DE1145014B - Photographic material composed of one or more halosilver emulsion layers - Google Patents

Description

GERMAN

PATENT OFFICE

G29624Ka / 57b

REGISTRATION DAY:

NOTICE THE REGISTRATION AND ISSUE OF EDITORIAL:

May 6, 1960

MARCH 7, 1963

This invention relates to improved photographic material, and more particularly to Halogen silver emulsion layers with increased developability and general light sensitivity.

It is known that the general sensitivity of photographic emulsions which have already been used for the whole range of the spectrum by means of so-called chemical sensitizers, such as sulfur sensitizers, can be optimally sensitized, even further by adding polyglycols to the photographic elements (see British Patents 548 019 and 600 058).

It is also known that this speed increase is achievable if in the photographic material Alkylene oxide polymers are processed, which by polymerization of alkylene oxide in the presence of hexitol ring dehydrogenation products, aliphatic alcohols, aliphatic acids, amines, Amides and phenols are produced (see. British Patents 592 676, 748 745 and 748 750).

It is also known that these polyglycols and alkylene oxide polymers have a molecular weight of at least 400 must have and that it is necessary in practice to achieve a significant Effect of using compounds whose molecular weight is 1500 to 2000 and more.

In contrast to the other known methods of increasing the sensitivity of halogen silver emulsions, like these after the self-sensitivity caused by the chemical sensitizers and those after the spectral absorption is increased by the cyanine dyes, it has been found that the The final sensitivity of the halogen silver emulsion layers containing such compounds is higher, because these compounds promote the development of these halosilver layers in the ordinary developer beneficial influence. So these compounds can be viewed as development accelerators will.

However, it is also known that these compounds, regardless of the fact that they are in more sensitive Halogen silver layers can be used as additives, cause are that the layers concerned are less suitable for supporting, especially at high temperatures and relative humidity, because they bring about a considerable increase in fogging. It was also found that by Incorporation of these compounds in the photographic material with the intention of making more sensitive halide silver emulsion layers to achieve the generated from one or more halosilver

emulsion layers built up

photographic material

Applicant:

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

Representative: Dr. W. Miffler-Bore

and Dipl.-Ing. H. Gralfs, patent attorneys,

Braunschweig, Am Bürgerpark 8

Claimed priority:
Great Britain 7 May 1959 (No. 15 695)

Dr.-Chem. Jozef Frans Willems, Wilrijk,

Dr.-Chem. Robrecht Julius Thiers, Brasschaat,
and Dr.-Chem. Joseph Louis de Munck,

Beveren-Waas (Belgium),
hat have been named as the inventor

Image tone of the developed silver is impaired and gives rise to brown and red-brown images gives.

It has now been found that the developability of photosensitive emulsions is very advantageous can be influenced by adding one or more emulsion layers or other layers of a photographic material of compounds which by polycondensation of per se not reactive low molecular weight alkylene oxide derivatives with functional binding agents available are.

By applying this new procedure, it was found

1. that the compounds according to the invention generally have higher sensitization effects than can be achieved with the known polyoxyalkylene compounds;

2. That these new connections should be kept give rise to less fogging, and on

3. That the image tone of the developed silver remains unchanged.

309 538/328

3 4

These new compounds correspond to the fol-filtered. After evaporation of the chloroform and

Following general formula: washing the residual powder with ether is obtained

, 13 g white powder. RO- (R ₁ O) * - Q- (R ₁ O) * - -R

^{L l} v ₅ manufacture 3

in which means: _ 50 g polyglycol (average molecular weight

R ₁ = an alkylene group, such as ethylene, propylene 1000) and 4.9 g of maleic anhydride are added

and isopropylene; together under a nitrogen atmosphere for 3 hours

χ = a positive integer, at least equal to 2; heated to 200 to 23O ⁰ C. The obtained reaction

y = a positive integer, at least equal to 2; io product is made with a mixture of 4 parts of ether

Q = first and washed 1 part benzene. 30 g of one are obtained

CHO - light brown solid soluble in water and in alcohols

I borrowed substance.

R ₂ production 4

in the R ₂ a hydrogen atom or a 30 g polyglycol (average molecular weight

Denotes alkylene group; 300) and 4.9 g of maleic anhydride are combined

secondly - CO - R ₃ - COO - in which R ₃ under a nitrogen atmosphere for 1 hour on a divalent aliphatic, cycloaliphatic 200 ⁰ C heated. The reaction product obtained is table or unsaturated aliphatic carbon dioxide with a mixture of 3 parts of ether and 4 parts of hydrogen radical, which is washed by a hetero-benzene. After vacuum drying, 17 g of a viscous yellow oil are obtained, atomically like oxygen and the like. can, or another aromatic or a

means heterocyclic radical; Manufacturing 5

third, -CO-NH-R ₄ -NH-COO-, ² S ⁵⁰ S. polyglycol (average molecular weight

1000) and 10 g of sebacic acid are taken together under

in which R _{4 has the} same meaning as R ₃ ; Nitrogen atmosphere at 210 ^° C. for 7 hours

R = a hydrogen atom or - CH ₂ OH, if Q warms up, developing water vapor. To

Cooling gives 52 g of a water-soluble resinous

CHO - 3 ° like product.

I manufacture 6

T)

² 50 g polyglycol (average molecular weight

is ₅ - CO - R ₃ - COOH, if Q 1000) are dissolved in anhydrous acetone, too

- CO - R ₃ - COO 35 are added to the 4.2 g of hexamethylene diisocyanate.

is, or -CO-NH-R ₄ - NH ₂ , if Q For 7 hours, the reaction mixture is

- CO - NH - R ₄ -NH COO - is. boils, whereupon the solvent at reduced

Pressure is removed. 52 g of a white powder are obtained. These compounds can be prepared: solid, water-soluble powder.

1. by polyacetalization of polyoxyalkylenes with 40 "

by means of an aliphatic aldehyde; Manufacturing 7

2. by heating to about 200 ⁰ C of 30 g polyoxyethylene octylphenol polyglycol (average molecular weight alkylenes with carboxylic anhydrides, such as ma- 600), 6.7 g of diglycolic acid and 3 mg of p-Toluolsulfonleinsäureanhydrid, succinic anhydride and acid under nitrogen inlet for 1 hour phthalic anhydride, or with dibasic carboxylic acids at normal pressure and then for 5 hours, such as. B. adipic acid, maleic acid, heated ^{to 200 ° C. in a vacuum of 2 mm Hg.} Sebacic acid and diglycolic acid; After cooling, a water-soluble one is obtained

3. by heating polyoxyalkylenes with a viscous oil.

isocyanates. Manufacturing 8

^: Manufacture 1 * "°

20 g polyglycol (average molecular weight

A solution of 20 g of polyglycol (average 1000), 2.68 g of diglycolic acid and 2 mg of p-toluenesulfone molecular weight 400), 4.5 g of p-formaldehyde and acid are for 1 1/2 hours with normal drops of concentrated sulfuric acid in 25 cm ^{3 of} pressure and then for 5 hours in a toluene is boiled for 2 days. The toluene is heated ^{to 200 °} C. under a vacuum of 2 mm Hg. After then distilled off at reduced pressure. Cooling back gives a water-soluble viscous oil. stand is dissolved in chloroform and filtered. To

Evaporation of the chloroform gives 16 g of a preparation y

viscous product. A solution of 30 g of polyglycol (average

" _1? 60 molecular weight 300) and 14.8 g phthalic acid an-

Prepare 2 hydride under a nitrogen atmosphere during

A solution of 25 g of polyglycol ( ^{heated to 210 °} C. for an average of 6 hours. After cooling, the molecular weight is 1000), 2.25 g of p-formaldehyde and a very viscous oil. Drops of concentrated sulfuric acid in 30 cm ³

Toluene is boiled for 2 days. Before joining 65 Manufacture 10

trieren another 50 cm ⁸ toluene are added. A solution of 20 g of polyglycol (average

The toluene is distilled off under reduced pressure. molecular weight 1000) and 3 g of phthalic anhydride The residue is dissolved in chloroform and kept under a nitrogen atmosphere for 6 hours

5 6

heated to 21O ⁰ C. After cooling one obtains a ben in British patent 789823, or from

Resin. small amounts of precious metal compounds, such as from

Manufacture 11 gold, platinum, palladium, iridium, and ruthenium

Rhodium. Of course, the new procedure can

22.5 g (0.075 mol) of polyglycol 300, dissolved in 5, very advantageously in combination with the sensitizing 75 cm ^{3 of} tetrahydrofuran, are dried over the sodium sulphate effect of the originally in gelatine. This solution will be carried out to 60 to 65 ⁰ C over essential compounds. 5 hours dropwise of a suspension of 16.3 g when applying the method of the invention

(0.075 mol) pyromellitic dianhydride, dissolved in can also stabilizers, such as. B. mercury 80 cm ^{3 of} tetrahydrofuran added. The io compounds obtained in this way and the full solution in the Belgian patents is filtered through Norit and stressed in vacuum 571916 and 571917 and evaporated in the state on a water bath. Use the compounds mentioned, backward technique. It's thick oil is still washed with benzene and ether. also common, the halogen silver emulsions by yield: 25 g of oil. absorption of cadmium salts or through treatment

15 to sensitize and / or stabilize these emulsions in the presence of cadmium-based dough salts.

50 g (0.05 mol) of polyglycol (average molecular weight), dissolved in 125 cm ^{3 of} tetrahydrofuran, antifoggants, colorants, development can be dried over sodium sulfate. Lersubstanzen this solution, hardeners and wetting agents in a known is at 60 to 65 ⁰ C for 5 hours dropwise Weis Eder emulsion be added 20 to exert adverse influence ohnehierauf a suspension of 10.9 g (0.05 mol) of pyromellitic, dianhydride dissolved in 75 cm ³ Tetrahydrofuran, due to its property of being better developed

added. The complete solution obtained in this way will be provided via Norit availability, the new connections are filtered and placed in vacuum on a water bath- very effective for increasing the sensitivity steams. The residual oil is washed with ether, sensitive to X-rays and general light. Yield: 30 g of end product. ability of orthochromatic and panchromatic

The compounds according to the invention can all special emulsions as well as from the Added to emulsions or in the acting compound of ordinary non-spectrally sensitized emulsions. can be brought with the emulsion layers, so by you can separately or in combination with Dissolution in water or in an aqueous mixture 30 optically sensitizing dyes are added; of organic solvents, which are not harmful - in the latter case the addition must be added before or after the borrowed influence on the halogen silver emulsions from the addition of the optical dyes. Further practice, whereupon the resulting solution of an emulsion can be used very advantageously in the most varied added or used as a layer-forming co-emulsions, because the pronounced setting is poured onto an emulsion layer. 35 Increase in sensitivity both in negative and in

The compounds according to the invention can be effected on positive emulsion types, different points in time of the emulsion preparation The following examples illustrate the invention,

be used; for example, they can be saved as

separate addition or in a mixture with one or Example 1

several other, for the initial precipitation 40 A washed, negative coarse-grained ingredient of the halide silver grains used, gelatin iodobromide silver emulsion (average grain during physical or chemical ripening size 0.8 μ), in which the halide silver from 94.5 mole process or any other percentage is ripened bromide and 5.5 mole percent iodide beZeitpunkt prior to pouring of the emulsion was added t _{e s} ht, at 45 ° C. After adding a panchromatic. However, they are preferably added after the sensitizing dye and other customary chemical ripening and just before the emulsion ingredients are poured onto a coating. Carrier (pattern 1).

The optimal amount of the compound that the

Emulsion has to be added, depends on the choice of pouring to specific amounts of the same emulsion of the compound in question, the type of colloidal binder for the halogenated silver grains given in the following list and the amount of development accelerator per mole of the amount and type of that present in the emulsion _{sen of} the halogen silver too. Then you treat them to hang in halogen silver. Generally, however, the same way as sample 1. After drying, the inventive compounds are used in an _U nd exposing developed to the pattern mg 7 minutes amount of 50 to 7 g per mol of silver halide 55 at 2O ⁰ C in a solution of the following composition course Sets. If necessary, the relevant relocations can:
bindings are always added in such quantities,

that extend beyond these limits. Water 800 cm ³

The method according to the invention can be described in _{Λ ,. ,,,, 1f} , "

Combination with a method of increasing the 60 monomethyl p-ammophenol sulfate 2 g

Sensitivity of the photographic material to hydroquinone 5 g

turn by incorporating a small amount of sodium sulfite (anhydrous) 100 g

Amounts of a sulfur-containing compound such as allyl

isothiocyanate, allyl thiourea and sodium thio-borax 10g

sulfate; of small amounts of reduction-sensitive 65 boric acid 5 g

Sators, like the tin compounds, described in the _r ,., _Λ <.

Belgian patents 493464 and 568687, the potassium bromide U ₅ Dg

Iminoaminomethanesulfinic acid compounds, described- water up to 1000 cm ³

Sensitometric results

template

Added
Connection

no

0.34 g polyglycol,
Average molecular weight
400

0.34 g polyglycol,
Average molecular weight
1000

0.34 g compound
after manufacture 1

0.34 g of polymer
after manufacture 2

Relative sensitivity

100

107

138

186

gamma

veil

0.75 0.71

0.59 0.76 0.77

0.06

0.06

IO

0.08 0.06

template Added
link Relative
Sensation
possibility- gamma veil 4th
5
6th
7th 0.34 g compound
after manufacture 3
3.4 g of compound
after manufacture 3
0.34 g compound
after manufacture4
3.4 g of compound
after manufacture4 132
145
91
105 0.67
0.68
0.62
0.65 0.13
0.14
0.10
0.11

Example 4 After adding the information given in the following list

Example 2

Q 06 ^ao surrounded amounts development accelerator and the same 'treatment as in the example 1, the following

sensitometric results achieved.

After adding the amounts of development accelerator given in the list below and the same ^Z 5 ^sample treatment as in Example 1, the following sensitometric results are achieved.

template Added
link Relative
Sensation
opportunity gamma veil 1 no 100 0.58 0.06 2 3.4 g polyglycol
Average
molecular weight
400 74 0.56 0.06 3 3.4 g polyglycol
Average
molecular weight
1000 127 0.60 0.08 4th 3.4 g of compound
after manufacture 1 170 0.67 0.04 5 3.4 g of compound
after manufacture 2 174 0.65 0.05

35

45

Example 3

After adding the amounts of development accelerator given in the list below and the same treatment as in example 1, the following sensitometric results are achieved.

template Added
link Relative
Sensation
opportunity gamma veil 1 no 100 0.61 0.13 2 0.34 g compound
after production 5 151 0.63 0.14 3 3.4 g of compound
after production 5 138 0.70 0.14 4th 27.2 g of compound
after production 5 112 0.93 0.25 5 0.34 g compound
after production 6 138 0.62 0.14 6th 3.4 g of compound
after production 6 132 0.63 0.14 7th 0.34 g compound
after manufacture9 115 0.71 0.14 8th 3.4 g of compound
after production 9 138 0.76 0.15 9 0.34 g compound
after
Manufacturing 10 147 0.72 0.16 10 3.4 g of compound
after
Manufacturing 10 206 0.78 0.16

template Added
link Relative
Sensation
opportunity gamma veil 1
2
3 no
0.34 g polyglycol,
Average
molecular weight
300
3.4 g polyglycol
Average
molecular weight
300 100
98
85 0.65
0.65
0.65 0.10
0.10
0.10

55

Example 5

A washed, coarse-grained gelatin iodobromide silver emulsion is matured, in which the halogen silver consists of 98.2 mole percent bromide silver and 1.8 mole percent iodized silver exists, at 42 ° C. After adding a stabilizer such as 5-oxy-7-methyl-s-triazolo- (4,5a) -pyrimidine and other common ingredients, the emulsion is poured onto a carrier (sample 1).

To produce further samples, certain quantities of the same emulsion are used before casting in each case the amounts of development accelerator per mole present given in the list below Halogen silver too. They are then treated in the same way as sample 1.

9 10

After drying and exposure, the patterns are in a solution of the following for 4 minutes Composition developed:

Water 800 cm ³

Monomethyl p-aminophenol sulfate .. 4 g

Sodium sulfite (anhydrous) 65 g

Hydroquinone 10 g

Sodium carbonate (anhydrous) 45 g

Potassium bromide 5 g

Water up to 1000 cm ³

Added
link Sensitometric gamma Results After 36s
Relative
sensitivity hourly incut
gamma ration
veil template no
0.2g of manufacture?
0.2 g of manufacture 8 Relative
sensitivity 3.27
3.28
3.02 veil 100
120
135 2.89
3.00
2.89 0.09
0.11
0.16 1
2
3 100
131
131 0.04
0.05
0.06

Example 6

Two samples of emulsion as indicated in Example 1 are contemplated. Before the For this purpose, 0.40 g of polyglycol with an average molecular weight of 6,000 is added per mole of halogenated silver to pour pattern 1. To pattern 2 The same emulsion is instead of 0.40 g of polyglycol with an average molecular weight before pouring of 6000 0.40 g of the compound after preparation 2 added. The two samples are packed and a whole year in a relatively humid atmosphere at temperatures between 15 and 35 ° C preserved. After this period, the samples are exposed and in a developer for 7 minutes developed according to Example 1.

Sensitometric results

Sensitometric results

45

template Added
link Relative
Sensation
opportunity gamma veil 1
2 0.4 g polyglycol
Average
molecular weight
6000
0.4 g compound
after manufacture 2 100
100 0.80
0.78 0.18
0.12

Example 7

Two samples of emulsion as indicated in Example 5 are contemplated. To the Sample 1 is added 0.2 g of Carbowax 6000, which is the maximum amount allowed, with none excessive haze occurs. The compounds according to the invention become sample 2 of the same emulsion added in such amounts that the extremely permissible haze limit is also reached. After 4 minutes long development as in Example 5, the sensitivities obtained are checked.

template Added
link Relative
Sensation
opportunity gamma veil ■ 1
■ 1 0.2 g of Carbowax
6000
1 g compound
after manufacture 3
0.2 g of Carbowax
6000
1 g compound
after production 5 100
123
100
114 4.00
3.50
3.50
3.25 0.06
0.06
0.07
0.05

Example 8

Before casting, 0.2 g of Carbowax (sample 1) is added to an emulsion sample according to Example 5 0.2 g of the compound after preparation 8 (sample 2) was added to another sample. The two patterns are kept at high relative humidity and high temperature for several days and then 4 minutes long developed in the developer of Example 5.

55 template Sensitometric results Relative
Sensation
opportunity gamma veil 60 l
2 Added
link 100
116 2.93
2.84 0.17
0.16 0.2 g of Carbowax
6000
0.2 g compound
after manufacture 8

Although only gelatin halide silver emulsions are described in the above examples, this invention is not limited to such colloid emulsions. Also emulsions from others

309 538/328

water-permeable colloids can be treated according to the invention. Such colloids are among others Agar-agar, zein, collodion, water-soluble cellulose derivatives such as hydrolyzed cellulose acetate; Cellulose ester of oxycarboxylic acids, such as. B. lactic acid or glycolic acid; Alkali metal salts of cellulose esters of dicarboxylic acids such as phthalic acid; Polyvinyl alcohol and partially hydrolyzed polyvinyl acetate and interpolymers of vinyl acetate with unsaturated compounds such as styrene and maleic acid, water-soluble Polyvinyl acetate and other synthetic or natural hydrophilic resins or polymeric compounds.

The new development accelerators can be used for sensitizing the known types of chlorosilver, bromosilver and iodosilver emulsion and the like Mixtures of these silver halides can be used.

Furthermore, the methods described in the above examples are neither on the amount and type of Development accelerator to be added is still limited to the time of addition. As a matter of fact To achieve an optimal effect, you can use all for the production of light-sensitive emulsions viable special techniques can be applied.

An advantage of this invention is the compatibility of the new development accelerators Dye formers and optically sensitizing dyes, which is extremely important when applying the new development accelerator to increase the general light sensitivity from one or color photographic material composed of several light-sensitive layers.

Another advantage of the method according to the invention is in the simplicity of its general applicability, for example in the manufacture of photosensitive materials for amateur and professional photography and cinematography, for graphic Purposes and for scientific and industrial applications.

Claims (1)

Claim: Photographic material composed of one or more halide silver emulsion layers, which contains a compound of the following general formula: RO- (R ₁ O) ^ fQ- (R ₁ O) XI- R in which means: R ₁ = an alkylene group such as ethylene, propylene and isopropylene; χ = a positive integer, at least equal to 2; y = a positive integer, at least equal to 2; Q = first - CHO-, in which R _{2 represents} a hydrogen atom or an alkyl group; second - CO - R ₃ - COOO -, in which R _{3 is} a divalent aliphatic, cycloaliphatic or unsaturated aliphatic hydrocarbon radical, which can be interrupted by a heteroatom such as oxygen and the like, or an aromatic or heterocyclic radical; third — CO — NH — R ₄ —NH — COO—, in which R _{4 has the} same meaning as R ₃ ; a hydrogen atom or - CH ₂ OH if R = Q —CHO- is - CO - R ₃ - COOH if Q - CO - R ₃ - COO - is, or - CO - NH - R ₄ - NH ₂ , if Q - CO - NH - R ₄ - NH - COO is. References considered: U.S. Patent No. 2,423,549. © 309 538/328 2.