US3827890A - Process for the preparation of photographic silver salt emulsions - Google Patents

Process for the preparation of photographic silver salt emulsions Download PDF

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Publication number
US3827890A
US3827890A US00308565A US30856572A US3827890A US 3827890 A US3827890 A US 3827890A US 00308565 A US00308565 A US 00308565A US 30856572 A US30856572 A US 30856572A US 3827890 A US3827890 A US 3827890A
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United States
Prior art keywords
gelatin
emulsions
polymer
water
silver salt
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Expired - Lifetime
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US00308565A
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English (en)
Inventor
W Saleck
G Balle
W Himmelmann
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Agfa Gevaert AG
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Agfa Gevaert AG
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Priority to US451543A priority Critical patent/US3877944A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F28/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur

Definitions

  • Photographic silver salt gelatin emulsions are made by precipitating the silver salt in the presence of gelatin, flocculation and washing the flocculate, with an aqueous solution of a polymer containing disulfonimide groups.
  • This invention relates to a process for the preparation of photographic silver salt emulsions.
  • Photographic silver salt emulsions which contain gelatin and, in particular, silver halide emulsions, are generally prepared as follows:
  • the emulsion After precipitation of the silver halide in a gelatin solution the emulsion is solidified by cooling and the gel is shredded and freed from soluble salts by washing with cold water.
  • This washing process requires a certain amount of time owing to the finite rate of diffusion of the salts.
  • the gel increases in volume to a greater or lesser extent, depending on the type of gelatin used and this increase in volume is frequently accompanied by an undesirable decrease in viscosity. This decrease in viscosity must often be compensated for by the addition of gelatin during a subsequent melting stage (ripening or casting). In this process, it is difficult to vary the ratio of silver halide to gelatin as desired.
  • the emulsions can be coagulated after precipitation by the addition of a precipitating agent and then separated from the supernatant aqueous solution which contains the dissolved salts.
  • the coagulate is then washed with water and redispersed after the addition of afurther quantity of gelatin solution; often the pH is adjusted to assist the redispersing.
  • afurther quantity of gelatin solution often the pH is adjusted to assist the redispersing.
  • this method it is possible with this method to vary the character of the emulsions and to achieve improvements in their photographic properties.
  • the oldest method of flocculating silver halide gelatin emulsions is that of salt flocculation.
  • An excess of a salt such as sodium sulfate, is added to the emulsions so that the gelatin separates by flocculation together with the silver halide.
  • the disadvantage of this method lies in the large excess of salt required to achieve complete flocculation.
  • the precipitates obtained cannot be washed with water because they readily redissolve.
  • the emulsions have a certain conductivity which is caused by a high residual salt content.
  • the emulsions may also be flocculated by adding organic liquids which are miscible with water and in which gelatin is insoluble.
  • the disadvantage of this method lies in the large amount of organic solvents used and in the fact that various salts which are insoluble in the solvent mixture are precipitated at the same time.
  • the coagulates obtained cannot be washed with water and it therefore becomes necessary to use a solvent mixture.
  • the fire risk and the high solvent costs are quite out of proportion to the technical advantage obtained.
  • gelatin may be reacted with phthalic anhydride and the reaction product added to the gelatin used as protective colloid during precipitation.
  • the gelatin derivatives can be precipitated from aqueous solution at pH 3 but the preparation of gelatin derivatives often leads to difliculties. It is necessary to maintain high pH values (above 10) during the reaction, which causes partial decomposition of the gelatin. Moreover, derivatives of this kind make it impossible to obtain very sensitive emulsions.
  • flocculating agents may be e.g. polymeric compounds which contain carboxyl or sulfonic acid groups, such as polysytrene sulfonic acid and its derivatives. It is particularly with the last mentioned class of flocculating agents that acceptable flocculation of the silver halide emulsion can be achieved, but even this method has various disadvantages. Often, for example, the casting properties of the silver halide emulsion are deleteriously affected by the polymeric flocculating agent.
  • R is a divalent organic bridge member containing 2-l8 carbon atoms, e.g. (1) a divalent aliphatic chain, preferably an alkylene chain, having preferably up to 5 carbon atoms, which chain may be interrupted by heteroatoms such as oxygen or nitrogen or by phenylene groups, (2) cycloalkylene such as cyclopentylene or cyclohexylene or (3) arylene bridges, preferably phenylene or naphthylene; the organic bridge member may contain further substituents such as alkyl, alkoxy, halogen such as chlorine or bromine, carboxyl, esterified carboxyl or nitrile;
  • R is (l) a saturated or unsaturated aliphatic group with up to 18 carbon atoms, preferably an alkyl group with up to 5 carbon atoms, (2) cycloalkyl such as cyclopentyl or cyclohexyl, (3) aryl, in particular a phenyl group or (4) the group R also may contain further substituents of the kind indicated for R Y is -OCO or -CO- in which the carbonyl group is in all cases attached to the double bond;
  • Z is a hydrogen atom, an alkyl group with up to 4 carbon atoms or a carboxyl group
  • Z Z Z are hydrogen atoms or alkyl groups with up to 4 carbon atoms, Z being a carboxyl group when Z is an alkyl radical.
  • cap-unsaturated carboxylic acids and dicarboxylic acids containing 3-5 carbon atoms e.g. acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid as well as half esters and half amides of maleic, fumaric or itaconic acid;
  • vinylethyl ether such as vinylethyl ether, vinyl esters such as vinyl acetate or vinyl chloroacetate or vinyl ketones such as vinyl ethyl ketone;
  • esters of a,f3-unsaturated carboxylic acids with 3-5 carbon atoms and alcohols with 1-4 carbon atoms e.g. methyl acrylate, ethyl acrylate, butyl acrylate or methyl methacrylate;
  • the solution is introduced into a suitable reaction vessel equipped with an efiicient stirrer, additionfunnel, thermometer and reflux condenser, the air is displaced fromthe apparatus byinert gas such as nitrogen and polymerization is started by the addition of an initiator.
  • the polymerization initiators used may be inorganic per "-co'mpourids" s uch"as potassium or ammonium peroxidisulfa'te, hydrogen peroxide,-'percarbonates or organic peroxides such as acyl"'peroxides,"e.g. benzoyl or lauryl peroxide, alkyl peroxides, e.g. di-tert.-butyl hydroperoxide, alkyl hydroperoxides, e.g. tert.-butyl hydroperoxide, cumenc hydroperoxide, or p-menthane hydroperoxide.
  • the inorganic or organic per compounds are advantageously used in combinations.
  • Suitable reducing agents are, for example, alkali metal or ammonium bisulfites, sodium formaldehyde sulfoxylate, triet'h'anol'a'mine of eiraethyiene pentamine.
  • the catalysts are used in quantities of 0.05-l% of the monomers.
  • Thepoly'inerization temperature employed depends on the activity of the catalyst and is preferably in the region of 0-80 C.
  • the polymers have average molecular weights in the region of 5.000 to 500.000.
  • the molecular weight can be influenced by the usual molecular weight regulating agents usually applied in polymer chemistry, provided they are photographically inert.
  • Polymer 2 copolymer of 50%- methyl .acrylate and 50% compound I
  • Polymer 3 copolymer of 40% methyl acrylate and 60% compound I
  • Polymer 4 copolymer of 30% methyl a crylateand 70% 'compound I
  • Polymer 5 copolymer of 30% ethyl acrylate and Polymer .6: copolymer of acrylate .30% acrylic acid and 30% com- 70% compound I
  • 40% ethyl pound I 1 Polymer 7 scopolymer of 80%- acrylic acid amide and 20% compound I Bolymerflz copolymer of 1 I 60% acrylic acid amideand 40% compound I
  • Polymer 9' copolymer of 40% acrylic acid amide and 60% compound I
  • Polymer 11 copolymer of 60% 'acrylic'acid and 4'0% compound I
  • Polymer 12 copolymer of 40% acrylic acid and 60% compound I
  • the following polymers are prepared
  • Polymer 13 Poly-N-(B-methacrylamidoethylsulfonyl)- methane sulfonamide
  • Polymer 14 Poly-N-(fi-methacrylamidoethylsulfonyl)- benzene sulfonamide
  • Polymer 15 Poly-N-(m-methacrylamidobenzenesultonyl)-methane sulfonamide
  • Polymer 16 Poly-N-(S-acrylamidonaphthalene-1-sul fonyl)-benzene sulfonamide
  • Polymer 17 Poly-N- (m-acryloyloxybenzenesulfonyl methane sulfonamide
  • Polymer 18 PolyN-(m-methacryloyloxy-p-chlorobenzenesulfonyl -benzene sulfonamide
  • Polymer 19 Poly-N-(m-methacryloyloxy-p
  • the process according to the invention is suitable for preparing any type of silver salt gelatin emulsion and particularly for preparing silver halide gelatin emulsions.
  • the silver halides used for the emulsions may be e.g. silver chloride or silver bromide, if desired with a small silver iodide content of up to 10 mol percent.
  • the process according to the invention may be used for preparing either fine-grained or coarse-grained emulsions with either a low or a high silver content.
  • Preparation of the emulsions is carried out in known manner.
  • Flocculation may be carried out with the usual flocculating agents, preferably with polymeric fiocculating agents and especially those which contain sulfonic acid groups, e.g.
  • the concentration of polymeric disulfonimides in the first wash water may vary within wide limits. Quantities of between 0.01 and 10% by weight have been found to be sufiicient, 0.05 to 1% being preferred. Based on the quantity of gelatin, this corresponds to a concentration of 1- 10% by weight.
  • Centrifugin'g is generally not required
  • the process according to the invention is particularly advantageous for the preparation of silver halide emulsions which are precipitated in the presence of silicic acid s61.- These processes have been described in German Offenlegungsschrift No. 2, 015,404 and in US. Patent Specification No. 3,637,391.
  • the polymeric disulfonimides used according to the invention also unexpectedly have the effect of improving the photographic properties of the emulsion.
  • coarse-grained silver halide emulsions more straight characteristic curves are observed.
  • Higher sensitivities iri- G. creased by 1-1,5 DIN are generally obtained.
  • No such Sodium sulfite anhydrous 70.0 elfects are observed when using the known fiocculating Borax .70 agents such as polystyrene sulfonic acid or long chain ali- Hydroquinone a- 3.5 phatic sulfates which are also added to the wash water.
  • a neutral silver iodobromide emulsion containing 6% d up to 1 h with water of silver iodide is precipitated to produce particles with an average grain size of 1.1 m. 100 g. of gelatin are used for precipitating 1 kg. of silver halide.
  • the emulsion is cooled to 35 C. 10 ml. of a 10% polystyrene sulfonic acid oped for 7 minutes and 16 minutes at C. in a developer of the following composition: v 1
  • Example 2 pH 3.0 with sulfuric acid.
  • the fiocculate is left to settle and the supernatant solution is removed.
  • the flocculate is then washed twice with 20 litres of water in which it is agitated by stirring for 5 minutes. After the last re- Silver halide emulsions are prepared and processed as described in Example 1.
  • N o'rE.-3 1 shutter stop.
  • Both emulsions are made rady for casting in the usual 70 Z2 Z3 manner with 200 mg. 4-hydroxy-6-methyl-1,3,3a,7-tetra- I I azaindene as stabilizer, 600 mg. saponin as wetting agent [Z CHZC*(Y) R TSO' N SOl'RZ and 10 ml. of a 10% aqueous solution of formaldehyde in Which z i I as hardener and cast on a cellulose acetate support. After 5 R i a di l Organic b id member i 2 1g exposure behind a step wedge, the emulsions are develbon atoms;
  • R is 1) a saturated or unsaturated aliphatic radical with up to 18 carbon atoms, (2) cycloalkyl, (3) aryl or (4) the group Y is -OCO-- or --CO- in which the carbonyl group is attached to the olefinic double bond;
  • n is or 1;
  • Z represents hydrogen, an alkyl group with up to 4 carbon atoms or carboxyl
  • Z Z and Z stand for hydrogen or alkyl groups with up to 4 carbon atoms, Z being a carboxyl group when Z is an alkyl radical.
  • polymeric disulfonimide is a polymer of acrylic acid or methacrylic acid, the disulfonimide group being attached to the carboxyl group of acrylic acid or methacrylic acid via an amide or ester bond.
  • polymeric disulfonimide is a homopolymer or copolymer of the following monomer 5.
  • polymeric di sulfonimide is a copolymer of acrylic acid, acrylic acid esters,, acrylic acid amide or methacrylic acid.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US00308565A 1971-11-24 1972-11-21 Process for the preparation of photographic silver salt emulsions Expired - Lifetime US3827890A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US451543A US3877944A (en) 1971-11-24 1974-03-15 Photographic silver salt emulsions comprising polymers with disulfonimide groups

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2158196A DE2158196C3 (de) 1971-11-24 1971-11-24 Verfahren zur Herstellung photographischer Silberhalogenidemulsionen

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US3827890A true US3827890A (en) 1974-08-06

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US (1) US3827890A (enExample)
JP (1) JPS4860916A (enExample)
BE (1) BE791289A (enExample)
CA (1) CA1007090A (enExample)
CH (1) CH570635A5 (enExample)
DE (1) DE2158196C3 (enExample)
FR (1) FR2161081B1 (enExample)
GB (1) GB1370706A (enExample)
IT (1) IT973663B (enExample)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4352873A (en) * 1980-04-25 1982-10-05 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
US9160021B2 (en) 2008-04-24 2015-10-13 3M Innovative Properties Company Proton conducting materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2007125845A1 (ja) * 2006-04-28 2009-09-10 国立大学法人横浜国立大学 スルホンイミド型モノマー及びその重合体

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4352873A (en) * 1980-04-25 1982-10-05 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
US9160021B2 (en) 2008-04-24 2015-10-13 3M Innovative Properties Company Proton conducting materials

Also Published As

Publication number Publication date
CH570635A5 (enExample) 1975-12-15
BE791289A (nl) 1973-05-14
DE2158196A1 (de) 1973-05-30
GB1370706A (en) 1974-10-16
IT973663B (it) 1974-06-10
JPS4860916A (enExample) 1973-08-27
FR2161081B1 (enExample) 1976-04-23
DE2158196B2 (de) 1979-05-23
CA1007090A (en) 1977-03-22
DE2158196C3 (de) 1980-01-31
FR2161081A1 (enExample) 1973-07-06

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