US3671248A - Stain inhibitor in photographic paper bases - Google Patents

Stain inhibitor in photographic paper bases Download PDF

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Publication number
US3671248A
US3671248A US44965A US3671248DA US3671248A US 3671248 A US3671248 A US 3671248A US 44965 A US44965 A US 44965A US 3671248D A US3671248D A US 3671248DA US 3671248 A US3671248 A US 3671248A
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United States
Prior art keywords
paper
layer
stain
silver halide
emulsion
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Expired - Lifetime
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US44965A
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English (en)
Inventor
Merle K Eldridge
Roy C Bloom
Douglas C Joseph
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/42—Developers or their precursors
    • 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
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • 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
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes

Definitions

  • This invention relates to light-sensitive photographic elements and more particularly to, a process for preventing discoloration thereof due to migration of developing agent from an emulsion layer to the support.
  • An element of particular use in photography comprises a polymer coated paper support provided with a silver halide emulsion layer and contiguous silver halide developing agent such as a polyhydric phenol, e.g. hydroquinone. It is observed that after storage of this paper, stain is visible particularly when viewing this paper from the side opposite the emulsion layer. We have unexpectedly discovered that this stain arises, during storage, from gradual migration of the developing agent from the emulsion through the relatively impervious underlying polymer layer to the paper fiber where it is oxidized to produce the observed stain.
  • a polyhydric phenol e.g. hydroquinone
  • Another element of use in photography comprises-a polymer coated paper support having a hydrophilic organic colloid backing layer, suchas an antistatic backing, on one surface and on the other surface a silver halide emulsion layer and contiguous silver halide developing agent such as hydroquinone.
  • a hydrophilic organic colloid backing layer such as an antistatic backing
  • a silver halide emulsion layer and contiguous silver halide developing agent such as hydroquinone.
  • this brown stain does not appear on fresh or aged polymer coated paper if the paper stock has been treated, for example coated or tub sized, with a composition containing a lower-aldehyde bisulfide so as to obtain at least about 30 milligrams per square foot.
  • the hydrophilic backing layer if it is present, it must be acidic having a pH less than 7 and preferably about 3 to 4, otherwise the stain still appears.
  • FIG. 1 layer 10 is ordinary photographic paper base sized with an aldehyde bisulfite and carrying extruded polyethylene layers 11 and emulsion layer 13 containing developing agent.
  • FIG. 2 element an antistatic layer of low pH is provided to avoid stain.
  • the polymer coated paper used in production of the sensitive photographic elements as illustrated in the drawing can be prepared by first tub sizing a photographic paper base of about 30 pounds per thousand square feet with an aqueous composition containing the aldehyde bisulfite, followed by coating or extruding polymer layers, e.g. polyester, polyolefin and the like, preferably a polyolefin layer, onto both surfaces of the paper.
  • polymer layers e.g. polyester, polyolefin and the like, preferably a polyolefin layer
  • polymers include polyolefins such as polyethylenes and polypropylenes and ethylene-propylene copolymers, polystyrene, polybutenes, polypentenes, polyacrylic acid esters, linear polyesters such as polyethylene terephthalates, polycarbonates, polyamides such as nylon, cellulolose esters, polyacrylonitrile, polyvinylidene chloride and other copolymers of the indicated monomers such as ethylenevinylacetate copolymers.
  • polyolefins such as polyethylenes and polypropylenes and ethylene-propylene copolymers
  • polystyrene polybutenes
  • polypentenes polyacrylic acid esters
  • linear polyesters such as polyethylene terephthalates
  • polycarbonates polyamides such as nylon, cellulolose esters, polyacrylonitrile, polyvinylidene chloride and other copolymers of the indicated monomers such as ethylenevinylacetate copolymers.
  • the paper can first be treated with corona discharge as described in US. Pat. 3,411,908 to facilitate adhesion of the polymer layers to the paper. About 8 pounds of polyethylene per thousand square foot of paper surface is useful for this purpose.
  • this polymer coated paper (FIG. 1) is activated, especially with controlled speed and corona frequency as disclosed in Ambusk, US. patent application Ser. No. 724,491, filed Apr. 26, 1968, now Pat. No. 3,549,406 and coated with the emulsion containing developing agent, no stain appears after winding in the roll or on storage of the paper. In another case (FIG.
  • a useful ionic antistatic composition includes an alkali metal salt of an alkylaryl polyether sulfonate or of a polymeric carboxylic acid, or a mixture thereof. In some cases it may be desirable to incorporate colloidal silica into the antistatic composition to obtain the desired antistatic properties.
  • the above sulfonates are described in detail in US. Pat. 2,600,831, for example, the salt sold under the trade name of Triton X200 (p-[1,l,3,3 tetramethylbutyl]phenoxyethoxyethyl sodium sulfonate) sold by Du Pont de Nemours and Company.
  • the polymeric carboxylic acids are illustrated by polymerized acrylic acids such as polyacrylic acid, polymethacrylic acid, and polyethacrylic acid such as Daxad 30 (trade name for the sodium salt of polymethacrylic acid) sold by Dewey and Almy Chemical Company.
  • alkali metal salts of polymeric carboxylic acids may also be utilized as the ionic organic antistatic agent, for example, potassium polyacrylatcs, alkali metal salts of acrylic acidmethyl acrylate copolymer, and the like.
  • the sodium salt of cellulose sulfate can be used alone for the antistatic layer.
  • a gelatin layer may separate layers 11 and 12 for controlling curl.
  • Useful developing agents for the emulsion layer include the polyhydric phenol silver halide developing agents such as hydroquinone, substituted hydroquinone, e.g. chlorohydroquinone, aminophenols, 3-pyrazolidones, catechol, substituted catechols, reductones, hydrazines and hydroxylamines. Mixtures of these developing agents are especially useful such as a mixture of hydroquinone and a 3-pyrazolidone, e.g. 50 to 200 milligrams hydroquinone per square foot and 0-20 miligrams 1-phenyl-3-pyrazolidone per square foot.
  • the developed agent can also be made contiguous to the silver halide of the emulsion layer by being coated either in a subbing layer under the emulsion layer or in a layer.
  • the silver halide emulsions useful with this invention can comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromiodide or-mixtures thereof.
  • the emulsions may be coarse or fine grained and can be prepared by any of the well-known procedures. Surface image emulsions or internal image emulsions may be used if desired. Regular grained emulsions may be used.
  • the silver halide emulsion .grains may, in a particular coating, vary widely in grain size or mono-dispersed emulsions may be used.
  • the emulsion used may comprise grains which have irregular crystal structures or they may be regular grained emulsions such as cubic gained emulsions. Negative type emulsions may be used or, if desired, direct positive emulsions may be used in the practice of the invention. The following examples will serve to illustrate the invention.
  • EXAMPLE 1 A photographic papersupport of about 30 pounds per thousand square foot is tub sized with the following compositions:
  • the sizing operations A, B and C yield coverages of about 125 milligrams, 62.5 milligrams and 3l.2 milligrams of the aldehyde bisulfite per square foot, respectively. At least about 30 milligrams per square foot is useful to produce the advantageous results mentioned below.
  • polyethylene is extruded onto the corona activated surfaces of the papers A, B, C and D at about 8 pounds per thousand square feet.
  • the wireside of the polyethylene paper is then coronaactivated and coated with the following aqueous acidic antistatic composition, applying approximately 3 grarns/m. (dry weight).
  • the face side of the polyethylene coated paper is corona activated and coated with a gelatin-silver chlorobromoiodide emulsion containing hydroquinone and 1- phenyl-S-pyrazolidone so as to obtain about :125 milligrams hydroquinone and 6 milligrams 1-phenyl-3- pyrazolidone per square foot.
  • Papers A, B, C and D are exposed to black-and-white images and processed by use of an alkaline activator solution to initiate silver halide development followed by fixing and washing.
  • White pigment can be incorporated into the polymer layer under the emulsion layer.
  • the polyethylene layers can be replaced with other polymeric layers including cellulose ester and linear polyesters. Similarly, other antistatic agents and hydrophilic.
  • organic colloid carriers may comprise the acidic backing layer.
  • a light-sensitive photographic element comprising a paper support treated with a lower aldehyde bisulfite, eX-' truded polymer layers on each surface 'of the paper,-a silver halide emulsion layer and contiguous silver halide developing agent adhered to thesurface of one of the polymer layers, and a hydrophilic organic colloid layer having a. pH less'than 7 adhered to the surface of the other polymer layer.
  • developing agent' is a polyhydric phenol contained in the emulsion layer. 4. The element according to claim 1 wherein the hydro.-
  • philic organic colloid layer is an antistatic layer contain-.- a ing an alkali metal salt of an alkylaryl polyether sulfonate' or of a polymeric carboxylic acid, or a mixture thereof.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Laminated Bodies (AREA)
US44965A 1970-06-10 1970-06-10 Stain inhibitor in photographic paper bases Expired - Lifetime US3671248A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US4496570A 1970-06-10 1970-06-10

Publications (1)

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US3671248A true US3671248A (en) 1972-06-20

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US44965A Expired - Lifetime US3671248A (en) 1970-06-10 1970-06-10 Stain inhibitor in photographic paper bases

Country Status (6)

Country Link
US (1) US3671248A (fr)
JP (1) JPS5512584B1 (fr)
BE (1) BE768363A (fr)
DE (1) DE2128832C2 (fr)
FR (1) FR2096123A5 (fr)
GB (1) GB1338639A (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4410619A (en) * 1981-04-11 1983-10-18 Mitsubishi Paper Mills, Ltd. Photographic material
US4419433A (en) * 1981-12-03 1983-12-06 Mitsubishi Paper Mills, Ltd. Photographic material
US4547445A (en) * 1982-04-21 1985-10-15 Fuji Photo Film Co., Ltd. Photographic material
US4678742A (en) * 1984-05-11 1987-07-07 Fuji Photo Film Co., Ltd. Photographic printing paper support
US5168034A (en) * 1991-03-20 1992-12-01 Fuji Photo Film Co., Ltd. Photographic printing paper support
US6077656A (en) * 1999-05-06 2000-06-20 Eastman Kodak Company Photographic paper backing containing polymeric primary amine addition salt
US6120979A (en) * 1999-05-06 2000-09-19 Eastman Kodak Company Primer layer for photographic element
US6171769B1 (en) 1999-05-06 2001-01-09 Eastman Kodak Company Antistatic backing for photographic paper
US6197486B1 (en) 1999-12-27 2001-03-06 Eastman Kodak Company Reflective print material with extruded antistatic layer
US20160032162A1 (en) * 2013-04-18 2016-02-04 3M Innovative Properties Company Buried clay/nanosilica static dissipative coatings

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57183677U (fr) * 1981-05-18 1982-11-20
JPH0955239A (ja) * 1995-08-09 1997-02-25 Nichifu Co Ltd 電線接続用コネクター

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2571725A (en) * 1946-08-15 1951-10-16 Eastman Kodak Co Eliminating stain in photographic color material
US2865745A (en) * 1955-08-25 1958-12-23 Eastman Kodak Co Photographic reproduction process
US3212895A (en) * 1960-12-20 1965-10-19 Eastman Kodak Co Stability of rapid-processed photographic materials
FR1360660A (fr) * 1962-06-25 1964-05-08 Eastman Kodak Co Nouvelle composition d'encollage et papier photographique encolle par la dite composition
GB1005631A (en) * 1964-03-10 1965-09-22 Eastman Kodak Co Photographic materials

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4410619A (en) * 1981-04-11 1983-10-18 Mitsubishi Paper Mills, Ltd. Photographic material
US4419433A (en) * 1981-12-03 1983-12-06 Mitsubishi Paper Mills, Ltd. Photographic material
US4547445A (en) * 1982-04-21 1985-10-15 Fuji Photo Film Co., Ltd. Photographic material
US4678742A (en) * 1984-05-11 1987-07-07 Fuji Photo Film Co., Ltd. Photographic printing paper support
US5168034A (en) * 1991-03-20 1992-12-01 Fuji Photo Film Co., Ltd. Photographic printing paper support
US6077656A (en) * 1999-05-06 2000-06-20 Eastman Kodak Company Photographic paper backing containing polymeric primary amine addition salt
US6120979A (en) * 1999-05-06 2000-09-19 Eastman Kodak Company Primer layer for photographic element
US6171769B1 (en) 1999-05-06 2001-01-09 Eastman Kodak Company Antistatic backing for photographic paper
US6346370B1 (en) 1999-05-06 2002-02-12 Eastman Kodak Company Antistatic layer for a photographic element
US6197486B1 (en) 1999-12-27 2001-03-06 Eastman Kodak Company Reflective print material with extruded antistatic layer
US20160032162A1 (en) * 2013-04-18 2016-02-04 3M Innovative Properties Company Buried clay/nanosilica static dissipative coatings

Also Published As

Publication number Publication date
BE768363A (fr) 1971-11-03
FR2096123A5 (fr) 1972-02-11
DE2128832C2 (de) 1983-08-11
DE2128832A1 (de) 1971-12-16
GB1338639A (en) 1973-11-28
JPS5512584B1 (fr) 1980-04-02

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