US3615531A - Antistatic layers containing polymers of sulfo-substituted n-phenyl maleic imides - Google Patents

Antistatic layers containing polymers of sulfo-substituted n-phenyl maleic imides Download PDF

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Publication number
US3615531A
US3615531A US881599A US3615531DA US3615531A US 3615531 A US3615531 A US 3615531A US 881599 A US881599 A US 881599A US 3615531D A US3615531D A US 3615531DA US 3615531 A US3615531 A US 3615531A
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United States
Prior art keywords
polymer
sulfo
antistatic
substituted
parts
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US881599A
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English (en)
Inventor
Karl-Otto Meyer
Wulf Von Bonin
Wolfgang Himmelmann
Julius Geiger
Werner Wagenknecht
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/48—Isomerisation; Cyclisation

Definitions

  • the present invention relates to photographic materials which have improved antistatic protective layers.
  • the electrostatic charge on the surfaces of films can be reduced by adding matting agents to the protective layers so as to reduce the adhesion between two films when they are in contact. Once a charge has accumulated, it can be removed by means of electrically conductive additives which are applied to the surface of the film so as to increase the electrical conductivity of the film. Many substances which are effective for this purpose, however, are not photographically inert with the result that the photographic properties of the film are impaired.
  • quaternary salts usually cannot be used in photographic materials because they cause fogging.
  • Hygroscopic substances such as glycerol, potassium acetate or LiCl cause sticking of the layers and are ineffective when the humidity is low.
  • carboxylic or sulfonic acids such as the sodium salt of polystyrene sulfonic acid and the sodium salt of polyvinyl sulfonic acid are applied directly to a hydrophobic layer support, they show a good antistatic effect but this effect is greatly reduced when the compounds are used in gelatine and are, therefore, only of limited utility.
  • antistatic agents which are photographically inert and which can be used either alone or in admixture with gelatine.
  • photographic material having at least one silver halide emulsion layer and a topmost antistatic layer which contains as an antistatic agent, a polymer of olefinically unsaturated monomers having a molecular weight of at least 15,000, the polymer containing at least 40 mol. percent of sulfo-substituted Nphenyl maleic imides in polymerized form.
  • Copolymers which consist of between 40 to 60 mole percent of units of sulfo-substituted N-phenyl maleic imides are preferred.
  • Polymers which have a molecular weight of between 50,000 and 500,000 are particularly useful.
  • polymerizable olefinically unsaturated aliphatic compounds which have up to 5 carbon atoms, e.g., ethylene, propylene, butylene or isoprene
  • vinyl alcohol vinyl esters with aliphatic carboxylic acids which have up to 5 carbon atoms, e.g., vinyl acetate, vinyl propionate or vinyl butyrate, and vinyl ethers in which the ether component is aliphatic and contains up to 5 carbon atoms, e.g., vinyl isobutyl ether
  • styrene or substituted styrenes e.g., styrenes which contain sulfo groups.
  • Copolymers of ethylene, isobutylene andlor styrene with sulfo-substituted N-phenyl maleic imides are particularly advantageous
  • the sulfo groups are generally present in neutralized form as alkali metal salts in particular as sodium or potassium salts.
  • the excellent properties of the antistatic layers according to the invention are due to the sulfo substituted N-phenyl maleic imide units.
  • the aromatic character of the imide group is particularly important for this purpose.
  • Copolymers which contain an aliphatic group instead of the phenyl ring in a corresponding position are much inferior to N-phenyl maleic imide copolymers in their antistatic effect in their suitability for photographic layers.
  • the polymers to be used according to the invention also have an excellent ability to form films. They are eminently compatible with other binders and are photographically unreactive so that the light-sensitive layers are in no way adversely affected.
  • the compounds to be used according to the invention are obtainable by employing various methods of the prior art, particularly by reaction maleic acid anhydride copolymers with suitable aromatic amino sulfonic acids or their alkali metal salts in aqueous or nonaqueous media at temperatures above 120 C., the maleic acid imide ring being formed with elimination of water.
  • the polymers can also be obtained by sulfonating copolymers of N-phenyl maleic imide which can be obtained either by the copolymerization of N-phenyl maleic imide or subsequent to the reaction of maleic anhydride copolymers with aniline in a reaction involving imidation.
  • Polymer I 600 parts of NaOH and 4,500 parts of the monopotassium salt of aniline-3,5-disulfonic acid are dissolved in 17,000 parts H O.
  • 3,000 parts of a maleic anhydride styrene copolymer which has an approximately alternating structure and which has an n value of 0.56 (molecular weight approximately l00,000) determined in dimethyl formamide at 25 C. are then added and the reaction mixture is heated in an autoclave at 175 C. for 10 hours, a clear solution of polymer 1 being ob tained.
  • Polymer 11 The procedure is the same as for polymer 1 but a maleic anhydride styrene copolymer which has an n value of 1.5 (molecular weight approximately 2,500,000) and which has an approximately alternating structure is used.
  • Polymer III 300 parts of the monopotassium salt of aniline-3,5disulfonic acid and 40 parts of NaOH are dissolved in 900 parts of water, and to this are added 130 parts of an ethylene maleic anhydride copolymer of value 0.91 (molecular weight approximately 50,000) which has an alternating structure. The reaction mixture is then heated at 170 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-disulfonic acid and 40 parts of NaOH are dissolved in 1,500 parts of water. 152 parts of an isobutylene maleic anhydride copolymer of 11 value 0.7 (molecular weight approximately 65,000) which has an approximately alternating structure are then added and the reaction mixture is heated at 175 C. for 10 hours, a clear solution of polymer 1V being obtained. Polymer V 10 parts of anhydrous liquid S are dissolved in 300 parts by volume of anhydrous $0 at -60 C.'20.2 parts of styrene maleic anhydride copolymer of alternating structure are then introduced with vigorous stirring. Stirring is continued for 8 hours at about 50 C.
  • the polymers to be used according to the invention are preferably completely imidized ln principle, however, the corresponding polymers which still contain a small amount of maleic acid or maleic anhydride units or the half-amide are also suitable.
  • the polymers are worked up in the form of aqueous solutions with a polymer content of up to percent by weight, preferably 2 to 4 percent, to yield layers which have a thickness when dry of 1.5 to 2pm.
  • the conductivity depends on the thickness of the layer. Sufficient conductivity is ensured with the thickness mentioned above.
  • the above-mentioned compounds have layer forming properties and dry to form a clear, transparent layer. They can be used alone or with the addition of water permeable protective colloids such as gelatine.
  • the amount of protective colloids may be up to 50 percent of the quantity of antistatic agent but is preferably not layers according to the invention as auxiliary'agents. Smooth layers with an excellent antistatic action are obtained in this way.
  • the layers according to the invention are arranged in the usual manner, with protective layers uppermost on the other layers and can be used for black-white and color photographic materials.
  • these antistatic layers could be arranged in any position, both on the front side and on the rear side of the support.
  • the antistatic action is tested after two days air-conditioning of the sample strip.
  • the test is carried out with a rotating electrostatic field strength measuring instrument of the type FM 300-NR l by Prof. Dr. lng. F. Schwenckhagen (manufacturers: Bergischer Feingeratebau, Wuppertal).
  • the concentration of charge at 60 percent relative atmospheric humidity was measured.
  • the surface resistance is determined in a measuring instrument of Firma Lindenblatt, Elektrotechnik und Elektronik, Berlin-Halensee.
  • the instrument has two comb electrodes 10 cm. in length which are situated parallel to each other at a distance of 2 cm. apart. When the samples have been sufficiently air-conditioned they are pressed at a constant pressure against these electrodes. The resistances are read off a Terraohmeter connected to the instrument.
  • EXAMPLE 1 A silver iodobrom'ide gelatine emulsion layer on a cellulose acetate support is coated with a protective layer about 1.5 to 2 pin thickness.
  • the casting solution for this protective layer has the following composition: 1 liter of water. 20 g. of a maleic imide polymer (see following table) and 10 ml. of 7.5 percent aqueous solution of saponin as wetting agent.
  • the pH of the casting solution is adjusted to 6.5 with sodium hydroxide solution.
  • the casting solution can be sprayed or applied by any of the usual casting processes at 20 C.
  • a prior art antistatic compound a polyurea sulfonic acid) containing units of the following formula S'O;Ns
  • the photographic material containing the layers according to the invention does not flash on processing whereas the comparison material can only be processed at high atmospheric moistures. The photographic properties are not affected.
  • EXAMPLE 2 Thirty grams of compound I are dissolved in 1,000 ml. of cold distilled water with stirring, using a paddle stirrer. The pH is adjusted to between 6.0 to 7.0 with l N sodium hydroxide solution. This antistatic casting solution is applied to a silver chloride emulsion layer after the addition of 24 ml. of 7.5 percent aqueous saponin solution. The layer thickness is 0.5, 1.0 or 2.0
  • These antistatic layers do not only substantially reduce the surface resistance but also prevent the films from sticking.
  • EXAMPLE 4 A silver iodobromide gelatine emulsion layer on a cellulose acetate support is coated with a protective layer of about 1.5 to 2 p. in thickness.
  • the casting solution for this protective layer has the following composition: 1 liter of water, 18 g. of polymer l, 2 g. of polyvinyl alcohol and 10 ml. of 7.5 percent saponin.
  • the pH of the casting solution is adjusted 6.5 with sodium hydroxide solution.
  • a photographic material for use in photographic films said material including a support, at least one silver halide emulsion layer on the support, an outer layer on the emulsion layer, the outer layer containing a polymer of olefinically unsaturated monomers having a molecular weight of at least 15,000 and containing at least 40 mol percent of a sulfo-substituted N-phenyl maleic imide in polymerized form.
  • copolymer contains not more than 60 mol percent of units of styrene, sulfosubstituted styrene, ethylene or isobutylene.
  • a photographic material according to claim 1 characterized in that the polymer contains 40 to 60 mol percent of units of a sulfosubstituted N-phenyl maleic imide.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (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)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US881599A 1968-12-20 1969-12-02 Antistatic layers containing polymers of sulfo-substituted n-phenyl maleic imides Expired - Lifetime US3615531A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1815944A DE1815944C3 (de) 1968-12-20 1968-12-20 Antistatisches photographisches Material

Publications (1)

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US3615531A true US3615531A (en) 1971-10-26

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US (1) US3615531A (enrdf_load_stackoverflow)
JP (1) JPS4841208B1 (enrdf_load_stackoverflow)
BE (1) BE742959A (enrdf_load_stackoverflow)
CH (1) CH524158A (enrdf_load_stackoverflow)
DE (1) DE1815944C3 (enrdf_load_stackoverflow)
FR (1) FR2026725A1 (enrdf_load_stackoverflow)
GB (1) GB1265519A (enrdf_load_stackoverflow)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3791831A (en) * 1970-03-12 1974-02-12 Agfa Gevaert Ag Photographic materials with antistatic layers
US4287299A (en) * 1979-05-16 1981-09-01 Agfa-Gevaert Ag Process for the production of matting layers
US4644035A (en) * 1983-10-31 1987-02-17 Atlantic Richfield Company Process for sulfonating of polymers containing dicarboxylic acid cyclic imide units
US4797450A (en) * 1983-10-31 1989-01-10 Arco Chemical Company Additives for water-base drilling fluid and process
US4983669A (en) * 1988-03-07 1991-01-08 Aristech Chemical Corporation Thermosetting composition from maleimide, olefinic monomer and unsaturated polyester
US5238706A (en) * 1992-06-26 1993-08-24 Minnesota Mining And Manufacturing Company Antistatic film bases and their process of manufacturing
US5674671A (en) * 1994-07-18 1997-10-07 Minnesota Mining And Manufacturing Company Light senitive material having improved antistatic behavior
US5759701A (en) * 1994-02-15 1998-06-02 Xerox Corporation Recording sheets containing amine salts and quaternary choline halides
EP2385425A1 (en) 2010-05-07 2011-11-09 Fujifilm Corporation Silver halide photographic light-sensitive material for movie
CN103275419A (zh) * 2013-05-31 2013-09-04 苏州市景荣科技有限公司 一种pvc鞋底防静电剂及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3874879A (en) * 1972-05-22 1975-04-01 Eastman Kodak Co Article with oxidation protected adhesive and anti-static layer
JPS57195353A (en) * 1981-05-26 1982-12-01 Victor Co Of Japan Ltd Magnetic tape driver

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR956692A (enrdf_load_stackoverflow) * 1941-02-18 1950-02-02
US3039870A (en) * 1960-01-29 1962-06-19 Eastman Kodak Co Antistatic copolymers comprising salts of n-sulfoalkyl-alpha, beta-unsaturated dicarboxylic imides

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3791831A (en) * 1970-03-12 1974-02-12 Agfa Gevaert Ag Photographic materials with antistatic layers
US4287299A (en) * 1979-05-16 1981-09-01 Agfa-Gevaert Ag Process for the production of matting layers
US4644035A (en) * 1983-10-31 1987-02-17 Atlantic Richfield Company Process for sulfonating of polymers containing dicarboxylic acid cyclic imide units
US4797450A (en) * 1983-10-31 1989-01-10 Arco Chemical Company Additives for water-base drilling fluid and process
US4983669A (en) * 1988-03-07 1991-01-08 Aristech Chemical Corporation Thermosetting composition from maleimide, olefinic monomer and unsaturated polyester
US5238706A (en) * 1992-06-26 1993-08-24 Minnesota Mining And Manufacturing Company Antistatic film bases and their process of manufacturing
US5759701A (en) * 1994-02-15 1998-06-02 Xerox Corporation Recording sheets containing amine salts and quaternary choline halides
US5674671A (en) * 1994-07-18 1997-10-07 Minnesota Mining And Manufacturing Company Light senitive material having improved antistatic behavior
EP2385425A1 (en) 2010-05-07 2011-11-09 Fujifilm Corporation Silver halide photographic light-sensitive material for movie
CN103275419A (zh) * 2013-05-31 2013-09-04 苏州市景荣科技有限公司 一种pvc鞋底防静电剂及其制备方法

Also Published As

Publication number Publication date
CH524158A (de) 1972-06-15
BE742959A (enrdf_load_stackoverflow) 1970-06-11
DE1815944C3 (de) 1979-11-22
GB1265519A (enrdf_load_stackoverflow) 1972-03-01
FR2026725A1 (enrdf_load_stackoverflow) 1970-09-18
DE1815944A1 (de) 1970-07-02
DE1815944B2 (de) 1979-03-15
JPS4841208B1 (enrdf_load_stackoverflow) 1973-12-05

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