US3671248A - Stain inhibitor in photographic paper bases - Google Patents
Stain inhibitor in photographic paper bases Download PDFInfo
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- 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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- paper
- layer
- stain
- silver halide
- emulsion
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- Expired - Lifetime
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- 239000003112 inhibitor Substances 0.000 title description 2
- -1 SILVER HALIDE Chemical class 0.000 abstract description 35
- 239000000839 emulsion Substances 0.000 abstract description 34
- 239000003795 chemical substances by application Substances 0.000 abstract description 20
- 229910052709 silver Inorganic materials 0.000 abstract description 13
- 239000004332 silver Substances 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 5
- 229920000098 polyolefin Polymers 0.000 abstract description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 abstract 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 2
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 2
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- FZQDYEPVHITTBB-UHFFFAOYSA-N Cl[Br][I][Ag] Chemical compound Cl[Br][I][Ag] FZQDYEPVHITTBB-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Images
Classifications
-
- 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)
Abstract
PHOTOGRAPHIC ELEMENTS HAVING POLYOLEFIN COATED PAPER SUPPORTS, PROVIDED WITH SILVER HALIDE EMULSION LAYERS CONTAINING SILVER HALIDE DEVELOPING AGENTS, WITH OR WITHOUT HYDROPHILIC BACKING LAYERS, EXHIBIT STAIN DUE TO MIGRATION OF THE DEVELOPING AGENT TO PAPER AND TO THE BACKING LAYER. STAIN IS AVOIDED BY SIZING THE PAPER WITH AN ALDEHYDE BISULFITE AND COATING ANY BACKING LAYER AT A PH LESS THEN 7 PREFERABLY ABOUT 3 TO 4.
Description
United States Patent Oflice 3,671,248 Patented June 20, 1972 3,671,248 STAIN INHIBITOR IN PHOTOGRAPHI PAPER BASES Merle K. Eldridge and Roy C. Bloom, Hilton, and Douglas C. *Joseph, Victor, ,N.Y., assignors to Eastman Kodak Company, Rochester, N.Y.
Filed June 10, 1970, Ser. No. 44,965 Int. Cl. G03c 1/48, N86
US. Cl. 96-76 R 7 Claims ABSTRACT or THE DISCLOSURE v 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.
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. It has been found that immediately after coating and drying the emulsion layer on the support and winding in a roll, particularly when the emulsion layer contains the developing agent or it is in a layer on the emulsion surface, a pronounced brown stain at once appears in the organic colloid backing layer. We have discovered that this fresh stain arises from migration of the developing agent to the adjacent polymer surface when the paper is wound in the roll. In addition, more stain arises upon storage of the paper due to the mentioned migration of developing agent from the emulsion through the relatively impervious underlying polymer layer to the paper fiber.
In a further aspect of our invention we have discovered that 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. However, if the hydrophilic backing layer is present, it must be acidic having a pH less than 7 and preferably about 3 to 4, otherwise the stain still appears.
The accompanying drawing shows in greatly enlarged cross-sectional views representative photographic elements of our invention wherein in 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. No
stain arises on winding the paper in a roll or on ageing the paper. In the 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. These 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.
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. When 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. 2) when the polyethylene paper is coated at pH less than 7 with a hydrophilic organic colloid backing layer 12 such as gelatin, or a water-soluble cellulose ether or a cellulose ester, starch, etc., optionally containing an ionic antistatic agent, after emulsion coating of this paper stain is not visible after winding the paper in a roll even with the emulsion and antistatic layers in contact in the roll or on ageing the paper. 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. Many other 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. In addition, 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. If desired, 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 .grainsmay, 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:
*Sodium formaldehyde bisulfite.
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.
Thereafter, 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).
Parts by wt. Starch 5.0 Daxad 30 5.0 Triton X200E 0.2 Water 85.9
Butyl alcohol pH 3.5 (adjusted with hydrochloric 4 acid) 4.0 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. It is observed that just after preparation of papers A, B, C and D as described above and winding in the roll, papers A, B and C viewed from the surface opposite the emulsion layer had high reflectivities (about 80% reflectance of light of wavelength 460 mm.) whereas the corresponding surface of paper D not containing SFB showed a pronounced brown stain (reflectance about 55% of 460 mm. light). Additional stain appears on D after storage. The papers A, B, ,C and D have structures essentially as shown in FIG. 2 of the aclayer. on top oftheemulsion.
companying-drawing is.-..t-he-..case. .of paper. D. thev stain. being visible on viewing from the side opposite layer 13.
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. As a result; papers-A", B and showed no stain in the highlights of the images or on the rear surface wh'ereas some stain is still visible-on the'corresponding surfaces of paper D not containing the SFB.
' EXAMPLE -2 The processes of Examples 1A and are carried out except omitting the antistatic layer (FIG. 1). As a result,
followed by extrusion or solvent coating ofpolymer layers on each paper surface. If desired, 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.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
What we claim is:
1. 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.-
2. The element according to claim 1 wherein'the polymer layers contain-a polyolefin or olefin copolymer.
3. The element according to claim 1 wherein the aldehyde bisulfite is sodium formaldehyde bisulfite and the veloping agent is hydroquinone.
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.
5. The element according to claim 1 wherein the developing agent is a polyhydric phenol.
6. The element according to claim '1 7. The element according to claim 1 wherein the developing agent is a mixture of hydroquinone and a 3-- pyrazolidone.
' a References Cited UNITED STATES'PATENTS 3,212,895
wherein the de-
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US4496570A | 1970-06-10 | 1970-06-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3671248A true US3671248A (en) | 1972-06-20 |
Family
ID=21935281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 (en) |
| JP (1) | JPS5512584B1 (en) |
| BE (1) | BE768363A (en) |
| DE (1) | DE2128832C2 (en) |
| FR (1) | FR2096123A5 (en) |
| GB (1) | GB1338639A (en) |
Cited By (10)
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57183677U (en) * | 1981-05-18 | 1982-11-20 | ||
| JPH0955239A (en) * | 1995-08-09 | 1997-02-25 | Nichifu Co Ltd | Wire connection connector |
Family Cites Families (5)
| 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 (en) * | 1962-06-25 | 1964-05-08 | Eastman Kodak Co | New sizing composition and photographic paper glued by said composition |
| GB1005631A (en) * | 1964-03-10 | 1965-09-22 | Eastman Kodak Co | Photographic materials |
-
1970
- 1970-06-10 US US44965A patent/US3671248A/en not_active Expired - Lifetime
-
1971
- 1971-06-09 DE DE2128832A patent/DE2128832C2/en not_active Expired
- 1971-06-09 FR FR7120901A patent/FR2096123A5/fr not_active Expired
- 1971-06-10 JP JP4067371A patent/JPS5512584B1/ja active Pending
- 1971-06-10 GB GB1989571*[A patent/GB1338639A/en not_active Expired
- 1971-06-10 BE BE768363A patent/BE768363A/en not_active IP Right Cessation
Cited By (11)
| 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 |
|---|---|
| FR2096123A5 (en) | 1972-02-11 |
| GB1338639A (en) | 1973-11-28 |
| DE2128832A1 (en) | 1971-12-16 |
| JPS5512584B1 (en) | 1980-04-02 |
| BE768363A (en) | 1971-11-03 |
| DE2128832C2 (en) | 1983-08-11 |
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