DE1944745A1 - Silver halide photographic emulsion - Google Patents

Description

The invention relates to new photographic silver halide »emulsions which, in combination with one, reduce fogging preventive additive are used, the invention further relates to the use of such silver halide emulsions for dividing the hearth of photographic recording material.

The development of the non-exposed areas of the photographic silver halide which precipitates metallic silver is commonly referred to as a "veil""The ~

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. ₂ . 194 * 745

This veil formation is often based on the action of certain Components of the photographic emulsion in question, on the composition or the type of developer used, on atmospheric oxidation, on aging phenomena, and similar influences. Also the kind of for the photographic Film used can affect fogging and the type of carrier film on which the Silver halide emulsion has been applied. For example, a carrier film made of a polyester is more prone to fogging in the emulsion layer applied thereon ale a carrier film made of cellulose ester. Also the aging of the silver halide emulsion at high temperatures and high humidity contents of the surrounding atmosphere generally contributes Haze formation with.

Although such a veil is generally in a uniform blackening of the emulsion layer of a photographic recording material is noticeable, show such Layers often also include small areas in which the fogging is greater or less than in the surrounding areas Areas. Such small areas are usually called "sensitized" or "desensitized" or simpler than "Black * and white spots denote- such spots stir often from the presence of small metal particles, for example ' of iron, copper or tin particles, or of Residues of such metal compounds in the emulsion layer itself or in a layer adjacent to it. Such

Metal particles or residues of metal compounds can be made from

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19 ** 7 * 9

originate from the carrier filra used, for example a polyester, or they can generally arise from the environment in which the photographic recording material was produced has been or is being applied.

It is therefore of great importance in practice, both the formation of fog and the formation of spots described above in silver halide demulsions as far as possible or to prevent them entirely.

Surprisingly, it has been found that Azodlcarbonamld itself and its derivatives prevent soleplate loosening or pecking very well. Both phenomena are summarized below under the term "fogging ¹¹ ".

The silver halide photographic emulsion of the present invention is 1st characterized in that they are connected to the Schleiorblldung preventive additive, namely with azodicarbonaadd and / or its derivatives, preferably with an azodicarbonamide compound the following general form combined 5at.

- C - H = N - C - N ^ (I)

in which R ₁ b: * s R ^ js'.ieils mean a Wacsorstoffatom or an optionally substituted alkyl, Ar.vl- or heteroiiyclisohe group orier in which the groups Rj and H ₀ or R 1 and R ₁₁ susamrsen r < ii · - the nitrogen atom is a heterocyclic one

0098 1 5/1307

0AD

Form ring,

Particularly preferred in the context of the invention are azodicarbonamide compounds of the above formula in which at least one of the radicals K ₁ to JL is an alkoxyalkyl, alkoxyaryl, hydroxyalkyl, haloaryl or allyl group, a heterocyclic group or a heterocyclically substituted alkyl group.

The Si ^ verhalide emulsions according to the invention are very suitable for the production of photographic recording material, the azodicarbonateide compound used for fogging prevention can also be incorporated in a layer adjacent to the silver halide emulsion layer.In Examples 1 to 27 below, the production of the silver halide emulsions according to the invention is also used Azodicarbonamide Compounds Explained

example 1 Production of N.N'-dimethyl-azodicarbonamide

¹ 7.4 g (0.1 mol) of ethyl azodicarboxylate are dissolved in 100 μl of diethyl ether. To this solution are 6.5 g (0.21 mol)

Methylamine added in a 33 ^ strength solution of ethanol. The reaction starts immediately 'and runs at a temperature of 0 ⁰ C smoothly "After washing with Diathyläther 9" 3 g of crude product as an orange Powders separated, wherefrom by recrystallization from ethyl acetate 7.79 g

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Leg product in the form of long orange-colored needles with a melting point of 169 ⁰ C can be obtained.

Theory Analysis: C # 33.40

5.56 38.87

found , 46 33 , 66 5 , 72 38

Example 2

Division of N ^ N'-diethyl azodicarbonamide

26.1 g Azodicarbonsäureäthylester are dissolved in 200 ml of diethyl ether and to this solution 13.5 g of ethylamine are added as a 33 $ ethanol solution, wherein the temperature is maintained below 20 ⁰ C. The product which separates out is filtered off, washed with diethyl ether and dried in vacuo. 19 g of yellow crystals with a melting point of 134 are obtained

up to 135 ⁰ C obtain" theory found 4 ^, 90 . 41.97 Analysis i C5S 6.93 7.02 H £ 32.56 32.41 H*

Example 3 Production of N ^ ff'-Dipropyl-azodicarbonamide

17.4 g (0.1 mol) of azodicarboxylic acid ethyl ether are dissolved in 100 ml of diethyl ether and 12.4 g are added to this solution (0.21 mol) propylamine added in 50 ml diethyl ether »

The reaction is carried out at 0 ° 0 with external cooling.

The heat starts practically immediately and is moderate

009815/130 7

exothermic »

The product formed is separated off, washed with diethyl ether and 13 g of an orange powder are obtained. Obtained by limcrystallization from 500 tal of ethyl acetate one 10 g of a pure product in the form-small orange-colored Needles with a melting point of 152 ° C.

Analysis:

theory found 48.00 47.81 8.02 8.13 28.05 28.06

Example 4

Preparation of jST, IF-fli-2-iaethoxyäthyl - azodicarbonainid 7.8 g (0.1 mol) of 2-methoxy äthylarain are dissolved in 50 ml of diethyl ether and a solution of 8.7 g (0.05 mol) Azodicarbonsäureäthyle3ter added in 100 ml of diethyl ether, the reaction is carried out at a temperature of 0 ⁰ C. 6.5 g of crude product are obtained, from which 4.5 g of small orange-colored threads with a melting point of 106 ⁰ G are obtained by recrystallization from 120 ml of ethyl acetate.

Analysis: Cji H *

theory found 41.30 .. 41.28 6.90 7.11 24.15 24.41

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8AO ORJ & NÄL

-Example 5

Production of N, N'-kiallyl-azodicarbonamide 12.0 g (0; 21 mol) of allylamine are dissolved in three times the volume of diethyl ether and a solution of 17.4 g (0.1 mol) of ethyl azodicarboxylate in five times the volume of diethyl ether Temperature of O ⁰ C added. 14 g of the amide in question are deposited practically immediately. Recrystallization from 300 ml Athylacetut one 9.5 g of pure product is isolated in the form of small orangerotgefärbter Hadeln having a melting point of 144, O ⁰ C.

Analysis: C * N * example 6th

theory found 48.90 49.07 6.16 6.26 28.55 28.77

Preparation of N _t N ^t ~ T} iisopropyl-azodicar bu namide To a solution of 17.4 g (0.1 mol) of ethyl azodicarboxylate in 100 ml of diethyl ether, 12.4 g (0.21 mol) of isopropylamine in 50 ml of diethyl ether are added , the temperature being kept at ⁰ ° C. 5.3 g of a yellow-colored mass separate out as the reaction product, from which 5 g of small, pale orange-red colored needles are obtained by recrystallization from ethyl acetate. Evaporation of the mother liquors gives a further quantity of crystals with a melting point of 158 ° C., so that the total output is 4.3 g.

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Analysis:

H*

theory found 48.00 47.80 8.07 8.10 28.05 28.15

Example 7 Production of l?, H * -dibutyl-azodicarbonamide

A solution of 15 g (0.21 mol) of ji-butylamine in 50 ml of diethyl ether and a solution of 17.4 g (0.1 mol) of aryl azodicarboxylate in 100 ml of diethyl ether are mixed with one another ^{at a temperature of 0 ° C.} solid is washed with diethyl ether and purified by recrystallization from ethyl acetate. This gives 12 g of a pure product in the form of small orange-red needles with a melting point of 159 ° C.

theory found 52.90 52.86 8.78 8.74 24.52 24.53

Analysis:

Example 8

Preparation of N.N '- ^ i - ^ - äthoxyäthyl-azQdiearbonamld 18 g (.0.21 mol) of 2-ethoxymethylamine in 50 ml of diethyl ether are added dropwise to a solution of 17.4 g (0.1 mol) of azodicarboxylic acid ethyl ester in 100 tnl diethyl ether, the temperature being kept at ⁰ ° C.

The pesticide which is separated off is washed with diethyl ether

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Dl. ELISAtETH 3UNO. "Dl. VOLKER VOSSIUS

Patent application P 19 # * 7 * 5 · 1 - 1 9 A17 A ζ «>» m - 'ng. g.cou> ewev Minnesota Mining and Manufacturing Company '* "T' * ^ Patent Attorney"

_ t Some H, n- r.M

"" "" Τ · Ι · Ι <μ: MIO *?

and you get 17.5 g of a «raw product. By Uakriatalli eieren from ethyl acetate receives nan 12.5 g of pure product in the form of small orange-colored cycling, "it is a · 3ohaeIspunkt of 103 ⁰ C.

Analysis t C £

H*

theory found 46.20 45.68 7.69 7.72 21.57 2.1.66

Example 9 Production of HR ^> -Bls ~] "(2-pyridyl)» ethyl] -a »odlcarbona» id

-O

To a solution of 17.4 g (0.1 KoI) of azodicarboxylic acid ethyl ester in 50 ml of diethyl ether, 21.8 g (0.21 mol) of «(-AiliJio-2-picoline in 25 ml of diethyl ether are added, the temperature at 0 ° The reaction starts almost immediately and the amide which separates out is washed once with diethyl ether. 23 g of a pink powder are obtained in this way. Recrystallization from 600 ml of methanol and concentration of the mother liquors give a total of 10 g of orange-yellow crystals a melting point of 168 ⁰ C.

theory

Analysis ι Qf 56.35

H * 4.70

H * 28.15

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found 55, 4, 27, , 87 , 86 ρ 90

-10-

Example 10

Production of HtH * -Itt- (3-pyridylmethyl) -aaod icarbonaaid

- HH - CO - H - F - CO - SK - CH ₂ - IL-J'M

To a solution of 9 * 5 g Azodiearbonsäureäthyleeter in 100 ml of diethyl ether, 10.8 g of oC-amino-5-picoline in 50 al of diethyl ether was added, the temperature being kept below 20 C · ψ The reaction proceeds isothermally and dae solidified amide separates practically immediately. By recrystallization from methanol, orange-yellowish colored crystals with a melting point of 164 to 165 ° C. are obtained.

theory found 56.35 56.38 4.70 5.06 28.15 28.16

Analysis:

N *

Example 11

Preparation of K, N '-: Di «- (4-T> yridylmethyl) azodicarbonamide

^ -CH ₂ - HH - CO - H = H ^r - CO- - HH - CH ₂ - / \]

J * 5 g To a solution of 9 Azodiearboneäuröäthy! Ester in 100 ml of diethyl ether are employed 10.8 g c4 ~ amino-4-pieolin added in 50 ml of ether, the temperature being maintained below 20 ° C, The reaction proceeds isothermally and the solid amide separates

■ off practically immediately. Ea is washed with diethyl ether, .Duron *

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Recrystallization from ethanol gives small orange-colored crystals with a melting point of 157 to 159 ⁰ CL

theory found 56.25 56.31 4.7 4.99 28.15 27.88

Analysis s -

Example 12

Production of H.K''Bis (2-hydroxyethyl) azodicarbonamide To a solution of 17.4 g (0.1 mol) of azodicarboxylic acid ethyl ester in 100 ml of diethyl ether, 12.4 g (0.21 mol) of ethanolamine are exposed in a mixture 25 ml of ethanol and 25 ml of diethyl ether are added - the temperature is kept at ⁰ ° C.

The reaction starts almost immediately and 17 g of amide separate out, which are recrystallized from 350 ml of methanol. This gives 9.5 g of small pink-colored needles with a melting point of 141 ^° C.

Analysis: C $ H *

N *

Example 13

theory found 35.83 35.35 5.97 6.00 27.88 27.28

Preparation of N, S ^t -Bi8 (3-hydro3cypropvl) -azodicarbonamide 15.5 g (0.21 mol) of 3-propanolamine are added to a solution of 17.4 g (0.1 mol) of ethyl azodicarboxylate in 100 ml of diethyl ether

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-ιέ- '134 * 745

added in a mixture of 25 ml of ethanol and 25 ml of diethyl ether. The temperature is kept at ⁰ ° C. * The reaction starts practically immediately and 21 g of amide are deposited, which are purified by recrystallization from 150 ml of ethanol. This gives 16.5 g of small orange-colored needles with a melting point of 14O ⁰ G ₁ .

Analysis:

theory found 41.30 41.23 6.93 . 6.99 24.10 23.87

Example 14

Preparation of Ν, Ν ^ - Diphenyl-azodic arbonamide To 8.1 g of hydrazodicarbonamide, which has been prepared by pyrolysis of 4-phenylsemicarbazide and which is suspended in 200 ml of pyridine, a solution of 5.5 i of N-bromosuccinimide is added in 100 ml of pyridine added, the temperature at 35 ⁰ O is kept. The pesticide that separates out dissolves for a long time and the solution takes on a dark red color> After about 2 hours, the solution is filtered in a vacuum and the piltrate is poured very quickly into 2 liters of ice water. A fluffy red-colored pestilent separates out, which is then filtered off with water washed and recrystallized from 150 ml of hot ethyl acetate. This gives red-colored plate-shaped crystals with a melting point of. 175 to 177 ° CV

> * '009815/1307

Analysis ϊ

theory Refunds 62.70 62.80 4.47 4.69 20.85 20.74

Example 15

Production of N.N ' -Si-m- chlorophen yl-azodicarbonaiaia To 92.8 g of nitrochlorophenyl-4-semicarbazide in 1200 tnl of ethanol, while the solution is kept boiling, a proportion of a total of 25.4 g of iodine are added. The mixture is boiled for half an hour and then filtered off while hot. The whitish colored solid obtained in this way (the hydrazo compound) is washed out with hot water and then dried in vacuo at a temperature of 56 ° C. To 6.8 g of the N, N ^p ~ di 3-chlorophenylhydrazodicarbonamide, which in 100 ml of pyrldine is suspended, is set at a temperature of 45 to

ο ⁷ * ⁶ «

At 50 ° C., a solution of / Ef-bromosuccinimide in 150 ml of pyridine is added dropwise. The resulting solution is poured into 1.5 l of ice water and the orange-red colored precipitate which separates out is washed with water. It is then recrystallized from 200 ml of hot ethyl acetate. In this way, extremely thin orange-red colored needles are obtained which decompose at a temperature of 172 - 174 ⁰ C «

Analysis:

theory found 49.80 48.94 2.97 2.96 16.62 16.67

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Example 16

Production of NN ^c -I) i "P-tolyl-azodiearbonamide To 14.9 g of N, N'-i) ip-tolylhydrazodicarbonamide, which has been obtained by pyrolysis from 4-p-oleyl-semicarbazirl and in 300 ml Pyridine is suspended, a solution of 17.8 g of N-bromosuccinimide in 200 μl of pyridine is added dropwise at a temperature of 70 ° C. The resulting solution is poured into biswater, the orange-red precipitate which separates out v; It is filtered off, washed and dried in a vacuum W at room temperature. It is then crystallized from hot ethyl acetate. The pure compound is thus obtained in small, deep, dark orange-red needles which decompose at a temperature of 172 to 175 C. «

Analysis: C ₅ S

theory found 64.76 65, 9 5.40 5.72 18.80 18.26

Example 17

Preparation of N, N ^ -I) i - p-methoxyphen, yl-azodicarbonamide To 6.6 g of hydrazodicarbonamide, which has been obtained by pyrolysis of p-methoxyphenyl.4-semicarbazide and is suspended in 150 ml of pyridine, is added added dropwise a solution of 7.2 g of F-Broasuccinimid added in 100 ml of pyridine, the solution is poured into ice water, which separates dark colored precipitate wi ^r * d washed with water and dried in vacuo. Then crystallized '

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from hot ethyl acetate. A product in the form of deep dark red needles with a melting range of 169 to 177 ° C. is thus obtained.

theory found 58.50 58.50 4.78 4.92 17.06 16.92

Analysis:

H * N *

Example 18

Production of N _f N ⁷ -P i ^ 00- ^ y_riayl) -azodicarbonamide Aquitnolecular proportions νοηοΰ aminopyridine and diethylazo-dicarboxylic acid are reacted with one another at a temperature of not more than 15 ° C in alcohol solution. After the reaction has ended, the reaction mass is left to stand undisturbed overnight and the precipitate which has separated out is then filtered off with suction. It is to this we "ISSE a dark-yellow-colored powder with a melting point from 177 to 179 ⁰ C received.

Example 19

Production of N _t N * -33i- {ß-pyridyl) -azodicarbonamide. Equimolecular proportions of ß-amino-pyridine and diethyl-azodicarboxylic acid are brought to reaction at a temperature of 10 to 15 ° C in an alcoholic solution the reaction mass is left to stand undisturbed overnight and the product which has precipitated is then filtered off with suction. Repeated extraction of the reaction product with hot alcohol and concentration of the extract in vacuo gives needle-like

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1 * 44745

T6-

shaped crystals with a melting point of 164 ⁰ Co

Example 20

Hey, position of lf _? N ⁸ _r Pi - (^ pyridyl -azodicar bona mid equimolecular proportions of Ϊ amino pyridine and diethyl azodicarboxylate are reacted at 15 ⁰ C in pyridine to "You can implement overnight at room temperature ablaufenο to an end

P The reaction product is colored as a crystalline yellow

! Tested product with a melting range of 178 to 181 ⁰ C

keep.

Example 21 Preparation of N ₁ N ^t -di ~ (flk --- furyl) ~ azodicarbonamide

2.5 g N, N ^? - is & ~ furyl hydrazodicarbonamide "represented by Beak · tion of & ~ Isocyanfuran with anhydrous hydrazine in toluene obtained are suspended in 100 ml of dry methylene chloride and oxidized at a temperature of about -45 ⁰ G with a solution of F-Bromsuccinitnid in pyridine . The reaction takes about 3 to 5 hours. to remove all by-products ο

The chemical structure of the compound N-, N ^C · di- (■ «<> - furyl) -azodi- · '■ 009815/1307

• -17- '

carbonamide is confirmed by infrared spectroscopy

Example 22

The development of N, y-Bia (2-tetrahydrofurfuryl) -azodicarbonamide

CH

CH ₂

- CH ₀ - KH - CO - N = H - CU - NH - Ch ₀ - OH

CH

To 19.2 g Azodicarbonsäureäthylester in 150 ml of diethyl ether are at a! Temperature below 10 ⁰ C, 20.2 g of tetrahydrofurfurylamine in 150 ml Biäthyläther added = Pas orange yellowish solid separates amide calibration and has a melting point of 100-104 ⁰ C. By Recrystallization from ethyl acetate gives orange-red colored crystals with a melting point of 104 to 107 ° C «

Analysis:

theory 65 found 50, 03 50.73 7, 70 7.11 19 19.89

■ example 23 Manufacture of

-thienylj-azodi carbonaEid

2.8 g Ν, Ν '- ^ - IRiienyl-hydrazodicarbonamide, which is the acidic decomposition of & -Isocyanthiophthn with anhydrous! Hydrazine obtained in toluene / suspended in 100 ml of dry Methylenehlorid and then at a temperature of about -45 ⁰ C by means of zitier solution ίοχϊ H "Eromsüooiiiiisid In 20 al

098S1S / 1307

. *:, .. «! SAP ORIQWM.

oxidized.

The reaction takes about 3 to 4 hours »The reaction product remains in solution. The mixture is filtered in order to remove the unreacted hydrazo compound and wash successively with water, the Piltrat _s 2 #iger hydrochloric acid, again with water, with 2 ^ coward nocbmals sodium bicarbonate solution and with water, The structure of the compound H, N * di- {oi> ~ thienyl) azodicarbonamide is confirmed by infrared spectroscopy.

Example 24

Manufacture ν on K, h '-Diiaorpriolinoazodleagbonanld

H ₃ C ^ - H ₂ C HpC \ 0 y ■ ft 0 H θ / C -

0 / \ CH ₂ - \ 0 - CH ^
2 H - H - G - CH ₂ - - CH ₂

A solution of 17.5 g (0.1 mol) Diätnyl-azo-dicarboxylic acid in 100 ml of ether is f at a temperature of 5 to 1O ⁰ C it a "dissolution of 17.4 g {0.2 mol) in Morphblin! 100 ml ether reacted "Very quickly, a reddish-colored precipitate is coming off and in another 20 minutes is the implementation au end abgelaufenο the product is abflivriert · on the water jet pump and gereinige by recrystallization from ethyl acetate. This gives small yellow-red colored needles with a melting point of 135 to 137 ⁰ C ₁ ,

BADORlGlNAt Example 25 Manufacture of »Η, N * ~ Β1β [2 (N-aorpholino) ethyl 1 -agodloarbonamid

JDHp - GH "CH ₂ - -CH ^ O- CHp _{9 9} -CH -NHCO-NN-CO-NH-Ch _{9 9} -CH-N> 0

To a solution of 19.2 g Azodiearbonsäureäthylester in 200 ml Diäthylather> ei a temperature below 2O ⁰ C 25.2 g

M-8-AiBiöelthyl-niorphülin added in 100 ml of diethyl ether. It separates eitfh a crystalline, orange 'amide-colored solid having a melting point of 143-150 ⁰ C of .. By Umkristalli aieren from propanol erbäJt one örangerot colored crystals with a melting point 155-160 ⁰ C,

Iheory found 49.15 47.69 7.61 7.53 24.55 24.35

Analysis:

UjL

N *

Example 26 Production of N, N -Di-CK-piperidinyD-azodicarbonamld

CH ₉ - CH ₉ CC CH ₉ - CH ₉ CH ₂ N - C - N = N - C - % CH ₂

A solution of 17.4 g (0.1 mol) of diethyl-azo-dicarboxylic acid in 100 ml of ether is conducted at a temperature of 5 to 10 ^0. C with a solution of 17.0 g (0.2 mole) of piperidine in 100 ml Ether transformed As the heat progresses, it changes

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r20 ~

the color of the solution from orange to red out After about 30 minutes, the solution to a volume of about 30 ml aufkonaentrierto IEUs yellow orange-colored crystals precipitate with a melting point of 132 to 134- ⁰ O from.,

Example 27

Production of N, H ⁵ -sicyclofaexyl-azodioarbonamide

'"" HH - CO - N β H - CO ~ NH

To a solution of 17.4 g Azodicarbonsäureäthylester in 100 ml of diethyl ether 19,85g cyclohexylamine in 150 ml of diethyl ether are added at a temperature below 10 ⁰ C. The reaction proceeds isothermally .and it separates immediately a yellow-colored solid in a powder form from . This yellow solid ■ ^ is washed with diethyl ether and then has a melting point of 187-190 ⁰ C. By recrystallization from ethanol gives orange yellow colored needles rail a melting point of 201 to 2O3 ° C,

Analysis:

theory found 60.00 60.06 8.54 8.66 19.98 19.99

The silver halide emulsions according to the invention can contain silver " cta & o-pid, silver bromide and / or silver iodide, for example also mixtures of such silver halides, such as silver

• ·
_v bromoiodide., The emulsions can also be of the most varied

009815/1307 _?

synthetic polymers as a replacement or supplement for gelatine • contain as colloid binding agent, for example dextran, -Polyvinyl alcohol, polyvinylpyrrolidone, partially hydrolyzed polyvinyl acetate, polyethyl acrylate, polymethyl methacrylate and / or polyamides.

.The emulsions according to the invention can by adding chemical

or sensitizers are chemically sensitized / by maturing them with natural active gelatin. Such additives are thiosulfates, allyl thiourea, thiocyanates and thiosulf «anates». Sensilization can be facilitated by the use of noble metal salts, for example gold salts. In addition, they can contain couplers, surface-active substances, hardeners, stabilizers, and additives preventing fogging, plasticizers, antioxidants, additives accelerating development and, in general, all those additives which are commonly used in photographic silver halide emulsions Polystyrene, polyester, cellulose acetate, polycarbonate, paper and glass are suitable. other common carrier material! enο

The azodiearbonamide compounds used as additives according to the invention are very appropriately mixed into the emulsions during the production process

1944748

• · also has a good effect "in terms of preventing the sole and flecking achieved when these asoäicarbonamid -verbindungen at least Iu reactive combination with the silver? - halide layer The Azodicarbonaaiid-Verl) in ^ i3Sigon can also be seen in the photograph! Recording material in an adjacent to the silver halide layer Layer located, The amount of azodiearbonamide compound can vary within a wide range and it can easily be determined by simple preliminary tests. If the

^w .. ■ · ■ *

Additives is present directly in the photographic silver halide emulsion, it is preferably used in a concentration of

0.01 »

The 15 ϊίίοΐ per mole of silver applied *

The beneficial effect of the afsodicarbonamide compounds than that Sueatzatoffe, which prevents the formation of eggs, results from the examples below »

Example 28

A photographic highly sensitive® silver halide emulsion, which 2. Mol $ AgJ i ^ nd contains 98 mol% AgBr »is divided into four samples. A sample is applied directly to a carrier material made of polyester without further treatment. Azodicarbonaride is added to the other emulsion samples in the concentrations given in Table I and only then are these applied to the polyether surface. Bi © Hang® all Aeodicarbonaaiid is specified in isMol ^ e Mol Ag, The so e * Äalten © B photographisebeia Aufrtafemematerialien are then % n © iBasi Sensitosieter supplied for 3 minutes

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BAD OfIfGJNAl.

Developed at 20 ° C in a developer with the following composition:

Monomethyl p-aminophenol sulfate anhydrous sodium sulfite hydroohinone

anhydrous sodium carbonate potassium bromide

Water, remaining amount up to

3 S 50 g

9 g 50 g

3 g 1000 ml.

In Table I below, the results are given in relation to lent to fogging and relative sensitivity, on the one hand for fresh emulsions and on the other hand for emulsions

ο when stated which 15 days at 50 C / eiv> er relative humidity

been stored for 50 i "Bind

Table I Fresh emulsion

Relative haze AEodicarbon sensation amide mM / mol ag ility

3
10

1.00 92 85 76

0.15 0.09 0.06 0.04

15-day storage at 50 C and a relative heat of 50 years »

Fogging

Lative sensitivity 108
92
92
76

0.24 0.17 0.10 0.08

Example 29

A sample of a silver bromoiodide emulsion layer which Contains 2 mol- £ AgI and 98 mol- $ AgBr and on a support material made of cellulose triacetate is applied with

009815/1307

■ ■ '■' jr

'* covered with a protective layer in a thickness of 1, ^, which the following composition comprises gelatin 15 g

10 # saponin water solution 5 ml

Water, party days up to 1000 ml »

A second sample of the emulsion layer is coated with the same * protective layer, which, however, an additional 1 g of azodicarbonamide Contains, the two photographic recording materials were exposed and then again divided into several samples at 20 ⁰ C in the developer of Example 28 even 3 minutes and other samples are lacg developed for 10 minutes.

The results obtained are summarized in Table II below.

Table II

Fresh emulsion storage for 15 days at 50 C and a relative humidity of 50 fo

Relative haze- Helative haze formation

Sensation formation jicapfind-

■ licliiceit 3 min lu milility 3 min 10 min

Comparison (without

Azodicarbonamide) x 100 0.11 0.25 107 0.14 0.28 with azodicarbon

amide 99 0.06 0.20 97 0.11 0.22

00981 5/1307 SAD ORIGINAL

Example 30

A highly sensitive silver brosaiodide emulsion, which contains 1.5 AgJ and 98.5 mol ~ # AgBr, is divided into sample amounts, to which the various azodicarbonamide compounds according to the invention are added in a concentration of 1.5 mol per mol Ag. One develops 3 ^ between For 10 minutes at a temperature of 20 ^° C. in the developer of Example 28 «The results obtained are shown in Table III below

summarized.

00 * 815/1307.

8AD ORIGINAi.

Aft ä & m additive {© ta ©

a ι 11th 3 ti 4th 5 » 5 ts 6th ? 5 7th S? 8th 53 9 ω . 12th Si 13th

Tabel 0.51 III Storage at 50 ° C and one 0.20 0.60 fresh emulsion 0.35 15-day Moisture from 50 9 & 0.15 0.33 Relative 0.30 relative Relative sensation of fogging
opportunity. 3 min 10 min O ₅ OS O ₉ 23 Sensation
opportunity 0.31 92 0.08 0.29 100 3 ©! Ile ierbildwng
3 min 10 min 0.29 88 0.0 & 0.28 78 0.14 O _S 3O 82 0.08 0.28 72 0.09 0.33 86 0.10 0.30 79 0.06 0.41 82 0.14 0.40 80 0.06 0.29 93 0.08 0.28 90 0.05 0.29 88 0.05 0.31 87 G, 06 0.37 94 0.08 0.43 87 0, OS 0.37 89 0.08 0.43 80 0 ₉ 12 77 37 0.08 90 90 U * 06 90 90 0.08 0.08

Example 31

^{Azodicarbonamide or N, H 5} -diethyl azodicarbonamide are added to samples of an emulsion containing 1.75 col. 6 AgI and 98.25 AgBr as well as in the case of emulsion samples which have been ^{aged for 15 days at 50 °} C. and a relative humidity of 50 fd, determined experimentally - the results obtained are summarized in the table IT below:

Additive

Table IV Fresh emulsion

Amount of Kelative Schleier-V Ag sensation

15 days of storage at 50 C and a relative Moisture at

50 #

Relative lead sensation
opportunity

Comparison (without) 0.3 ίσο 0.24 100 0.43 Azodicarbonaeid ' 0.5 100 0.23 100 0.28 M. 0.6 90 0.22 110 0.28 It 0.3 90 0.21 110 0.28 I, H ^f -diethyl-
azodicarbonanide 0.6 110 0.20 110 0.36 H 0.9 100 0.20 110 0.32 W. 100 0.19 100 0.32

Example 32

Ub the anti-fog effect of the additives according to the invention to show with regard to the formation of flecks - soft resulting from the presence of ketallic particles becomes the following Trial carried outϊ

009815/1307

A highly sensitive emulsion chemically ripened with gold thiosulphate and gold thiocyanate is divided into two sample sizes A (comparison sample) and B. To the sample amount B, 0.5 raMbl azo dicarbonamide / mol Ag are added. These two emulsions are applied to a polyester carrier material which has been dusted beforehand with fine iron powder. After drying, the two samples are developed in the manner described in Example 28 without exposure. The ability of the additive to prevent the formation of black and white spots * is determined by counting the number of spots in 3 samples per unit area for emulsion A and emulsion B.

The results obtained are in the table below V summarized:

Table V '

Number of spots

Sample 2 - Sample 3 Sample

A (comparison) 52 47 80

B (0.5 mmol azodicarbonamide / Mo1
Ag) 5 13

Example 33

A photographic silver halide emulsion containing 98 mol% AgBr and contains 2 mol $ AgJ, is divided into several test portions A comparison sample is applied to a polyester carrier material without further treatment applied .. The other sample quantities are applied to identical polyester substrates, after which they can be used

00981 5/1307

BATH ORIGINAL

has added selected additives according to the invention., The photographic recording materials thus obtained are then exposed in a sensitometer and developed for 90 seconds in the developer of Example 28

and

Emulsions {aging: 15 hours at 72 ° c / one; relative humidity of 30 <p) carried out »The results are summarized in the following table VI:

ÖÖ9815 / 1307

Additive Added
lot
mM / M Ag Table VI i
Relative
sensitivity
(aged
Emulsion) Fogging
(fresh) (aged) - 0.60 comparison
(without) Relative
sensitivity
(fresh emulsion) 100 0.52 0.37 Example H 0.5 100 104 0.33 0.41 - ο η ₁₅ 0.5 99 103 0.39 0.44 OO to «16 0.5 102 103 0.37 0.46 cn it! 7th 0.15 102 103 0.34 Oil 100

Example 34

.To sample quantities of a photographic silver halide emulsion, which contains 1.5 MoI-Ji AgJ and 98.5 Hol- # AgBr additives according to the invention in the table below VII specified concentrations added. A polyester carrier material is then coated with each sample, which with a base layer of gelatin »which is suspended Contains iron powder, has been coated; · D-is so obtained photographic recording material is before drying Chilled for 10 minutes and then in. For 90 seconds Subsequently developed using the developer of Example 28 those caused by the presence of the iron particles black spots counted. The results obtained are summarized in Table YII below.

Table VII

Additive lot Layer with Number of black _ of example ι K / M Ag Iron powder Spots on 70 cnr without 2 - - - with 175 H 0.5 η 53 H 1.0 K 3 15th 0, £ N 180 15th 1.0 η 117 16 0.5 H 10 16 1.0 H 0 17th 0.15 If 55 17th 0.5 η 6th

009815/1307

BATH

Example 35 '

A photographic silver halide emulsion which contains 98 mol% AgBr and 2 mol% AgI and is characterized by a high β ratio of silver to gelatin is divided into several sample quantities. One of these sample quantities is placed on a support without further treatment applied from cellulose triacetate * The other sample amounts are given an addition of compounds according to the invention according to Examples 18 and 19 in varying concentrations before they are applied to the same carrier material _and samples of these emulsions become

then exposed in a sensitometer and at for 5 minutes

ο *

developed at a temperature of 20 C in a tray using the developer of Example 28. Table VIII shows the results of the sensitometer tests on fresh emulsions and on aged emulsions (aging time: 15 hours at a temperature of '
summarized ,

Temperature of 72 C and a relative humidity of 30

0098 15/1307

BAD ORKStNAL Table VIII

Additive

Comparison (without)

example 18th O
O-
CCH "
OD I Il
Il 18th
18th Cn H 19th 307 If 19th

lot

m / u Ag

0.1 0.5 2.5 0.1 0.5 Relative sensitivity of fogging (15 SM * at 72 ⁰ C equal-

Relative

Sensitivity Π 5 SM <, at 72 "C equal-

(fresh emulsion) learns relative moisture (fresh) (aged) speed 30 ⁰ A)

100 100 95 76 95 80

100 100 80 67 80 80

0.31 0.32 0.31 0.32 0.25 0.28 0.19 0.19 0.31 0.31 yy 0.20 0.20

Example 36

The procedure of Example 35 is mixed with one sample corresponding emulsion repeated, which 98 mol $ AgBr and 2 mol% AgI, and the compounds of Example as additives 21 and 23 included. The results obtained are summarized in Table IX below:

009815/1307

8AD ORIGINAL

Table IX

Additive (ohw?) lot
mM / M Ag Relative
sensitivity
(fresh emulsion) Relative sensitivity
(15 hours, geal at 72 ° C
tert, relative humid
30 to) Fogging
(fresh) (aged) 0, 57 v, r _S l.trh 21 «Η km 100 100 0.50 0, 35 098 example 21 o, i 80 110 0.30 0, 32 cn It ? 3 0.5 63 97 0.26 0, 38 ^ U) ¹ ^ 'Il 0.05 70 80 · 0.36 , Oi 33Os O
• ■ J It 0.1 50 68 0.31

3 <

Example 37

Example 35 is repeated using a corresponding emulsion which contains 98 mol% AgBr and 2.0 mol% AgJ, and the compounds of Examples 24 and 26 as additives Results are summarized in Table X below:

0098 15/1307

! Table X

Additive

Quantity M /

Comparison, (without)

ο Example 24 co

Ξ "24 cn

24

26th

26th

26th

0.1 0.5 2.5 0.1 0.5 2.5

Relative Relative Sensitivity Fogging

Sensitivity (15 hr, at 72 geal- ⁰ G {fresh emulsion) tert, relative humidity 30 io)

100

107

93

57

100

96

74

100 105 105

61 100 105

76

(fresh) (aged) 0.25 0.28 0.25 0.26 0.16 0.16 0.09 0.09 T ⁹ 0.23 0.24 0/20 0.19 0.10 0.13

Example 38

Samples of a ffeotograpiiiscti.es silver halide emulsion, which contain 98 mol / 4gBi? Usd 2.0 mol% AgI, as well as the compounds of Examples 24 and 26 as additives, are applied to a carrier layer of cellulose triacetate, many pretreated with a gelatin layer has been contains ile suspended Eiseapalver, Hiese Proaea - «- ver ground eng drying 1O minutes laag cooled and then for 90 seconds in the developer w VQM example 28 treated anschließend-" v / ground by the Eisssteilchen liarvorger-üfeneti. black 'J lesken counted, Me results are nachet-sheiid in Table Xl " zn- saaimengefaSt ,' ■ -

009815/1307

Table XI

Additive g'yjjäß example

Amount of layer with .aieenpulver on the number of black spots

mM / M Ag 70 cm ²

ο ο ω co

Comparison hair dryer ")

24

without a layer

with "

85 48 24

Example 39

Example 35 is repeated, but with all additives the compounds of Examples 10, 11, 22, 25 and 27 are used The results are shown in Table XII below summarized:

009815/1307

Table XII

Additive amount according to example mM / M Ag

Ye comparison (without)

approx

11th

0.025 0.050

0.10 0.50 2.50

OyS

Fresh Emulsion Relative "Sensitivity Veil

15 hours * storage at 72 ^° C

relative humidity; 30 9

Relative

Sensitivity veil

0.31

0.18

100

0.32

O 10 0 _; 0125 79 0.17 81 0.20 CO
OO
—X

79 0.29 85 0.28 79 0.18 85 0.17 95 O ₉ 28 96 0.30 95 0.20 96 0.20 68 0.11 68 0.11

O ₉ 20

27

0.10 0.50

0.22
0.19

89 89

Ov 30 0.18

Claims (2)

- 42 claims 1. A photographic silver halide emulsion, characterized in that they R ₁ 0 0 is preferably combined with a fog preventing ZusatEsfcoff, nSalieh with Azodlcarbon & mid and / or its derivatives with an azodicarbonamide compound of the following general formula s- in which R ₁ to R ^ each represent a hydrogen atom or an optionally substituted alkyl, aryl or heterocyclic group or in which the groups R ₁ and R _g bsw, E. and R ^ ziisaiamen with the nitrogen atom form a heterocyclic ring. 2. Photographer see silver halide emulsion according to claim 1, characterized in that it is combined with an azodicarbonaoild compound of the formula I, in which at least one of the radicals R _{1 to R 1 is} an alkoxyalkyl, alkoxyalkyl, hydroxyalkyl, haloaryl or Allyl group or a heterocyclic group or a heterocyclic substituted alkyl group 3 «PhotograpMsshe Silb @ rhalogenid © sMlslon according to claim I wad 2 _C. thereby gek @ snz @ iebp. @t _$ ' u & ß stm with ^ 15 umöl der AKodicarboaasaid-VerbisöMg | ® Mal ffS is » 009815/1301 ^
8AO OBfQIHAl. 4- use a photograph! See silver balogenide muleion according to claim 1 to 3 for the production of photographiechem On recording material ~ 5- Ausführungsungefora according to claim 4, characterized in that the aeodicarbonamide compound in one of the superhalide mules is neighboring Layer is stored, 009815/1307