US3791831A - Photographic materials with antistatic layers - Google Patents

Photographic materials with antistatic layers Download PDF

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Publication number
US3791831A
US3791831A US00120761A US3791831DA US3791831A US 3791831 A US3791831 A US 3791831A US 00120761 A US00120761 A US 00120761A US 3791831D A US3791831D A US 3791831DA US 3791831 A US3791831 A US 3791831A
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Prior art keywords
polymer
photographic material
parts
mixture
percent
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Expired - Lifetime
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US00120761A
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English (en)
Inventor
Bonin W Von
J Geiger
W Himmelmann
G Meinhardt
W Wagenknecht
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Agfa Gevaert AG
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Agfa Gevaert AG
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Priority claimed from DE19702011649 external-priority patent/DE2011649A1/de
Priority claimed from DE19712103197 external-priority patent/DE2103197A1/de
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Application granted granted Critical
Publication of US3791831A publication Critical patent/US3791831A/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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • G03C1/89—Macromolecular substances therefor

Definitions

  • ABSTRACT The antistatic properties of photographic materials can be improved by applying an antistatic layer containing as antistatic agents a mixture of polymers, or a graft polymer, containing sulfo as well as carboxyl groups.
  • the present invention relates to photographic elements comprising a film or paper support having at least one improved antistatic layer.
  • Electrostatic charging of the surfaces of the film can be reduced by adding matting agents to the protective layers on the film; these matting agents reduce the bond between two films placed in contact. Once a charge has been produced, it can be removed by electrically conductive additives.
  • the two charge combatting techniques may be combined.
  • a conductive or hygroscopic material is usually applied to the surface of the film in order to increase its electrical conductivity.
  • Many of the substances which are effective in this respect, however, are not photographically inert and, therefore, they deleteriously affect the photographic properties.
  • quaternary salts in most cases cannot be used in photographic materials because they cause fogging.
  • Hygroscopic substances such as glycerol, potassium acetate or LiCl cause the layers to stick and are ineffective at low atmospheric humidity.
  • Higher molecular weight carboxylic acids or sulfonic acids e.g., polystyrene sulfonic acid sodium and polyvinyl sulfonic acid sodium, have a good antistatic effect when applied directly to a hydrophobic layer support, but this effect is greatly reduced if the substances are applied in gelatine layers or emulsion layers. Chromium complexes react with gelatine and, therefore, can only be used under certain conditions.
  • a photographic material having at least one silver halide emulsion layer which has an antistatic layer containing, as an antistatic agent, the following substances in the form of a mixture or of a graft polymer:
  • the mixture of polymers containing carboxyl groups and sulfonic acid groups can be prepared quite simply by mixing the two polymers in the required proportions.
  • One advantageous method of procedure consists in producing the carboxylcontaining polymers directly in the aqueous solution of a polymer which contains sulfonic acid groups preferably by radical polymerisation.
  • the proportion by weight of polymer which contains carboxyl groups to polymer which contains sulfonic acid groups may vary within wide limits. Proportions by weight of 1:10 to 10:1 are generally sufficient. Mixtures in a proportion by weight of between 1:3 and 3:1 have been found to be especially advantageous.
  • the polymers may be used in the form of dispersions or emulsions or in the form of their solutions in suitable solvents, especially in water or methanol. They may be partly or completely neutralised. The pH should preferably be between 4 and 8.5.
  • the carboxyl-containing polymers preferably used, either directly or in the form of their salts, are watersoluble homopolymers and copolymers based on itaconic, maleic, fumaric or methacrylic acid or especially those based on acrylic acid, the homopolymers being preferred.
  • the comonomers are preferably hydrophilic monomers such as short-chain vinyl esters, e.g., vinyl acetate, or derivatives of acrylic or methacrylic acid such as amides or short-chained esters of alcohols having up to five carbon atoms particularly those having hydrophilic groups such as esters which contain hydroxyl groups, e.g., hydroxypropylme thacrylate, or allyl compounds such as trimethylolpropane monoalkyl ether.
  • Other comonomers are, of course, also suitable provided they are present in such small quantities that the copolymer remains water soluble in the form of its salt.
  • Such monomers are olefins such as ethylene or propylene, styrene, vinyl chloride, longer chained acrylic acid esters such as butyl acrylate, decylmethacrylate, acrylonitrile etc.
  • the carboxyl-containing copolymers which are preferably water-soluble, or the preferred homopolymers should have molecular weights above 10,000 preferably between 50,000 and 3,000,000 and more particular between 50,000 and 1,000,000. Copolymers of higher molecular weights may also be used but these give rise to certain technical difficulties because of the high viscosity of their solutions.
  • Suitable polymers containing sulfo groups are for example polystyrenesulfonic acid, polyvinylsulfonic acid, poly-N-acryloyl-taurin or the corresponding methacryloyl product, poly-N-acryloyldimethyltaurine or the corresponding methacryloylpolymer, sulfonated polyphenylether or sulfonated rubber.
  • copolymers which consist to an extent of 40 to 60 mols percent of units of sulfosubstituted N-phenylmaleic imides and which have a molecular weight of between 50,000 and 70,000.
  • comonomers suitable for these copolymers Polymerisable olefinically unsaturated aliphatic compounds containing up to five carbon atoms,
  • Copolymers of ethylene, isobutylene and/or styrene with sulfosubstituted N- phenylmaleic imides are especially suitable.
  • the above polymers may be obtained by various methods known per se, especially by reacting copolymers of maleic acidanhydride with suitable aromatic aminosulphonic acids or their alkali metal salts in aqueous or non-aqueous media at temperatures above C. Water is eliminated in this process and the maleic acid imide ring is formed.
  • the polymers may also be prepared by the sulphonation 'of copolymers of N- phenylmaleic imide, which itself may be obtained either by the copolymerisation of N-phenylmaleic imide or subsequent reaction of maleic anhydride copolymers with aniline in a reaction involving imidisation.
  • POLYMER I 600 parts of NaOH and 4,500 parts of the monopotassium salt of aniline-3,4-disu1phonic acid are dissolved in 17,000 parts of water.
  • 3,000 parts of a copolymer of maleic anhydride and styrene which has an approximately alternating structure and which has a viscosity ofn 0.56 determined in dimethylformamide at 25C (molecular weight approximately 100,000) are then added and the reaction mixture is heated in an autoclave at 175C for 10 hours, a clear solution of Polymer 1 being formed.
  • POLYMER ll The same method is employed as for polymer 1 but a copolymer of maleic anhydride and styrene having an approximately alternating structure and a viscosity of 1 1.5 (molecular weight approximately 2,500,000) is used.
  • POLYMER I11 300 parts of the monopotassium salt of aniline-3,5- disulphonic acid and 40 parts of NaOH are dissolved in 900 parts of water, and parts of a copolymer of ethylene and maleic anhydride which has an alternating structure and an 1; value of 0.91 (molecular weight approximately 50,000) are added. The reaction mixture is then heated to C for 10 hours and a clear solution of Polymer 111 is obtained.
  • POLYMER IV 300 parts of the monopotassium salt of aniline-3,5- disulphonic acid and 40 parts of NaOH are dissolved in 1,500 parts of water. 152 parts of a copolymer of isobutylene and maleic anhydride which is approximately alternating in structure and has an 1; value of 0.7 (molecular weight approximately 65,000) are then added and the reaction mixture is heated to C for 10 hours, a clear solution of Polymer IV being obtained.
  • POLYMER V 10 parts of anhydrous liquid 80; aredissolved in 300 parts by volume of anhydrous S0 at 60C. 20.2 parts of alternating styrene/maleic anhydride copolymer are then introduced with stirring. Stirring is continued for 8 hours at approximately 50C and the reaction mixture is then left to evaporate. The resulting polymer, which is sulphonated in the aromatic nucleus, is then dissolved in 140 parts of water with 8 parts of NaOl-l and 17.4 parts of sulphanilic acid and heated to 175C for 10 hours, during which time imidisation is completed. A clear solution of polymer V is obtained.
  • POLYMER VI 80 parts of NaOH and 346 parts of sulphanilic acid are dissolved in 3,300 parts of water. 400 parts of an equimolar copolymer of styrene and maleic anhydride, 1 value 0.62, are stirred into this solution and the reaction mixture is heated in an autoclave at 170C for 10 hours. A clear, approximately 20 percent solution of the polymeric imide is obtained.
  • the polymers are preferably completely imidised. In principle, however, the corresponding polymers containing only a slight amount of maleic acid or maleic anhydride units or the half amide are also suitable.
  • POLYMER vm A mixture of 100 parts of a 10 percent aqueous solution of the sodium salt of polystyrene sulfonic acid, 10 parts of acrylic or methacrylic acid, 0.1 parts of potassium persulfate and 0.05 parts of sodiumpyrosulfite are stirred in a nitrogen atmosphere for 10 hours at 30C and for 1 hour at 50C. A clear aqueous polymer solution witha solid 'content of about 16.5 perc'entgbyweight is obtained which, as desired, can be neutralized by addition of aqueous sodium hydroxide. The above solution can be added directly to the casting solution for the antistatic layer.
  • sulfonated polymers can be used for producing graft polymers with acrylic or methacrylic acid.
  • Mixture 1 polyacrylic acid (molecular weight approximately'90,000) is dissolved in a percent aqueous solution of polymer 1 at 65C in such an amount that the resulting mixture has a solids content of 30 percent after neutralisation with NaOH to pH 6.5
  • Mixture 2 The same as mixture 1 but instead of polymer l, polymer V1 (molecular weight 150,000) is used.
  • Mixture 3 The sameas mixture 1 except that instead of polyacrylic acid, a copolymer of 90 parts of methacrylic acid and 10 parts of oxypropyl methacrylate (molecular weight approximately 100,000) is used.
  • Mixture 4 7,500 parts of a 15 percent aqueous solution .of polymer VI (molecular weight approximately 80,000) are stirred up with 1,275 parts of acrylic acid at 40C. 6 parts of potassium persulphate and 3 parts of sodium pyrosulphite are then added. The polymerisation temperature is maintained at a maximum of 50C. After about 15 hours, polymerisation is completed and the material is ready for use after it has been neutralised to a pH of 6.5 with 30 percent NaOH. The solids content is 30 percent.
  • Mixture 5 The same as mixture 4 except that a polymer Vl having a molecular weight of about 160,000 is used in this case.
  • Mixture 6 The same as mixture 4 except that 640 parts of acrylic acid are used. The solids content after adjustment to pH 6.5 is about 22 percent.
  • the polymers or polymer mixtures used as antistatic agents according to the invention may be clear or cloudy solutions or dispersions. They are photographically inert so that the light sensitive layers are in no way adversely affected.
  • the polymers are worked up in the form of aqueous solutions having a solids content of up to about 15 percent by weight and preferably 2 to 4 percent so that layers having a thickness of 1.5 to 2 p. when dry are obtained.
  • the conductivity depends on the thickness of the layer. With the thickness indicated, sufficient conductivity is ensured.
  • the compounds mentioned above have layer forming properties. They may be used alone or with the addition of water permeable protective colloids such as gelatine.
  • the amount of layer colloids present may be up to 10 times the quantity of antistatic agent but is preferably not more than 20 percent (based on the dry weights).
  • Surface active substances such as anionic or nonionic wetting agents or anti-Newton matting additives may be added as auxiliary agents to the layers according to the invention, e.g., particles measuring 1 to 5 u .of polystyrene, polymethacrylic acid esters or urea formaldehyde condensates or SiO Smooth layers which have an excellent antistatic action are obtained in this way.
  • the layers according to the invention are applied in the usual manner as uppermost protective layers to the set of layers and may be used for black and white as well as for colour photographic materials. In principle, however, these antistatic layers could be arranged anywhere, both on the emulsion side and on the rear surface or they may be applied directly to the support or in the emulsion itself.
  • the antistatic action is tested after 2 days air conditioning of sample strips, using rotating electrostatic field strength measuring instruments of the type FM 300 NR I of Prof. Dr. Ing. F. Schwenckhagen (Manufacturers: Bergischer Feingeratebau, Wuppertal). The extent of charging at 60 percent relative humidity is measured.
  • the surface resistance is determined with a measuring instrument of Lindenblatt, Elektrotechnik und Elektronik Berlin-Halensee. The instrument has two comb electrodes 10 cm in length which are parallel to each other 2 cm apart, and the samples, which have been sufficiently air conditioned, are pressed against these electrodes at a constant pressure. The resistances are read off a Tera-Ohmmeter connected to the instrument.
  • EXAMPLE 1 Onto a photographic silver halide gelatine emulsion layer on a baryta coated paper support were applied the following antistatic layers from a 2 percent aqueous In a protective layer for photographic materials con- SOlUtlOll Of the antistatic agent.
  • the dried layers had a taining 20 g of gelatine per litre of water, half the gelathlCkneSS f mlCrOnS! tine was replaced successively by antistatic agents 1 to 85 percent b weight of a polymerization product 6.
  • a photographic material including a support, at least one silver halide emulsion layer on the support and an antistatic layer, the improvement according to which the antistatic layer contains a mixture or a graft polymer of a polymer having a molecular weight of at least 10,000 of olefinically unsaturated monomers having sulfo substitution, with a water-soluble polymer having a molecular weight of at least 10,000 of monomers at least 50 mol percent of which are substituted by carboxyl groups that are free or neutralized, the proportion by weight of the two polymers being from 1:10 to 10:1.
  • the photographic material of claim l,-wherein the polymer containing sulfo groups is a polystyrene sulfonic acid containing between 15 and percent by weight sulfo groups.
  • polymer containing sulfo groups is a copolymer containing at least 40 percent by weight of units of sulfosubstituted N-phenylmaleicimides.
  • polymer containing sulfo groups is a copolymer selected from the group consisting of ethylene and isobutylene and sulfosubstituted N-phenylmaleicimide units.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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US00120761A 1970-03-12 1971-03-03 Photographic materials with antistatic layers Expired - Lifetime US3791831A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19702011649 DE2011649A1 (en) 1970-03-12 1970-03-12 Antistatic photographic material
DE19712103197 DE2103197A1 (en) 1971-01-23 1971-01-23 Antistatic photographic material

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BE (1) BE764085A (enExample)
CA (1) CA923359A (enExample)
CH (1) CH553427A (enExample)
FR (1) FR2084593A5 (enExample)
GB (1) GB1339960A (enExample)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3938999A (en) * 1974-03-30 1976-02-17 Fuji Photo Film Co., Ltd. Antistatic photographic sensitive materials
US4008087A (en) * 1974-08-05 1977-02-15 Fuji Photo Film Co., Ltd. Photographic light-sensitive material
US4147550A (en) * 1977-07-15 1979-04-03 Eastman Kodak Company Photographic silver halide element with a layer of sulfonated polymer
US4225665A (en) * 1978-12-20 1980-09-30 E. I. Du Pont De Nemours And Company Photographic element in which the antistatic layer is interlinked in the base
US4268623A (en) * 1979-01-11 1981-05-19 Fuji Photo Film Co., Ltd. Photographic light-sensitive material having a carboxylic acid polymer antistatic layer
US4388402A (en) * 1980-08-15 1983-06-14 Fuji Photo Film Co., Ltd. Photographic light-sensitive material
US4424273A (en) 1981-05-26 1984-01-03 Minnesota Mining And Manufacturing Company Subbing polyester support bases and photographic film comprising said improved support bases
US4895791A (en) * 1986-08-21 1990-01-23 Fuji Photo Film Co., Ltd. Silver halide photographic element containing a polymer latex
EP0391402A1 (en) * 1989-04-07 1990-10-10 Konica Corporation Plastic film with antistatic layer and silver halide photographic light-sensitive material using the same
US5045441A (en) * 1989-02-23 1991-09-03 Konica Corporation Silver halide photographic light-sensitive material inhibited in producing pin-holes
US5104779A (en) * 1987-01-06 1992-04-14 Felix Schoeller Jr Gmbh & Co. Kg Multifunctional layer for a photographic element and a coating
US5302501A (en) * 1991-10-25 1994-04-12 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5589324A (en) * 1993-07-13 1996-12-31 International Paper Company Antistatic layer for photographic elements comprising polymerized polyfunctional aziridine monomers
US6444416B1 (en) * 2000-12-19 2002-09-03 Eastman Kodak Company Color photographic element with improved developability
US20040097657A1 (en) * 2000-12-01 2004-05-20 Roman Morschhaeuser Acryoyldimethyltaurine acid-based grafted copolymers
US20040166416A1 (en) * 2001-06-08 2004-08-26 Randell E Christopher F Separator for electrochemical cells
US20050123833A1 (en) * 2003-12-08 2005-06-09 Schubert Mark A. Separator for electrochemical cells

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3525621A (en) * 1968-02-12 1970-08-25 Eastman Kodak Co Antistatic photographic elements
US3573093A (en) * 1967-03-15 1971-03-30 Konishiroku Photo Ind Method for the antistatic treatment of plastic films
US3615531A (en) * 1968-12-20 1971-10-26 Agfa Gevaert Ag Antistatic layers containing polymers of sulfo-substituted n-phenyl maleic imides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3573093A (en) * 1967-03-15 1971-03-30 Konishiroku Photo Ind Method for the antistatic treatment of plastic films
US3525621A (en) * 1968-02-12 1970-08-25 Eastman Kodak Co Antistatic photographic elements
US3615531A (en) * 1968-12-20 1971-10-26 Agfa Gevaert Ag Antistatic layers containing polymers of sulfo-substituted n-phenyl maleic imides

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3938999A (en) * 1974-03-30 1976-02-17 Fuji Photo Film Co., Ltd. Antistatic photographic sensitive materials
US4008087A (en) * 1974-08-05 1977-02-15 Fuji Photo Film Co., Ltd. Photographic light-sensitive material
US4147550A (en) * 1977-07-15 1979-04-03 Eastman Kodak Company Photographic silver halide element with a layer of sulfonated polymer
US4225665A (en) * 1978-12-20 1980-09-30 E. I. Du Pont De Nemours And Company Photographic element in which the antistatic layer is interlinked in the base
US4268623A (en) * 1979-01-11 1981-05-19 Fuji Photo Film Co., Ltd. Photographic light-sensitive material having a carboxylic acid polymer antistatic layer
US4388402A (en) * 1980-08-15 1983-06-14 Fuji Photo Film Co., Ltd. Photographic light-sensitive material
US4424273A (en) 1981-05-26 1984-01-03 Minnesota Mining And Manufacturing Company Subbing polyester support bases and photographic film comprising said improved support bases
US4895791A (en) * 1986-08-21 1990-01-23 Fuji Photo Film Co., Ltd. Silver halide photographic element containing a polymer latex
US5104779A (en) * 1987-01-06 1992-04-14 Felix Schoeller Jr Gmbh & Co. Kg Multifunctional layer for a photographic element and a coating
US5045441A (en) * 1989-02-23 1991-09-03 Konica Corporation Silver halide photographic light-sensitive material inhibited in producing pin-holes
EP0391402A1 (en) * 1989-04-07 1990-10-10 Konica Corporation Plastic film with antistatic layer and silver halide photographic light-sensitive material using the same
US5302501A (en) * 1991-10-25 1994-04-12 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5589324A (en) * 1993-07-13 1996-12-31 International Paper Company Antistatic layer for photographic elements comprising polymerized polyfunctional aziridine monomers
US20040097657A1 (en) * 2000-12-01 2004-05-20 Roman Morschhaeuser Acryoyldimethyltaurine acid-based grafted copolymers
US7151137B2 (en) * 2000-12-01 2006-12-19 Clariant Gmbh Acryloyldimethyltaurine acid-based grafted copolymers
US6444416B1 (en) * 2000-12-19 2002-09-03 Eastman Kodak Company Color photographic element with improved developability
US20040166416A1 (en) * 2001-06-08 2004-08-26 Randell E Christopher F Separator for electrochemical cells
US20050123833A1 (en) * 2003-12-08 2005-06-09 Schubert Mark A. Separator for electrochemical cells

Also Published As

Publication number Publication date
CH553427A (de) 1974-08-30
CA923359A (en) 1973-03-27
GB1339960A (en) 1973-12-05
FR2084593A5 (enExample) 1971-12-17
BE764085A (nl) 1971-09-13

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