DE1177929B - Use of a new anti-bronzing agent for photographic printing materials - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN VMTQSSl PATENT OFFICE Internat. KL: G 03 c

EXTENDED

German class: 57 b -8/02

Number: 1177 929

File number: G 40007 IX a / 57 b

Filing date: March 4, 1964

Opening day: September 10, 1964

The invention relates to agents which prevent photographic print material from being obtained Image bronzed by warm high gloss or by machine drying at high temperature.

Those in light-sensitive silver halide emulsion layers of a photographic print material The images obtained often experience changes during the warm high-gloss or during the machine Drying at high temperature, because there is a loss of density during these treatments, the also called "partial burning" or "bronzing" of the silver image.

It is known to the photosensitive material containing a halide silver emulsion copying layer or the treatment baths for such material to prevent this loss of density Incorporating small amounts of certain chemical compounds.

Most of the time, these compounds only partially turn off bronzing and also work pretty well desensitizing the photosensitive material when incorporated into this material.

It has now been found that optionally substituted 6 - thioxo - 5,6 - dihydrobenzimidazo- [1,2-c] quinazolines, prevent their tautomeric forms and the salts of these tautomeric forms, that the developed silver-containing image by warm mirroring or drying at high temperature loses its density in a noteworthy way.

These anti-bronzing agents can be incorporated into the photographic material, namely the Halogen silver emulsion layer and / or at least one water-permeable layer on the same side of the support such as the halogen silver emulsion layer. However, the anti-bronzing agents can also be used in at least dissolved in one of the baths in which the photographic material is processed.

These benzimidazoles, 2-c] quinazolines can, for example be substituted by an alkyl, alkoxy, halogen, amino or acetylamino function.

Some particularly suitable compounds to be used according to the invention are:

6-thioxo-5,6-dihydrobenzimidazo [1,2-c] quinazoline, 6-thioxo-9-methyl-5,6-dihydrobenzimidazo [1,2-c] -

quinazoline,
6-thioxo-9-methoxy-5,6-dihydrobenzimidazo [1,2-c] -

quinazoline,
6-thioxo-l l-methyl-5,6-dihydrobenzimidazo [l, 2-c] -

quinazoline,
6-thioxo-9-chloro-5,6-dihydrobenzimidazo [1,2-c] -

quinazoline,

Use of a new anti-bronzing agent for photographic printing materials

Applicant:

Gevaert Photo-Producten N.V.,

Mortsel, Antwerp (Belgium)

Representative:

Dr. W. Müller-Bore, Dipl.-Ing. H. Gralfs
and Dr. G. Manitz, patent attorneys,
Braunschweig, Am Bürgerpark 8

Named as inventor:

Dr. Jozef Frans Willems,

Dr. Albert Luden Poot, Wilrijk, Antwerp,

Paul Desire van Pee, Edegem, Antwerp

(Belgium)

Claimed priority:

Belgium of March 29, 1963 (42 481, 630 297) -

their tautomeric forms and salts of these tautomeric forms.

These benzimidazoles, 2-c] quinazolines can, like described by A. Poot, J. Willems and F. Huygebaert, Bull. Soc. Chim. BeIg., 72 (1963), 365.

When the benzimidazoles, 2-c] quinazoline in one of the composing layers of the photosensitive Material are processed, they protect the silver-containing image not only from loss of density during warm high gloss or drying at elevated temperature, as already described, but put also down the veil without affecting the sensitivity and gradation in any noteworthy way. The 6-oxo-5,6-dihydrobenzimidazo [l, 2-c] quinazolines, their tautomeric forms and the salts of these tautomeric forms.

When the benzimidazo [1,2-c] quinazolines to be used according to the invention are incorporated into the photographic These compounds are mostly used as copying material for the photosensitive halogen silver emulsion copying layer incorporated. You can copy the silver emulsion at any moment their production, but preferably after chemical ripening or just before

409 660/346

Potting can be added. This addition will be 100 mg / l dissolved in the bath. If the photoim generally passed through such a bath from a solution of the compound in graphic copy material A suitable solvent, such as water, alcohol will take it into its water-permeable layers etc., made. Instead of the compounds in the some amount of Benzimidazo [l, 2-c] quinazoline Incorporate photographic copy layer, can: ■ on what the retention of the density of the silver also a water-permeable layer, such as a containing picture with warm high gloss or with Gelatin top layer or an intermediate layer, drying at high temperature is equally well guaranteed will. Of course, it is also possible, as does the presence of the anti-bronzing mixtures of various benzimidazoles, 2-c] - means in the photosensitive copying material of use quinazolines. io whose manufacture depends.

The total concentration of benzimidazo [l, 2-c] - The following examples illustrate the invention,

quinazolines in photosensitive copying material B e i s d i e 1 1 can vary within wide limits, but will

preferably chosen so that between some muli-material grams and 500 mg of this compound or compound 15 A gelatin chlorosilver emulsion made with

fertilize per square meter of light-sensitive material a ratio of silver nitrate to gelatin of

be found. 1: 4 (28.3 g / 113.2 g) per kilogram of emulsion

The light-sensitive material can be any in this way on a baryta-coated paper support.

Copy halogen silver emulsion layer have as brought that after drying per square meter a gelatin chlorosilver, a gelatin chlorobromomine light-sensitive material a lot of halosilver

silver, a gelatin chloroiodosilver, a gelatin is present, equivalent to 1.5 g of silver nitrate. on

Silver bromide, a gelatine silver bromide and a light-sensitive layer are cast

Gelatin chlorobromiodosilver emulsion layer. The Ha- thin gelatin top layer that is hardened Logensilberemulsion can contain all known additives such as

anti-fog agents, stabilizers, hardeners, 25 material 2a

Contain plasticizers and dispersants. Proceed as in the production of material 1,

It can also be used chemically as well as spectrally, but per kilogram of ready-to-cast light-sensitive

be sensitized. It can be chemically sensitized sensitive emulsion 0.3 g 6-thioxo-5,6-dihydrobenz-

be done by ripening in the presence of imidazo [l, 2-c] quinazoline, which consists of a l%

small amounts of sulfur-containing compounds, added to a solution in dimethylformamide, for example allyl isothiocyanate, allyl thiourea, Na-

trium thiosulfate, etc., performs. The photosensitive material 2 b

borrowed copier emulsions can also be carried out by Reduk- Man as in the production of material 1,

tion means, e.g. B. those used in the Belgian patents but per kilogram of cast-clear light-

493 464 and 568 687 described tin compounds, 35 sensitive emulsion 1 g 6-thioxo-5 ~, 6-dihydrobenz-

in the Belgian Patent 547,323 described imidazo [l, 2-c] quinazoline, "which consists of a l ° / _o by weight solu-

benen iminoaminomethanesulfinic acid compounds, _S ung in dimethylformamide was added, or by small amounts of noble metal compounds,

such as compounds of gold, platinum, palladium, Iri material 3 a

dium, ruthenium and rhodium. 40 Proceed as in the production of material 1,

It is also possible to use the emulsions with polyalkylene but use "pourable clear light" per kilogram

to sensitize oxide derivatives, e.g. B. Polyethylene oxide sensitive emulsion 0.3 g 6 - thioxo - 9 - methyl-

a molecular weight between 1000 and 20,000, 5,6-dihydrobenzimidazo [1,2-c] quinazoline, which from

condensation products of alkylene oxides added with and l ° / _o by weight solution in dimethylformamide

aliphatic alcohols, glycols, cyclic dehy- 45 was.

Dratization products of hexitols, with alkyl _M. . ,,

substituted phenols, aliphatic carboxylic acids, ^{a eria}

aliphatic amines, aliphatic diamines and you proceed as in the preparation of material 1,

Amides. The condensation products have a mole used but per kilogram of ready-to-cast light-

kular weight of at least 700, preferably ₅ o sensitive emulsion 1 g 6-thioxo-9-methyl-5,6-di-

more than 1000. To achieve special effects, hydrobenzimidazo [l, 2-c] quinazoline, which consists of a

If these sensitizers of course added l com- ° / _o by weight solution in dimethylformamide

ned use, as was stated in the Belgian patent specification.

537,278 and in British patent specification 727,982. One strip of each of these five materials is used

is described. 55 exposed for a few minutes and 5 minutes in one

Instead according to the invention corresponds to use encryption bath of the following composition at 2O ⁰ C

wraps bonds in the photographic print material:

you can incorporate them in one of the hand water 800 cm ³

dissolve treatment baths, like the development bath the p-monomethylaminophenölsulfat ". '. 1,5ε

Fixing bath, an additional hardening bath and a bath, 60 anhydrous sodium sulfite 50 g "

which contains surface-active compounds and the hydroquinone '....'. '.'. '. 6g

The last treatment bath before the warm high- Anhydrous sodium carbonate 32 g

shiny or drying, for example with increased potassium bromide 2 2

Temperature, of the image-containing material switched on _water ".". '. ".".'. ". '.". ".". ".' Z to '1000 cm *

became. Most often the 6-thioxo-5,6-dihydro-65

benzimidazofl, 2-c] quinazoline as alkali salts in con- The strips of material are placed for a moment

centrations that vary within very wide limits and then 5 minutes in the following

can ieren, but preferably fixed between 50 and composition at room temperature:

Water 800 cm ³

Sodium thiosulphate anhydrous .... 120 g

Potassium metabisulphite 25 g

Water up to 1000 cm ³

Then they are rinsed for another 30 minutes and immersed in the following preservation solution for a few seconds :

2 - SuIf ο - 2 '- [(3,4 - dichlorophenyl) - ureylene] - 4,4' - dichlorodiphenyl ether (under
the trade name MITIN FF from
JR Geigy AG, Basel, Switzerland

brought to market) 2 g

Water 80 cm ³

Acetone 20 cm ³

The five strips of material are finally pressed with their light-sensitive page 6 minutes against a polished plate at a temperature of 80 ⁰ C.

Then the densities of the various strips of material were measured using a Macbeth densitometer measured before as well as after high gloss. The following results were obtained:

Material 1 (comparison material)

Material 2a

Material 2b

Material 3 a

Material 3b

Density
shine before after high-high gloss j

2.12
2.12
2.08
2.13
2.12

1.82 2.02 2.08 2.08

2.12

From this it can be clearly seen that a material according to this invention has a very high gloss due to its warm high gloss suffers little or no loss of density.

Example 2
Material 1

A gelatin bromoiodosilver emulsion (3 mole percent iodide) made with a ratio of silver nitrate to gelatin of 1: 3 (31.6 g / 94.8 g) per kilogram of emulsion, is so on a barite Paper backing shed that after drying a lot per square meter of photosensitive material Halogen silver is present, which corresponds to 2.2 g of silver nitrate. On this photosensitive Layer you pour a thin gelatin top layer, which you harden.

Material 2

Material 3

Proceed as in the production of material 1, but uses 0.3 g of 6-thioxo-9-methyl-5,6-dihydrobenzimidazo [l, 2-c] quinazoline per kilogram of ready-to-cast light-sensitive emulsion, which was added from a 10% solution in dimethylformamide.

6o

The procedure is the same as for the production of material 1, but using light-sensitive ready-to-cast materials per kilogram Emulsion 0.3 g of 6-thioxo-9-methoxy-S.o-dihydrobenzimidazofl ^ -cjquinazolin, which was added from a 1% solution in dimethylformamide.

One strip of each of these three materials is produced in the same way as the material strips from Example 1 treated. The following results are obtained:

Material 1 (comparison material)

Material 2

Material 3

Density
before ι after
High- I high-gloss I shine

1.98
2.04
1.97

j ₀ The same conclusions can be drawn from these results as from the results from Example 1.

Example 3
Material 1

, A gelatin chlorobromide silver emulsion (50 mole percent Chloride), made with a ratio of silver nitrate to gelatin of 1: 5 (36 g / 180 g) per Kilogram of emulsion is poured onto a baryta paper carrier in such a way that after Dry an amount equivalent to 2.2 g of silver nitrate per square meter of light-sensitive material Halogen silver is present. A thin gelatin top layer is poured onto this light-sensitive layer, which is hardened.

Material 2

The procedure is as in the preparation of material 1, but used per kilogram ready for casting light-sensitive emulsion 0.3 g of 6-thioxo-5,6-dihydrobenzimidazo [l, 2-c] quinazolin which ^s from a l% solution in dimethylformamide iS became.

Material 3

The procedure is the same as for the production of material 1, but using light-sensitive ready-to-cast materials per kilogram Emulsion 0.3 g of 6-thioxo-9-methyl-5,6-dihydrobenzimidazo [l, 2-c] quinazoline, from a 10% solution in dimethylformamide was added.

Material 4

The procedure is as in the preparation of material 1, but used per kilogram ready for casting light-sensitive emulsion 0.3 g of 6-thioxo-9-methoxy-5,6-dihydrobenzimidazo [l, 2-c] quinazoline, which consists of a l ° / _o igen solution in dimethylformamide was added.

These strips of material were treated in the same manner as that of Example 1, and the following were obtained Results:

Material 1 (comparison material)

Material 2

Material 3

Material 4

before
High gloss

Density
after
High-

2.06
1.98
1.98
1.94

shine

1.88
1.96
2.02
1.98

The same conclusions as can be drawn from the results of Example 1 can be drawn from these results.

Example 4

Four strips of material, composed like the comparative material from Example 3, are like that Treated strips of material from Example 1. For the

However, when the strips of the second, third, and fourth material were treated, 0.5 g of 6-thioxo-5,6-dihydrobenzimidazo [1,2-c] quinazoline dissolved in the developing bath, in the fixing composition or in a hardening bath (40% aqueous formaldehyde solution), which was also switched on as the last treatment bath and in which the fourth material Was treated for 10 minutes.

Density
before ' after
High- ; High
shine: shine 1.34
2.05
1.94
1.78 Material 1 (comparison material) ....
Material 2 1.78
2.02
1.88
1.74 Material 3 Material 4

The anti-bronzing agents to be used according to the invention are therefore very effective if they are one are incorporated into the treatment baths.

Claims (1)

Claim: Use of an optionally substituted 6-thioxo-5,6-dihydrobenzimidazo [l, 2- c] quinazoline, a tautomeric form of this compound and / or a salt of this tautomeric form as ίο Anti-bronzing agents for photographic copy material with at least one photosensitive halide silver emulsion layer, which Compounds in particular of the photographic emulsion layer and / or at least one water-permeable Layer on the same side of the support as the silver halide emulsion layer or a photographic processing bath can be added. 409 660/346 9.64 © Bundesdruckerei Berlin