DE1597469A1 - Over-sensitized silver halide emulsions - Google Patents

Description

AGFA-GEVAERTAG

PATENT DEPARTMENT

LEVERKUSEN 1597469

Za / Pk August 12, 1969

Over-sensitive silver halide emulsions

The invention relates to a silver halide emulsion which Contains streptocyanin dyes and hypersensitizing additives.

The streptocyanins - as the prototypes of the cyanine dyes have Strikingly enough, they have not played a practical role as sensitizers so far. The intensity of their sensitizing effects was too small and therefore they are of practical interest only as intermediate products for the manufacture of the known actual cyanine dyes found.

Streptocyanins per se would be advantageous from an economic point of view because they are easy and inexpensive to prepare. There was therefore great interest in using these dyes to sensitize silver halide emulsions as well. especially since quite a number of them go through a close

009824/0286

Absorbance curve and a corresponding sensitization curve distinguish. This advantage is particularly important in color photography, because here the so-called "Secondary maxima" must lead to color distortions. However the streptocyanins are practically completely useless here, because their already moderate capacity for sensitization is further reduced by the presence of color couplers and the like.

The invention is based on the object of hypersensitizing To find additives for streptocyanin dyes; another task is the development of silver halide emulsions, which are spectrally sensitized with streptocyanins and oversensitizing additives.

It has now been found that · the sersitizing effect of Streptocyanin dyes to an extraordinarily high degree by acidic, aromatic or mercapto groups heterocyclic compounds can be increased and that by adding this combination silver halide emulsions can be sensitized in an excellent way.

Usable streptocyanin dyes correspond to the following formula:

'v> RKK V _x

.K ^ ι ι ι s K *

H - c -4- c = ο -4- h '.;

wherein mean; 009824/0286

AG 266 - 2 - ■

R and R = hydrogen, alkyl with up to 6 carbon atoms,

Cycloalkyl such as cyclopentyl or cyclohexyl, olefinically unsaturated aliphatic radicals with up to 6 carbon atoms, aralkyl such as benzyl or iflienylethyl, aryl, preferably phenyl or heterocyclic rings such as pyridine, thiazole, triazole.

R ¹ and R ^VI - alkyl with up to 6 carbon atoms;

R ¹¹ JR ¹¹¹ UnU R ^IV = hydrogen, alkyl with up to 3 carbon atoms,

Cycloalkyl such as cyclopentyl or cyclohexyl, aralkyl such as benzyl or phenylethyl, aryl, in particular phenyl halogen such as chlorine or bromine, alkoxycarbonyl, alkoxycarbimmo, Alkoxy, alkylthio, carbamoyl or Moro- or dialkylsarbamoyl, where the alkyl groups the last-mentioned substituents preferably contain up to 5 carbon atoms;

η = 1-5 preferably 1-3

τ y vT

R and R or R and R can also be used to complete

of a 5- or 6-membered preferably saturated ring are required ring members, for example a pyrrolidine, piperidine, hexamethyleneimine, morpholine, dihydroindole, tetrahydroquinoline, phenmorpholine, piperazine or hexahydrocarbazole ring.
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BATH ORIGINAL

The hypersensitizing, acidic mercapto compound has the following formula

X -j Ä - SH

where mean:

X = an acidic group such as sulfonic acid, sulfinic acid, carboxylic acid such as acrylic acid, sulfonamides, phosphonic acid, arsenic acid, thiosulfonic acid, hydroxy, mercapto, acyl-sulfamyl; these Groups can also be present several times, the acidic groups can also be in the form of their salts, e.g. alkali metal, Alkaline earth metal or ammonium salts are present;

R = an aromatic or heterocyclic ring e.g. phenyl, Naphthalene, Furan, Thiophenj Carbazole, DiphenylenoxyC, Imidazole, benzimidazole, pyr: .midin, oxazole, benzoxazole, Naphthoxazole, Thiazole, Benzthiazole, Naphthiazole, Oxazine, Naphthoxazine, Thiazine, Thiaöiazole, Oxadiazole, Pyrim: .din, Triazole, triazine, tetrazole, pyridine, quinoline, isoquinoline, selenazole, benzselenazole, pyrrole, indole and their

VT T

partial hydrogenation products, the radical R can also contain substituents such as alkyl, cycloalkyl, alkenyl, aralkyl, aryl, hydroxy, halogen, alkoxy, alkylthio, sulfone, acyl, carbonamide, carboxyalkyl, CN, CF ,, NR ₉ , dioxymethylene, furan, Thiophene and the like.

Suitable streptocyanins are, for example, the following:

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BATH ORIGINAL

CH _Q - CH,

I ²

CH ₂ -

^{L }} .CH ₉ - CH ₉

CH-4 CH = CH -4 Ν ' ^ά I ^d ClO,

^N CH ₂ - CH ₂

CH ₂ -

: N-CH-4 CH = CH -CH

NO,

- CH ₀

■ CH-4 CH = CH CH ,, - CH

Br

<CZ>

CH ,, -

- CH,

2 ^CH 2

(+) CH - CH H CH ₃
CC = CH

N) H ₂ - OI

CH ₉ - CH ₉ j ^l ^ N

CH ₀ - CH ^

(+) CH-4 CH - CH,

= CH 4-N

CH

', j - CH,

2 - ^0E 2

- CH-4 CH = CH 4o N ^ - CH

- ^CH 2 '

(CH ₉

N - CH-4 CH = CH ·) - N

(CH ₉ )

2'6

VIII HIGH ₉ CH ₉ I

, CH ₀ - CH ₉ _ (+)

² "^ CH ₂ - CH ₉ ^ - CH ₉

ClO,

-CH ₂ -CH ₂ -OH

~ ^CH 2

- ^ N-CH ₂ -CH ₂

ClO,

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BATH ORIGINAL

r *

- CH - CH = CH - N I Cl O.

^ c-CHj, ⁴

Hq "O Hr) Hrv

, C- (T (+) p — C ² (-)

Cf JT - CH (CH CH) N y

() pC

CH - (CH = CH) ₂ - N y Cl

Hq Hp Hp

₃ ^ CH ₅

XI / VN - CH- ^ CH = CH) ₉ - N - / \\ ClO ₄

XII / V ^ ~ ^CH - ( ^{CH = CH} ) 2 ~ ^ - / Λ ^C1

^H 3 ° V Θ / ^CH 3

^XI11 N-CH - (- CH = CH) ₂ - if ClO ₄

Hyper-sensitizing mercapto compounds are preferred Oxazoles, Benzoxazoles, Thiazoles, Benzthiazoles, Naphthothiazoles, Oxazines, Benzoxazines, Naphthooxazines or Benzimidazoles suitable e.g. the following:

1. 2-Mercapto-2 ', 3'-naphtho-7'sulfonic acid-oxazole-4,5

2. 2-Mercapto-5-chlorobenzoxazole-7-sulfonic acid

3. 2-mercapto-naphth-1,8'-oxazine-4,6-3'sulfonic acid 4. ' 2-mercapto-5-acryl8 acid-7-ynethoxybenzoxazole

5. 2-mercapto-benzothiazole-5-8ulfonic acid

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BATH

6. 2-mercapto-5- (4 'chloritheityl-amino-sul Γο) -benzthiazole

7. l-.dodecyl-2-mercaptobenzimidazole sulfonic acid

8. Sodium thiophenol-4-sulfonic acid

9. ^ -Mercapto-l ^^ -triazol-l-Cphenyl-? ¹ , 5'dicarboxylic acid)

The streptocyanins are produced by known methods.

Strepfcocyanin No. IV is obtained as follows: 5.8 g of 1- (2 ', 4'-dinitrophenyl) -3-methyl-pyridinium chloride, dissolved in 20 ml of methanol, are mixed with a mixture of 7 ml of pyrrolidine and 10 ml of methanol and heated to 70 °. This is removed on cooling and the dye is precipitated from the filtrate by adding 15 ml of 5C # Na perchlorate solution. It is dissolved from 150 ml of CHOl- + 15 ml of m-propanol, clarified with Α-charcoal and the solution is concentrated. It is recrystallized again from 100 ml of propanol. Yield 1 g Pp. 187-188 ⁰ C.

The unsymmetrical streptocyanin # V is obtained in the following way:

2 g of dihydroindole-N-pentadienal are in 50 ml of methanol dissolved. This is a mixture of 2 ml of pyrrolidine and

5 ml of glacial acetic acid were added and briefly warmed on the steam bath.

Then will
10 ml of 25 # potassium iodide were added. The crystallized

Dye is turned off
250 ml of methanol recrystallized.
Yield: 1 g. Mp 292-293 ° C.

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009824/0286 ORIGINAL BATHROOM

The combination to be used in the manner according to the invention from the streptocyanin and the hyper-sensitizing mercapto compound leads to silver halide emulsions of high sensitivity, Surprisingly, the mercapto compound In addition, the stability against other necessary emulsion additives such as coupling components for the production of color images, Colorants, developers, wetting agents and other organic or inorganic substances greatly improved. The preparation of the silver halide photographic emulsion essentially comprises three steps:

1. Precipitation of the silver halide in the presence of a Schulz colloid and physical ripening;

2. if necessary, removal of the excess water-soluble salts resulting from the precipitation from the Emulsion, generally by washing and

5. Chemical ripening or post-ripening, which is used to give the emulsion the desired sensitivity.

The streptocyanins and mercapto compounds can be used in any sequence and in any silver halide emulsions will. Silver halide in particular are silver chloride, silver bromide or mixtures thereof, possibly with a small amount Silver iodide content up to 10 mol- # suitable. The silver halides can be dispersed in the usual hydrophilic compounds, for example carboxymethyl cellulose, Polyvinyl alcohol, polyvinylpyrrolidone, alginic acid and its salts, esters or amides or, preferably, gelatin.

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0 09 82 k / 02 86 BAD ORIGINAL

The streptocyanins to be used according to the present invention and supersensitizing compounds are preferably added to the photographic emulsion after the chemical one Maturing and added before potting. The methods used for this are generally known to those of ordinary skill in the art. the Compounds are generally incorporated into the emulsion in the form of solutions e.g. in alcohol or alcohol / water tables. Of course, the solvents must be compatible with Gslatine and must not have any adverse effects exert the photographic properties of the emulsion. Water, methanol, dimethylformamide, pyrrolidones, phenols or mixtures thereof are generally used as solvents. The amount of streptocyanine added can vary within wide limits, e.g. between 1 - 100 mg, preferably between: i 10-45 mg per kg of the silver halide emulsion. The concentration can meet the respective requirements, depending on the type of emulsion, the desired sensitization: 'fect etc. can be adjusted. The most suitable concentration for any given emulsion may be determined by those used in photographic practice usual tests can be determined without difficulty.

The same applies to the hypersensitizing additives that can be added in amounts of 10 mg to 2000 mg per liter of emulsion. Concentrations of 30 mg to 300 mg are preferred per liter of emulsion. Otherwise, these compounds are added to the emulsions in the usual way, with the further The method described above can be used.

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BATH ORIGINAL

The mercapto compound is generally roughly "the 5-20 times the amount of streptocyanine added.

The emulsions can also contain chemical sensitizers, e.g. reducing agents such as tin-II salts, polyamines, such as diethylenetriamine, sulfur compounds, as in American U.S. Patent 1,574,944. The specified emulsions can also be used for chemical sensitization Containing salts or complex compounds of noble metals such as ruthenium, rhodium, palladium, iridium, platinum or gold, such as in the article by R. Koslowsky, Z.wiss.Phot. 46, 65-72 (Ϊ951) described.

* · The emulsions can also be used as chemical sensitizers Contain polyalkylene oxides, especially polyethylene oxide and derivatives thereof.

The emulsions according to the invention can also be customary Contain 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 organic Mercury compounds. Also suitable as stabilizers are azaindenes, preferably tetra- or penta-azaindenes, especially those with hydroxyl or amino groups

are substituted. Such compounds are described in the article by Birr, Z.wiss.Phot. 47 _f 2-58 (1952). Other suitable stabilizers include other heterocyclic mercapto compounds, for example phenyl mercaptotetrazole, quaternary

009824/0286
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BATH ORIGINAL

Benzothiazole derivatives, benzotriazole and the like.

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

The emulsions according to the invention can be used for the most varied find photographic processes use. For example for recording materials, for copy materials, for reprotechnical films, for X-ray films, for materials that are suitable for the silver salt diffusion process, for color photographic materials such as for chromogenic development, color developers, silver color bleaching processes, and others.

Example 1 :

To 1 kg of a silver chloride gelatin emulsion, 30 mg of streptocyanin I are added in the form of a 3% methanolic Solution added. The sensitization maximum is 452 nm.

During the sensitometric test in a standard sensitometer you get a step wedge with 21 visible steps

The effect of the mercapto compound 1 is as follows Table:

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BAD ORIGfNAl. '

103 / fb Λ Sensitivity in
Levels 13/2 " Table 1: 24 Amount of mercapto compound
in mg 25.5 30th 26.5 60 27 90 27.5 120 27.5 150 27.5 190 240

The effect of other mercapto compounds with an additive. 2 of 200 mg per liter of the same emulsion shows the following Table 2:

Table 2 chkeit'in levels \ V ~ 2 Mercapto compound Sensitive after 7 days γ
Tropical cabinet immediately 18th - 21 27.5 2 27.5 29 3 28.5 28.5 4th 29 26th VJl 26.5 28.5 6th 27 26th 7th 26.5

The effect is special in the tropical cabinet test

(40 ° C / 85 # rel. Humidity) very noticeable and is through-

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- 11 BAD ORIGINAL

average pactor 10.

With the well-known sensitizer 3,3 ^f -diethyl-bis (-benzthiazol-) monomethine-cyanine with an addition of 30 mg / l of the same emulsion a sensitivity of only 25.5 steps | ^ 2 is achieved with the same position of the sensitization maximum.

Example 2 :

To one liter of a silver chlorobromide gelatin emulsio :! 20 mg of the streptocyanine II are added (dissolved in methanol 1: 20000). The sensitization maximum is in the green area at 574 nm. The sensitometric test in a conventional sensitometer gives a step wedge y of 14.5 steps.

The emulsion of the same structure but with a further addition of 240 mg of the mercapto pre-compound 2 (as the sodium salt 1: 100 dissolved in methanol) shows a sensitivity: t with the same processing of 27 _f 5 levels of sensitivity is around the factor 20 increased.

Example 3 :

To the emulsions of Example 2, 10 g per liter of emulsion of the sodium salt of the blue-green coupler 1-hydroxy-4-sulfo-N-n-octadecyl-2-naphtharide are added added as a 50 # solution in water.

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BAD ORiQINAi.

With the same processing, you get the emulsion without the mercapto compound a step wedge with 4.5 steps. The emulsion containing the mercapto compound has sensitivity of 35.5 steps, which corresponds to an increase in sensitivity of around 300 times.

Example 4 :

To a silver chlorobromide gelatin emulsion which contains the color coupler of Example 3 contains in the indicated concentration, 300 mg of Streptocyaninea III are added. The sensitometric test behind a red filter leaves practically no sensitivity to red light recognize.

Will the same emulsion with 200 mg of the mercapto compound

2, a relatively high sensitivity in the red spectral range is achieved with the same processing a maximum at about 682 nm can be seen. The sensitivity is 15 levels

Example 5 :

A silver chloride emulsion is ver with a streptocyanin and the sensitivity of this emulsion with and without another addition of a mercapto compound checked. The experimental conditions and results are from the following 'Table 3 can be seen.

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BATH ORIGINAL Table 3

Streptocyanin mercapto compound 2 sensitivity 30 mg / l emulsion 150 mg / l emulsion in stages

IV

9.5 17.5

VI

7.5 14

YII

8th
13.5

VIII

14.5 15.5

Example 6 ;

An ammonia silver bromide gelatin emulsion is 30 mg per Liters of streptocyanines V are added and processed in the usual way. The maximum of sensitization is at 510 nm.

The dependence of the sensitivity on the amount of mercapto compound 2 added, measured behind a step wedge \ 72 and a bright yellow filter (transparent above 490 nm) is compiled in the following table 4.

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BATH ORIGINAL

Table 4

Mercapto compound 2 sensitivity

in stages V ^

0 17

10 mg 17.5

20 mg 18

40 mg 19.5

80 mg 20

120 mg 20.5

150 mg 20

Example 7 :

A chlorobromosilver gelatin emulsion gives 20 mg per Liter dee Streptocyanine V a sensitization with eirem Maximum at 513 nm.

The dependence of the sensitivity on the type of mercapto compound added per 1 l of emulsion, measured in levels γ without a color filter, is shown in the following table:

Table 5 sensitivity
in steps W ^ " Streptocyanin
20 mg Mercapto compound
200 mg 13th without without 19.5 V cvj 17.5 V 9 19th V 8th A-G 266 - 15 .- 009824/0286

Example 8;

The streptocyanin IX gives 50 mg / l in a chlorosilver emulsion a spectral sensitization with a maximum at approx. 465 mn. The sensitivity to exposure behind a gray level wedge was 10 levels i ^ 2. When adding of 200 mg / l of Mereapto Compound 2, the sensitivity was 14.5 levels.

Example 9 :

The streptocyanin X with 30 mg / l of a chlorosilver emulsio.i results in a spectral sensitization with a maximum at 447 mn. The sensitivity was 6 levels γ2. After 200 mg of the mercapto compound 1 was added, the sensitivity was 11.5 levels. **

Example 10:

20 mg of the compound XI become a silver chlorobromide gelatin emulsion admitted. The spectral sensitization obtained shows a broad maximum at about 495 nm of moderate intensity. The exposure through a yg step wedge results in * the exposure behind a yellow filter 12 fields.

If an additional 20 mg of mercapto compound 1 are added, a new sensitization maximum occurs at 552 nm with a steep drop and the sensitivity increases to 19 fields.

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BATH ORIGINAL

Example 11:

In a silver chloride bromide gelatin emulsion, 20 mg of compound XII result in broad sensitization in blue-green with a flat maxxumum at 500 nm. The sensitivity to 24.5 fields achieved by exposure behind a Gebfilter and a gray scale wedge with the factor g. If 200 mg of mercapto compound 2 were added in the same way, the sensitivity was even 28 fields. In addition, the spectral sensitization curve was changed in such a way that a new, well-defined maximum emerged at 540 nm.

Example 12

20 mg of the Streptocyanins II result in a Silberchloridbromidgelatineemulsion in the presence of the sodium salt of 1 (4'-phenoxy-3'-sulfophenyl) -3-heptadecyl-pyrazolone (5) as the magenta coupler has a sensitivity of 3 steps \ f ~ ^ behind a yellow filter with a sensitization maximum in yellow-green at 563 nm. If increasing amounts of the mercapto compound 2 are also used, the following sensitivities result:

Table 5

Step wedge behind the yellow filter immediately after 7 days

Tropical chränk

without , . 3 2

10 mg mercapto compound 3 » 5 - 3.5

20 mg 009824/0286 ^{4 5} » ⁵

BATH ORIGINAL A-ö 266 - 17 -

1597469 9 9 18th 17th 21 20.5 21.5 21.5 22nd 22nd 21.5 22nd

45 mg 90 mg 150 mg 200 mg 250 mg 300 mg

The maximum of sensitization is increased by approx. Postponed 10 mn after long waves.

Example 13 ;

30 mg of the compound XIII result in a silver chloride gelatin emulsion a sensitization in the spectral blue-violet with a maximum at 438 nm. The sensitivity behind a Step wedge Yv "^ covered 16 fields. If 200 mg of the mercapto compound 2 are added, the sensitization has a maximum at 441 nm and the sensitivity was 22 fields.

Example H:

20 mg of compound I in 1 liter of a silver chloride gelatin emulsion result behind a step wedge V2 without a color filter a sensitivity of 19 fields. If 90 mg of 2-mercapto-5- (3'-sulfobenzoylamino) -benzoxazole are also added, the sensitivity increases to 23.5 fields; when 90 mg of 3-mercapto-5- (3'-sulfophenyl) -1,2,4-triazole are added the sensitivity even increases to 25 fields.

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Claims (3)

Patent claims: 1. Optically sensitized silver halide emulsion, characterized by a content of a streptocyanin and a Bauren aromatic or heterocyclic supersensitizing compound containing mercapto groups. * 2. Optically sensitized silver halide emulsion Claim 1, characterized by a content of a streptocyanin of the following formula: _R II ,, !!! "IT ^{C = C} - * n K) _v ⁿ \ _R VI ' where mean: R and R ■ hydrogen, alkyl with up to 6 carbon atoms, Cycloalkyl olefinically unsaturated aliphatic radicals with up to 6 carbon atoms, Aralkyl, aryl; R ¹ and R ^VI = alkyl with up to 6 carbon atoms; R ¹¹ , R ¹¹¹ and R ^IV = hydrogen, alkyl with up to 3 carbon atoms, Cycloalkyl, aralkyl, aryl, halogen, alkoxycarbonyl, alkoxycarbimino, alkoxy, Alkylthio, carbamoyl, mono- or dialkylcarbamoyl; η = 1 - 5 R and R ¹ or R ^V and R can also be used to complete a 5-, 6- or 7-membered ring required ring members mean 009824/0286
AG 266 - 19 - BATH ORIGINAL and an acidic mercapto compound of the following formula: X ■ (■ - R ™ - SH where mean: X = an acidic group;
VTT R = an aromatic or heterocyclic ring. 3. Optically sensitized silver halide emulsion by characterized in that X is sulfonic acid or an aliphatic acid saturated or unsaturated with one carboxyl group VII substituted radical and R is one of the following rings: Phenyl} oxazole, benzoxazole, thiazole, benzthiazole, Naphthothiazole, oxazine, benzoxazine, or naphthooxazine Triazole. 009824/0286
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