DE1597511A1 - Photographic silver halide emulsion with increased sensitivity - Google Patents

Description

AG FA-G EVAERT AG

Za / Ρο Haywriting ¹ ^ - ⁸ ·

photographic halo gel emulsion with ''

increased sensitivity

The invention relates to photographic silver halide emulsions, whose sensitivity is improved by adding silicon-containing amines.

The sensitivity of a photographic emulsion can be influenced in two ways. First of all, it is possible at the so-called chemical ripening during emulsion production through an extended ripening time or through the addition of suitable ones Substances such as thiosulfate or other, mostly sulfur-containing preparations to increase the sensitivity. The other way of increasing the sensitivity of a photographic emulsion consists in adding so-called development accelerators or chemical sensitizers. These are usually added to the already fully ripened emulsion.

BATH

009820 / 08SA

Compounds with an onium structure, e.g. quaternary ammonium, phosphonium, and ternary sulfonium salts and very often also polyalkylene oxides and polyalkylene oxide derivatives. With the last-mentioned class of substances in particular, many attempts have been made the sensitivity gains achieved by modifying the derivatives or by combining them with others Increase Connections.

Also aliphatic amines are used as development accelerators or also as chemical sensitizers in the chemical Maturation has been described. ■

However, all these compounds do not fully meet the properties required in practice, be it that the increase in sensitivity is unsatisfactory or that the veil associated with the sensitization is an application prevented.

The invention is based on the object of new chemical sensitizers to find that do not have the above disadvantages and with their help an increase in the sensitivity of photographic Halogen silver emulsions without causing undesirable fogging becomes possible.

It has now been found that there are very good speed B increases can be achieved at low fog levels using silver halide emulsions which are cyclic contain silicon-containing amine.

AG 323 - 2 - BAD ORfGINAt "

009820/0854

The compounds according to the invention have the following general formula:

y / χ

C CHo

where mean:

Z = oxygen or the grouping NR; X = methylene or a dialkylsilyl group, where the alkyl groups preferably contain up to 3 carbon atoms, in particular dimethylsilyl;

R = a saturated or olefinically unsaturated aliphatic group with up to 18, preferably with up to 12 carbon atoms, which group may be substituted, e.g. B. with hydroxyl, amino, alkylamino or dialkylamino, cyano, alkylthio, alkoxy, Dialkylsilyl or alkylsilyloxy;

R = alkyl with up to 6 carbon atoms; wherein the compound contains at least one dialkylsilyl group. Preferred are those connections wherein X represents at least one dialkylsilyl group, in particular a dimethylsilyl group.

Suitable are e.g. B. the following connections:

CH, .CH,
I.

'0

/ γ

N-CHo CH ₂ OH SA ₀ ORIGINAL

009820/0654
AG 323 - 3 -

A-G 523

III.

CH, CH _x 5 \ / 3

CH ₃

N-CH ₉ CH ₉ -OS i-CH, CH ₃

IV.

CH,

H _x CN
3 \

-CH

V. CH, CH-

3/3

/ ^Si - \

O N-

CH ₀ CH ₀ CH ₀ -N 2 2 2

CH ₃ CH ₃

VI.

CH, CH, 3 _N / 3

Si

0 N

^V Si_7 CH ₃ CH ₃

N-C

VII. CH, CH-

3 SJ N-CH ₂ -CH = CH ₂

CH,

CH ₃

VIII.

~ . CH ₃

0 N-CH ₉ -Si-C ₉ H _C

VV 6- ² '

009820/0854

The preparation of the compounds is described in "Chemical Reports" 94, (1961), pp. 1585-1591 and 96, (1963), pp. 349-356.

The substances to be used in the manner according to the invention are, insofar as they are silamorpholines, stable to hydrolysis. The silapiperazines which can also be used are less resistant to hydrolysis and it can be assumed that this is the case with these compounds the hydrolysis products are also effective.

The substances according to the invention can be used in the photographic emulsion at any stage of its preparation before, during or added after chemical ripening. They can also be added to the semolina solution immediately before pouring. The amount added depends on the desired effect and can be determined at any time using the usual tests. Usually, amounts of 0.005 to 5 g per liter of ready-to-cast emulsion, preferably 0.05 to 1 g per liter, are sufficient Emulsion.

The substances according to the invention can be used in any halogen silver emulsions. Silver chloride, silver bromide or mixtures thereof, even with a low content of silver iodide of up to 10 mol- #, are suitable as the silver halide. The silver halides can be dispersed in the usual hydrophilic compounds, for example in Carbox7i.'iothyl '. irt '' loaded eggs .'αϊ '-.>-.,''-.iw ort, r Aruiükai oder vorzug'-

ORIGINAL

'χΛ ! ; ■ ί ι · ιί ·.

I U ':

The emulsions can also contain other chemical sensitizers contain, e.g. quaternary ammonium and phosphonium as well as ternary sulfonium salts, reducing agents such as tin-II salts, Polyamines such as diethylenetriamine or sulfur compounds, as described in US Pat. No. 1,574,944. The specified emulsions can be used for chemical sensitization also salts of precious metals, such as rutenium, rhodium, Contain palladium, iridium, platinum or gold, as described in the article by R. Koslowsky, Z.Wiss. Phot. 46, 65-72 (1951) has been described.

A particularly high sensitivity is achieved when the accelerators according to the invention are used in combination with polyalkylene oxides and / or onium compounds such as quaternary ammpnlum- or phosphonium compounds and ternary sulfonium compounds are used. In these cases it is a synergistic one Effect present. The effect of the combination considerably exceeds that of the individual components.

These include, for example, those of the following formula:

RO- (CH ₂ CH ₂ O) _n -R

wherein R is hydrogen, alkyl with preferably up to 18 carbon atoms such as ethyl or dodecyl, acyl, preferably acyl radicals aliphatic carboxylic acid with up to 18 carbon atoms, such as lauric acid or oil, or a residue of the phenyl series, such as Phenyl or alkyl-substituted phenyl e.g. p-dodecylphenyl

ÖAO ~~ ~~

A_- J jt'J - h ■■ "

0 0 '? ? 2 0 ■ '(IH ii f.

"means; η should generally be an integer between 8 and 200. Products with molecular weights between 1500 and 10,000 are preferred. Such polyalkylene oxides are described in US Pat. No. 2,240,472 or k 2,400,532.

Likewise suitable as chemical sensitizers for combination are derivatives of phosphoric acid with polyalkylene oxide chains. Such preparations are described in British patents 1,045,183 and 1,045,184, as well as the French U.S. Patent 1,423,680.

The compounds are condensation products of spirocyclic pentaerythritol diphosphoric acid halides with polyalkylene glycols, the approximately 3 to 100 polyalkylene oxide units contain. They correspond to the following formula:

O - CH ₂ CH ₂ -

OH

where R _{1 is} hydrogen or an alkylene oxide chain with 3 to 100 alkylene oxide units, m is an integer between 3 and 100 and y is an integer between 1 and 10.

This group of chemical sensitizers also includes condensation products of amidophosphoric acid derivatives Polyalkylane glycols of the type mentioned above. Such compounds are represented by the following formula:

_{A. p 323} 00982_0 / 0_864 bad

HO - (CH ₂ CH ₂ O) - .. ρ - O - (CH ₂ CH ₂ O) _1n -

■ Λ

R ₂ R ₅

here mean:

R _{2 is} hydrogen, alkyl with preferably up to 18 carbon atoms, aryl such as phenyl or aralkyl such as benzyl or phenylethyl and R, alkyl, preferably with up to 18 carbon atoms, aryl such as phenyl or aralkyl such as benzyl or phenylethyl; R ₂ and R ₅ together can represent the ring members required to complete a 5- or 6-membered heterocyclic ring; m. has the meaning given above, ρ is an integer between 0 and 10Q, q. has a value between 1 and 5.

The accelerators according to the invention can also be used in combination with the morpholine or thiomorpholine derivatives described in French patents 1,506,230 and 1,548,191. Good effectiveness is also achieved with the accelerators described in the published Dutch applications 6 614 230 and 6 711 152,

The emulsions can also be optically sensitized, e.g. with the usual polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like. Such Sensitizers are described in the publication of P.M. Hamer, The Cyanine Dyes, and related Compounds "(1964).

AG 323 - 8 -

009820/085 /; ^BATH

The emulsions can contain the usual stabilizers, such as homopolar or salt-like compounds of mercury with aromatic or heterocyclic rings (such as mercaptotriazoles), simple mercury salts, sulfonium mercury double salts and other mercury compounds. Further suitable stabilizers are. Azaindenes, preferably Tetra or pentaazaindenes, especially those substituted with hydroxyl or amino groups. Such compounds are described in the article by Birr, Z.Wiss. Phot. 47, 2-58, (1952). More suitable Stabilizers include heterocyclic mercapto compounds, e.g. phenyl mercaptotetrazole, quaternary benzothiazole derivatives, Benzotriazole and the like.

The emulsions can be hardened in the usual way, for example with formaldehyde or halogen-substituted ones Aldehydes containing a carboxyl group such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes and the like.

The compounds according to the invention and the specified synergistic combinations limit their advantageous ones They do not act on black-and-white emulsions, but also show their effects on color photographic emulsions. You can accordingly also added to emulsions containing color couplers will. Particularly noteworthy here is the only slight haze, which is the case with these emulsions which are particularly susceptible to haze occurs.

BATH ORIGINAL

bdLJ £ l - 9 -

0 0 9 8 2 0/0854

Example 1:

A silver bromide iodide gelatin emulsion per liter 60 g of silver as halogen silver with a content of silver iodide of 6 Mol- # contains were added per liter:

600 mg of saponin as a sedative

200 mg of 4-hydroxy-1,3,3a, 7-tetraazaindene as a stabilizer 75 ml of a 1: 1000 solution of an optical sensitizer for the blue spectral region with the following formula:

N-N-CCH ^

H, C-S C-S

O-C C = S

C ₂ H ₅

and 10 ml of a 10 # aqueous solution of formaldehyde. The emulsion was divided into 24 equal parts and the substances given in the table below were added to the individual samples Liter of emulsion added. It is then poured onto a base made of cellulose triacetate and the layer is dried.

The exposure takes place in a conventional sensitometer behind a gray level wedge. Development takes place in a developer with the following composition. The development time is 10 min., The development temperature 2O ⁰ C. p-Monomethyl-aminophenol 2 g

Sodium sulfite sicc. 100 g

Hydroquinone 5g

Borax 2 g

Make up to 1 liter with water. bath

009820/0854

A- (J 121 - 10 -

The results of the sensitometer test are compiled in Table 1 below. _ / [ ^/ ) ~ - 1597511

substance

Type

III
III
III

Amount · ReI. Recommended g / kg emulsion in ° Din

veil

Type _ Type 0.79 0.05 II 0.1 + 0.6 0.79 0.05 II 0.3 + 0.9 0.78 0.05 II 1.0 + 1.7 0.75 0.08 Type _ Type 0.70 0.05 I. 0.01 . + 1.5 0.70 0.05 I. 0.3 + 0.6 0.70 0.05 I. 1.0 + 0.5 0.65 0.05 Type - Type 0.67 0.05 . . -V. .. . . .0.1 ....... .-, + 3.4. 0.70 • 0.05 V 0.3 + 2.5 0.72 0.06 V 1.0 + 1.9 0.70 0.10 Type - Type 0.73 0.05 VI 0.1 + 0.5 0.70 0.05 VI 0.3 + 1.0 0.70 0.05 VI 1.0 + 2.1 0.67 0.05

0.1
0.3
1.0

Type + 0.8 + 1.4 + 2.3

0.71
0.77
0.72

0.71

0.04 0.04 0.04 0.05

Type
IV

0.4

Type + 2.0

0.86
1.00

0.07 0.10

Tpy
VII

0.4

Type + 2.0

0.86
0.87

0.07 0.10

Type - type

N- (β-hydroxy-0.1 + - O

ethyl) morpholine 0.3 + - O

(as a comparison to 1.0 - 0.6

ID 009820/0854

A-G 323

- 11 -

0.73 0.05 0.78 0.05 0.78 0.06 0.75 0.07

ORIGlNAi,

Example 2:

A silver bromide iodide emulsion according to Example 1 is shown in divided equal parts and added the substances mentioned in Table 2 below to the individual parts. Developed is six minutes at 20 ° in a developer with the following composition:

Sodium sulfite sicc. 70.0 g

Borax ■ 7.0 g

Hydroquinone 3.5 g

p-Monomethyl-aminophenol 3 ^ 5 g · - · ....-... ·. .

Sodium citrate 7.0 g

Potassium bromide 0.4 g

Fill up to one liter with water. Then it is fixed as usual.

Compounds A and B, the formulas of which are given below, were used as additional accelerators:

A) -0- P

) -CH

PO- (CH ₂ CH ₂ O) ₉₀ --H

9.1

■ Κ)

Br

A-G 323

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009820 / 08B4

substance Tabel 2 43 Type 0 r veil Type Quantity Rel. Rec.
g / kg Emuleic η Din + 3.0 0 , 53 0.06 Accelerator A - + 0.5 0 , 54 0.07 Substance VIII 0.48 + 3.5 0 , 63 0.06 Substance VIII and
Polyethylene oxide A 0.24 Type 0 , 55 0.06 Type 0.24
0.48 + 2.0 0 , 65 0.06 Polyethylene oxide A - + 1.0 0 , 55 0.06 Substance V 0.48 + 3.0 0 , 60 0.05 Substance V and
Polyethylene oxide A 0.12 ...... + -2, .O- ·· · 0 , 63 0.14 Substance VI. .., .. ... 0.12
0.48 + 3.0 ' 0 .59 ... 0.08 Substance VI and
Polyethylene oxide A . 0, -12 ... .... Type 0 , 59 0.18 Type 0.12
0.48 + 1.5 0 , 59 0.06 Quaternary salt B - + 1.0 0 , 69 0.06 Substance V 0.48 + 2.0 0 , 66 0.12 Substance V and
Quaternary salt B 0.24 Type 1, , 61 0.12 Type * J 0.24 + 1.0 1, 20th 0.09 Quaternary salt B - + 1.0 1-, 20th 0.13 Substance VI 0.48 + 2.0 1, 20th 0.13 Substance VI and
Quaternary salt B 0.24 Type 0, 11th 0.15 Tpy 0.24
0.48 + 1.0 ο, 67 0.05 Quaternary salt B - + 0.5 0, 60 0.08 Substance III 0.48 + 2.0 0, 61 0.04 Substance III and
Quaternary salt B 0.12 Type 1, 59 0.06 ο
O Type * ^; 0.12
0.48 + 1.5 1, 25th 0.10 CD
OO Quaternary salt B - + 1.0 1, 18th 0.14 (s>
O Substance VIII 0.48 + 3.0 1, 29 0.09 .. / ■ · ■% Substance VIII and
Quaternary salt B 0.24 05 0.13 C- /
00
σι '*) At these sales
AG 323 0.24
0.48 was the development z €
BATH sit 16 min
ORIGINAL lend
- 13

Example 3:

45 mg / kg emulsion of the sensitizing dye of the following formula are added to a miBchemulsion, which is composed of 90 # of a silver bromide iodide gelatin and 10 $> of a silver chloride bromide iodide emulsion and which has been ripened in a known manner with gold and sulfur compounds to optimum sensitivity:

0 \ C ₂ H ₅ η G-CH = C-CH = C

The following are also added per liter to the emulsion:

15 g (1- (3'-SuIf0-4'-phenoxy) -phenyl-3-hepta-

decyl-pyrazolone as purple coupler 250 mg 1,3,3a, 7-4-hydroxy-6-methyl-tetraazaindene

as a stabilizer
20 ml of a 5 # aqueous solution of saponin as

Wetting agents

2.5 ml of a 30 # aqueous solution of formaldehyde as Hardening agents.

The above emulsion is divided into 20 equal parts and the The additives shown in Table 3 are added to individual parts per liter of emulsion:

AG 323 -14-

009820/0854

Tabel lot 3 A * r veil substance g / kg emulsion ReI.Rec. - ⁰ Din 0.70 0.10 Type 0.3 Type 0.64 0.11 II 1.0 4 2.8 0.68 0.12 II 3.0 + 2.8 0.72 0.12 II - + 3.0 0.64 0.18 Type 0.3 Type 0.66 0.25 I. 1.0 + 0.5 0.64 0.26 I. 3.0 + 2.6 0.64 0.28 I. - + 1.0 0.45 0.15 Type 0.3 Type 0.51 0.12 V - .-. I ₁ Q. + 0.4 - 0.34 0 _r 15 V .. .... 3.0 .. + t., 2. 0.22 0.15 V - + 0.2 0.42 0.12 Type 0.3 Type 0.42 0.16 VI 1.0 + 3.2 0.48 0.17 VI 3.0 + 4.0 0.44 0.25 VI - + 2.8 0.53 0.14 Type 0.3 Type 0.54 0.14 III 1.0 + 0.8 0.50 0.14 III 3.0 + 2.6 0.47 0.10 III + 0.8

The samples are poured onto a carrier made of cellulose acetate and dried. Then it is exposed behind a step wedge and processed in the usual way. The processing process is as follows:

AG 323 - 15 -

009820/086 /; BAD ₀ RlGfNAL

Fart) development 7 minutes

Stop bath 5 minutes

Soaking for 5 minutes

Bleach bath 5 minutes

Soaking for 5 minutes

Fixing bath 5 minutes

Soaking for 10 minutes

The color developer has the following composition:

"Diethyl p-phenylehdiamine sulfate 2.75 g

Hydroxylamine sulfate 1.2g

Sodium sulfite sicc. 2.0 g

Sodium hexametaphosphate 2.0 g potassium carbonate sicc. 75.0 g

Potassium bromide 2.0 g

Make up to one liter

The remaining processing baths had the following composition setting:

Stop bath: sodium acetate 30.0 g glacial acetic acid 6.0 g

Fill up with water to 1

Bleach bath: potassium ferricyanide 100 g potassium bromide 20 g

Glacial acetic acid 4 g - ^

Fill up with water to 1 1 ^Q * ö

009820/0854 AG 523 - 16 -

Fixing bath: sodium thiosulphate 200 g Fill up with water to 1 1

The color density of the purple layers was measured with the densitometer "Macbeth Quanta log, model TD 102" measured with the switching of the green color filter in the beam path of the measuring light.

Example 4

A silver bromide iodide gelatin emulsion according to Example 1 is divided into 13 equal parts and added the substances listed in the following table. You pour and dry as in example 1 and developed for 6 minutes at 20 ° in the developer given in example 2. The name of the accelerator A and B also relate to the formulas given in Example 2.

AG 323 - 17 -

BATH ORIGINAL

009820 / 005A

"· .. ..afc

At

Table 4 rel. NS. t veil substance lot DIN 0.92 g / kg emulsion Type 1.13 0.21 Type + 2.0 0.96 0.31 Accelerate A. 0.480 + 1.5 0.97 0.28 Accelerate B. 0.480 + 2.0 0.24 Substance III 0.240 1.07 Substance III + ' ) 0.240) + 4.2 0.28 Acceleration A + ' ) 0.480) 1.02 Acceleration B] ) 0.480) + 1.8 0.24 Substance VIII 0.120 1.12 Subst. VIII +; ) 0.120) + 4.4 0.26 Acceleration A +] > 0.480) 0.90 Acceleration B] ) 0.480) Type 1.06 "0.15 Type + 2.0 0.92 0.11 Accelerate A. 0.480 + 1.4 0.97 0.10 Accelerate B. 0.480 + 1.80 0.18 Substance V 0.120 1.10 Noun V +] I 0.120) + "3.1 0.40 Acceleration A +] I 0.480) 1.01 Acceleration B) I 0.480) + 2.3 0.16 Substance VI 0.120 1.10 Noun VI +) ι 0.120) + 3.7 0.30 Acceleration A +) 0.480) Acceleration B) 0.480)

A-G 323

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Claims (7)

Patent claims: 1. Photographic light-sensitive material with at least a silver halide emulsion layer used as chemical The sensitizer contains a silicon-containing amine of the following formula: κ ¹ where mean: Z = oxygen or the grouping NR; ·. . -..'.... .. X = methylene or a dialkylsilyl group; R = a saturated or olefinically unsaturated aliphatic Group with up to 18 carbon atoms; R = alkyl with up to 6 carbon atoms, the sensitizer containing at least one dialkylsilyl group. 2. Photosensitive photographic material according to claim 1, characterized in that at least one X is a dialkyl lyl group represents. 3. Photosensitive photographic material according to claim 2, characterized in that at least one X is a diaethyleilyl group. AG 523 - 19 - 009820/0854 ^BAD original 4. A photosensitive photographic material according to claim 1, characterized in that as an additional sensitizer a polyalkylene oxide is included. 5. Photographic light-sensitive material according to claim 2, characterized in that a polyethylene oxide is used as the sensitizer is contained in the following formula: R. 0 CH ₂ . CH ₂ . where R is hydrogen, alkyl, acyl or a phenyl group and η is an integer between 8 and 200. 6. Photographic light-sensitive material according to claim 2, characterized in that it contains a polyalkylene oxide of the following formula as an additional sensitizer: O
0-p ' 0 - CH ₉ O - CH, CL -OO ^N P- (0 CH ₂ .CH ₂ ^ - 0 ^/ where R _{1 is} hydrogen or an alkylene oxide chain with 3 to 100 alkylene oxide units, m is an integer between 3 and 100 and y is an integer between 1 and 10. A-G 323 - 20 - 009820/0854 7. Photosensitive photographic material according to claim 1 or 5, characterized by the additional content of an onium compound represented by the following formula; OO AG 323 - 21 - ORIGINAL BATHROOM 009820/0854