied to a base made of a cellulose acetate film and the resulting photographic Recording material according to that described in Example 1 Process was exposed and developed. In a corresponding manner, a comparison sample that was free of addition compounds was made and tested. the The results obtained are shown in the following table:

0098ΛΑ / 1606

fm Sting HeI.
Recommend'-
lichk. fresh veil 2 weeks incub
at 49 ⁰ O and 50 f
humidity rel. 100
82 jT value 0.15
0.11 ReI. /"-Value
Sensation
lichk. veil Cf.
sample (-)
. (3.0.) 1.66
1.67 32 0.91
60 1.02 0.77
0.10

The results show that the addition of the specified addition compound leads to a high stabilizing and anti-fogging effect.

Example 3

It became a radiation-sensitive gelatin silver bromoiodide photographic emulsion made as in the USA

P * t «nt8chrift 3 447 927 described.

Samples of the emulsion obtained were mixed with the following halogen acceptors and aldehydes:

Sample 1: dithiourazole hydrazine salt (20 g / mol) and Formaldehyde (15 g / mol)

Sample 2: Dithiourazole (20 g / mol) and crotonaldehyde (20 g / mol)

Sample 3i dithiourazole crotonaldehyde monoaddition compound according to working method L).

The emulsion samples obtained were

2
ger made of paper in such a way that per m of carrier

area accounted for about 755 mg of silver (70 mg / sq.ft.).

The photographic materials obtained
were then imagewise for 1 second through a density wedge with a continuous density with a
500 watt Iampe exposed, whereupon it on an aluminum blook at a block temperature of 235 ⁰ C for 5 seconds
were heated. The resulting film samples were then exposed to two 8 watt ultraviolet lamps for 5 minutes
developed at a distance of 12 cm by exposure to light.

009844/1606

Individual samples of the developed recording materials obtained were then exposed to fluorescent room light in the following manner: No irradiation (comparative sample) 24 Hours of exposure - 7 days of exposure - H days of exposure. The following results were obtained: ■■

under-heat stabilized at

sought exposure to gluorescent light

PiIm- comp. 24 hours 7 days 14 days

sample sample.

max min max min max min max min

1 1.12 0.20 1.22 0.27 1.30 0.42 1.30 0.42

2 1.00 0.16 1.12 0.22 1.20 0.41 1.21.0.44

3 0.92 0.08 1.15 0.10 1.28 0.16 1.32 0.1-9

The results clearly show the advantages to be achieved by adding an addition compound of the specified type in Regarding the maximum and minimum density of the images obtained. '

Example 4

A radiation sensitive gelatin silver bromide iodide photographic emulsion was prepared as described in U.S. Patent 3W927.

Samples of the emulsion obtained were measured with a spectral sensitizing dye at a concentration of 150 g Dye per mole of silver and the following addition compounds, labeled a to i:

BATH ORIGINAL 0098ΛΛ / 1606

a) 3- ^ 2-Garboxamido-ß-methylethylthio7-1,2,4-triazoline-5-thione ;

b) 3- / S-Oarbobutoxyäthylthio7-1,2,4-triazolin-5-thione;

c) 3- / 2-aoetylethylthio) -1,2,4-triazoline-5-thione;

d) 6, 7-dihydro-5-hydroxy-5-triazolo _< / 3 , 4- *> 7- / Τ »27-

thiazin-3- / 2H, 5H7thione;

ethyl

e) 3- (carbethoxyfthio) -1, 2,4-triazoline-5-thione;

f) 3- / S-carboxyethylthio7-1 »2,4-triazoline-5-thione;

g) 3- (ß ~ acetylethylthio) ~ 6,7-dihydro-5-hydroxy-5-

methyl-5-H- »- triazolo / 3,4-b7 / T, 37-tmazine;

h) 3- / B-0arboxyethylthio7-4-hydroxy-1,2,3a-triaza ~

7-thia-4,5 »6-trihydroindene;

i) 3- / B-Acetylethylthio7-4-hydroxy-6-ynethyl-1,2,3a-triaza-7-thia-4 »516-trihydroindene;

The emulsion samples obtained were made on film supports

2 Paper applied in such a way that about 755 mg of silver (70 mg / sq.ft.) Were used per m of support surface. The film samples were then exposed, then heated for 5 minutes on a group consisting of "Teflon" surface to 25O ⁰ C and finally developed with the aid of light. The following results were obtained:

009844/1606

Added Addition link (g / mol Ag) a 15th b 15th C. 34 d 15th e 15th f 34 G 34 H 34 i 46 Example 5

Max 0.16 0.86 0.12 0.70 0.05 1.30 0.14 1.20 0.08 1.12 0.07 1.04 0.04 1.16 0.04 1.13 0.04 1.09

This example shows the influence that the working conditions under which the addition compounds give the silver halide emulsions be incorporated, exercise.

It became a radiation-sensitive gelatin silver bromoiodide photographic emulsion made as described in U.S. Patent 5,447,927.

The type of compounds added and the conditions under which the addition was made are shown below. The specified compounds were incorporated into the emulsions in concentrations of 20 g / mol. Furthermore, the spectral sensitizing dye i-XtiiyX-S ^ J-ethyl-a-benzothiazolinylideÄ) -1 * was added to the emulsions in a concentration of 150 mg / mol silver meth3rliden7-2-thio-2,4-oxazolidinedione added * The emulsions obtained were then applied to the support, whereupon the skin samples obtained were exposed, initially heated for 5 seconds at a temperature of 235 ⁰ O to a liquid blanket and finally developed with the help of Mekt »

- 50 -

Is the following connection lengths were used and the following Conditions of addition applied:

Sample 1 - An addition compound of the one described under L) Type was dissolved in methanol and added to the specified emulsion in the form of the resulting solution. The resulting emulsion was coated on a support at pH 5.0.

Sample 2 - An addition compound of the type described under L) was dissolved in methanol and obtained in the form of Solution of the specified emulsion added. The pH of the emulsion obtained was with Sodium hydroxide adjusted to pH 6.5, whereupon the emulsion was applied to a support.

Sample 3 - An addition compound of that described under L) Type was dissolved in water, whereupon the resulting solution after adjusting the pH to 11.4 with Sodium hydroxide was added to the specified emulsion. The emulsion obtained was at applied to a layer support at a pH of 6.5.

Sample 4 - Equal parts by weight of dithiourazole and Orotonaldehyde mixed in water, whereupon the resulting mixture after adjusting the pH to 11.4 with the help of sodium hydroxide about 1/2 hour left standing for a long time and then the specified Emulsion was added at a concentration of 40 g / mole silver. The resulting emulsion became applied to a substrate at a pH of 6.5.

009844/1606

Sample 5 - An addition compound of that described under M) Type was dissolved in water, whereupon the resulting solution after adjusting the pH to 11.4 with With the help of sodium hydroxide, left to stand for about 1 hour became. The specified addition compound, which is in chemical equilibrium, was then in the form of the resulting solution of the specified Emulsion added at a concentration of 25 g / mole silver. The emulsion obtained was at a pH 6.5 applied to a layer support.

The pilm samples obtained were tested in the manner indicated. The following results were obtained:

Sample results of photographic tests

^D min Υ value Eel. sensitivity 1 0.10 0.40 100. 2 0.10 0.54 132, 3 0.09 0.74 501 4th 0.12 0.63 631 5 0.06 , 0.80 / 631

The results obtained show that emulsions with significantly improved photographic properties, e.g. comparatively high photographic sensitivity can be obtained when the dithiourazole compounds specified .and (X, ß-unsaturated carbonyl compounds formed Addition compounds first in an alkaline solution must be dissolved before they are added to the emulsions.

Correspondingly advantageous results were obtained when the Replaced addition compounds from crotonaldehyde and dithiourazole were carried out using acrolein and dithiourazole or acrylic acid and monothiourazole according to the procedure

009844 / 1.606

- 32 E) produced addition compounds.

Correspondingly advantageous results were also obtained when the resulting alkaline solutions of the addition compounds are evaporated to dryness and the solids obtained were dissolved in water before being added to the emulsions «

Example 6

This example shows that the specified addition compounds also in the form of the keto or aldehyde groups present in the reaction with reactive ones The reaction products formed in compounds exert their advantageous anti-fogging and stabilizing effect.

Emulsion samples of the type described in Example 1 became the following addition compounds and reaction products incorporated by addition compounds:

a) Oxime of 3- / -Ketobutylthio-I, 2,4-triazolin-5-thione;

b) semicarbazone of 3-y-ketobutylthio-1,2,4-triazoline-5-thione;

c) Phenylhydrazone of 3 ~ ^ ~ / ^fc -Ketobutylthio7-1,2,4-triazolin-5-thione j

d) 3- (β-carboxyethylthio) -4-methyl-1,2,4-triazolin-5-one; e) 3- (^ -ketobutylthio) -4-methyl-1,2,4-triazolin-5-one; f) 3- (f-ketobutylthio) -4-methyl-1,2,4-triazoline-5-thione;

g) 4-hydroxy-4,5,6,7-tetrahydro-7-thia-1,2,3a-triazaMMüqc-indene-3-thione;

h) 6,7-dihydro-5-hydroxy-3 (γ-ketobutylthio) -7-methyl-5H-e-triazolo / 3,4-b7- / T, 37-thiazine _;

BATH ORIGINAL 00984W1606

i) 3- (β-Acetylethylthio) -6,7-dihydro-5-hydroxy-6-methyl / 3-H7-s-triazolo / 3,4-b // T »37-thiazine;

ethyl

j) 3- (Öarbäthoxy / Ehio) -6, T-

, 37-thiazine;

ethyl

k) 3- (CarbathoXyffchlo) -6,7-dihydro-5-llydroxy- _< / 5H7-s -tri-

azolo - / ^ >> 4-57 / ¹ T >> 37- "tM azin; iy 3_ (^ -Ketobutylthio) -5-oxo-1,2,4-triazolidine;

m) 3 (öi -Methyl-ß-carbäthoxyäthylthio) .- 1,2,4 ~ triazoline-5-thione;

With the aid of the emulsion samples obtained, photographic Recording materials manufactured and tested. The following results were obtained

fresh

Addition-

2 weeks incubation at 49 C u, 50 H> rel.humid.

connection
(g / mole) (-) HeI.
Sensation
lich *. /"-Value veil ReI.
Sensation
lichk. _r value veil Yergl.
sample (0.09) 100 1.41 0.16 35.5 0.99 0.72 a ) 0.09) 82 1.17 0.11 71 1.18 0.29 b (0.009) 71 1.27 0.10 62 1.17 0.34 C. (3.0) 85 1.38 0.11 74 1.30 0.15 d (0.06) 91 1.72 0.11 59 1.15 0.17 e (0.03) 118 1.55 0.10 62 1st, 20th 0.27 f (0.12) 120 1.68 0.10 67 1.30 0.18 G (0.15) 102 1.45 0.15 24 0.83 0.26 H (0.75) 95 1.48 0.12 52 1.00 0.25 i (0.15) 91 1.43 0.11 73 1.03 0.15 j (0.15) 74 1.40 0.14 71 1.25 0.22 k (0.75) 71 1.25 0.12 80 1.22 0.19 1 (0.09) 53 1.10 0.14 33 0.88 0.17 m 60 1.43 0.13 52 1.13 0.15

O OO CJ

Example 7

This example shows the beneficial anti-fog and Stabilizing effect of addition compounds of the specified type in recording materials intended for color photography.

A gelatin-silver bromoiodide emulsion was sensitized to red light with the aid of sulfur and gold sensitizers, the cyan dye forming phenolic couplers of that described in U.S. Patent 2,474,293 and there with "Compound 1" designated type in the form of a dispersion. Individual The following addition compounds were incorporated into emulsion samples:

a) 3- / ß "-carboxyethylthio7-1,2,4-triazolin-5-thione;

b) 3- / B-IT, N-dimethylcarboxainidoethylthio7-4-phenyl-1,2,4-triazoline-5 ^ thione;

c) 3- / B-methyl-ß-carboxyethylthio7-1,2,4-triaaolin-5-thione;

d) 3- / S-methyl-ß-carbomethoxyethylthio7-1,2,4-triazoline-5-thione;

e) 3- (2-acetylethylthio) -4-phenyl-1,2,4-triazole * 5-thione; f) Oxime des 3-V ^ -Ketobutylthio-1,2,4-tr ± azoline-5-thione .;

g) 3- (ß-methyl-ß-carbäthoxyäthylthio) -1,2,4-triazoline-5-thione;

The emulsion samples obtained and an emulsion sample free of addition compounds and used as a comparison sample, were on film base made of cellulose acetate films in the Applied so that (m7 support area 1.08 g of silver

009844/1606

(100 mg / sq.fto) and 2.93 g gelatin (272 mg / sq.ft.) Were omitted. The film samples obtained were exposed in a so-called "Eastman 1B sensitometer", whereupon the exposed Film samples using the process known as the Eastman Oolor Negative Process C-22, 12 minutes have been developed for a long time. The photographic tests carried out resulted in those listed in the following table Results.

009844/1606

happy

1 week incubation

(i / ml

C «■

Sensation

100

a (0 | 02) 89 % (0.06) 91 C. (0.02) ή a (0.036) 65 e (0.18) 91 f (0.045) 50 e (0.03) ° 62

1.22

Söhieiei?

0.12

1.15 0.11 1 * 27 0.05 1 * 05 0.07 1 | Ö3 0.05 1.12 0 * 07 0.07 0.04 1.13 0.06

Rfel *

lichk *
91

85
94
74
95
105

123

0.85

0.98 0.98 0.77 0.91 0.92

0.85 1.12

Schlei he

0.24

0.14 0.11 0.13 0.11 0.13 0.14

0.16

- 58 -

Example 8

This example shows "that in photographic emulsions which contain hydrophilic colloids, e.g. gelatin, as binders, in combination with the specified hardening agents, vinyl sulfonyl ethers are particularly advantageous as hardening agents be used.

Eb has a radiation sensitive silver bromoiodide gelatin whose halide component consisted of 6 mol% of iodide and silver halide grains which were precipitated in the presence of bismuth ions produced, namely by the procedure described in US Patent 3,447,927 method.

The emulsion obtained was in the manner on a paper

P layer carrier applied that per m carrier area about

0.65 g silver (60 mg / sq.ft.) And 5.9 g gelatin (550 mg / sq. ft.). The emulsion used contained 2.4 g of bis (vinvlsulfonylmethyl) ether / and 34 g of one per mole of silver alkaline solution of 3- (1-thiapentan-4-one) -1,2,4-triazolin-5-thlone with a pH of 11.2.

The photographic material obtained with hardened Gelatin layer was exposed and developed as follows!

(1) Exposure for 1/10 seconds on a so-called ^w E * etman 1B-Sensitometer ^M through a step wedge with 0.15 dioh steps;

(2) 4 seconds of heating to 235 ^° C. on an inclined plate as well

(3) Developing for 5 minutes with the aid of light at a distance of 15 »25 cm using a reflector photo lamp Mr. 2.

/ "« 1 · Hlrtun «s» ittel

The developed film sample revealed 16 visible steps and had a maximum density of 1.27 and a minimum density of 0.09.

0098ΛΑ / 1606

Claims (16)

Claims Photographic process for the production of images, in which a photographic recording material consisting of a support, at least one light-sensitive, silver halide-containing layer applied thereon, and optionally intermediate and / or top layers, is exposed and developed in the presence of thiourazoles, characterized in that: the exposed photographic recording material is developed in the presence of addition compounds from thiourazoles and Qi , β-unsaturated organic carbony compounds of the following or a corresponding tautomeric general formula: ! J- Y-S-C in which: X is a radical of the formula -ÜH, -SH, -NH ₂ or -S-GHR ¹ -CHR ² -OR ⁵ , wherein R ¹ and R ^{2 are} hydrogen atoms or an alkyl radical having 1 to about 4 carbon atoms, and R- ^{3 is} an alkyl radical having 1 to Represent 10 carbon atoms, Y alone is a radical of the formula -CHR ¹ -0HR ² -CR ⁵ , 1 2
in which R and R have the meaning given and R is a hydrogen atom, a hydroxyl, amine, alkyl ether or alkyl radical having 1 to 10 carbon atoms, or 00984W1606 ■ - 41 - together Z rait what is necessary to close the ring divalent hydrocarbon radical of the formula OH ■ -GHR -CHR-CR ⁴ -, in which R and R have the meaning given and the carbon atom bearing the OH-G group is intended to be bonded to the nitrogen atom, and in which "87" is a hydrogen atom or an alkyl radical having 1 to ^N 10 Represents carbon atoms, as well Z alone is a hydrogen atom, with an alkyl radical 1 to 8 carbon atoms or an aryl radical of Phenyl or haphthyl series, or together with Y the divalent ones required for ring closure Hydrocarbon radical of the specified Meaning, · where X does not represent a radical of the formula -S-CHR-CHR-CR ⁵ when Y is a radical of the formula -CHR -CHR ² -CR ^ means, optionally in the form of hydrazones, phenylhydrazones, oximes, semicarbazones or thio-. s emi c arbazonen. 2. The method according to claim 1, characterized in that addition compounds are used which arise in the form of bieyclischen monoaddition products in the reaction of thiourazoles with <X, ß-unsaturated aldehydes or ketones , or in the form of monocyclic monoaddition products in the implementation of Ihiourazoles with OC _f ß-unsaturated acids, beters or amides, arise _t or in the form of bicyclic diadducts in the reaction; of dithiourazoles with pi | ß-unsaturated ketones and / or aldehydes are formed 003844/1606 3. The method according to claims 1 and 2, characterized in that that one uses addition compounds that are used in the reaction of thiourazoles or dithiourazoles with orotonaldehyde or methyl vinyl ketone or mixtures of crotonaldehyde and methyl vinyl ketone are formed. 4. Process according to Claims 1 to 3, characterized in that that as addition compounds 3- (ß-acetylethylthio) -1 , 2,4-triazoline-5-thione, 3- (carbethoxythio) -1,2,4-triazoline-5-thione or 3- / S-acetylethylthio7-6,7-dihydro-5-hydroxy-5-methyl-5H - »- triazolo / 3", 4-b7 / T, 27-thiazine used. 5. The method according to claims 1 to 4, characterized in that photographic recording materials with silver halide emulsion layers, which the addition compounds are incorporated. 6. Process according to Claims 1 to 5 »characterized in that that photographic recording materials with silver halide emulsion layers, their silver shark grains included trivalent metal ions, and those the addition compounds are incorporated in concentrations in which antifoggants are usually present, used. 7. The method according to claim. 6, characterized in that photographic recording materials s with silver halide emulsion layer containing bismuth ions included whose Silberhalogenidkb'rner and those addition compounds, used in the form of Diadditonsprodukten in concentrations of about 1 to 25 moles #, based on silver present, einvefc "leibt are. 009841Μβ0β - ■ 43 - " 8. The method according to claims 1 to 7, characterized in, that photographic recording materials are coated with silicon-overhalide emulsion layers, which contain a hydrophilic colloid as a binder and a vinyl sulfonyl ether as a hardener, are used. 9 »Process according to claims 1 to 5» characterized in that that photographic recording materials intended for color photography, which contain the addition compounds in concentrations in which usually antifoggants are used. 10. Procedure naißh. Claims 1 to 9 »characterized in that that photographic recording materials with silicon halide emulsion layers, which addition compounds with an alkylcarbonyl group are incorporated in concentrations in which antifoggants are usually present, used. . . 11. The method according to claims 1 to 10, characterized in that that photographic recording materials are used, for the preparation of which the addition compounds are initially described in Dissolved alkaline solutions, then the solutions obtained are added to the emulsions and then the obtained solutions Emulsions are applied to the substrate. 12. The method according to claims 1 to 10, characterized in that that photographic recording materials are used, for their production first the thiourazoles and 0 (, ß-unsaturated organic Garbony! compounds in alkaline -Solutions mixed, then those obtained in the form of solutions Addition compounds are added to the emulsions and then the emulsions obtained on the substrate be applied. 13 · The method according to claim 12, characterized in that one heat-stabilizable photographic recording materials which can be copied out used. 14 · The method of claims 1 to 4, characterized in that photographic recording materials with s binderless, vapor deposited Si lberhalogeni ds chi hastened adjacent tienen the addition compound s are arranged in the form of layers used. 15. The method according to claims 1 to 4, characterized in that one uses photographic developers in which the addition compounds are incorporated, 16. Photographic recording material for implementation of the method according to claims 1 to 15 »consisting of a layer support, at least one applied thereon light-sensitive, silver halide-containing layer, as well optionally intermediate and / or outer layers, with a content of thiourazoles in at least one of the layers, characterized by a content of addition compounds from thiourazden and i \, ß-unsaturated organic carbonyl compounds of the following or a corresponding tautomeric general formula: -N Il Y-S-C ^ ^ G-X Z in which mean: X is a radical of the formula -OH, -SH, -NH ₂ or c 1 -R ", where R and I. > twa -S-ÜilH ¹ -OEH ² -GR ⁵ , wherein R ¹ and R ^{2 are} hydrogen atoms or alk, ylreate with 1 to / 4 Rohlenstoff- 009844/160 6; BAD ORiGiNAL atoms, and B, an alkyl radical with 1 to Represent 10 carbon atoms, Y by itself is a remainder of the formula -GHR ¹ -OHR ² -GB ^, 1 2
where E and B have the meaning given and B is a hydrogen atom, a hydroxyl, Amine, alkyl ether or alkyl radical with 1 to .10 Represents carbon atoms, or together with Z the necessary to conclude the Bing divalent hydrocarbon radical of the formula OH -QHE ¹ -OHB ² -GB ^ in which B ¹ and E ^{2 have} the meaning given 'and the carbon atom bearing the OH-G group is intended to be bonded to the nitrogen atom, and in which B ^ "also has a hydrogen atom or an alkyl radical Represents 1 to 10 carbon atoms, and ' Z alone is a hydrogen atom, with an alkyl radical 1 to 8 carbon atoms or an aryl radical of. Phenyl or laphthyl series, or according to / insaiB with Y the bivalent necessary to conclude Hydrocarbon radical of the specified Meaning;:, . where Z does not have a Best of the formula -S-CTO ¹ -GHB ² -CB ⁵ . if Y is a Best of the formula '-EAR -EAR -ö-iB? mean A, possibly in the form of hydra- Öximen, S «micarbazonan or thio- BATH ORIGINAL