DE2044622A1 - Photographic material with improved properties - Google Patents

Description

Photographic material with improved properties

The invention relates to a photographic material having at least one silver halide emulsion layer, its stability by adding N- (1,3,4-thiadiazol-2-yl) -dithiocarbamic acid estern is improved.

It is known that photosensitive silver halide emulsions, in particular chemically sensitized ones, tend to form fog, ie nuclei which can be developed without exposure. The formation of fog occurs in particular when stored for too long, especially at elevated temperature and humidity, too long or too long development or development at too high temperatures, due to certain additives, with excessively ripened emulsions, etc. To a certain extent it is possible to reduce the tendency of photographic silver emulsions to fog to suppress the addition of so-called stabilizers or antifoggants. This effect has, for example, heterocyclic mercapto compounds or inorganic or organic mercury compounds.
AG 715 209813 / 1U9

However, the stabilizers have the disadvantage that they .in their effective concentrations in general the lilmpj.ina.LicJn reduce the speed of the stabilized emulsions, thereby reducing their Applicability is affected. The gradation of the emulsions can also be adversely affected by stabilizers v / earth.

The invention is based on the object of finding stabilizers for photographic silver halide emulsions that contain a concentration causing sufficient stabilization no sensitivity or at least the lowest possible sensitivity. ^ decline.

A photographic material has now been found with at least one silver halide emulsion layer which contains N .- (1,3,4-thiadiazol-2-yl) -dithiocarbamic acid esters of the following formula:

NNR ²

r ¹ J! ^ _s JLn_c - sr ³ (ι)

S. where mean:

R ¹ = (1) hydrogen, (2) a saturated or olefinically unsaturated straight-chain, branched or cyclic aliphatic group with 1-18, preferably with 1-8 carbon atoms, which can be substituted by halogen, such as fluorine, chlorine or bromine , Alkoxy or alkylthio with preferably up to 5 carbon atoms, aroxy or arylthio, preferably phenoxy or phenylthio, (3) alkoxy with preferably up to 5 carbon atoms, (4) alkylthio with preferably up to 5 carbon atoms, (5 ) Aryl, in particular a group of the phenyl series, (6) aroxy, preferably phenoxy, (7) arylthio, preferably phenylthio or (8) a nitro group, the alkyl or aryl radicals having further substituents, for example one or more halogen atoms, the aryl radical 1-3 alkyl groups and / or can carry 1-3 alkoxy groups and halogen atoms are to be understood as meaning fluorine, chlorine or bromine atoms;

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Hydrogen, an alkyl, alkenyl or alkynyl radical with 1-4 carbon atoms;

(1) a saturated or unsaturated, straight chain, branched or cyclic aliphatic group with
preferably 1-8 carbon atoms, which can be substituted, for example by halogen, such as fluorine, chlorine or bromine, alkoxy or alkylthio with preferably up to 5 carbon atoms, aroxy or arylthio, preferably phenoxy or phenylthio,

(2) aryl such as phenyl or (3) aralkyl such as benzyl or a phenylethyl radical, whose aryl radicals can be substituted by 1-3 alkoxy groups and / or 1-2 alkyl groups and / or 1-3 halogen atoms, for example fluorine, chlorine or bromine , said alkyl and alkoxy groups 1-3
Contain carbon atoms.

For example, those given in the following tables can be used Links:

Table 1 '

link

R ¹

R ²

R-

Mp. ⁰ C

1
2

H -CH ₂ -CH = CH ₂

CF

CF

CF

5
6th

CF ₃ CF,

CF ₅

CH,

-CH ₂ -C = CH Cl Cl

-CH.

ro "

Cl
Cl

CH,

CH

^ CH ₂ -CH = CH ₂

CH,

173 171

100 202

95 48

105

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link

12 13 14

15 16 17

18th

19 20

OpT

CH (CK ₃ )

C ₆ H ₅

CF

CF

CH ₃ -O

CH,

R-

CH- -CH ₂ -CH-CH ₂

-CH ₀ - // \\ - Cl

CpH ₁₅ -CH ₂ - f / \ -Cl

H -CHp-CH = CH ₂

CH ^ CH

CH

CH ₃
CH ₃
CH,

63 110

108

201

A-G

0 9 8 1 3/1 A 4

Tabel

^ J N

C_ S_R ^:

Connection

R ³ m.p. ⁰ C

21 CH ₃ -0 - / "CH ₂ __7 ₂ -0 - /" CH ₂ _7 _{2 -H}

168

22 CH ₃ -0- / ~ CH ₂ _7 ₂ -0- / ~ CH _2> _7 ₂ - H -CH ₂ -CH = CH ₂ 72

23

C ₆ H ₅ -O-CH ₂ -H -CE ₂ - //

232

24

Cl

-0-CH ₂ -H -CH ₂ -A Vv-Cl 212

25 Cl- / * S -S-CH ₂ -

CH,

173

26 Cl- // \ -S-CH ₂ -H -CH ₂ - // ^ -Cl 198

27 Cl- C \ -S-CH ₂ - -CH ₂ - //

204

28 r ^. / Z \ -S-CH ₂ -

CH,

183

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The above compounds are prepared in analogy to known methods by reacting 2-aminio-1,3,4-thiadiazoles the formula

NNR ²

ι Il Ii f

R ¹ IL _c JJ NH (II)

in which

1 2

R and R have the meaning given above, with carbon disulfide in the presence of a diluent and bases to the salt of the dithiocarbamic acid of the formula

N -NR ²

R ¹ ILoJ CC-SMe (III)

in which

R 'and R also have the meaning given above and Me represents alkali metal or tertiary amine. Then this intermediate with alkyl or aryl halides is the

general formula XR- ⁵ alkylated (R- ^5. has the meaning given above and X denotes halogen such as chlorine, bromine or iodine). The thiadiazoles are prepared by reacting the corresponding acyl-thiosemicarbazides with polyphosphoric acid according to J.ehem. Soc.

1949, pages 1163-1167.

Preferred diluents are polar solvents, such as dimethylformamide, dimethyl sulfoxide, alcohols, water, Ethers such as tetrahydrofuran and dioxane in question. All common acid binding agents, such as alkali hydroxides, Alkali carbonates, alkali alcoholates or tertiary amines can be used.

The reaction temperatures can be varied over a wide range. Generally carried out between 0 ° and 10O ⁰ C. Conveniently, are employed in the preparation of the compounds of equimolar amounts of 2-amino ~ l _f 3 _{»4-thiadiazoles, (carbon} disulfide and alkali metal hydroxide at about 0 to 5 ⁰ C eu ·. and does not add the equivalent amount of alkylating agent until after about 1/2 hour.

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Establishing the connection Vp

A solution of 50.7 g (0.3 mol) of 2-amino-5-trifluoromethyl-1,3,4-thiadiazole in 300 ml of dimethylformamide is mixed with a solution of 17 g (0.3 mol) of potassium hydroxide in 100 ml of water offset. Then 22.8 g (0.3 mol) of carbon disulfide are added, the mixture is stirred for 1 hour and 37.8 g (0.3 mol) of dimethyl sulfate are then added dropwise. After diluting with water, the resulting precipitate is filtered off with suction and recrystallized from ethanol. The N- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -dithiocarbamidsäure-methylester melts at 218 ⁰ C.

Establishing the connection 16

A solution of 20.3 g (0.12 mol) of 2-amino-5-trifluoromethyl-1,3,4-thiadiazole in 200 ml of dimethylformamide is treated with a "solution of 6.8 g (0.12 mol) of potassium hydroxide in 40 After 9.12 g (0.12 mol) of carbon disulfide have been added, the mixture is stirred for 1 hour.Then 15.2 g (0.12) mol) of benzyl chloride are added dropwise for 2 hours, ^{heated to 60 °} C. and on ice The precipitate is filtered off with suction and recrystallized from ethanol. The benzyl N- (5-trifluoromethyl-1,3,4-thiadiazol-2-yl) dithiocarbamate melts at 224.degree.

The N- (1,3,4-thiadlazol-2-yl) dithiocarbamic acid esters to be used in the manner according to the invention have opposite

many of the known stabilizers have the advantage that they |

contain no free mercapto groups. The photographic properties such as sensitivity, gradation and clarity are excellently stabilized by the compounds according to the invention without deteriorating graininess or haze will.

With many stabilizers, which are particularly effective against changes in the fog are, one often has to accept an often disturbing decrease in sensitivity to freshness. Other Stabilizers that still have a practically usable shelf life

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the haze values can be achieved, cause when used during storage a more or less strong, in any case undesirable change in sensitivity, mostly with simultaneous flattening of the gradation. In contrast stabilize the N, - (l, 3,4-thiadiazol-2-yl) dithiocarbamic acid esters mentioned here excellent both the clarity and the gradation and sensitivity, such, that the properties mentioned remain unchanged over long periods of time.

The N- (1,3,4-thiadiazol-2-yl) dithiocarbamic acid esters to be used in the manner according to the invention can both the silver halide layers, as well as other water-permeable Layers, e.g. sub-pouring, intermediate layers, protective layers or the baryage can be added. Puts if these compounds are added to the light-sensitive silver halide emulsions, this can be done at any stage of the preparation of the emulsion. Preference is given to adding before Post-ripening and as a pouring additive. The amount added can vary within wide limits. Generally have Quantities between 0.001 g and 5 g have proven to be sufficient. Particularly good results are obtained when the emulsion per mole Silver halide contains 1-50 mg of compounds according to the invention.

It is advantageous to add the compounds according to the invention in the form of solutions. Suitable as solvents are, for example, lower alcohols, tetrahydrofuran, acetone or dimethylformamide.

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4 20U622

The usual silver halide emulsions are used for the present invention suitable. These can be ala silver halide Dilberchlorid, Silberbroinid or mixtures thereof possibly with a small amount of silver iodide of up to 10 moles.

The preferred binder for the photographic layers is Gelatin used. However, this can be wholly or partly through other natural or synthetic binders be replaced. Natural binders include, for example, alginic acid and its derivatives v / ie salts, esters or amides, cellulose derivatives such as carboxymethyl cellulose, alkyl cellulose such as hydroxyethyl cellulose, starch or their derivatives such as ether or esters or caragenates are suitable. Synthetic binders may be mentioned polyvinyl alcohol, partly saponified | Polyvinyl acetate, polyvinyl pyrrolidone and the like.

The emulsions can also be chemically sensitized, e.g. by adding sulfur-containing compounds to chemical nucleation, for example Ayl isothiocyanate, Ax.i.yxthiourea, Sodium thio sulfate and the like. As a chemical Sensitizers can also be reducing agents, e.g. those in Belgian patents 493,464 or 568,687 "described tin compounds, also polyamines such as diet lylenetriamine, or aminomethylsulfinic acid derivatives, e.g. according to dor Belgian patent 547 323 can be used.

Also suitable as chemical sensitizers are precious metals "or precious metal compounds such as gold, platinum, palladium, Iridium, ruthenium or rhodium. This method of chemical sensitization is described in the article by R. Koslowsky, Z.Wiss. Phot. 46, 65-72, (1951).

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

A-G 7} 3 - 9 -

pick up, Clykolen, cyclischen Dehydratisierim ^ -produkteu υ on Hexitols, with alky! -Substituted phenols, aliphatic -Carboxylic acids, aliphatic amines, aliphatic diaiuinon and amides. The forii? ensat ionprodukie have a molecule?: · - Weight of at least 700, preferably more than 1000. These sensitizers are germinated to achieve special effects use in combination, of course, as in Belgian patent 537 278 and British patent 727 982.

The emulsions can also be optically sensitized, for example with the usual polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styrofoam dyes, oxonols and the like. Such sensitizers are described in the work of PM Hamor ¹¹¹ Ihο Cyanine Dyes and related Compounds ", (1964).

The emulsions can contain those in addition to the N- (1,3,4-thiadiazol-2-yl) -diihixiarbamic acid esters contain other well-known stabilizers, such as homeopolar or sa3aL.rt.ige compounds of the Mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds. Also suitable as stabilizers are azainuenes, preferably tetra- or pentaazaindenes, in particular those which are substituted with hydroxyl or amino groups. Such compounds are described in the article by Birr, Z. Wies. Phot. 47, 2-58 (1952). Other suitable stabilizers include heterocyclic mercapto compounds, e.g. Phenylmercaptotetratfol, quaternary bensthiazole derivatives, Benzotriazole and the like.

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

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The emulsions can also be in dissolved or dispersed form Color coupler included.

example 1

A highly sensitive silver bromide iodide emulsion with 6 Mo] -% . of silver iodide is produced in the usual way, with the silver nitrate solution running into a solution which, in addition to KBr and KJ, contains gelatine with intermittent breaks. The emulsion is flocculated in a known manner with ammonium sulphate and freed from the usual salts. The flocculate is redispersed in warm water, the desired amount of sulfur-containing frosting gelatine is added and matured in the presence of gold (I) thiocyanate complexes and sodium thiosulphate until it is optimally sensitive.

Before the emulsion is brought to maturation temperature, it is divided into 22 parts. The first part is matured without any further addition, while the other parts are mixed with a compound according to the following table.

After chemical ripening, 200 mg of 4-hydroxy ~ 6 ~ methyl-l, 3,3a, 7-tetraazaindene as a stabilizer, 600 mg of saponin as a wetting agent and 10 ml of a 10% aqueous solution of formaldehyde in each case based on 1 kg of Emulsion added.

The samples are then coated on a cellulose acetate support and dried, exposed in a sensitometer behind a gray wedge, and developed at 20 ⁰ C, 7 and 16 minutes in a developer i the following composition:

Sodium sulfite sicc. 70.0 g

Borax 7.0 g

Hydroquinone J 5.5 g

p-monomethyl arainophenol sulfate 3.5 g

Sodium citrate 7.0 g

Make up to 1 liter of potassium bromide 0.4 g with water

The results of the sensitometric evaluation can be seen from the following table 4:

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BATH ORIGINAL

Tabel

O CO OO

Ver
bind
No. per mole
. Ag X 7 'development time
E Γ ski 1.15 0.16 16 'development time
E IT ski 1.30 0.24 3 days of storage in a heating cabinet
7 'development time
E f Schi 0.90 0.35 Type 1.00 0.12 Type 1.35 0.15 -1.0 ° 0.80 0.20 1 2.5 mg + 1.5 ° 0.90 0.12 + 1.0 ° 1.30 0.17 -i, o ° 0.70 0.20 2 2.5 mg + 1.9 ° 0.95 0.11 + 1.9 ° 1.25 0.22 -i, o ° 0.70 0.25 3 5.0 mg + 1.0 ° 1.00 0.13 + 0.5 ° 1.30 0.23 -1.5 ° 0.90 0.27 4th 2.5 mg + 1.0 ° 0.95 0.12 + 0.5 ° 1.15 0.16 -1.5 ° 0.85 0.21 VJl 5.0 mg + 1.0 ° 1.20 0.12 + 0 ° 1.35 0.23 -1.0 ° 0.95 0.28 7th 2.5 mg + 2.0 ° 1.25 0.14 + 2.0 ° 1.35 0.20 + 0 ° 0.95 0.29 8th 5.0 mg + 1.0 ° 1.10 0.12 + 0.5 ° 1.20 0.18 -i, o ° 1.00 0.22 9 5.0 mg + 0 ° 1.15 0.14 + 0 ° 1.30 0.18 + 0 ° 0.90 0.27 10 2.5 mg I 0.5 ° 1.00 0.13 + 0.5 ° 1.05 0.20 - i, o ° 0.85 0.24 11 10.0 mg + 0.5 ° 1.25 0.14 + 0.5 ° 1.30 0.18 -i, o ° 0.95 0.23 12th 2.5 mg + 1.9 ° 1.05 0.12 + 2.0 ° 1.20 0.17 + 0 ° 0.90 0.21 13th 5.0 mg + 0 ° 0.90 0.14 -0.5 ° 1.10 0.18 Ιι, ο ° 0.90 0.28 17th 2.5 mg + 2.0 ° 0.95 0.13 + 1.0 ° 1.25 0.21 -ι- 0 ° 0.85 0.29 18th 2.5 mg + 2.0 ° 1.00 0.14 + 2.0 ° 1.30 0.23 + 0 ° 0.95 0.30 19th 2.5 mg + 1.9 ° 1.00 0.13 + 1.9 ° 1.25 0.23 I 0 ° 0.95 0.28 20th 2.5 mg + 0.5 ° 1.20 0.14 + 1.0 ° 1.35 0.20 I 0 ° 0.95 0.28 21st 2.5 mg + 0 ° 1.10 0.13 + 1.0 ° 1.20 0.17 I 0 ° 1.00 0.22 22nd 5.0 mg + 0 ° 1.10 0.14 + 0 ° 1.15 0.21 -i, o ° 0.90 0.28 23 2.5 mg + 0 ° 1.15 0.13 + 0 ° ■ 1.35 0.23 + 0 ° 1.00 0.30 25th 2.5 mg il _f 0 ° 1.10 0.14 + 1.0 ° 1.35 0.23 + 1.0 ° 1.00 0.29 26th 2.5 mg + 1.0 ° + 1.0 ° + 0.5 °

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3 ° = 1 aperture

In the last column of the table shows the sensitometric results are reported of samples which were stored prior to the exposure for 3 days in a heat chamber at 60 ⁰ C and then developed long Alike 7. ¹

Example 2

A highly sensitive silver bromide iodide emulsion with 5% Silver iodide is produced in the usual way, with the Silver nitrate solution runs into a solution that contains KJ and KBr gelatine, with breaks in between. the The emulsion is flocculated with ammonium sulphate in a known manner and freed from the soluble salts by washing. That Flocculate is redispersed in warm water, the desired amount of sulfur-containing frosting gelatine is added and in the presence of gold (I) thiocyanate complexes and sodium thiosulphate matured to optimal sensitivity.

Then 200 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene are added to the emulsions as a stabilizer, 600 mg of saponin as a wetting agent and 10 ml of a 10% aqueous solution of Formaldehyde based on 1 kg of emulsion was added. The emulsion is then divided into 19 parts. The 1st part remains without addition, the other parts contain the compounds according to the following table 4.

The emulsions are poured onto a layer support made of cellulose acetate, dried and, as already described, exposed and developed. Some of the samples are stored at 60 ° for 3 days and developed at 20 ° for 16 minutes. The results of the sensitometric test are listed in the following table. It can be seen from this that a clear fog-stabilizing effect can also be observed in the heating cabinet. The substances can therefore be added both as a frosting agent and as a pouring additive to significantly improve the haze of the emulsion. In the last column of the table shows the sensitometric results are reported of samples that are stored prior to the exposure for 3 days in a heat chamber at 60 ⁰ C and then processed in the same way.

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Table 4

Ver
bind.
No. per mole
Ag X I.
7 'development time
E <T ski 1.00 0.15 16 'development time
Ξ ΐ Ski 1.20 0.22 3 days of storage in a heating cabinet
16 'development time
E ΐ ski 1.05 0.35 r Type 1.07 0.10 Type 1.20 0.15 -0.5 ° 1.22 0.20 1 3 mg -0.5 ° 1.00 0.10 + 0 ° 1.25 0.16 + 0 ° 1.10 0.23 2 3 mg -0.5 ° 1.05 0.10 + 0 ° 1.20 0.14 I 0 ° 1.15 0.19 3 3 mg + 0 ° 1.00 0.09 -0.5 ° 1.20 0.14 I 0 ° 1.15 0.19 4th 3 mg - 0.5 ° 1.00 0.08 -0.5 ° 1.25 0.12 + 0 ° 1.20 0.17 5 3 mg + 0 ° 1.00 0.12 + o ° 1.15 0.17 + 0 ° 1.05 0.22 7th 15 mg - 0.5 ° 1.05 0.12 - 1.0 ° 1.25 0.18 + 0 ° 1.20 0.23 204 8th 3 mg -0.5 ° 1.05 ο, ιο - 0.5 ° 1.10 0.13 + 0 ° 1.10 0.18 9 15 mg + 0 ° 1.06 0.13 -0.5 ° 1.26 0.19 -0.5 ° 1.10 0.25 10 3 mg ΐθ, 5 ° 1.10 0.12 + 0 ° 1.25 0.18 + 0 ° 1.15 0.23 11 3 mg + 0.5 ° 1.00 0.11 + 0 ° 1.20 0.18 I 0 ° 1.30 0.22 12th 3 mg + 0 ° 0.95 0.10 + 0 ° 1.05 0.12 ± °° 1.00 0.19 13th 3 mg -1.5 ° 1.05 0.12 -1.5 ° 1.25 0.18 - i, o ° 1.30 0.20 17th 3 mg + 0 ° 1.15 0.11 -0.5 ° 1.25 0.15 + 0.5 ° 1.25 0.20 19th 15 mg + 0 ° 1.00 0.10 + 0 ° 1.20 0.17 + 0.5 ° 1.05 0.24 21st 3 mg - 0 5 ° 1.05 0.10 -0.5 ° 1.10 0.13 + 0 ° 1.10 0.18 23 15 mg 4- 0 ° 1.00 0.11 - 0.5 ° 1.15 0.16 -0.5 ° 1.20 0.23 25th 15 mg + 0 ° 1.00 0.10 -0.5 ° 1.20 0.16 -0.5 ° 1.15 0.20 26th 3 mg I 0 ° -0.5 ° + 0 °

3 = 1 aperture

- 14 -

Claims ;

ClJ Light- sensitive photographic material with at least one silver halide emulsion layer, characterized by a content of at least one N- (1,3,4-thiadiazol-2-yl) -dithiocarbamic acid ester of the following formula:

NNR ²

R ¹ 1! ^ S ^ JL NC -SR ³

where mean:

R ¹ = (1) hydrogen, (2) a saturated or olefinically unsaturated, straight-chain, branched or cyclic aliphatic group, (3) alkoxy, (4) alkylthio, (5) aryl, (6) aroxy, (7) arylthio or

(8) a nitro group;
ρ
R = hydrogen, an alkyl, alkenyl or alkynyl radical

with 1-4 carbon atoms;

R = (1) a saturated or unsaturated, straight-chain, branched or cyclic aliphatic group, (2) aryl or (3) aralkyl.

2. Photographic light-sensitive material according to

ρ claim 1, characterized in that R is hydrogen or

represents an alkyl radical with 1-3 C atoms.

3. Photosensitive photographic material according to claim 1, characterized in that R is trifluoromethyl, Alkylthio with up to 5 carbon atoms, phenylthio or one Alkoxy represents alkyleneoxy grouping.

4. Photosensitive photographic material according to claim 1, characterized in gel
Represents chlorobenzyl.

■ χ

Claim 1, characterized in that R is methyl or

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