US3552972A - Antistatic layer for photographic materials - Google Patents

Antistatic layer for photographic materials Download PDF

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Publication number
US3552972A
US3552972A US681094A US3552972DA US3552972A US 3552972 A US3552972 A US 3552972A US 681094 A US681094 A US 681094A US 3552972D A US3552972D A US 3552972DA US 3552972 A US3552972 A US 3552972A
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United States
Prior art keywords
antistatic
gelatin
layer
layers
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US681094A
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English (en)
Inventor
Karl-Otto Meyer
Richard Schiffmann
Wolfgang Himmelmann
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Agfa Gevaert AG
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Agfa Gevaert AG
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Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/85Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • G03C1/89Macromolecular substances therefor
    • G03C1/895Polyalkylene oxides

Definitions

  • R is an alkyl having- 6l8 carbon atoms, a phenyl group including a substituted phenyl group;
  • X is 0 or an imino group
  • R is a y-valent organic group of the phenyl or naphthyl series
  • n or n is an integer from 4 to 8;
  • n 0 or 1 and y is 1, 2, or 3.
  • Electrostatic charging of the film surface can be reduced by adding matting agents to the protective layers to diminish the adhesion between two surfaces of the photographic material which are in contact with each other.
  • the formation of electrostatic charges can also be avoided by the addition of electrically conductive materials to an outermost layer.
  • quaternary salts cannot be used in photographic materials because they cause fogging.
  • Hygroscopic materials such as glycerol, potassium acetate or lithium chloride cause the layers to adhere to each other and are ineffective at low humidities.
  • High molecular carboxylic or sulfonic acids such as sodium salts of polystyrene sulfonic acid and polyvinylsulfonic acid have agood antistatic effect when applied direct to a hydrophobic layer support, but this effect is greatly reduced when used in gelatin or emulsion layers. Chromium complexes react with gelatin and therefore can only be used under certain conditions.
  • R alkyl having preferably 6-18 carbon atoms, aryl, preferably phenyl, aralkyl such as benzyl or phenylethyl or cycloalkyl such as cyclohexyl; the above substituents, especially the phenyl groups, may be further substituted in any way desired;
  • X a simple chemical bond or a bivalent imino group
  • R is a y-valent organic group of the kind defined under R;
  • n, and 11 are integers from 4 to 8 inclusive;
  • y 1, 2 or 3.
  • the compounds to be used in accordance with the invention are generally highly viscous, syrupy substances. When used for photographic purposes, they are dissolved in a photographically inert solvent, preferably a low molecular weight aliphatic alcohol, and this solution is emulsified into the casting solution of the protective layer. In the final layer the antistatic agents are substantially heterogeneously distributed in the layer in the form of fine particles.
  • a photographically inert solvent preferably a low molecular weight aliphatic alcohol
  • the compounds according to the invention are employed in quantities of 0.03 to 0.20 g., preferably 0.05 to 0.075 per g. of the binding agent. They may be used alone or in combination with surface active substances such as anionic or non-ionic wetting agents or in combination with anti-Newton additives such as polystyrene, polymethacrylic acid esters or urea formaldehyde polymers.
  • surface active substances such as anionic or non-ionic wetting agents or in combination with anti-Newton additives such as polystyrene, polymethacrylic acid esters or urea formaldehyde polymers.
  • anti-Newton additives such as polystyrene, polymethacrylic acid esters or urea formaldehyde polymers.
  • the last mentioned additives are also present in the final layer in the form of heterogeneously distributed particles having a size of 1-3 microns. Smooth layers that have an excellent antistatic effect are thereby obtained.
  • binding agents for the antistatic layer there can be used the hydrophilic and water-permeable film-forming compounds customarily employed for photographic layers, for example proteins preferably gelatin, cellulose derivatives such as alkyl cellulose for instance hydroxyethyl cellulose or carboxyl methyl cellulose, alginic acid and derivatives thereof, polyvinyl alcohols, polyvinyl pyrrolidone and the like.
  • proteins preferably gelatin
  • cellulose derivatives such as alkyl cellulose for instance hydroxyethyl cellulose or carboxyl methyl cellulose
  • alginic acid and derivatives thereof alginic acid and derivatives thereof
  • polyvinyl alcohols polyvinyl pyrrolidone and the like.
  • the compounds to be used according to the invention can be used in light-sensitive silver halide emulsion layers, antihalation layers and NC-layers for black-white or color-photographic films. They do not cause fogging, do not accelerate development, do not migrate from the layers or cause sticking of the layers.
  • the antistatic agents are sparingly soluble in water and are photographically inert.
  • they have preferably at the most a total of 8 ethylene oxide units.
  • the groups R are strongly hydrophobic, the compounds contain preferably more than 8 ethylene oxide units so that they are more readily capable of being emulsified.
  • Suitable compounds include those of the following formulae:
  • a I A (VII) (VIII) The compounds to be used according to the invention are prepared by known methods. The preparation of compounds 1 and 7 is described in detail below. The other compounds are prepared in a similar manner.
  • COMPOUND l moved in a rotary evaporator.
  • the oily, yellow brown product is again filtered at to C.
  • COMPOUND VII A solution of 9.9 g. of 3,5-dinitrobenzoyl chloride in ml. of benzene is added dropwise to a mixture of 42 g. of n-dodecylphenol which has been hydroxyalkylated in a manner analogous to Compound 1, 20 ml. of benzene and 5 g. of pyridine, and the reaction mixture is stirred at room temperature for 5 hours and at 50 C. for one hour. After cooling, the reaction mixture is poured on ice, acidified with 2 N H 50 treated with saturated sodium chloride solution, and extracted several times with methylene dichloride. The combined extracts are freed from solvent after drying over K in a vacuum.
  • the 10% methanolic solution of the antistatic agent is emulsified into the casting composition at temperatures between 30 and 40 C. with stirring.
  • the pH of the casting solution which is to form the protective coating is adjusted to 6.5 with sodium hydroxide solution.
  • the protective coating is applied by usual methods after the emulsion layer has solidified or simultaneously with the application of the emulsion layer -by the vacuum air brush process.
  • the antistatic effect is tested after air conditioning the sample strips for 2 days, the electrostatic charging in volts per cm. (v./cm.) is determined by means of the rotating field strength measuring instrument according to Schwenkhagen. The intensity of charge was measured at 60% relative humidity.
  • v./cm.(60% humidity) 45 ml. of a 10% methanolic solution of one of the above mentioned antistatic materials is incorporated by emulsification as described in Example 1 into a gelatin solution of the following composition:
  • the casting solution is applied onto the rear side of a transparent support of cellulose acetate and dried.
  • the layer serves as a non-curling layer.
  • the other side of the support is coated with a silver halide gelatin emulsion layer.
  • Example 1 The antistatic test of the resulting layer are preformed as in Example 1:
  • This solution is applied as protective layer onto the light-sensitive silver halide gelatin emulsion layers of a multi-layered color photographic material and dried.
  • a photographic material comprising a silver iodobromide gelatin emulsion layer and an uppermost protective layer which does not contain an antistatic agent is treated with 0.01 to 0.25% solutions of the antistatic agents mentioned hereinafter (a) in water or (b) in methylene dichloride.
  • the electrostatic charge of the air conditioned samples is measured at 60% humidity. Comparison measurements are carried out on samples of photographic material which have been treated only with water or methylene dichloride but have otherwise the same composition.
  • the antistatic agents are incorporated into a protective gelatin layer which is applied onto a silver iodobromide gelatin emulsion layer according to Example 1.
  • This layer contains, either alone or in combination, as will be seen from the following tables, based on the dry weight of gelatin, 20% by weight of polystyrene sulfonic acid (PSS), 6% by weight of alkali metal salt or 6% by weight of the antistatic agent according to the invention.
  • PSS polystyrene sulfonic acid
  • the surface resistivity is determined with a measuring instrument which has two comb electrodes cm. in length arranged parallel to each other at a distance of 2 cm., and the samples which have been adequately air conditioned, are pressed at a constant pressure against these electrodes.
  • the resistivity is registered with a teraohmmeter connected to the instrument.

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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)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Laminated Bodies (AREA)
  • Polyethers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US681094A 1966-11-15 1967-11-07 Antistatic layer for photographic materials Expired - Lifetime US3552972A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1966A0054080 DE1522408B2 (de) 1966-11-15 1966-11-15 Photographisches material mit einer antistatischen schicht

Publications (1)

Publication Number Publication Date
US3552972A true US3552972A (en) 1971-01-05

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Family Applications (1)

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US681094A Expired - Lifetime US3552972A (en) 1966-11-15 1967-11-07 Antistatic layer for photographic materials

Country Status (7)

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US (1) US3552972A (de)
BE (1) BE706563A (de)
CH (1) CH504024A (de)
DE (1) DE1522408B2 (de)
FR (1) FR1549600A (de)
GB (1) GB1167559A (de)
NL (1) NL6715513A (de)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3769022A (en) * 1969-12-31 1973-10-30 Agfa Gevaert Nv Photosensitive silver halide emulsions comprising coating aids
US3850642A (en) * 1971-07-16 1974-11-26 Eastman Kodak Co Multilayer radiation sensitive element having controlled triboelectric charging characteristics
US3888678A (en) * 1971-07-16 1975-06-10 Eastman Kodak Co Method for adjusting triboelectric charging characteristics of materials
US4196001A (en) * 1974-07-24 1980-04-01 Eastman Kodak Company Antistatic layer for photographic elements
US4221861A (en) * 1978-04-06 1980-09-09 The Dow Chemical Company Backside antistatic coated film bearing a light sensitive emulsion
US4272616A (en) * 1978-06-07 1981-06-09 Fuji Photo Film Co., Ltd. Photographic radiation-sensitive materials having improved antistatic property
DE3436622A1 (de) * 1983-10-07 1985-04-25 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Photographisches silberhalogenidmaterial
EP0180668A1 (de) * 1984-11-09 1986-05-14 Agfa-Gevaert N.V. Photographische Elemente, die Schutzschichten mit Antistatikmitteln enthalten
US4624913A (en) * 1984-02-09 1986-11-25 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
US5011739A (en) * 1989-10-02 1991-04-30 Eastman Kodak Company Moisture stable biasable transfer members and method for making same
US5156915A (en) * 1991-11-26 1992-10-20 Eastman Kodak Company Moisture stable polyurethane biasable members
US5212032A (en) * 1991-11-26 1993-05-18 Eastman Kodak Company Moisture stable polyurethane biasable transfer members
US5217838A (en) * 1991-11-26 1993-06-08 Eastman Kodak Company Moisture stable biasable transfer members
US5250357A (en) * 1991-11-26 1993-10-05 Eastman Kodak Company Moisture stable elastomeric polyurethane biasable transfer members
JPH0610728B2 (ja) 1986-05-28 1994-02-09 コニカ株式会社 新規な界面活性剤を含有するハロゲン化銀写真感光材料
JPH0648350B2 (ja) 1987-03-20 1994-06-22 富士写真フイルム株式会社 ハロゲン化銀写真感光材料

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2219557A1 (de) * 1972-04-21 1973-10-31 Bayer Ag Neue antistatika
EP0014921A1 (de) * 1979-02-16 1980-09-03 EASTMAN KODAK COMPANY (a New Jersey corporation) Beschichtungszusammensetzungen und Verfahren

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3769022A (en) * 1969-12-31 1973-10-30 Agfa Gevaert Nv Photosensitive silver halide emulsions comprising coating aids
US3850642A (en) * 1971-07-16 1974-11-26 Eastman Kodak Co Multilayer radiation sensitive element having controlled triboelectric charging characteristics
US3888678A (en) * 1971-07-16 1975-06-10 Eastman Kodak Co Method for adjusting triboelectric charging characteristics of materials
US4196001A (en) * 1974-07-24 1980-04-01 Eastman Kodak Company Antistatic layer for photographic elements
US4221861A (en) * 1978-04-06 1980-09-09 The Dow Chemical Company Backside antistatic coated film bearing a light sensitive emulsion
US4272616A (en) * 1978-06-07 1981-06-09 Fuji Photo Film Co., Ltd. Photographic radiation-sensitive materials having improved antistatic property
DE3436622A1 (de) * 1983-10-07 1985-04-25 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Photographisches silberhalogenidmaterial
US4624913A (en) * 1984-02-09 1986-11-25 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
JPS61118747A (ja) * 1984-11-09 1986-06-06 アグフア・ゲヴエルト・ナームロゼ・ベンノートチヤツプ 静電防止剤を含有する保護層を有する写真素子
EP0180668A1 (de) * 1984-11-09 1986-05-14 Agfa-Gevaert N.V. Photographische Elemente, die Schutzschichten mit Antistatikmitteln enthalten
US4670376A (en) * 1984-11-09 1987-06-02 Agfa-Gavaert, N.V. Process of making a photographic elements comprising protective layers containing antistats
JPH0656479B2 (ja) 1984-11-09 1994-07-27 アグフア・ゲヴエルト・ナームロゼ・ベンノートチヤツプ 静電防止剤を含有する保護層を有する写真素子
JPH0610728B2 (ja) 1986-05-28 1994-02-09 コニカ株式会社 新規な界面活性剤を含有するハロゲン化銀写真感光材料
JPH0648350B2 (ja) 1987-03-20 1994-06-22 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
US5011739A (en) * 1989-10-02 1991-04-30 Eastman Kodak Company Moisture stable biasable transfer members and method for making same
US5156915A (en) * 1991-11-26 1992-10-20 Eastman Kodak Company Moisture stable polyurethane biasable members
US5212032A (en) * 1991-11-26 1993-05-18 Eastman Kodak Company Moisture stable polyurethane biasable transfer members
US5217838A (en) * 1991-11-26 1993-06-08 Eastman Kodak Company Moisture stable biasable transfer members
US5250357A (en) * 1991-11-26 1993-10-05 Eastman Kodak Company Moisture stable elastomeric polyurethane biasable transfer members

Also Published As

Publication number Publication date
DE1522408A1 (de) 1969-08-14
CH504024A (de) 1971-02-28
GB1167559A (en) 1969-10-15
NL6715513A (de) 1968-01-25
FR1549600A (de) 1968-12-13
BE706563A (de) 1968-04-01
DE1522408B2 (de) 1976-11-18

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