DE1155330B - Photographic copy material or treatment bath with anti-bronzing agent - Google Patents

Description

GERMAN

PATENT OFFICE

G36782IXa / 57b

REGISTRATION DAY; 4. J A N U A R 1963

NOTICE
THE REGISTRATION
AND ISSUE DEK
EDITORIAL: OCTOBER 3, 1963

Those in photosensitive halogen silver emulsion copier layers The images obtained often experience changes during treatment, including during the high-gloss treatment or during the bath machine drying at high temperature. Loss of density easily occurs during these edits by "partial burning" or "bronzing" of the silver picture.

It is known to use a photosensitive material or certain treatment baths containing halide of silver add small amounts of chemical compounds to prevent the loss of density caused by high gloss.

Besides the fact that these compounds do not completely eliminate bronzing, they still show various disadvantages of adding them to a silver halide emulsion.

The most important disadvantage is their usually very strong desensitizing effect.

It has now been found that, when the photosensitive halogen silver emulsion layer and / or at least one water-permeable layer of the photographic print light-sensitive material on the same side of the support as this emulsion layer and / or at least one photographic Bath incorporates a compound of the general formula

Ri-NH-C-Xi-R ₂ -SX ₂
O

in which Ri is an aryl group or a substituted aryl group, R _{2 is} a divalent group such as an alkylene group, Xi is an oxygen atom or an imide group, and X _{2 is} a hydrogen atom, an alkali metal atom, an ammonium group or a silver atom, which is caused by the warm high gloss or the machine The disadvantages caused by drying are eliminated.

The compounds to be used according to the invention can be used both in free mercapto form also in the form of their alkali salts, their ammonium salts or their colloidal silver salts.

The photosensitive silver halide emulsion to which compounds of the present invention are incorporated can be any copier halogen silver emulsion, such as gelatin chlorine silver, a Gelatine chlorobromosilver, a gelatine chloroiodosilver, a gelatine bromide silver, a gelatine bromoiodosilver and a gelatin chlorobromoiodosilver photographic material

or treatment bath
with anti-bronzing agent

Applicant:

Gevaert Photo-Products NV,
Mortsel, Antwerp (Belgium)

Representative: Dr. W. Müller-Bore and Dipl.-Ing. Grailfs, Patent attorneys, Braunschweig, Am Bürgerpark 8

Claimed priority:
Beige from January 5, 1962 (No. 41 269)

Dr.-Chem. Jozef Frans Willems,

Hendrik Adolf Pattyn
and Dr.-Chem. Gerard Michiel Sevens,

Wilrijk, Antwerp (Belgium),
have been named as inventors

emulsion. It can be sensitized chemically as well as spectrally. After all, it can do all of them known additives such as anti-fog agents, stabilizers, hardeners, plasticizers and dispersants, contain.

You can the compounds to be used according to the invention at any stage of the Emulsion production, including during the formation of the halogen silver or during the physical or add chemical ripening. But they are preferably placed after the chemical one Maturation too.

The added amount of the compounds to be used according to the invention depends on the one used Emulsion, but is generally between 0.150 and 9 g (preferably between 0.25 and 4.7 g) per mole of halogen silver, if it is the free mercapto compounds, their alkali or ammonium salts regards. When using the silver salt in the form of a colloidal dispersion in gelatin or in another protective colloid, this amount is between 0.3 and 18 g (preferably between 0.5 and 10 g) per mole of halogen silver.

When using the silver salts of the compounds to be used according to the invention, neither occurs

309 690/225

Loss of speed nor loss of contrast of the photographic print material while occasionally when using the compounds in free mercapto form or as alkali or ammonium salts slight reductions in sensitivity and irregular haze are caused.

However, this can be counteracted in a convenient manner by incorporating a small amount of p-toluenesulfinic acid, usually in a concentration between 0.06 and 0.35 g / m ² , into the photographic material, preferably in its water-permeable layers.

It is also possible to use the compounds of one of the light-sensitive compounds to be used according to the invention Layer adjacent water-permeable layer, including the top layer, or a incorporated into another layer, from which it then afterwards in free mercapto form during fixation the halogen silver emulsion can diffuse over.

The amount of compound to be used according to the invention added to the top layer or water-permeable auxiliary layers varies mostly from 5 to 150 mg / m ² when it comes to the free mercapto form, the alkali metal or ammonium salts, and from 10 to 350 mg / m ² when it comes to the silver salts regards.

You can the compounds according to the invention a treatment bath such as the fixer or add a separate treatment bath, e.g. B. just before the warm high gloss or machine Dry. This bath can optionally contain surface-active compounds. The concentration the compounds according to the invention present in such baths mostly vary from 0.5 to 2.5 g / l.

Preparation examples of some compounds according to the invention now follow. These manufacturing examples concern the free mercapto form of the compounds, of which, if necessary, the salts are easily accessible.

Make 3 NH-CO-CH ₂ -CH ₂ -SH

N ^ -Naphthyl ^ '- mercaptoethyl carbamate

In a 500 ml three-necked flask equipped with a stirrer, thermometer, dropping funnel and condenser with a calcium chloride tube, 33.8 g of naphthyl isocyanate are dissolved by warming up in 150 cm ^{3 of} anhydrous benzene. It is cooled to about 40 ⁰ C., and this solution was added dropwise a solution of 17.2 g yS-mercaptoethanol in 50 cm ³ of anhydrous benzene is added, while ^x / a hour at boiling point the whole was heated. 1 After 24 hours, the precipitate formed is filtered off with suction and the filtrate is concentrated. Is extracted for the first precipitation, together with the residue obtained in a Soxhlet apparatus at 90 to 120 ⁰ C with gasoline. After cooling and filtering off with suction, 16 g of solid reaction product are obtained. Melting point: 88 ° C.

Manufacturing 4

NH-CH ₂ -CH ₂ -SH

Manufacturing 1

^ NH-CO-CH ₂ -CH ₂ -SH +5 O

N-phenyl-2'-mercaptoethyl carbamate

The preparation of this product is described by J. F. Smith and E. C. Friedrich in J. Am. Chem. Soc, 81, p. 161 (1959).

N-phenyl-N'-2-mercaptoethylurea

^{8.5 g of β-mercaptoethylamine are dissolved in 350 cm 3 of} anhydrous benzene in a 500 ml three-necked flask equipped with a stirrer, thermometer, dropping funnel and condenser with a calcium chloride tube. The solution is cooled to about 45 ⁰ C and then dropwise add a solution of 11.9 g of phenyl isocyanate in 50 cm ³ of anhydrous benzene, while keeping the temperature at about 50 ° C. The solution immediately becomes cloudy, whereupon a precipitate forms. It is allowed to digest on a water bath for a further 2 hours. After cooling, suction and recrystallization from ethanol, 9.5 g of solid product are obtained. Melting point: 193 ⁰ C.

Manufacturing 5

- C —NH — CH ₂ —CH ₂ —SH

Manufacturing 2

NH-CO-CH ₂ -CH ₂ -SH

N-1 -naphthyl ^ '- mercaptoethyl carbamate

The preparation of this product is also described by J. F. Smith and E. C. Friedrich in J. Am. Chem. Soc, 81, p. 161 (1959).

N-1-naphthyl-N'-2'-mercaptoethylurea

In a 500 ml three-necked flask equipped with a stirrer, thermometer, dropping funnel and condenser with a calcium chloride tube, 8.5 g /? - mercaptoethylamine are dissolved in 300 cm ^{3 of} anhydrous benzene. The solution is cooled to about 35 ° C and then dropwise add a solution of 16.9 g of a-naphthyl isocyanate in 50 cm ³ of anhydrous benzene, while keeping the temperature at about 40 ⁰ C. A white precipitate is immediately obtained, which is allowed to digest on a boiling water bath for 2 hours. After cooling, suction filtration and recrystallization from acetonitrile, 20 g of product are obtained. Melting point: 168 ° C.
The following examples illustrate the invention.

example 1

An ammoniacal gelatin bromoiodide emulsion is used medium gradation, which contains 3.5 mole percent iodized silver, based on the total amount of halogen silver, the following specified amounts of products according to the invention. You pour these emulsions on you like that barytized paper backing that the emulsion layers obtained have one with 2 g of silver nitrate per square meter contain equivalent amount of halogen silver. These photosensitive emulsion layers are then coated with a gelatin-containing one Cover layer and exposes the materials behind a sensitometric step wedge. After developing, Rinsing and fixing, the materials are glossy by placing the image sides against them a heated, polished metal surface is pressed. They are measured before and after the high-gloss finish Reflection densities with the Macbeth densitometer. The results obtained can be found in following table:

Maximum blackening after before High High- shine shine Comparison material (without inventive anti 1.80 bronzing agent) 2.13 Material like the comparison material, but with 15 mg des Product according to manufacture 1 2.03 per square meter 2.10 Material like the comparison material, but with 15 mg des Product according to manufacture 2 2.08 per square meter 2.08 Material like the comparison material, but with 15 mg des Product according to manufacture 3 2.06 per square meter 2.15 Material like the comparison material, but that per square meter 27 mg of the colloidal Silver salt of the product according to production 1 in the form incorporated into a dispersion 2.11 became 2.12

Example 2

One pours ammoniacal gelatin bromoiodosilver emulsions of medium gradation, the 3 mole percent Iodized silver, based on the total amount of halogen silver, and those in the following table The specified amounts of anti-bronzing agent contain, on a barytaed paper backing, in such a way that the emulsion layers per square meter Contain an amount of halogen silver equivalent to 2.5 g of silver nitrate. You treat the materials like the material of example 1 and obtains the following results:

Comparison material (without
anti-bronzing agent according to the invention)

Material like the reference material, but 20 mg of colloidal per square meter
Silver salt of the product
incorporated according to preparation 5 in the form of a dispersion
became

Material like the reference material, but 20 mg of colloidal per square meter
Silver salt of the product
incorporated according to preparation 3 in the form of a dispersion
became

Maximum blackening after

High gloss

1.90

1.93

1.93

High gloss

1.75

1.87

1.97

Example 3

Cast ammoniacal gelatin bromoiodosilver emulsions with high contrast, the 1 mole percent Iodized silver, based on the total amount of halogen silver, and those in the following table specified amounts of anti-bronzing agent · contain, on a baryta-coated paper backing that the emulsion layers an amount equivalent to 2.8 g of silver nitrate per square meter of halogen silver contain. After treatment as in Example 1, the following results are obtained:

Comparison material (without Maximum blackening after 40 inventive anti before High bronzing agent) High shine Material like the comparison shine material, but with 10 mg 45 Product after manufacture 5 1.82 or its sodium salt 2.11 per square meter Comparison material (without inventive anti So bronzing agent) 1.94 Material like the comparison 2.13 material, but with 10 mg Product after manufacture 1 1.78 or its sodium salt 2.11 55 per square meter Material like the comparison material, but with 10 mg Product after manufacture 3 2.03 60 or its sodium salt 2.10 per square meter Comparison material (without inventive anti bronzing agent) 1.98 65 2.10 1.87 2.17

I 155 330

Maximum blackening after before High High shine shine Material like the comparison material, but that per square meter 17 mg of the colloidal Silver salt of the product after Manufacturing 1 in the form of a 2.01 Dispersion were incorporated 2.14 Material like the comparison material, but that per square meter 17 mg of the colloidal Silver salt of the product after Manufacture 3 in the form of a 1.97 Dispersion were incorporated 2.19

Example 4

A photosensitive material as described in Example 1, but without products according to the invention, is exposed, developed and treated in a fixing bath containing 1 g of the compound per liter Manufacture 1 contains. The following results are obtained:

After the usual fixation

After fixing as described
in this example

Example 5

Maximum blackening

after
High-

before
High gloss

2.11
2.10

shine

1.78
1.98

After the usual casting solutions have been added, a gelatin chloroiodosilver emulsion with 1.5 mol percent is cast Iodide, based on the total amount of halogen silver, on a barite-coated paper carrier. After drying, this material is exposed behind a step wedge, developed, fixed and rinsed. The treated material is made shiny by placing the image side against a heated polished metal surface is pressed. A strong bronzing of the silver picture is obtained, especially in the area of the pointed lights. Assuming the same emulsion, but before the potting an alcoholic solution of 385 mg of the product according to preparation 1 was added per 12 g of silver, only a very slight reduction in blackening is found after high gloss. When measuring the Maximum densities of these two materials with a Macbeth densitometer are as follows Results:

Example 6

The silver halide emulsion from Example 5 is poured onto a barite-coated paper support. This emulsion layer is covered with a top layer of an aqueous composition which contains 20 g of gelatin and 50 cm ^{3 of} a 1% alcoholic solution of the compound according to preparation 2 per liter. This top layer solution is poured so that 1 liter covers ^{15 m 2.}

Example 7

An orthosensitized gelatin chloroiodosilver emulsion for reproduction purposes (0.6 mol percent iodide, based on the total amount of halogen silver), made with 45 g of silver nitrate per kilogram of emulsion, is poured onto a barite paper support of 90 g / m ² . One exposes one

ao strip of this material behind a step wedge, develops, fixes and rinses. Then you dry this strip by machine by adding it the back presses against the heated metal surface. The material treated in this way shows There is considerable bronzing, especially in the areas of high density.

If, however, 20 cm ^{3 of} a 1% alcoholic solution of the product according to preparation 2 are added per kilogram of emulsion, a noticeably better result is achieved after machine drying, as can be seen from the following table.

Comparative material

Material according to the invention

Maximum blackening

after ordinary drying

1.45 1.49

after machine drying

1.28 1.43

Claims (1)

PATENT CLAIM: Comparative material Material according to the invention Maximum blackening after
High- before
High gloss 2.22
2.14 shine 1.73
2.08 Photographic copy material with at least one light-sensitive halogen silver emulsion positive layer or photographic processing bath, characterized in that this halogen silver emulsion layer and / or at least one water-permeable layer on the same side of the support as the halogen silver emulsion layer or the bath contains at least one compound of the general formula: Ri-NH-C-Xi-R ₂ -SX ₂ O in which Ri is an aryl group or a substituted aryl group, R _{2 is} a divalent group, Xi is an oxygen atom or an imide group and X _{2 is} a hydrogen atom, an alkali metal atom, an ammonium group or a silver atom.