DE1961842B2 - LIGHT SENSITIVE PHOTOGRAPHIC SILVER HALOGENIDE EMULSION - Google Patents

Description

p - B - CO - B 'A' - S - R X ^L - - B - CO - Β '-' - S --R

wherein A represents a lower alkylene group or a polyalkylene ether group of the formulas

- (CH ₂ CH ₃ C) L-

, 60

65 - (CH ₂ CHjO) ₁₁ -CH ₂ CH ₂ -

and CH ₂ NHCONHCHXh ₁ SC ₁ H ₅

i CH-, (4)

- (CHCH ₂ O) j "

_j 5 CH ₂ NHCONHCH ₁ Ch ₁ SC ₂ H _{5 the} latter bonded to B via the carbon atom:

A 'is a lower alkylene group or a polyalkylene- CH ₁ CHXH ₁ NHCONHCh ₇ CH ₁ SC ₁ H ₅

ether group of the formulas |

CH, -N (5)

- (CH ₂ CH ₂ O) P-CH ₂ CH ₂ - ₁₀ I

and CH ₂ CH ₂ CH ₂ NHCONHCH ₁ Ch ₂ SC ₁ H ₅

CHj CH ₃

1 I 1- (OCH ₁ CH ₁ J ₆ OCONHCh ₁ CH ₁ SC ₁ H,

- (CHCH ₂ O) ₁ , -CHCH ₂ - I - " ⁶ - - - -

I ₅ ι ^{2 (6)}

where either only A or A 'for polyalkylene ether-'

groups and ρ is 2 to 30, B and B 'an imino | -

group or an oxygen atom, but not equal to- L- (OCH ₁ CH ₂ J ₆ OCONHCH ₁ CH ₁ SC ₁ H ₅ time the oxygen atoms, R a lower alkyl, phenyl

or "aralkyl group or - (CH ₂ ), - COOR 'where 20 is CH ₂ CH ₁ NHCOO (CH ₁ CH ₁ O) XH ₁ Ch ₁ SC ₄ H ₉

^ Is 1 to 3 and R 'is a lower alkyl group |

and X is an oxygen or sulfur atom, S (7)

an alkylene group of the formulas |

CH ₁ CH ₁ NHCOO (CH ₁ Ch ₁ O) XHXH ₂ SC ₄ H ₉ CH ₂ - ₂₅

[- (CHXH ₁ O) ₁ XH ₁ CH ₁ OCONHCHXH ₁ SCh ₅

r 's

-CHCH ₁ - L- (CH ₂ CH ₁ O) ₂ XHXH ₁ OCONHCHXh ₂ SC ₂ H ₅

and 30

-CH ₂ CH ₁ - CH ₂ CH ₁ OCONHCHXh ₁ SC ₂ H ₅

a phenylene group or a group of the formula O (9)

R "35 CHXH ₂ OCONHCH ₁ Ch ₂ SC ₁ H ₅

- N - ^CH 3

where R "is a lower alkyl group. _r (OCH ₂ CH) ₃ OCONHCHXH ₂ SC ₂ H ₅

From the silver halide 40 CH ₂ Hi according to the invention

emulsion-made recording materials |

have an er-CH ₃ -CH compared to the prior art

higher gamma, increased sensitivity, an I _ιηι ^ υ ^ w ₁ <~> / ~ r \ Mu / ~ u ru cn u

higher maximum density, lower fog (OCH ₂ CH) ₃ OCONHCHXH ₁ Sc ₂ H ₅

tendency and an improved shelf life. ₄₅ ^

Typical examples of the inventive door sensitivity

are listed below:

o \ I 1 /

S (I)

I CH ₂ NHCONHCH ₂ Ch ₂ SC ₂ H ₅

CH ₂ CH ₂ NHCOOCH ₂ CH ₂ SCH ₂ CH ₂ COOc ₂ H ₅

55 Mj (12)

CHXH ₂ NHCOOCH ₂ CH ₂ SCh ₃
i CH ₂ NHCONHCH ₂ CH ₂ Sc ₂ H ₅

CHXH ₂ NHCOOCH ₂ CH ₂ SCh ₃ * ° ^ ¹ ^ ^H '

CH ₂ NHCOOCH ₂ CH (OCH ₂ CH) ₂ Sq ₁ H ₁₃

CHXH, OCONHCH ₂ CII ₂ SCVI ₅ CH ₂ (13)

ί 65 I.

S (3 | CH ₁ CH ₃ CH ₃

CH, CH ₃ OCONHCH ₂ CH ₂ SC ₂ H _S CH ₂ NHCOOCH ₂ CH (OCH ₂ CH) ₂ Sq ₁ H ₁₃

CH ₂ CH ₂ NHCOOCH ₂ CH ₂ SCIi ₂

The following information describes the preparation of some of the above compounds, without ι ο that protection is desired for the production.

Preparation of compound (1) A solution of 17.8 g

HIGH ₂ CH ₂ SCh ₂ CH ₂ COOC ₂ H ₅ ' ⁵

in 100 ml of dry benzene was mixed with 8.6 g of S (CH ₂ CH ₂ NCO) ₂

offset. The mixture was refluxed for 2 hours heated and then reduced by depilation Freed from solvent pressure. The residue was dissolved in 200 ml of ether. The solution was cooled, leaving the compound (1) in the form of crystals having the melting point of 45 to 46 ° C was obtained.

siert, the connection (12) with the melting. point of 207 to 208 ° C was obtained.

The other compounds can also be made np.ch (14) in the manner described above. The sensitizers according to the invention can be added to the emulsions at any point in time during the chemical ripening can be added. It is most advantageous, however, that this should be done at the beginning of the chemical ripening can be added. Suitable solvents are water or water-miscible solvents organic solvents such as methanol or ethanol. The amount to be added varies depending on on the type of compound and the type of silver halide emulsion used. Usually lies however, it ranges from 0.1 mg to 1000 mg per kg of silver halide emulsion.

As silver halide, all compositions are. in particular silver chlorobromide or silver iodobromide, usable. This can advantageously be the case with the silver halide emulsions according to the invention are color photographic emulsions with oil- or water-soluble color couplers.

The present invention will now be further illustrated by the following examples, without the To limit the invention.

³ °

Preparation of compound (5) A solution of 7.3 g

CH ₃ - N (CH ₂ CH ₂ CH ₂ NH ₂ ) ₂ in dry benzene was added with 13.1 g of C ₂ H ₅ SCH ₂ CH ₂ NCO

offset. The mixture was refluxed on a water bath for 2 hours and then cooled, a crystalline mass separated. This was recrystallized from benzene, the Compound (5) having the melting point of 82 to 83 ° C was obtained.

Preparation of compound (6) A solution of 15 g

HO (CH ₂ CH ₂ O) ₁₃ H

in 50 ml of dry benzene was mixed with 6.1 g of C ₂ H ₅ SCH ₂ CH ₂ NCO

offset. The mixture was refluxed for 8 hours. Then the benzene was removed by distillation under reduced pressure, whereby the compound (6) was obtained in the form of a pale yellow transparent solution, n'i 1.4873.

45

Preparation of compound (12) A solution of 13.6 g

H ₂ N-CH ₂

-CH ₂ -NH ₂

in dry benzene was gradually added with 26.2 g of C ₂ H ₅ SCH ₂ CH ₂ NCO

offset. The mixture was refluxed for 3 hours and then cooled, whereby a crystalline mass parted. This was separated off by filtration and recrystallized from methanol

example 1

One for highly sensitive negative photographic material certain silver bromide iodide emulsion containing 2 mol% silver iodide was used of sodium thiosulfate (10 mg / mol AgX) as sulfur sensitizer and chloroauric acid (2 mg / mol AgX) chemically matured as a gold sensitizer. This emulsion was divided into 100 g portions. The individual portions were each separated with the compounds mentioned in Table 1 of the present invention, on cellulose triacetate carrier applied and dried.

For comparison, the compound known from US Pat. No. 3,021,215

HO (CH ₂ J ₂ -S- (CH ₂₎ - (CH _{2) 2} -OH

treated in the same way as described above. to make a control sample.

These samples were measured by a sensitometer at 160 Lux-5400 ° K with a tungsten lamp with a Blue filter B number 49 exposed from a distance of 638 mm. Then they became 5 minutes long developed using a developer of the following composition at 20 ° C:

N-methyl-p-aminophenolsulfa »3 g

Anhydrous sodium sulfite 50 g

Hydroquinone 6 g

Sodium carbonate (monohydrate) .... 29.5 g

Potassium bromide Ig

Made up to 1 liter with water

This developer was diluted 1: 1 with water before use.

The samples were then examined sensitometrically, with those listed in Table 1 Results were obtained.

The photographic properties were determined as described in connection with Example 4 in each case procedure.

55

Table 1 lot Receive Gamma Maxi- times Schli Added fincl- density Sensitizer I mg / light- 100 g wedge Emul sion) 2.25 50 120 0.95 2.27 0.06 Connection (2) 50 130 0.95 2.30 0.07 Connection (8) 50 125 1.00 2.05 0.07 Connection (10) 50 120 0.88 0.09 According to US-PS 2.02 3021 215 100 0.80 0.09 Without

From Table 1 it can be seen that according to the present invention recording materials with improved sensitivity, steeper gradation, higher maximum density and reduced fog than was previously possible.

Example 2

A silver bromite iodide emulsion determined by the neutral process, photographic negative material determined by Tür for photographic negatives, containing 5 mol% silver iodide, was made with sodium thiosulfate (10 mg / mol AgX) as a sulfur sensitizer and chloroauric acid (2 mg / mol AgX) as a gold sensitizer and then in two servings of

ίο divided 100 g each.

The two portions were each separated with the compounds mentioned in Table 2 according to of the invention. Each serving was heated to 56 ° C and chemically ripened. Subsequently were 20 mg of 4 hydroxy-6-methyl-1,3,3 a, 7-tetrazaindene were added to each portion. In addition, suitable Amounts of a gelatin hardener and a coating aid were added and applied as in Example 1 and dried. These samples were kept for 3 days at different temperature and humidity stored and then examined sensitometrically in the manner described in Example 1, the values compiled in Table 2 were obtained.

Table 2

Added
Scnsibiiisaloi

lot

Stored for 3 days at room temperature

(mg'IOOg sensitivity- maximum haze emulsion) density

Stored at 55 ° C for 3 days

Sensitive maximum veil
chance density

3 days at 55 C and
80% relative humidity

Sensitive maximum veil
chance density

Connection (4) 1.0 125 2.35 0.05 125 2.32 0.07 130 2.30 0.06 Connection (7) 1.0 140 2.40 0.07 135 2.42 0.08 135 2.41 0.07 Connection (ii) 1.0 115 2.30 0.04 120 2.32 0.05 115 2.30 0.05 Without 100 2.02 0.08 105 2.08 0.08 100 2.05 0.07

From the table it can be seen that silver halide emulsions according to the invention are recording materials deliver which show less haze even after storage under difficult conditions and not lose sensitivity.

Example 3

A color photographic silver bromide iodide emulsion. containing 4 mol% of silver iodide was used of sodium thiosulphate (10 mg / mol AgX) as sulfur sensitizer and chloroauric acid (2 mg ' Mol AgX) chemically sensitized as a gold sensitizer. Then the emulsion was in portions of divided into 100 g each. The portions obtained in this way were each separated from those mentioned in Table 3 Connections staggered.

After being subjected to chemical ripening, the individual servings were made with the same stabilizer as in Example 2 was added. These portions were then used as a magenta coupler a dispersion was added. This dispersion was made by dissolving 1- (2,4,6-trichlorophenyl) - 3 - [3 - (2,4 - di - tert - amylphenoxyacetamide V-benzamide] -5-pyrazolone in a mixture containing di-n-butyl phthalate and ethyl acetate, at increased Temperature and then dispersing the resulting solution in a gelatin solution below Use of sodium alkylbenzenesulfonate. The portions were stirred thoroughly and then up Adjusted to pH 6.8 and applied as in Example 1 and dried.

These samples were exposed in the same way as described in Example 1 and then exposed for 10 minutes developed at 21 ° C with a color developer of the following composition:

N-ethyl-N-0-methanesulfonamido-

ethyl 3-methylaminoaniline sulfate .. 2.5 g

Anhydrous sodium sulfite 2.0 g

Benzyl alcohol 3.8 g

Sodium hexametaphosphate 2.0 g

Sodium carbonate (monohydrate) 50.0 g

Potassium bromide 1.0 g

Soda 0.6 g

Made up to 1 liter with water

The samples were then subjected to the usual bleaching, fixing and washing with water. They were then examined sensitometrically, the results compiled in Table 3 were found.

609530/206

Table 3 (1)
(3) lot
(mg / HX) g
Emulsion) Sensation
opportunity gamma veil Added
stabilizer 1.5
1.5 125
130
100 0.85
0.07
0.65 0.03
0.03
0.03 link
link
Without

It can be seen from Table 3 that silver halide emulsions according to the invention, if they are a male taker, color photographic recording materials deliver that have high sensitivity and only low fog.

Example 4

To demonstrate the technical progress achieved according to the invention compared to the state of the art, as represented by DT-AS 11 24 351, the applicant has those described below Comparative tests carried out. In these experiments, the effect of the invention used sensitizers in comparison to that known from Example 9 of DT-AS 11 24 351 Sensitizer on the photographic properties of light-sensitive silver halide emulsions unTable 4th

investigates. The tests were carried out in detail as follows:

A silver iodobromide emulsion prepared by the neutral process and intended for negative photographic material, containing 5 mol% silver iodide was treated with sodium thiosulfate (10 mg / mol AgX) and Chloroauric acid (2 mg / mol AgX) added as sulfur or gold sensitizer and then in 100 g portions divided up. For the individual portions of the emulsion, those given in the table below were given Sensitizers or no sensitizer added to the comparison material.

Each emulsion was heated to 56 C and chemically ripened. Each 100 g portion was used as a stabilizer Emulsion with 20 mg each of 4-hydroxy-6-methyll, 3,3a, 7-tetraazaindene added, then usual amounts of a gelatin hardener and a coating aid were added added and applied as in Example 1 and dried. These samples were 3 days stored for a long time at different temperatures and humidity and then sensitometrically in the in Example 1 described manner investigated, the values summarized in Table 4 were obtained.

The sensitivity values given in Table 4 are relative sensitivity values, measured at a density of 0.1 above fog, the sensitivity being the Sample was set at 100 without the addition of a sensitizer.

Added

Sensitizer

Amount stored for 3 days at room temperature

(mg / 100 g sensitivity - maximum haze emulsion) density Stored at 55 ° C for 3 days

Sensitive maximum veil
opportunity dichie

3 days at 55 C and

80% relative humidity

stored

Sensitive maximum veil

chance density

Compound (4 | 1.0 125 2.35 0.05

Compound (4) 5.0 123 2.38 0.07

Compound (7) 1.0 140 2.40 0.07

Compound (7) i 5.0 134 2.43 0.09

Compound (A) ⁺ ) 1.0 120 2.21 0.08

Compound (A) ⁺ ) 5.0 115 2.24 0.10

Without - 100 2.02 0.08

I comparative material)

*) (CHJCH ₂ SCH ₂ CHjCONH) ₂ CH ₂ according to example 9 of DT-AS 11 24

125 120 135 130 118 115 105 2.32
2.40
2.42
2.45
2.22
2.27
2.08

0.07
0.09
0.08
0.09
0.14
0.16
0.08

130
125
135
132
120
110
100

2.30 2.40 2.41 2.44 2.20 2.25 2.05

0.06 0.08 0.07 0.10 0.16 0.17 0.07

From the results shown in the table above, it can be seen that the compounds Photographic emulsions of the present invention containing (4) and (7) excellent photograph! - S5 see properties similar to the photographic properties of the two comparative materials both in terms of the lower fogging and in terms of the lower decrease in maximum density and relative sensitivity also bo are superior after prolonged storage at high temperature and high relative humidity.

The sensitometric examination according to JIS (Japanese Industrial Standard) -Meihode K-7604 is carried out by measuring the photographic sensitivity. A photographic recording material is used for this purpose exposed by means of a scale-type intensity sensitometer. The exposed film then becomes Treated for 10 minutes at 2OC with a developer solution of the following composition:

N-methyl-p-aminophenol sulfate 2.0 g

Sodium sulfite (anhydrous) 80.0 g

Hydroquinone 4.0 g

Potassium bromide 0.5 g

made up to Γ liter with water

and then treated for 15 minutes at 20 ° C with the following fixing solution:

Sodium thiosulfate 250 g

Sodium sulfite (anhydrous) 15 g

Glacial acetic acid 13 _m ]

made up to 1 liter with water

The film is then washed with water at a temperature less than 25 "C and in a stream of air dried at 2OC.

The photographic density log against the amount of exposure, ₀ (lux · sec) was applied. A point "/ 4" is marked on the curve which corresponds to the exposure amount (EA) at which a photographic density [A) which is 0.1 above the fog is obtained. Furthermore, a point »ß« is marked on the curve, which is the value of the logarithmic exposure of point »A«. + 1.5 units. The photographic density (B ) corresponding to this amount of exposure (EA + 1.5 = EB) must be 0.75 to 0.90 above the photographic density of 0.1 above the fog (A)

ie BA must be 0.75 to 0.90. If this condition is met, the value of the exposure amount (EA) corresponding to the photographic density (A) at point "/ 1", ie 0.1 above fog, becomes the photographic speed according to the formula

Photographic sensitivity =

1.0

calculated. From the definition for the point "ß" of the sensitivity curve it follows that the values for gamma or the density in the upper part of the curve correspond to the practical requirements.

Claims (3)

Patent claims: 1. Photosensitive silver halide photographic emulsion containing a chemical sensitizer, characterized in that it is a compound of the chemical sensitizer contains general formula pA-Β-CO-B'-A'-S-R X LA-B-CO-B'-A'-S-R (D in which A is a lower alkylene group or ι s a polyalkylene ether group of the formulas - (CH ₂ CH ₂ O) ,, - - (CH ₂ CH ₂ O) P-CH ₂ CH ₂ - CH ₃ - (CHCH ₂ O) the latter bonded to B via the carbon atom. A 'is a lower alkylene group or a polyalkylene ether group of the formulas - (CH ₂ CH ₂ O) ,, - CH ₂ CH ₂ - CH ₃ CH ₃ where either only A or A 'stands for polyalkylene ether groups and ρ is 2 to 30, B and B' an imino group or an oxygen atom, but not oxygen atoms at the same time, R a lower one Alkyl, phenyl, or aralkyl group or - (CH ₂ L-COOR ' where q is I to 3 and R 'is a lower alkyl group and X is an oxygen or sulfur atom, an alkylene group of the formulas CH ₂ - CH ₃ -CHCH ₂ - and -CH ₂ CH ₂ - a phenylene group or a group of the formula R " wherein R "is a lower alkyl group. 2. Silver halide emulsion according to claim I. characterized in that it additionally has a Contains color coupler. The invention relates to a photosensitive silver halide photographic emulsion containing a chemical Sensitizer. Several methods are known to get photosensitive to sensitize photographic silver halide emulsions. Typical of such a chemical Sensitization is the use of a sulfur compound that is a silver sulfide or an appropriate one reducing compound, or the use of a noble metal salt. It is still known that by using these compounds together, the sensitivity of the emulsion is increased can be further strengthened (cf. for example "The Theory of the Photographic Process", 3. Edition [1967], pp. 113 to 117). This known chemical sensitization method however, it is severely limited on the amount of the compound added and has the disadvantage that the emulsion has a greatly increased fog and poor stability during the storage of the recording material produced therewith at higher temperatures, if this amount exceeds a certain limit. It is also known that when a photographic Emulsion at a higher temperature in the presence of one of the above-mentioned sensitizers Is subjected to ripening process, only the fogging of the emulsion is increased, while the desired Sensitivity enhancement cannot be effected if a certain degree of sensitivity is reached has been. From the DT-AS 11 24 351 it is already known that the photosensitivity of photographic silver halide emulsions are thereby increased can by giving them certain thioethers with amide bonds, in particular 7,9-diaza-3,13-dithiapentadecane-6.10-dione. clogs. It has been shown, however, that the increases in sensitivity that can be achieved therewith no longer meet today's requirements suffice and that this is accompanied by an undesirable increase in the formation of fog (cf. Example 4 below). The present invention has for its object based on a photosensitive silver halide photographic emulsion indicate that, compared to the state of the art, there is a lower tendency to obscure and nevertheless has an increased sensitivity. It has now been found that the object can be achieved in that certain chemical sensitizers can be added to the silver halide emulsion. Accordingly, the present invention provides a photosensitive silver halide photographic emulsion with a chemical sensitizer, which is characterized. that they as chemical sensitizer contains a compound of the general formula