DE1904147A1 - Process for making photographic silver halide emulsions - Google Patents

Description

EASTMAN KODAK COMPANY, 3 ^ 3 State Street, Rochester, New York State, United States of America

Process for making photographic silver halide

emulsions

The invention relates to a method for producing photographic ones Silver halide emulsions, which are carried out in aqueous solutions in the presence of a peptizing agent Reaction of soluble silver salts with soluble halides silver halide crystals precipitate.

In the production of photographic silver halide emulsions, a so-called "double conversion" from a soluble silver salt, ζ. B. silver nitrate and a soluble halide, ζ. B. an ammonium halide, or an alkali metal halide, usually potassium halides, a photosensitive silver halide is precipitated. While the precipitation of the insoluble silver halide, it is necessary the formation of silver halide crystals with To control the aid of a peptizing agent, whereby this the crystal growth and the distribution of the silver halide crystals affected in the emulsion. The crystal growth involved in the manufacture of photographic emulsions Distribution conditions essentially determine the basic sensitometric and photographic properties the emulsion in question, such as its photographic

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tographic sensitivity, their contrast, their "graininess" and their ÄÄäsiiMMMiMiiMlüiPiäiiiMJi ^ iiM ^ MiiÄiiäMiiliii sharpness of the contour.

Gelatin has hitherto been mainly used as a peptizer for photographic emulsions. Although gelatin is a suitable peptizer, "it has certain disadvantages. For example, gelatin can be attacked by bacteria and fungi, which can sometimes damage the photographic emulsions in question. Another disadvantage of gelatins is their animal origin. Due to this, the control forms the evenness or uniformity of
gelatin masses used for peptization purposes (often) pose a serious problem.

The invention was therefore based on the object of providing a process for the production of photographic silver halide emulsions, in which one works in aqueous solutions in the presence of a peptizing agent by reacting soluble silver salts precipitates silver halide crystals with soluble halides, indicate in which the precipitation of the silver halide crystals takes place in the presence of a peptizing agent, which is not attackable by bacteria and fungi and has a more even and uniform composition as gelatin.

The invention was based on the knowledge that the ge was The problem can be solved if the precipitation of the silver halide in an aqueous dispersion in the presence of certain synthetic, sulfur-containing peptizers .

The invention thus provides a process for the preparation of photographic silver halide emulsions

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which one in aqueous solution in the presence of a peptizer silver halide crystals are precipitated by the reaction of a soluble silver salt with a soluble halide, which is characterized in that the precipitation is carried out in the presence of a peptizing agent which consists of a water-soluble, linear addition copolymer with or from esters and / or amides of maleic acid, acrylic acid and / or methacrylic acid, the amine and alcohol radicals of which are an organic radical with at least one two alkyl carbon atoms connecting sulfide-sulfur atom contain.

The addition copolymers used in the process of the invention for the production of photographic silver halide emulsions represent a completely new class of synthetic peptizers. The main advantage of these synthetic peptizers are that they are more uniform and uniform in composition than gelatin and practically not at all tend to degrade. The photographic ones that can be prepared using the copolymers Silver halide emulsions are particularly suitable for the production of photographic recording materials, which are developed physically, for example in the context of the diffusion transfer process. The addition copolymers used as peptizers represent a substitute for gelatin and give the Photographic silver halide emulsions prepared therewith had photographic properties which were definitely not achievable.

In the context of the process of the invention as a peptizer The addition copolymers used can each contain at least one sulfide-sulfur atom Vinylamide and / or ester monomers with at least one

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further, ethylenically unsaturated monomers, for example an α, ß-ethylenically unsaturated hydrocarbon, such as Ethylene; a vinyl ester such as vinyl acetate; a vinyl ether such as methyl vinyl ether; an amide such as acrylamide or methacrylamide; Acrylic and methacrylic acid and their esters, such as acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate and ethyl methacrylate; an α, ß-ethylenically unsaturated sulfonate, such as sodium 3-acryloyloxypropane-l-sulfonate and sodium 3-acryloyloxy-l-ftethylpropane-l-su.lfonate, and an α, ß-ethylenically unsaturated sulfate, such as sodium methacryloyloxyethyl sulfate, be copolymerized.

The optimal concentration of the under the procedure of Invention used peptizers in the precipitation medium depends on various factors, such as on the particular Temperature or the respective pH value of the precipitation medium and the silver and halide concentration in the precipitation medium away. The optimal peptizer concentration is in is generally low and, based on the total weight of the aqueous medium, - expediently between about 0.25 and about 5, preferably between about 0.5 and about 3 weight percent.

The addition copolymers used as peptizing agents according to the invention can be used in all precipitation processes customary for the production of photographic emulsions, for example in the single-jet and double-jet processes described in the photographic literature will.

The silver halide emulsion which can be prepared by the process of the invention using the peptizing agents described η may optionally contain further hydrophilic colloids, for example serving as film-forming binders contain. Examples of such hydrophilic colloids are gelatin, polyvinyl alcohol, synthetic, soluble ones

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Polymers and copolymers of acrylic acid, acrylic acid esters, Methacrylic acid and methacrylic acid ester! as well as mixtures thereof.

The silver halide emulsions which can be prepared by the process of the invention can also be used with all suitable chemical sensitizers or mixtures of such sensitizers, for example with common sulfur and / or gold sensitizers or others to sensitize Silver halide emulsions suitable compounds are chemically sensitized. Such silver halide emulsions can also be used spectrally, either as is usual for black-and-white negative emulsions, panchromatic or in special cases, e.g. B. for the production of color photographs Recording materials, are sensitized to a certain wavelength range.

The emulsions which can be prepared by the process of the invention can be used for the preparation of recording materials for X-rays, γ- and electron beams, for the production of a wide variety of color photographic recording materials and color copying materials and for making conventional black and white photographic recording materials. The silver halide emulsions which can be prepared by the process of the invention can, if so-called "fine-grain" Emulsions are to be produced which contain a wide variety of compounds that retard crystal growth. at A wide variety of crystal ripening processes can be used to prepare such silver halide emulsions.

As a rule, the preparable by the method of the invention, photographic silver halide emulsions practically all of the advantageous properties of using

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application of gelatin as a peptizing agent, customary, known emulsions. In addition, however, the SiI-berhalide emulsions which can be prepared by the process of the invention are obtained some properties of emulsions made using gelatin as a peptizer do not exhibit. As a rule, the silver halide emulsions which can be prepared by the process of the invention can be used in the same way as other photographic silver halide emulsions and by customary known additives or special treatments modify.

First, the preparation of some becomes more suitable as peptizers for practicing the process of the invention Addition copolymers described.

A) Copolymer of acrylic acid and Acryloy! Methionine methyl ester (molar ratio 3 ₃ 0: 1.0)

A solution of 10.0 g of acrylic acid and 10.0 g of acryloyl methionine methyl ester in 60 ml of dioxane, 0.2 g of azobisisobutyronitrile was added and the mixture was carried out under a nitrogen atmosphere at one temperature left to stand at 60 ° C overnight. The polymer formed in this way was isolated by precipitation in ether and purified by dissolving in a dioxane / methanol mixture and subsequent precipitation in ether. The yield at purified polymer was 19.0 g.

The elemental analysis of the copolymer resulted in the following values:

N S

Calculated: 3.2 7.3

Found: 3.2 6.4

S 69 8 4 1/12 8

ORIGINAL INSPECTED

1 9 O A 1 A 7

The copolymer obtained can be expressed by the following formula reproduce:

-CH,

CH

COOH

CH ^ CH

CO

NH I CH ₃ SCH ₂ CH ₂ Ch-COOCH ₃

B) Copolymer of acrylic acid and methylthioethyl acrylate (molar ratio 3.33: 1.0)

A solution of 8.7 g of acrylic acid and 5.3 g of methylthioethyl acrylate in HO ml of dioxane was admixed with 0.1 g of azobisisobutyronitrile and left to stand overnight at a temperature of 60 ° C. under a nitrogen atmosphere. The gelatinous, opaque precipitate formed in this way was dissolved in methanol, whereupon the clear solution obtained was poured into ether. A weak, partly colloidal precipitate was obtained. After drying in vacuo, the yield of copolymer was 10.1 g.

The elemental analysis resulted in the following values:

Calculated:
Found:

8.5 5.8

The copolymer obtained can be represented by the following formula:

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CH,

CH - COOH

CH,

CH-

CO

~ CH _O SCH -f

C) Copolymer of acrylic acid and methacrylyl methionine (Molar ratio 3.33: 1.0)

A solution of 3.85 g of acrylic acid and 3.5 g Methacryloylmethionin in 20 ml of dioxan was treated with 0.05 g of azobisisobutyronitrile under nitrogen atmosphere at a temperature of 6O ⁰ C allowed to stand overnight. The here formed
Polymer was isolated by precipitation in ether. After drying, the yield of copolymer was 8.0 g.

The elemental analysis resulted in the following values:

Calculated:
Found:

N S. 3.1 7.1 3.2 7.0

The copolymer obtained can be represented by the following formula:

CH;

CH-COOH

CH, t *

CH ₀ C r

² t

CO

NH CH ₃ S (CH ₂ J ₂ CHCOOH

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D) Copolymer of acrylic acid and methacryloylpyrolyl methionine methyl ester (Molar ratio 3.33: 1.0)

4.8 g of acrylic acid was obtained by a conventionally known method with the reaction product of 3.66 g of methacryloylproline and 3.26 g of methionine methyl ester copolymerized in the presence of triethylamine and ethyl chloroformate. The copolymer could not be obtained in crystalline form. The yield of dry copolymer was 9.1 g.

The elemental analysis resulted in the following values:

Calculated: Found:

2.8
3.1

6.1

The copolymer obtained can be represented by the following formula:

CH,

COOH

-Ix

CH.

= 0 0

It

COOCH ₃

'C-NH-CH- (CH ₂ ) ₂ SCH,

E) Copolymer of acrylic acid and acryloyl methionine (molar ratio 3.33: 1.0)

A solution of 11.9 g of acrylic acid and 10.15 g of acryloyl methionine in 60 ml of dioxane was admixed with 0.2 g of azobisisobutyronitrile and left to stand overnight ^{at a temperature of 60 ° C. under a nitrogen atmosphere.} The solution obtained was

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poured into ether, whereupon the precipitated copolymer was filtered off and dried in vacuo. The yield of copolymer was 22 g.

The elemental analysis resulted in the following values:

Calculated:
Found:

3.2 2.8

7.3 6.1

The copolymer obtained can be represented by the following formula:

• CH,

CH -

COOH

CHn 'CH * ^ ~ "~~" ■ - ^ - · ————— -

² i

C-O COOH

NH CH-CH ₂ -CH ₂ -S-CH ₃

P) Copolymer of acrylic acid and AcryloyMethionine (Molar ratio 3.33: 1.0)

A solution of 10.5 g of a copolymer of acrylic acid and acryloyl methionine methyl ester (molar ratio 3.33: 1.0), which was prepared as under A), but with instead of 10.0 g of acryloyl methionine methyl ester 11.0 g were used in 50 ml of methanol was mixed with 4.3 g of sodium hydroxide saponified in 50 ml of methanol. Some copolymer precipitated out, which was restored by adding 50 ml of water went into solution. The resulting solution was evaporated in vacuo, whereupon the residue was taken up in 50 ml of water became. After the obtained solution stand at room temperature

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was left, it was poured into methanol. The copolymer which precipitated out was at room temperature dried in vacuum. The yield of copolymer was 12.2 g.

The elemental analysis resulted in the following values:

N S. sodium 2.9 6.8 9.6 2.3 16.3

Calculated: Found:

G) Copolymer of acrylic acid and acryloyl methionine (Molar ratio 5.0: 1.0)

A solution of 9 _S O g acrylic acid and 5.1 g Acryloylmethionin in 35 ml of dioxan was treated with 0.1 g of azobisisobutyronitrile and under a nitrogen atmosphere at a temperature of 6o ° C for two days, allowed to stand. The copolymer formed in this way was isolated by precipitation in ether and filtering off. After drying in vacuo, 13.5 g of copolymer were obtained.

The elemental analysis resulted in the following values:

N S

Calculated: 2.5 5.7

Found ^: 2.6 4.9

H) Copolymer of acrylic acid and acryloyl methionine (molar ratio 1.0: 1.0)

According to the method described under G), 3.6 g of acrylic acid were obtained »R4 copolymerized with 10.2 g acryloyl methionine. The yield of copolymer was 12.5 g.

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The elemental analysis resulted in the following values:

N S

Calculated: 5.1 11.5

Found: 4.7 10.5

I) Copolymer of ethyl acrylate, acrylic acid and acryloyl methionine methyl ester (Molar ratio "5.8: 2.7: 1.0)

A solution of 12.0 g of ethyl acrylate, 4.0 g of acrylic acid and 4.5 g Acryloylraethionine methyl ester in 50 ml of dioxane was added with 0.2 g Azobisisobutyronitrile is added and the mixture is left to stand at 60 ° C. overnight. The viscous solution obtained was diluted with dioxane, whereupon the copolymer formed was isolated by precipitation in ether. That from the solvent The crude copolymer which had been separated off was purified by dissolving it in dioxane and reprecipitating it in ether. The yield of dry copolymer was 18.5 g.

The elemental analysis resulted in the following values:

N S

Calculated: 1.4 3.2

Found: _t 1.5 3.0

J) Copolymer of acrylic acid and acryloyl methionine amide (molar ratio 3.33: 1.0)

A solution of 2.4 g of acrylic acid and 2.02 g of acryloylmethionine amide in 12 ml of dioxane and 6 ml of water was mixed with 0.05 g of azobisisobutyronitrile added and left to stand for 3 days at a temperature of 60 ° C. Then the solution was with Diluted 30 ml of methanol and filtered to remove small amounts of insoluble matter. The one contained in the solution Copolymer was caused by precipitation in ether and

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Filter off isolated. After drying in vacuo, it was the yield of copolymer 5.2 g.

The elemental analysis resulted in the following values:

N S

Calculated: 6.5 7.4

Found: 4.1 4.7

The copolymer obtained can be represented by the following formula:

-CH,

CH-

COOH

CH ₂ CH ^;

NH

CH-CONH ₀

t ²

CH ₂ -CH ₂ SCH ₃

K) Copolymer of ethyl acrylate, acrylic acid and acryloyl methionine (Molar ratio 6.0: 3.0: 1.0)

A solution of 15 g of ethyl acrylate, 5.4 g acrylic acid and 5 g Acryloylmethionin _s O7 in 45 ml of acetone was treated with 0.1 g of azobisisobutyronitrile and under a nitrogen atmosphere at a temperature of 60 ⁰ C for 4 hours allowed to stand. The copolymer formed in this way was isolated by precipitation in ether and filtering off. The yield of dry copolymer was 23.1 g

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The elemental analysis resulted in the following values:

N S

Calculated: 1.4 3.2

Found: 1.2 3.2

L) Copolymer of ethyl acrylate, acrylic acid and acryloyl methionine (Molar ratio 5.0: 2.0: 1.0)

12.5 g of ethyl acrylate, 3.6 g of acrylic acid and 5.07 g of acryloyl methionine were copolymerized according to the process described under K). The yield of copolymer was 19s2 g. The elemental analysis resulted in the following values:

N S

Calculated: 1.4 3.2

Found: 2.3 3.8

1. Copolymer of acryloyl methionine methyl ester and sodium 3-acryloyloxy-1-methylpropane-1-sulfonate (molar ratio 1: 9)

2. Copolymer of N- (3-thiapentyl) acrylamide and sodium 3-acryloyloxypropane-1-sulfonate

1. A solution of 6.94 g of acryloyl methionine methyl ester and 66.24 g of sodium 3-acryloyloxy-1-methylpropane-1-sulfonate in 200 ml of redistilled dimethyl sulfoxide were flushed with nitrogen, then 0.37 g of azobisisobutyronitrile were added and left to stand at a temperature of 60 ° C overnight. The resulting copolymer was through Pouring the solution into acetone precipitated. The copolymer separated from the solvent was in vacuo at room temperature dried. The yield of copolymer was 76.4 g.

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The microanalysis of the copolymer C (molar ratio 1: 9) gave the following values:

C. H N N / A S. Calculated: 37.8 5 »0 0.6 9.0 14.0 Found: 34.8 5.2 - 9.1 15.2

The molar ratio of acryloyl methionine methyl ester to sodium 3-acryloyloxy-1-methylpropane-1-sulfonate in the copolymer was 1: 9.

2. A solution of 7.07 g of N- (3-thiapentyl) acrylamide and 86.4 g of sodium 3-acryloyloxypropane-1-sulfonate in 280 ml of redistilled dimethyl sulfoxide was flushed with nitrogen, then 0.47 g of azobisisobutyronitrile was added and left to stand at a temperature of 60 ^{° C. overnight.} The copolymer formed in this way was precipitated by pouring the solution into acetone. The copolymer separated from the solvent was dried in vacuo at room temperature.

The microanalysis of the copolymer ^c 6i ^H g4 ° 46 ^NS 10 ^Na 9 (Mo! Ratio 1: 9) gave the following values:

34 C. 4th H N 9 N / A S. 2 Calculated: 34 ,8th 4th »5- 0.7 9 ,8th 15, 5 Found: , 4 , 7 - ,8th 15,

N) Copolymer of N- (3-thiabutyl) acrylamide and sodium 3-acryloyloxypropyn-1-sulfonate (Molar ratio 1: 6)

A solution of 842.4 g (3.9 moles) sodium 3-acryloyloxypropane-1-sulfonate in 2809 ml of redistilled dimethyl sulfoxide was mixed with 94.25 g (0.65 mol) of N- (3-thiabutyl) acrylamide and 4.68 g of AEobisisobutyronitrile are added. The resulting mixture was purged with nitrogen for 15 minutes and placed in a 60 ° G bath overnight. The here

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The copolymer formed was precipitated, washed clean with a large excess of acetone, filtered off and dried in vacuo at room temperature. The copolymer consisted of a brittle, white, solid mass. The yield of copolymer was 968.7 g. The yield of the copolymer was greater than 100 % because it still contained solvent residues. The solvent dimethyl sulfoxide still contained in the copolymer could not be removed, so that the melting point of the copolymer could not be determined either.

The microanalysis of the polymer C ^ H ^ 5 5 ° 31 NS., Nag S. resulted in fol the following values: 15th CHN N / A 15th Calculated: 34.97 4.5 1.0 9, 6th , 6 Found: 34.5 4.7 9, 8th , 9

The copolymer obtained can be represented by the following formula:

CH,

-CH-

C = O

NHCH ₂ CHSCH,

-CH,

CH

0-CH ₂ CH ₃ CH ₂ SO ₃ Na

Others, within the scope of the method of the invention, as peptizing agents suitable copolymers consist of copolymers of maleic acid esters and / or amides. These Copolymers can be obtained by condensation of Ma ^ linic anhydride copolymers with amines and / or alcohols each containing at least one sulfide sulfur atom will. Suitable maleic anhydride copolymers dispersible in water can in addition to the maleic acid

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anhydride units, for example vinyl monomer units, for example alpha-olefin, vinyl ether, vinyl ester, and styrene monomer units contain. The copolymer containing the sulfide sulfur atom can be converted by reacting the maleic anhydride copolymer with an amine and / or alcohol with at least one divalent sulfur atom in a sulfide or produce thioether group. The reaction between the maleic anhydride group and the amine in question and / or alcohol consists in a condensation reaction, alcoholysis in the case of alcohols and alcoholysis in the case of amines an aminoysis takes place. The reaction product contains Maleic acid amide and / or ester units, the respective amine and / or alcohol condensation radical being the 2 alkyl carbon atoms having sulfide-sulfur atom connecting in an organic sulfide radical.

In the following, the preparation of the maleic acid amide and / or ester copolymers required to form such maleic acid amide copolymers will first be described Sulfur-containing amines and / or alcohols are described.

a) Production of 3-methylthiopropylamine

To a solution of 59.5 g of sodium methoxide. In 500 ml of methanol, 25 g of methanethiol and then 121 g of 3-bromopropylamine hydrobromide were added at a temperature of ^{0 ° C.} After the methanol had been distilled off, the residue was extracted with a total of 300 ml of ether, whereupon the ether was distilled off. In a fractional distillation of the ether-free residue, two main fractions were obtained. The higher-boiling fraction (boiling point 44-54 ° C. at a pressure of 1.1 to 1.7 mm Hg column) consisted of 19 g of 3-methylthiopropylamine.

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The elemental analysis of the compound CjjH ^ SN gave the following -, -; ■ Values:

Calculated: C-45.7; 'H - 10.5; N - 13.3; S - 30.5 Found: C - 45.7; H - XO.4; N - 12.7; S - 28.7

in A vapor phase chromatographic analysis indicated that the 3-methylthiopropylamine obtained has a purity of 98% owned.

b) Preparation of 3- (2-Dläthylaminoäthylthio) propanol

According to the method described under a), by reacting 85 g of diethylaminoethanthiol hydrochloride with 70 g 3-bromopropanol with 56 g of 3- (2-diethylaminoethylthio) propanol with a boiling point of 113 to 115 ° C. A chromatographic analysis in the vapor phase showed that the 3- (2-diethylaminoethylthio) propanol obtained was 92% pure owned.

c) Production of 2-methylthioethylamine

A solution of 25 g of methanethiol and 1 g of sodium methoxide in 100 ml of methanol was cooled to -5 ° C. and 25 g of ethyleneimine were added over the course of 20 minutes. The reaction temperature was then allowed to rise. The methyl mercaptan was retained in the reaction mixture with the aid of a dry ice condenser. The reaction mixture was left to stand overnight and then separated by distillation. The fraction boiling at a pressure of 15 mm Hg column at a temperature of 20 to 50 ^° C. was collected separately. A chromatographic analysis in the vapor phase showed that the product obtained was 69% pure. With renewed distillation at atmospheric pressure, 16.5 g of a liquid

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Obtained speed with a boiling point of 147 to 149 ⁰ C and a purity of 95 % .

In a similar way, other ThMLe with ethyleneimine implemented, the thioethylamines given in Table I below were obtained.

Tabel I. Amine With ethylene imine
converted thiol
component yield
in % Jf-uale Rein
is the name of the
Vapor phases
chromatography 2-ethylthio
ethylamine d) ethanethiol 50 99 2- (2-diethyl
aminoethylthio)
ethylamine e) diethylamino
ethane thiol 65 98 2- (2-carbethoxy
ethylthio) ethyl
amine f) carbethoxy
ethanthjbl 74 99 2- (2-purylme-
thylthio) ethyl
amine g) 2-furylmethane
thiol 65 94.4 2-propylthio
ethylamine h) propanethiol 57 96 2- (2-N-piperi-
dinoäthylthio) -
ethylamine i) N-2 mercapto
.ethy! piperidine 75 99 2- (2-N-morpho-
linoäthylthio) -
ethylamine j) N-2 mercapto
ethylmorpholine 42 99

By converting amines and / or alcohols containing sulfur
(a- 3) with maleic anhydride copolymers can be prepared in the manner described below which can be used in the process of the invention.

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O) Ethylene-N- (3-methylthiopropyl) maleic acid amide copolymer

10 g of an ethylene / maleic anhydride addition copolymer available from Monsanto Chemical Co. under the trade name Monsanto DX 830-11 with about 50 KoX% maleic anhydride were dissolved in 80 ml of dimethylformamide at room temperature, whereupon the resulting solution was mixed with 10 g of 3- Methylthiopropylamine was added. The resulting reaction mixture turned a deep purple color. The temperature of the reaction mixture rose rapidly to 53 ° C. After the reaction mixture was left to stand at room temperature overnight, it became almost colorless. The ethylene / N- (3-methylthiopropyl) maleic acid amide copolymer formed was precipitated in diethyl ether, filtered off and dried in vacuo. The yield was 19.2 g.

The elemental analysis resulted in the following values:

■ N S

Calculated: 6.0 l4.0 -.

Found: 7.1 13.9

In a corresponding manner, the sulfur-containing amines given in Table I can be reacted with equimolecular amounts of the same ethylene / maleic anhydride copolymer to give the corresponding maleic amide copolymers. The yield of maleic acid copolymer is between 81 % when using 2- (2-diethylaminoethylthio) ethylamine and almost 100 % when using 2-ethylthioethylamine and 2-methylthioethylamine.

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P) Addition copolymer made from a maleic anhydride copolymer and 3-methylthio-1-carbomethoxypropylamine

To a solution of 10 g of one of the General Aniline & Film Corp. Methyl vinyl ether / maleic anhydride copolymer in 80 ml of dimethylformamide sold under the trade name Gantrez 119 was 10 g of 3-methylthio-1-carbomethoxypropylamine, the preparation of which is described in the journal HeIv. Chim. Acta, Vol. 36, p. 1114 (1953) is added. The resulting solution was left to stand at room temperature for two days, after which the copolymer formed was isolated by precipitation in diethyl ether and filtering off. After drying in vacuo, the yield of maleic acid amide copolymer was almost 100 %.

20 g of 3- (2 ~ Diäthylaminoäthylthio) propanol (prepared by the under b) described procedure) and 10 of a g under the trade designation Monsanto DX83O-11 vertriebenenÄthylen / maleic anhydride copolymer were mixed together and are at a temperature of 60 ⁰ C overnight calmly. The pasty mass obtained was dissolved in water, whereupon the resulting solution was poured into ether to precipitate the ethylene / maleic acid 3- (2-diethylaminoethylthio) propyl monoester copolymer. The yield of copolymer after drying in vacuo was 17.4 g.

The elemental analysis resulted in the following values:

N S Found: 4.1 8.9

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The previously described, suitable as peptizing agents. Copolymers contain polymerized vinyl monomer units, each (per monomer unit) (at least) one two Have alky! Carbon atoms connecting sulfur atom. at a further embodiment of the method of the invention you can use peptizers, which are made from addition copolymers of ethylenically unsaturated monomers with per monomer unit have more than one sulfur bond. For example, within the scope of the method of the invention that in the United States patent application with the serial no. 701 114 Use mixed polymers as peptizers. These copolymers are made using acrylic acid esters and / or amides of the formula:

rtil ι / in λ ν τ- »

uiiÄ ^^ on ν λ η

wherein X is a -0- or -NH radical and R is a polythioalkyl radical having two sulfide sulfur atoms separated by at least one carbon atom mean manufactured.

Examples of such acrylic acid esters and / or amides are:

N- / ~ 2,2-bis (l-thiopropyl) ethyl_7acrylamide, N- (3,6-dithiohepty1) acrylamide, N- (3,6-dithiooctyl) acrylamide and bis (2-thiobutyl) methyl acrylate.

Acrylic acid esters and / or amides with a polythioalkyl radical of the type described can be combined with vinyl monomers and other Copolymerize ethylenically unsaturated monomers, where »ie useful in the context of the process of the invention Peptizers are incurred. In the above-mentioned US patent application, copolymers of the above-mentioned acrylates and

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Acrylamides with sodium 3-aeryloyloxypropane-1-sulfQnate described ben.

R) N-iSjß-dithiooctyDacrylamide / sodium-S-acryloyloxypropane-isulphonate copolymer (Molar ratio 1:15)

A solution of 21.9 g (0.1 mol) of N- (3,6-dithiooctyl) acrylamide, 324.0 κ sodium 3-acryloyloxypropane-1-sulfonate and 1.73 6 Aeobis in 1384 ml of redistilled dimethyl sulfoxide was 15 Flushed with nitrogen for minutes and then placed in a 6O ⁰ C warm bath overnight. The addition copolymer formed in this way was precipitated and washed clean with a large excess of acetone. The washed addition copolymer was finally dried in vacuo at room temperature. This gave 323.4 g of a brittle, white, solid addition copolymer in 93% yield.

The microanalysis of the copolymer ^c g8 ^H i52 ^O 76 ^N ^ 17 ^Na 15 gave the following values:

C. 3 4th H N 9 N / A ' S. , 6 Calculated: 34, 7th 4th , 4 0.4 9 , 96 15th , 7 Found: 33, , 5 - , 6 15th

When addition copolymers of the type just described, in which each sulfur-containing monomer unit has two sulfide sulfur atoms contains, are to be used as peptizers in the context of the method of the invention, so that should Molar ratio of the sulfur-containing monomer units to the other, ethylenically unsaturated comonomer units expedient et, wa.l: 1 to about 1:27 and preferably about 1:12 to about 1:18. It should be compared with those previously described Additive copolymers in which each sulfur-containing monomer contains a single sulfide-sulfur atom

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has, the molar ratio of .schulfelhaltigen monomer units to the other comonomer units expediently about 1: 1 to about 1: 13 * 5 "and preferably about 1: 3 to about 1:12, Surprisingly, it has been shown that the PoIythio units a peptization effect even at lower molar concentrations in the addition copolymers in question unfold than the monomer units containing only a single sulfide-sulfur atom.

The following examples are intended to further illustrate the process of the invention.

example 1

A neutral emulsion was prepared as follows: 20 ml of an aqueous solution with 3.82 g of silver nitrate were added within 30 minutes to 30 ml of an aqueous solution with _# 3.275 g of potassium bromide, 0.1 g of potassium iodide and 1.0 g of addition copolymer A) (as a peptizer) added. The resulting emulsion contained well-dispersed silver halide crystals 0.3 to 2.3 microns in diameter and had excellent stability against agglomeration of the silver halide crystals.

An anhydrous emulsion was prepared as follows: 20 ml of an aqueous solution with 3.82 g of silver nitrate and so much ammonium hydroxide that the first at the. Addition of AmmoniumhydroEyd precipitate formed to the silver nitrate solution just dissolves again, was under continuous Stir within 85 seconds to 30 ml of a solution 3.1 g potassium bromide, 0.1 g potassium iodide and 1.0 g addition copolymer A) (As a peptizer) added. Stirring was continued for an additional 39 minutes. The temperature the reaction mixture became while mixing

809841/1286

and kept ^{at 45 °} C. during the subsequent stirring. The resulting emulsion contained well dispersed silver halide crystals of mainly cubic shape with diameters of 0.6 to 1.6 microns. Furthermore, the emulsion obtained was excellently stable against agglomeration of the silver halide crystals.

Example 2

A neutral emulsion was prepared as described in Example 1, with the exception that it was used as a peptizing agent the addition copolymer B) was used in the reaction mixture. The emulsion obtained contained well dispersed, octahedral silver halide crystals with diameters from 0.3 to 1.8 microns. In addition, the obtained emulsion was excellent in anti-agglomeration of silver halide crystals atab11.

It was also, as described in Example 1, an ammoniacal Emulsion produced, however 'with the exception that as Peptizing agent the addition copolymer B) was used. The resulting emulsion contained well dispersed cubic ones Silver halide crystals with diameters from 0.7 to 1.2 Micron. The resulting emulsion was also excellently stable against agglomeration of silver halide crystals.

Example 3

As described in Example 1, a neutral and made an ammonia pool emulsion, but as Peptizing agent the addition copolymer C) was used in each case.

The neutral emulsion obtained contained well-dispersed silver halide crystals with diameters of 0.5 to 2.9 Microns and was against agglomeration of the silver halide crystals excellent stability.

809841/1286

The ammoniacal emulsion obtained contained well dispersed ones Silver halide crystals in the form of rounded cubes with diameters from 0.7 to 1.2 microns. The ammoniacal emulsion obtained was also against agglomeration Berhalide crystals extremely stable.

Example * t

As described in Example 1, a neutral emulsion was prepared, but the addition copolymer was used as the peptizing agent D) was used. The neutral emulsion obtained was against agglomeration of the silver halide crystals excellently stable and contained well dispersed silver halide crystals with diameters of 0.2 to 1.3 Micron.

Furthermore, as described in Example 1, an ammoniacal Emulsion produced, but the addition copolymer D) is also used as the peptizing agent became. The silver halide crystals in the emulsion obtained were mainly cubic and 0.25 in diameter up to 1.3 microns. The ammoniacal emulsion obtained was also against agglomeration of the silver halide crystals excellent stability.

Example 5

As described in Example 1, a neutral emulsion was prepared, but the addition copolymer E) was used as the peptizing agent. The silver halide crystals were well dispersed in the obtained emulsion and had a tabular octahedral shape. There were also numerous triangular crystal shapes with straight edges and sharp corners. The crystal diameter of the silver halide crystals ranged from 0.3 to 3.5 microns. The major crystal face was 1.714 y ² .

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1904U7

The width of the size distribution curve in the form of the known “Sigma function ^11” corresponded to a sigma value of 1.869 μ. The dislocation number per emulsion crystal, determined by X-ray analysis, was 16.4. These values differ from the corresponding values obtained by the same method The characteristic parameters of such an emulsion produced using gelatine as a peptizer have the following numerical values:

Main crystal face: Ο, 8θ8 μ ² ; Sigma value: '0.647 microns and

Dislocations per emulsion crystal: 8.5.

Example 6

As described in Example 1, an ammoniacal emulsion was prepared, but the addition copolymer F) was used as the peptizing agent. The resulting emulsion was excellent in stability as a photographic emulsion and contained well-dispersed silver halide crystals in the form of rounded cubes 0.3 to 1.2 microns in diameter. The main crystal face was 1.355 μ ² · The width of the size distribution curve corresponded to a sigma value of 0.502 μ, while the dislocation number per emulsion crystal had a value of 13.8. In the case of a comparative emulsion, which was prepared using gelatin as a peptizer, a principal crystal face of 1.048 μ ² , a sigma value of 0.464 μ ² and a dislocation number per emulsion crystal of 6.2 were found.

909841/1286

Example 7

It was "as described in Example 1, an ammoniacal Emulsion produced, however, the peptizing agent Addition copolymer Q) was used. The resulting emulsion was against agglomeration of silver halide crystals excellently stable and contained well dispersed silver halide crystals in the form of rounded cubes with diameters of 0.5 to 1.7 microns.

Example 8

As described in Example 1, an ammoniacal emulsion was prepared, but using the peptizing agent Addition copolymer H) was used. The silver halide crystals were well dispersed in the obtained emulsion the shape of rounded cubes with diameters ranging from 0.5 to 1.4 microns. Furthermore, the emulsion obtained was against The balls of silver halide crystals are extremely stable.

Example 9

It was, as described in Example 1, an ammoniacal Emulsion produced, but the addition copolymer I) was used as the peptizing agent. The received The emulsion was excellently stable against agglomeration of the silver halide crystals and contained well-dispersed octahedral ones Silver halide crystals from 0.5 to 1.7 microns in diameter.

Example 10

As described in Example 1, an ammoniacal emulsion was prepared, but using the peptizing agent Addition copolymer J) was used. The received

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The emulsion was extremely stable against agglomeration of the silver halide crystals and contained well dispersed silver halide crystals, mainly in the form of rounded cubes and almost spherical in appearance, with diameters from 0.3 to 1.2 microns.

Example 11

With photographic emulsions made using synthetic peptizers A through C, E and I and a comparative emulsion made using Gelatin was prepared as a peptizer, the relative dissolution rates of silver halide crystals in a photographic developer and the relative rates of physical development were constant Silver ion concentration maintained by a silver ion / thiosulfate complex was determined. The measurements were carried out according to the methods described by E. J. Perry in the publication "Photographic Science and Engineering", Vol. 5, page 349 (1961). Those using the Emulsions made using synthetic peptizers exhibit far greater relative dissolution rates and physical development rates than the comparative emulsion made using gelatin as the peptizer. The individual values are in the following Table compiled.

Peptizations
middle Relative solution
speed pepti-
sated AgX crystals Relative speed
physical
Development at kon
constant Ak "concentration Gelatin (ver
same as emulsion) 1.0 A. 21.4 B. 43.7 C. 108 I. 150 I. ί O 1.0 9.4 13.1 13, 9 13.9 9.4

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190AU7

Example 12

An emulsion with excellent physical characteristics Winding properties produced and examined as follows:

Under a red safety light, 20.5 ml of an aqueous solution with 2.73 ¹ g of silver nitrate and 20.5 ml of an aqueous solution with 2.30 g of potassium bromide and 0.072 g of potassium iodide were simultaneously with continuous stirring to 29.0 ml of an aqueous solution with 1.05 g of the addition copolymer K), which was kept at a temperature of 45 ^° C., was added. After the addition of the two solutions was complete, stirring was continued at the same temperature for an additional 6 minutes. The emulsion formed was then removed from the bath, which was kept at a constant temperature, and sufficient 1 η sulfuric acid was added to coagulate the silver halide crystals in the emulsion. After the shouting "dl";. <, The supernatant liquid was decanted off and the residue was washed with distilled water. The washed residue was extracted with stirring with 12.5 ml of water and enough sodium hydroxide to raise the pH to 7, whereupon half of the resulting suspension was dissolved in 20.1 ml of an 8.7% aqueous solution of de3 Addition copolymer K) was dispersed. Finally, to 9.1 g of the Emilsion I obtained were added 0.375 mg of silver protein sold under the trade name Silver Protein Mild by Mallikckrodt Chemical Works, 0.7 al of a 3.82 pounds aqueous solution of the company Ciba Co. under the trade name Araldlte RD-2 Epofiyd crosslinking agent and 0.15 ml of a 5% saponin solution. The emulsion prepared in the manner described was applied to a cellulose acetate support and dried. The thickness of the dried construction emulsion layer was about 0.008 am.

till

The photographic material thus obtained was made in a sodium thiocyanate without exposure to actinic light containing N-methyl-p-aminophenol / hydroehinone developer developed"

A comparative emulsion was produced in corresponding catfish, however, the peptizing agent K) was replaced by gelatin. The comparative emulsion obtained was in the described manner applied to a cellulose acetate support and developed.

The following table shows the err during development The results obtained can be seen, with those developing in the individual emulsion layers at different development times Silver amounts are given.

Development
time in sec Evolved silver in
mg / dm ^{2 support area} (at
Using a mix
polymer of the be
written type as
Peptizer K) ■ - " - Evolved silver
in mg / dm ² carrier area
che (when using
of gelatin as
Peptizer) VJl 1.72 - 10 5.81 - 15- 9.47 0.36 25th 16.36 0.51 45 1.02 85 2.80 125 6.46

The development of the individual drawing materials existed essentially from a physical development. The values in the table show that the physical Development of using by syntheti-3che, Copolymers containing sulfide, peptized emulsions, are essential for the production of recording materials takes place faster than the physical development of the under

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1904U7

Use of an emulsion peptized by gelatin Recording material.

The increased (physical) development rate of using certain synthetic, sulfide sulfur atoms containing copolymers produced recording materials can also be used in photographic Transfer process in which a silver halide complex is formed from a silver halide emulsion layer onto a receiving sheet with physical development nuclei contained thereon is transmitted, observe. Thus, in a diffusion transfer process, i. H. at a physical one Development method using one peptized with the above-mentioned sulfide-containing peptizing agents Emulsion solubilized larger amounts of silver halide, transferred and developed on a receiving sheet than in the case of Ver. use of an emulsion peptized by gelatin.

Example 13

Under red light, 20 ml of an aqueous solution with 2.377 g of silver nitrate and 20 ml of an aqueous solution with 1.871 g of potassium bromide and 0.067 g of potassium iodide were added simultaneously with continuous stirring to 30 ml of a 45 ° C. aqueous solution with 1.05 g of addition copolymer L) . Stirring was continued at a temperature of 45 ° C for an additional 6 minutes. The emulsion was then coagulated by adding about 25 ml of a saturated sodium sulfate solution. After quenching, the supernatant liquid was decanted from the coagulated emulsion. The latter was washed with distilled water. Water was then added until the weight of the emulsion was 15 g. ¹ Finally, the emulsion obtained was redispersed by adding it to 23.9 ml of a hot aqueous solution containing 2.65 g of addition

SQ9841 / 12

copolymer L) was stirred in. To 5.56 g of the redispersed Emulsion were 3.4 ml of water, 0.79 ml of a 3.82 # igen aqueous solution of the epoxy crosslinker sold by Ciba Co. under the trade name Araldite RD-2 and 0.15 ml of a 5 strength saponin solution were added. The resulting emulsion was finally coated on a cellulose acetate film support applied and dried. The thickness of the dry emulsion layer was about 0.008 mm.

It also became a receiver sheet for the diffusion transfer process manufactured as follows:

26.3 ml of an aqueous solution with 0.5 g of addition copolymer L), 1.25 ml of silver protein germs (Silver Protein Mild from Mallinckrodt), 0.9 ml of a 3.82 igen epoxy cross · ^ Crosslinker solution (Araldite RD-2) and 0.2 ml of a 0.5 strength saponin solution were applied to a reflection copy carrier. The dry layer thickness was about 0.001 mm.

For diffusion transfer, a developer of the following was used Composition used:

N-methyl-p-aminophen oil 6.25 g

Hydroquinone 2.5 g

Sodium sulfite 6.25 g

Sodium thiosulfate, pentanydrate 7.7 g

Potassium bromide 1.02 g

Sodium carbonate, monohydrate 25.0 g

Made up to 1 liter with water

The receiving sheet was immersed in the developer solution of the specified composition for 20 seconds and then dipped For 20 seconds against the recording material produced in the manner described with the silver halide

909841/1286

pressed emulsion layer. An X-ray spectral analysis showed that the amount of silver transferred to the receiving sheet and developed there was 0.67 mg ^{per dm 2 of support area.}

In a comparative experiment in which, under otherwise identical conditions, only part of the addition copolymer 1) Gelatin was used in each case, was the amount of silver transferred to the receiving sheet and developed there only 0.24 mg per dm of support surface.

The individual that can be used in the process of the invention Peptizers influence the respective emulsions differently to a certain extent. In this way special effects can be achieved by suitable selection of certain sulfur-containing peptizers of the type described achieve.

For example, as described, negatively sensitive silver bromoiodide emulsions were prepared and applied to layers applied, but once an addition copolymer of acrylic acid and acryloyl methionine methyl ester as a peptizing agent (Addition copolymer P) before saponification - molar ratio 3.3: 1.0) and the other time the addition copolymer E) was used. The photographic sensitivity of the acryloyl methionine methyl ester copolymer peptized emulsion was four times greater than the photographic sensitivity of that with the Acryloylme- · thionine copolymer peptized emulsion. The γ value of the emulsion peptized with the acryloyl methionine methyl ester copolymer was 1.45, while the γ value was that with the Acryloyl methionine copolymer peptized emulsion was 0.46. Both emulsions worked well, although they did considerably different in their photographic properties differentiated.

909841/1286

1904U7

This means that within the scope of the method of the invention sulfur-containing ones which can be used as peptizers Addition copolymers not only for the production of very specific emulsions, but also (in the case of silver halide precipitation and emulsification) are suitable for the production of a wide variety of emulsions. Thus, according to the method of Invention (using peptizers of the described Type) for example negative-sensitive emulsions, copy-sensitive emulsions, silver bromide, silver chloride, Silver bromoiodide or silver chlorobromoiodide emulsions, silver halide emulsions for special purposes, such as color films, direct positive films, direct copying recording materials, high resolution films, diffusion transfer films, copier papers and enlargement papers are produced.

The addition copolymers selected as peptizers for silver halide emulsions in the context of the process of the invention of the type described are (as a rule) in aqueous solutions for the precipitation of the respective emulsion Soluble in usual pH values. Most of the addition copolymers described dissolve in aqueous solutions pH values above 5. Some of the specified addition copolymers, for example those containing sodium sulfonate radicals Addition copolymers M) 1. and M) 2., dissolve at pH values above 1.5.

About the critical relationship between the organic sulfide residue and the peptization effect of such addition copolymers to show were using addition copolymers with analogous monomer units in which however, the divalent sulfide sulfur atom is replaced by another atom or another radical, different Emulsions produced. As in Example 1

809841/1 286

" ³⁶ " 1904U7

described, a silver halide emulsion prepared, but instead of the addition copolymer A) an acrylic acid / acryloyl methionine sulfoxide copolymer (Molar ratio 3 »33: 1.0) was used as the" peptizer ". The emulsion obtained was completely unstable, which indicates that the acrylic acid / acryloyl methionine sulfoxide copolymer has no useful peptization effect '. In a corresponding way, as described in the previous examples, were using appropriate addition copolymers, in which, however, the one bivalent Sulfide-sulfur atom-containing monomer units by others Monomer units, for example ethyl vinyl sulfone, ethylthioacrylate, acryloylleucine methy! Ester, methoxyethyl acrylate, Methacryloyl norleucine and methacryloyl proline units were replaced. Here it was found be that such addition copolymers without a divalent sulfide-sulfur atom containing monomer units, were not suitable as peptizers. In all cases the emulsions obtained were either completely unstable or allowed the silver halide crystals to agglomerate. This clearly shows that the one with the In particular, the addition copolymers used in the process of the invention are achievable peptization effects is due to the sulfide sulfur atom connecting two alkyl carbon atoms.

The following example illustrates a particularly preferred one Embodiment of the method of the invention in which an addition copolymer made from an acryloyl derivative with the critical sulfide bond and an acrylic monomer with a terminal sulfonic acid residue, which the solubility of the peptization device as such enlarged will.

09841/1286

" ³⁷ " 190A 147

Example l4

Three highly sensitive, negative silver bromoiodide emulsions (molar ratio bromide: iodide = 94: 6) produced, but during the silver halide precipitation for emulsion 1 gelatin, for emulsion 2 an addition copolymer of acrylic acid and acryloyl methionine methyl ester (Molar ratio 3.3: 1 »O. Addition copolymer P) before saponification) and in the case of emulsion 3, an addition copolymer from acryloyl methionine methyl ester and sodium 3-acryloyloxy-1-methylpropane-1-sulfonate (molar ratio 1: 9 addition copolymer M) 1.) was present as a peptizing agent.

After the emulsification of the silver halide crystals in the individual The soluble salts were emulsions from the precipitation medium in the usual way by coagulating and redispersing removed, whereupon the "washed" emulsions were redispersed in aqueous gelatin solution. Then the individual Emulsions digested in the usual way to increase sensitivity and after the addition of the usual auxiliaries and of spectral sensitizing dyes applied to photographic supports. The on the individual layers applied amounts of silver and gelatin are in the given in Table II below.

The photographic recording materials produced in the manner described were sensitometrically tested for their OD _R values (granularity at 0.80 above base and fog, measured according to the method described by Higgins and Stultz in the journal J. Opt. Soc. Am., Vol. 49 , Page 925 - September 1959 -), examined for their photographic sensitivity and their concealment.

»098A1 / 1286

For this purpose, the individual photographic recording materials

1) in a developer I of the composition:

Water (50 ° 0) 750 cm ³

ρ-methylaminophenol sulfate. 2 g

Sodium sulfite, dried 100 g

Hydroquinone 5 g

Borax 2 g

Made up to 1 liter with water

up to a γ value of 0.75

2) 5 minutes in a developer II of the composition:

Water (50 ⁰ C) 500 cm ³

p-methylaminophenol sulfate 2.5 g

Sodium sulfite, dried 30 g

Hydroquinone 2.5 g

Alkali 10 g

Potassium bromide 0.5 g

Made up to 1 liter with water

3) 12 minutes in Developer II and

4) 6 minutes in a developer III of the composition:

Water (about 50 ^° C.) 500 cm ⁵

p-methylaminophenol sulfate 2.0 g

Sodium sulfite, dried 90 g

Hydroquinone 8 g

Sodium carbonate, monohydrate 52.5 g

Potassium bromide 5 g

Made up to 1 liter with water

developed.

909841/1286

190AU7

The results obtained in the sensitometric investigations are given in Table II below.

9098 A1 / 1 286

SiI gelatin berry
salary

Emul- in rag / φη ² Tr äsion gerfläche

Development in developer I up to a γ value of O ₃ 7 ReI. Sensation

aD _w + lent- Schlei- ^Ά speed er

Table II

Development in
Developer II
(5 min / 12 min)

^ H

ReI.

Receive

find-

light-

speed

Development in Developer III (6 min)

Schleifer

Ίί

ReI.

Receive

flnd-

light-

speed

veil

82.53 152.79
48.42 89.74

J * 1 46.91 86.94

64.88 119.97

77.15 142.89
76.93 142.57

0.0276 380

0.0194 53

0.0344 129

0.0222 100

0.0232 339

0.0176 105

0.13 0.02

0.37 0.25

0.0240 / 69 / 1.18 / 0.01 / 0.0302 132 2.04 0.05

0.0300 129 1.82 0.10

0.0350 / 302 / 0.79 / 0.07 / 0.0430 457 0.93 0.18

0.0420 302 0.87 0.22

0.0360 / 339 / 0.92 / 0.07 / 0.0440 490 1.22 0.24

0.044O 339 1.10 0.26

0.16 0.0325 / 355 / 1.02 / 0.09 / 0.0460 525 1.45 0.28 O, O46O 398 1.40 0.30

RMS

-Graininess measurement. aD "= graininess at 0.80. above base and veil.

Measured according to that of Higgins and Stultz in the magazine. "J. Opt. Soc. Am.", 4j ?, 925 (September 1959) described method.

The results of the TabeiDe show that the with the addition copolymer of acryloyl methionine methyl ester and sodium 3-acryloyloxy-1-methylpropane-1-sulfonate (Molar ratio 1: 9 - addition copolymer M) 1.) peptislerte. Emulsion can penetrate into an area of high sensitivity and low granularity. This It becomes independent of the silver content of the emulsion layer in a development of comparative emulsions that on the one hand with gelatin and on the other hand with the addition copolymer of acryloyl methionine methyl ester and acrylic acid were peptized, not achieved. The same applies to a corresponding emulsion 4, which in a corresponding manner was prepared and investigated, in which, however, an addition copolymer of N- (3-thiapentyl) acrylamide was used as the peptizing agent and sodium 3-acryloloxypropane-1-sulfonate (Molar ratio 1: 9 - addition copolymer M) 2.) was used.

Example 15

An emulsion was prepared by adding a solution of 527 g of silver nitrate in 1190 ml of distilled water and a second solution of 366 g of potassium bromide and 18.5 g of potassium iodide in 1115 ml of distilled water simultaneously within 4 minutes to a well-stirred, 43 ° C warm solution of 124 g of addition copolymer N) in 3940 ml of distilled Water containing so much sodium hydroxide that its pH was 5> 9 was added. The received Emulsion was stirred for an additional two minutes after which it was distilled with a solution of 620 g of gelatin in 2600 ml Water was added. Stirring was continued for an additional 10 minutes at a temperature of 43 ° C. The emulsion was then allowed to settle by quenching, noodles and processed to remove soluble salts.

9098A 1/1 286

- H ₂ -

to wash. The average crystal diameter of the silver halide crystals contained in the obtained emulsion became determined by light scattering to be 62.7 millimicrons. For photomicrographic and electron micrographic examinations it was found that larger crystals or crystal clusters were not detectable in the emulsion.

The emulsion prepared in the manner described was then chemically sensitized to optimum sensitivity and after adding leveling and hardening agents in the

Way | applied to a pilm layer support that per dm of support surface about 10.8 mg of silver and about 62.9 mg of gelatin were used. A test strip of the preserved photographic Recordings were made in a seneitometer (Eastman IB) and then exposed for six minutes in a developer with the following composition:

Water (50 ⁰ C) 500 cm- ⁵

Metol (p-methylaminophenol sulfate) 2.5 g

Sodium sulfite, sicc. 30 g

Hydroquinone 2.5 g

Kodalk (alkali) 10 g

Potassium bromide 0.5 g

Made up to 1 liter with water

developed.

The emulsion produced in the manner described was extremely "fine-grained" and was suitable for the production of photographic recording materials for photomicrography, for a direct recording of electrons or for other photographic purposes that require a high resolution require.

909 8 Λ 1/1286

- Jl 3 -

19CH147

Furthermore, a comparative emulsion in the described Made in a manner that, however, used gelatin as a peptizer. Those contained in the comparison emulsion Silver halide crystals had approximately the same average crystal diameter as the silver halide crystals in the previously described emulsion. In the comparison emulsion, however, as can be seen from photomicrographic and electron micrographic examinations revealed considerable quantities of larger silver halide crystals approximately 1.5 microns in diameter. The emulsion produced using the peptizer N) was superior to the comparative emulsion made using gelatin as a peptizer in that it was contained no larger crystals or crystal clusters at all. Thus, the using is suitable Comparative emulsion produced from gelatin as a peptizing agent is not used in those areas in which "Fine grain" emulsions without larger silver halide crystals and crystal clusters are required.

Example 16

A silver halide emulsion was prepared as follows: A solution of 170 g of silver nitrate in 2070 ml of water was converted into a solution of 125 g of potassium bromide, 9.96 g of potassium iodide and 2k g of an ethylene / N-ethylthioethylraaleic acid amide Na salt within 40 minutes. Copolymer, which was prepared by a process similar to that of addition copolymer 0 using 2-ethylthioethylamine, was added in 1580 ml of water. The resulting emulsion was coagulated by adding enough sulfuric acid to lower the pH to 3.65, after which the soluble salts were removed by decantation. the

909841/1286

The coagulated emulsion was redispersed in 1500 ml of water which had been adjusted to a pH of 6.0 by adding sodium hydroxide. The redispersed emulsion was coagulated again by lowering its pH to 2.6 by adding a dilute sulfuric acid solution. After the supernatant liquid had been decanted off, the coagulate was ^{redispersed at a temperature of 1} JO ⁰ C in so much dilute sodium hydroxide solution that the total weight of the dispersion was 1200 g and the dispersion had a pH of 6.0. A solution of 200 g of gelatin in 1560 ml of water was then incorporated into the dispersion obtained. Finally, the emulsion obtained was digested and applied to a weight layer carrier in such a way that about 58.1 mg of silver and about 107.6 mg of gelatin were used ^{per dm 2 of carrier area.}

A strip of the photographic material prepared as described was measured in a sensitometer (Eastman IB) and then exposed for 5 minutes in a developer of the following composition;

Water (50 ⁰ C) 500 cm ³

Metol (p-methylaminophenol sulfate) 2.5 g

Sodium sulfite, sicc. 30 g

Hydroquinone · 2.5 g Kodalk (alkali) 10 g

Potassium bromide 0.5 g

Made up to 1 liter with water

developed.

The obtained photographic recording material represents a negative-sensitive film, which affects the most diverse photographic fields of application, for example

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" ⁴⁵ ~ · -19OA147

wise for use in a common photographic camera.

To produce corresponding silver halide emulsions, the addition copolymers O), P) and Q) were also used instead of the ethylene / N-ethylthioethyl maleic acid amide-Na salt copolymer used as a peptizer. In each case, silver halide emulsions suitable for photographic use were found obtained with well dispersed silver halide crystals.

Example 17

A highly sensitive, negative silver bromoiodide emulsion (molar ratio bromide: iodide = 9 ^: 6) of the type described by Trivelli and Smith in the journal "Phot. J.", Vol. 79, page 330, was prepared, but using the addition copolymer as the peptizing agent R) was used. The resulting emulsion was completely free of crystal agglomerations and contained octahedral silver halide crystals 0.35 to 2.0 microns in diameter. The soluble salts were removed from the emulsion by coagulation and redispersion, whereupon the redispersed emulsion was dispersed in gelatin. The emulsion obtained was digested to optimum sensitivity and, after the addition of customary auxiliaries, applied to a film support consisting of cellulose acetate in such a way that about 58.1 mg of silver and about 107.6 mg of gelatin were used ^{per dm 2 of support surface.}

A sample strip of the photographic material prepared in the manner described was in a Sensitometer (Eastman IB) exposed for 5 minutes in a developer of the following composition:

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190AU7 Water (50 ° C) 500 cffl ^ Metol (p-methylaminophenol sulfate) 2.5 g Sodium sulfite, sicc. 30 g Hydroquinone 2.5 g Kodalk (alkali) 10 g Potassium bromide • 0.5 g Topped up with water 1 liter

developed, then fixed, washed and dried. The photographic material developed in the manner described Material performed sensitometric investigations resulted in the following values:

relative sensitivity: 98 (The relative sensitivity of a similarly prepared gelatin
peptized emulsion was 100);

γ value: 0.72; Veil: 0.12.

809841/1286

Claims (1)

PATENT CLAIMS 1. Process for the preparation of photographic silver halide emulsions, in which one in aqueous solution in the presence of a peptizing agent by .Implementation of a soluble Silver salt with a soluble halide silver halide crystals precipitates, characterized in that the precipitation is carried out in the presence of a peptizing agent, that consists of a water-soluble, linear addition copolymer with or of esters and / or amides of Maleic acid, acrylic acid and / or methacrylic acid, the amine and alcohol radicals thereof an organic radical with at least one sulfide sulfur atom connecting two alkyl carbon atoms contain. 2. The method according to claim 1, characterized in that the precipitation in the presence of a maleic acid monoamide monomer unit addition copolymer containing or containing maleic acid monoester monomer units, their Amitl · or alcohol radicals an organic radical with at least a sulfide sulfur atom connecting two alkyl carbon atoms included, performs. 3. Process according to Claims 1 and 2, characterized in that the precipitation is carried out in the presence of an addition copolymer carries out, which in addition to the ester and / or amide units, monomer units from α, β-unsaturated hydrocarbons, Vinyl esters, vinyl ethers, acrylic acid, methacrylic acid, acrylic and / or methacrylic acid esters, Acrylic and / or methacrylic acid amides, each without a sulfide sulfur atom, and o, 3-ethylenically unsaturated sulfates or sulfonates. 90984 1/1286 k. Process according to Claims 1 and 3, characterized in that the precipitation is carried out in the presence of an addition copolymer which is built up from acrylic acid amide monomer units containing at least one sulfide-sulfur atom and acrylic acid monomer units and optionally also ethyl acrylate monomer units. 5. Process according to Claims 1 and 3 »characterized in that the precipitation is carried out in the presence of an addition copolymer which is composed of at least one sulfide-sulfur atom-containing acrylic acid amide monomer units and sodium 3-acryloyloxypropane-1-sulfonate monomer units. 6. Process according to Claims 1 and 3 »characterized in that the precipitation is carried out in the presence of an addition copolymer containing at least one sulfide-sulfur atom containing acrylic acid amide monomer units, acryloylmethionine methyl ester, acryloyl methionine, acryloylsiethionine amide-j N- (3-thamidiapentyl) acryl -, N- / ~ 2,2-bis- 11-thiapropy1) äthyl_7acrylamid- ₃ N- (3 »6-dithiaheptyl) acrylamide and / or N- (3,6-dithiaoctyl) aörylamidonomereeinheit contains. 7. The method according to claims 1 and 3, characterized. that the precipitation is carried out in the presence of an addition copolymer whose containing a sulfide-sulfur atom Acrylic ester monomer units from methylthioethyl acrylate monomer units exist. 8. The method according to claim 7, characterized in that one aie precipitation in the presence of an addition copolymer djorch leads, which from Methylthioäthylacrylatmonomereeinfceiten and acrylic acid monomer units. 90984 1/1286 9. The method according to claims 1 and 3 »characterized in that that the precipitation is carried out in the presence of an addition copolymer which is used as at least one sulfide-sulfur atom containing acrylic acid ester monomer units contains bis (2-thiabutyl) methyl acrylate monomer units. 10. The method according to claim 9> characterized in that one the precipitation is carried out in the presence of an addition copolymer composed of BlsC3-thiabutyl) methyl acrylate monomer units and sodium 3-acryloyloxypropane-1-sulfonate monomer units is constructed. 11. The method according to claims 1 and '3> characterized in that the precipitation is carried out in the presence of an addition copolymer performs which as at least one sulfide-sulfur atom containing methaeryl acid amide monomer units Contains methacryloyl methione monomer units. 12. The method according to claim 11, characterized in that the precipitation in the presence of an addition copolymer performs, which is built up from methacryloylmethionine monomer units and acrylic acid monomer units. 13 · Process according to claims 1 and 3 »characterized in that that the precipitation is carried out in the presence of an addition copolymer which is used as at least one sulfide-sulfur atom containing methacrylic acid amide monomer units contains methacryloylprolyl methionine monomer units. 14. The method according to claim Ί3, characterized in that one the precipitation is carried out in the presence of an addition copolymer composed of methacryloylprolylmethionine monomer units and acrylic acid monomer units is built up, 909841/1286 15 · Process according to claims 1 and 3 »characterized in that that the precipitation is carried out in the presence of an addition copolymer composed of maleic acid monoamide monomer units and ethylene or methyl vinyl ether monomer units is constructed. 16. Process according to Claims 1 and 3, characterized in that the precipitation is carried out in the presence of an addition copolymer carries out which as at least one sulfide-sulfur atom containing maleic acid monoamide monomer units N- (3-methylthiopropyl) maleic acid monoamide-; N- (2-EthylthioäthyDmaleinsäuremonoamid-; N- (2-methylthioethyl) maleic acid monoamide; N- / ~ 2- (2-carbethoxyethylthio) ethyl_7-maleic acid monoamide; N- / ~ 2- (2-diethylaminoethylthio) ethyl 7 · maleic acid monoamide-; N- (2-propylthioethyl) maleic acid monoamide-; N- / ~ 2- (2-N-piperidinoethylthio) ethyl / maleic acid monoamide; N- / ~ 2- (2-N-Morpholinoäthylthio) äthyl_7maleinsäuremonoamid- and / or N- (3-MethyIthio-1-carboxymethy1-propyl) maleic acid monoamide monombrene units contains. 17. The method according to claims 1 and 3 »characterized in that that the precipitation is carried out in the presence of an addition copolymer which is used as at least one sulfide-sulfur atom maleic acid monoester monomer units containing 3- (2-diethylaminoethylthio) propyl monoester monomer units contains. 18. The method according to claim 17, characterized in that the precipitation is carried out in the presence of an addition copolymer composed of 3- (2-diethylaminoethylthio) propyl monoester monomer units and ethylene monomer units
is constructed. ^809841/1 286