US3460945A - Ethyl acrylate,methyl methacrylate and acrylic acid terpolymer adhesive for polyester film supports and gelatin layers - Google Patents
Ethyl acrylate,methyl methacrylate and acrylic acid terpolymer adhesive for polyester film supports and gelatin layers Download PDFInfo
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- US3460945A US3460945A US488777A US3460945DA US3460945A US 3460945 A US3460945 A US 3460945A US 488777 A US488777 A US 488777A US 3460945D A US3460945D A US 3460945DA US 3460945 A US3460945 A US 3460945A
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- gelatin
- terpolymer
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- acrylic acid
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- Expired - Lifetime
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- 229920001897 terpolymer Polymers 0.000 title description 44
- 239000008273 gelatin Substances 0.000 title description 41
- 229920000159 gelatin Polymers 0.000 title description 40
- 108010010803 Gelatin Proteins 0.000 title description 38
- 235000019322 gelatine Nutrition 0.000 title description 38
- 235000011852 gelatine desserts Nutrition 0.000 title description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title description 13
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 title description 12
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 title description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title description 10
- 229920006267 polyester film Polymers 0.000 title description 8
- 239000000853 adhesive Substances 0.000 title description 3
- 230000001070 adhesive effect Effects 0.000 title description 3
- 239000010410 layer Substances 0.000 description 61
- 229940014259 gelatin Drugs 0.000 description 40
- 239000000975 dye Substances 0.000 description 36
- 239000000839 emulsion Substances 0.000 description 19
- 239000006229 carbon black Substances 0.000 description 12
- 235000019241 carbon black Nutrition 0.000 description 12
- 239000003605 opacifier Substances 0.000 description 12
- -1 silver halide Chemical class 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000004332 silver Substances 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- 239000005041 Mylar™ Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- 239000001043 yellow dye Substances 0.000 description 3
- CWNSVVHTTQBGQB-UHFFFAOYSA-N N,N-Diethyldodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CC)CC CWNSVVHTTQBGQB-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 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
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical class [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 1
- 238000009498 subcoating Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
- G03C1/93—Macromolecular substances therefor
-
- 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
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/42—Structural details
- G03C8/52—Bases or auxiliary layers; Substances therefor
Definitions
- the adhesion of a felatinous layer to a polyester film support may be facilitated by coating said support prior to application of said gelatinous layer with a terpolymer comprising ethyl acrylate, methyl methacrylate, and acrylic acid.
- the present invention is concerned with diffusion transfer processes and, more particularly, with photosensitive elements for use in said diffusion transfer processes.
- US. Patent No, 2,983,606 discloses and claims processes wherein dye developers (i.e., dyes which contain in the same molecule a silver halide developing function and a chromophoric system of a dye) are used to form color transfer images.
- dye developers i.e., dyes which contain in the same molecule a silver halide developing function and a chromophoric system of a dye
- a photosensitive element is exposed to create therein a latent image.
- the latent image is developed in the presence of the dye developer and an imagewise distribution of unreacted dye developer is formed in unexposed areas. At least a portion of said unreacted dye developer is transferred to a superposed image-receiving layer to provide the transfer image thereon.
- Multicolor transfer images may be produced by such processes by using photosensitive elements such as those claimed and disclosed in the copending U.S. appllcation of Edwin H. Land and Howard G. Rogers, Ser. No. 565,135, filed Feb. 13, 1956, now US. Patent No. 3,345,163 wherein at least two selectively sensitized photosensitive strata are superposed on a single support and are processed with a single processing solution and transferred to a common image-receiving layer.
- a suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a greensensitive silver halid emulsion stratum, and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer, and a yellow dye developer.
- the dye developers are disposed, prior to exposure, in a separate alkali-permeable layer behind the silver halide emulsion With which it is associated, i.e., on the side of the emulsion which is most distant from the photographed subject when the emulsion is exposed, and preferably also adapted to be most distant from the image-receiving layer when in superposed relation therewith.
- the dye developer is first dissolved in a water immiscible solvent such as diethyl lauramide and then dispersed in the alkali-permeable polymer.
- a multicolor negative comprising (1) a support which is coated in turn on one side with (2) a gelatin layer having dispersed therein a cyan dye developer which is dissolved in water immiscible solvent, (3) a red-sensitive silver halide emulsion layer, (4) a gelatin or synthetic polymer interlayer, (5) a gelatin layer having dispersed therein a magenta dye developer which is dissolved in a water immiscible solvent, (6) a green-sensitive silver halide emulsion, (7) a gelatm or 3,460,945 Patented Aug. 12, 1969 "ice synthetic polymer interlayer (8) a gelatin layer having dispersed therein a yellow dye developer which is dissolved in a water immiscible solvent, and (9) a bluesensitive silver halide emulsion.
- polyester film support such as Mylar (trade name of E. I. du Pont de Nemours & Company, Wilmington, Del., for an ethyleneglycolterephthalic acid polyester).
- Mylar trade name of E. I. du Pont de Nemours & Company, Wilmington, Del.
- ethyleneglycolterephthalic acid polyester ethyleneglycolterephthalic acid polyester.
- the use of such polyesters is accomplished, however, by disadvantages, e.g., it is generally only available commercially as a clear film and it is necessary to apply an opaque layer over it, when for example, it is intended to be used in film packs, such as disclosed in US. Patent No. 3,002,437 wherein development takes place outside the camera.
- Another disadvantage is that its adhesion to gelatin leaves much to be desired and usually it has to be surface treated, e.g., with a chromic acid-sulfuric acid solution.
- the adhesive problem is especially acute when the gelatin layer comprising the dye developer is immediately adjacent the film support.
- the dye developer which is generally present in substantial amounts (usually at least 1:1 by weight to the gelatin) and is often dissolved in a water immiscible solvent, has an adverse effect on adhesion and it is usually necessary to further sub-coat the film support.
- these disadvantages necessitate the use of special surface treatments and additional coating operations.
- results in the present invention are especially unexpected when the opacifier is present in the opaque layer in at least a 1:1 ratio by weight to the terpolymer and the amount of dye developer in the adjacent gelatin layer is also at least 1:1 by weight to the gelatin. Under such adverse conditions the fact that any adhesion at all is obtained, yet alone good adhesion, is quite surprising.
- One object of the present invention is to provide novel photosensitive elements for dye developer dilfusion transfer processes.
- Another object of the present invention is to provide novel photosensitive element for dye developer diffusion transfer processes having a layer of a terpolymer of ethyl acrylate, methyl methacrylate and acrylic acid adjacent a polyester film support, which layer serves both as a binder for an opacifier and as a subbing layer for the film support.
- the invention accordingly comprises the product possessing the features, properties and the relation of components which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
- the terpolymers which are used in the combined opacifying and subbing layers of the present invention comprise about 55 to 75% by weight of ethyl acrylate, about to 40% by weight of methyl methacrylate and 2 to 6% by weight of acrylic acid.
- Terpolymers comprising about 60% ethyl acrylate, about 36% methyl methacrylate and about 4% acrylic acid have been found particularly useful.
- the terpolymer layer also comprises a polymer selected from the group consisting of gelatin and polyvinyl alcohol.
- a polymer selected from the group consisting of gelatin and polyvinyl alcohol Such an embodiment has been found particularly useful when the dye developers in the adjoining gelatin layer are dissolved in a water immiscible solvent and are dispersed in this state in the gelatin layer.
- the addition of the polyvinyl alcohol and gelatin polymers has been found particularly effective in increasing the solvent resistance of the terpolymer layer and preventing the dye developers from migrating thereinto.
- the amount of gelatin or polyvinyl alcohol may be varied, particularly good results were obtained when they were present in amounts of about 15 to 30% by weight of the terpolymer. Especially good results were obtained when about of said polymers were employed.
- the terpolymers for use in the present invention may be prepared by well-known polymerization techniques, e.g., bulk, solvent, etc.
- the polymers are prepared by emulsion polymerization, e.g., dispersing the monomers, at room temperature, with vigorous stirring in an aqueous solution comprising an emulsifying or dispersing agent such as sodium lauryl sulfate and adding a redox catalyst.
- an emulsifying or dispersing agent such as sodium lauryl sulfate
- a redox catalyst emulsion polymerization
- the resulting emulsion may be compounded directly with the opacifier and used in this form in the coating operation.
- the opacifiers for use in the photographic elements of the present invention may be selected from the various pigments available, e.g., titanium dioxide, carbon black, etc., which have the required covering power and are inert to the photographic agents. Especially useful results have been obtained with carbon blacks. In using such carbon blacks it has been found advantageous to pro-disperse them in aqueous solutions before compounding them with the terpolymer emulsion.
- the amount of pigment used will vary depending on the covering power of the particular pigment employed. Usually about 300 to 1200 mgms. of the pigment per square foot and more particularly about 600 mgms. will provide adequate covering power.
- the ratio of pigment, e.g., carbon black, to terpolymer will be at least 1 to 1 by weight, and more particularly about 2 to 1.
- the photosensitive elements of the present invention are particularly useful in film packs, such as disclosed in the above-mentioned US. Patent No. 3,002,437, where development takes place outside the camera.
- film packs include a plurality of film units, each comprising a photosensitive sheet, a second sheet adapted to be superposed with the photosensitive sheet following exposure thereof for receiving the image, a container of a fluid processing composition adapted to be distributed between the superposed photosensitive and second sheets to effect the processing thereof, and leader means for moving the photosensitive and second sheets into superposition and in engagement with means for distributing the processing fluid.
- EXAMPLE A Carbon black-terpolymer dispersion An emulsion of a terpolymer comprising about by weight ethyl acrylate, 36% by weight methyl methacrylate and about 4% by weight of acrylic acid was added to a diluted 25 by weight carbon black dispersion (Aquablack M, sold by Columbia Carbon Co.), comprising 1% by weight (based on the carbon black) of Alkanol B (trademark of E. I. du Pont de Nemours &
- Cyan dye developer-gelatin dispersion 1 part by weight of 1,4-bis-[a-methyl-B-hydroquinonylethylamino]-5,S-dihydroxyahthraquinone (a cyan dye developer) was dissolved in 2 parts of diethyl lauramide and was dispersed by means of a colloidal mill in a solution comprising 0.9 part gelatin, 5.1 parts water and 0.5 part Alkanol B.
- a magenta dye developer e.g., 2- [p-(2',5 dihydroxyphenethyl-phenylazo]-4-isopropoxyl-naphthol.
- a gelatin layer having dispersed therein in a waterimmiscible solvent a yellow dye developer e.g., l-phenyl- 3 N n hexylcarbamyl 4 [p-(2',5-dihydroxyphenethyl)-phenylazo]-5-pyrazolone.
- the carbon black-terpolymer layer was substantially impermeable to the alkali, had no apparent photographic activity and provided good protection from light. No signs of delamination between the Mylar, terpolymer, and cyan dye developer layers were observed.
- EXAMPLE 2 A photosensitive element was prepared in a manner similar to Example 1 except that the terpolymer layer also comprised 25 by weight (based on the terpolymer) of gelatin.
- EXAMPLE 3 A photosensitive element was prepared in a manner similar to Example 1 except that the terpolymer layer also comprised 25% by weight (based on the terpolymer) of polyvinyl alcohol.
- the photosensitive elements prepared in Examples 2 and 3 were tested in a manner similar to the photosensitive elements of Example 1, they provided equally good results. In addition, they provided enhanced resistance to the solvent and substantially reduced dye developer migration.
- the carbon black-terpolymer layer was produced in a single coating step. For added insurance against light-leaks, said layer may be applied in several coating steps, e.g., two coatings comprising 300 mgs. of carbon per square foot.
- a photosensitive element comprising a polyester film support bearing on one side (a) an immediate adjoining terpolymer layer comprising an opacifier, said terpolymer comprising by Weight about 55 to 75% ethyl acrylate, about 20 to 40% of methyl methacrylate and about 2 to 6% acrylic acid; (b) a gelatin layer comprising a dye developer adjoining said terpolymer layer and (c) a silver halide emulsion layer.
- a photosensitive element comprising a polyester film support bearing on one side (a) an immediately adjoining terpolymer layer comprising carbon black pigment, said terpolymer comprising by weight about 55 to 75 of ethyl acrylate, 20 to 40% of methyl methacrylate and 2 to 6% acrylic acid, the ratio of carbon black to terpolymer in said layer being at least 1 to 1 by weight; (b) a gelatin layer comprising a dye developer adjoining said terpolymer layer, the ratio of dye developer to gelatin in said gelatin layer being at least 1 to 1 by weight; and (c) a silver halide emulsion layer.
- a photosensitive element as defined in claim 5 wherein said terpolymer comprises by weight about 60% ethyl acrylate, about 36% methyl methacrylate and about 4% acrylic acid.
- a photosensitive element comprising a polyester film support bearing on one side (a) an immediately adjoining terpolymer layer comprising an opacifier and a polymer selected from the group consisting of gelatin and polyvinyl alcohol, said terpolymer comprising by weight 6 about to ethyl acrylate, about 20 to 40% of methyl methacrylate and about 2 to 6% acrylic acid; (b) a gelatin layer comprising a dye developer adjoining said terpolymer layer; and (c) a silver halide emulsion layer.
Description
United States Patent 3,460,945 ETHYL ACRYLATE, METHYL METHACRYLA'I'E AND ACRYLIC ACID TERPOLYMER ADHESIVE FOR POLYESTER FILM SUPPORTS AND GELA- TIN LAYERS Henry S. Kolesinski, Burlington, and Peter H. Roth, Needham, Mass, assignors to Polaroid Corporation, Cambridge, Mass, a corporation of Delaware No Drawing. Filed Sept. 20, 1965, Ser. No. 488,777 Int. Cl. G03c 1/80, /54 US. Cl. 9687 13 Claims ABSTRACT OF THE DISCLOSURE The adhesion of a felatinous layer to a polyester film support may be facilitated by coating said support prior to application of said gelatinous layer with a terpolymer comprising ethyl acrylate, methyl methacrylate, and acrylic acid.
The present invention is concerned with diffusion transfer processes and, more particularly, with photosensitive elements for use in said diffusion transfer processes.
US. Patent No, 2,983,606 discloses and claims processes wherein dye developers (i.e., dyes which contain in the same molecule a silver halide developing function and a chromophoric system of a dye) are used to form color transfer images. In such processes a photosensitive element is exposed to create therein a latent image. The latent image is developed in the presence of the dye developer and an imagewise distribution of unreacted dye developer is formed in unexposed areas. At least a portion of said unreacted dye developer is transferred to a superposed image-receiving layer to provide the transfer image thereon.
Multicolor transfer images may be produced by such processes by using photosensitive elements such as those claimed and disclosed in the copending U.S. appllcation of Edwin H. Land and Howard G. Rogers, Ser. No. 565,135, filed Feb. 13, 1956, now US. Patent No. 3,345,163 wherein at least two selectively sensitized photosensitive strata are superposed on a single support and are processed with a single processing solution and transferred to a common image-receiving layer. A suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a greensensitive silver halid emulsion stratum, and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer, and a yellow dye developer.
In a preferred mode of carrying out both the monochromatic and multicolor processes, the dye developers are disposed, prior to exposure, in a separate alkali-permeable layer behind the silver halide emulsion With which it is associated, i.e., on the side of the emulsion which is most distant from the photographed subject when the emulsion is exposed, and preferably also adapted to be most distant from the image-receiving layer when in superposed relation therewith. In especially useful embod ments the dye developer is first dissolved in a water immiscible solvent such as diethyl lauramide and then dispersed in the alkali-permeable polymer. Illustrative of such photosensitive elements is a multicolor negative comprising (1) a support which is coated in turn on one side with (2) a gelatin layer having dispersed therein a cyan dye developer which is dissolved in water immiscible solvent, (3) a red-sensitive silver halide emulsion layer, (4) a gelatin or synthetic polymer interlayer, (5) a gelatin layer having dispersed therein a magenta dye developer which is dissolved in a water immiscible solvent, (6) a green-sensitive silver halide emulsion, (7) a gelatm or 3,460,945 Patented Aug. 12, 1969 "ice synthetic polymer interlayer (8) a gelatin layer having dispersed therein a yellow dye developer which is dissolved in a water immiscible solvent, and (9) a bluesensitive silver halide emulsion.
In the past, materials such as cellulose acetate have been employed as the film support. Although said cellulose acetate provides satisfactory results, it is desirable, in certain instances, to use a polyester film support such as Mylar (trade name of E. I. du Pont de Nemours & Company, Wilmington, Del., for an ethyleneglycolterephthalic acid polyester). The use of such polyesters is accomplished, however, by disadvantages, e.g., it is generally only available commercially as a clear film and it is necessary to apply an opaque layer over it, when for example, it is intended to be used in film packs, such as disclosed in US. Patent No. 3,002,437 wherein development takes place outside the camera. Another disadvantage is that its adhesion to gelatin leaves much to be desired and usually it has to be surface treated, e.g., with a chromic acid-sulfuric acid solution. The adhesive problem is especially acute when the gelatin layer comprising the dye developer is immediately adjacent the film support. In such embodiments the dye developer, which is generally present in substantial amounts (usually at least 1:1 by weight to the gelatin) and is often dissolved in a water immiscible solvent, has an adverse effect on adhesion and it is usually necessary to further sub-coat the film support. As can be seen, these disadvantages necessitate the use of special surface treatments and additional coating operations.
It has been found in the present invention that if a terpolyrner of ethyl acrylate, methyl methalcrylate and acrylic acid is employed as the polymeric binder for the opacifier that the resulting opaque layer will be firmly adhered to the Mylar and possess excellent subbing properties for the adjacent dye developer-gelatin layer. As can be seen, the use of such terpolymers eliminates the need for the surface treatment and sub-coating steps. Moreover, the use of the opaque layer on the same side of the support as the photosensitive element, further reduces the possibility of leaks due to light piping.
The results in the present invention are especially unexpected when the opacifier is present in the opaque layer in at least a 1:1 ratio by weight to the terpolymer and the amount of dye developer in the adjacent gelatin layer is also at least 1:1 by weight to the gelatin. Under such adverse conditions the fact that any adhesion at all is obtained, yet alone good adhesion, is quite surprising.
One object of the present invention is to provide novel photosensitive elements for dye developer dilfusion transfer processes.
Another object of the present invention is to provide novel photosensitive element for dye developer diffusion transfer processes having a layer of a terpolymer of ethyl acrylate, methyl methacrylate and acrylic acid adjacent a polyester film support, which layer serves both as a binder for an opacifier and as a subbing layer for the film support. I
Other objects of the invention will in part be obvious and will in part appear hereinafter.
The invention accordingly comprises the product possessing the features, properties and the relation of components which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
For a fuller understanding of the nature and objects of the invention, reference should be had to the following detailed description.
Generally the terpolymers which are used in the combined opacifying and subbing layers of the present invention comprise about 55 to 75% by weight of ethyl acrylate, about to 40% by weight of methyl methacrylate and 2 to 6% by weight of acrylic acid. Terpolymers comprising about 60% ethyl acrylate, about 36% methyl methacrylate and about 4% acrylic acid have been found particularly useful.
In an especially useful embodiment of the present invention the terpolymer layer also comprises a polymer selected from the group consisting of gelatin and polyvinyl alcohol. Such an embodiment has been found particularly useful when the dye developers in the adjoining gelatin layer are dissolved in a water immiscible solvent and are dispersed in this state in the gelatin layer. The addition of the polyvinyl alcohol and gelatin polymers has been found particularly effective in increasing the solvent resistance of the terpolymer layer and preventing the dye developers from migrating thereinto. Although the amount of gelatin or polyvinyl alcohol may be varied, particularly good results were obtained when they were present in amounts of about 15 to 30% by weight of the terpolymer. Especially good results were obtained when about of said polymers were employed.
The terpolymers for use in the present invention may be prepared by well-known polymerization techniques, e.g., bulk, solvent, etc. In especially useful embodiments, the polymers are prepared by emulsion polymerization, e.g., dispersing the monomers, at room temperature, with vigorous stirring in an aqueous solution comprising an emulsifying or dispersing agent such as sodium lauryl sulfate and adding a redox catalyst. The resulting emulsion may be compounded directly with the opacifier and used in this form in the coating operation.
Generally, the opacifiers for use in the photographic elements of the present invention may be selected from the various pigments available, e.g., titanium dioxide, carbon black, etc., which have the required covering power and are inert to the photographic agents. Especially useful results have been obtained with carbon blacks. In using such carbon blacks it has been found advantageous to pro-disperse them in aqueous solutions before compounding them with the terpolymer emulsion. Generally, the amount of pigment used will vary depending on the covering power of the particular pigment employed. Usually about 300 to 1200 mgms. of the pigment per square foot and more particularly about 600 mgms. will provide adequate covering power. Generally the ratio of pigment, e.g., carbon black, to terpolymer will be at least 1 to 1 by weight, and more particularly about 2 to 1.
The photosensitive elements of the present invention are particularly useful in film packs, such as disclosed in the above-mentioned US. Patent No. 3,002,437, where development takes place outside the camera. Generally, such film packs include a plurality of film units, each comprising a photosensitive sheet, a second sheet adapted to be superposed with the photosensitive sheet following exposure thereof for receiving the image, a container of a fluid processing composition adapted to be distributed between the superposed photosensitive and second sheets to effect the processing thereof, and leader means for moving the photosensitive and second sheets into superposition and in engagement with means for distributing the processing fluid.
The following nonlimiting examples illustrate the preparation of coating solutions for use in preparing the photosensitive elements of the present invention:
EXAMPLE A Carbon black-terpolymer dispersion An emulsion of a terpolymer comprising about by weight ethyl acrylate, 36% by weight methyl methacrylate and about 4% by weight of acrylic acid was added to a diluted 25 by weight carbon black dispersion (Aquablack M, sold by Columbia Carbon Co.), comprising 1% by weight (based on the carbon black) of Alkanol B (trademark of E. I. du Pont de Nemours &
Company for an alkylnaphthalene sodium sulfonate wetting agent) until the ratio of carbon black to terpolymer was about 2 to 1 by weight. The resulting dispersion, which contained about 15% by weight of carbon black and had a surface tension of 38 dynes/cm., was filtered through 3 sheets of 325 mesh stainless steel screen.
EXAMPLE B Cyan dye developer-gelatin dispersion 1 part by weight of 1,4-bis-[a-methyl-B-hydroquinonylethylamino]-5,S-dihydroxyahthraquinone (a cyan dye developer) was dissolved in 2 parts of diethyl lauramide and was dispersed by means of a colloidal mill in a solution comprising 0.9 part gelatin, 5.1 parts water and 0.5 part Alkanol B.
The following nonlimiting example illustrates the preparation of a photosensitive element within the scope of the present invention.
EXAMPLE 1 An unsubbed sheet of Mylar was successively coated with:
(l) A carbon black-terpolymer layer comprising about 600 mgs. of carbon per square foot (dispersion of Example A).
(2) A cyan dye developer-gelatin layer (dispersion of Example B).
(3) A red-sensitive silver iodobromide emulsion layer.
(4) A gelatin interlayer.
(5) A gelatin layer having dispersed therein in a waterimmiscible solvent a magenta dye developer, e.g., 2- [p-(2',5 dihydroxyphenethyl-phenylazo]-4-isopropoxyl-naphthol.
(6) A green-sensitive silver iodobromide emulsion layer.
(7) A gelatin interlayer.
(8) A gelatin layer having dispersed therein in a waterimmiscible solvent a yellow dye developer, e.g., l-phenyl- 3 N n hexylcarbamyl 4 [p-(2',5-dihydroxyphenethyl)-phenylazo]-5-pyrazolone.
(9) A blue-sensitive silver iodobromide emulsion layer.
When the above photosensitive element was incorporated in a film pack, such as disclosed in the abovementioned US. Patent No. 3,002,437, and processed outside the camera, the carbon black-terpolymer layer was substantially impermeable to the alkali, had no apparent photographic activity and provided good protection from light. No signs of delamination between the Mylar, terpolymer, and cyan dye developer layers were observed.
EXAMPLE 2 A photosensitive element was prepared in a manner similar to Example 1 except that the terpolymer layer also comprised 25 by weight (based on the terpolymer) of gelatin.
EXAMPLE 3 A photosensitive element was prepared in a manner similar to Example 1 except that the terpolymer layer also comprised 25% by weight (based on the terpolymer) of polyvinyl alcohol.
When the photosensitive elements prepared in Examples 2 and 3 were tested in a manner similar to the photosensitive elements of Example 1, they provided equally good results. In addition, they provided enhanced resistance to the solvent and substantially reduced dye developer migration. In the above examples the carbon black-terpolymer layer was produced in a single coating step. For added insurance against light-leaks, said layer may be applied in several coating steps, e.g., two coatings comprising 300 mgs. of carbon per square foot.
Since certain changes may be made in the above product without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.
What is claimed is:
1. A photosensitive element comprising a polyester film support bearing on one side (a) an immediate adjoining terpolymer layer comprising an opacifier, said terpolymer comprising by Weight about 55 to 75% ethyl acrylate, about 20 to 40% of methyl methacrylate and about 2 to 6% acrylic acid; (b) a gelatin layer comprising a dye developer adjoining said terpolymer layer and (c) a silver halide emulsion layer.
2. A photosensitive element as defined in claim 1 wherein the ratio of opacifier to terpolymer in said terpolymer layer is at least 1 to 1 by weight.
3. A photosensitive element as defined in claim 1 wherein the ratio of dye developer to gelatin in said gelatin layer is at least 1 to 1 by weight.
4. A photosensitive element as defined in claim 2 wherein the ratio of dye developer to gelatin in said gelatin layer is at least 1 to 1 by weight.
5. A photosensitive element comprising a polyester film support bearing on one side (a) an immediately adjoining terpolymer layer comprising carbon black pigment, said terpolymer comprising by weight about 55 to 75 of ethyl acrylate, 20 to 40% of methyl methacrylate and 2 to 6% acrylic acid, the ratio of carbon black to terpolymer in said layer being at least 1 to 1 by weight; (b) a gelatin layer comprising a dye developer adjoining said terpolymer layer, the ratio of dye developer to gelatin in said gelatin layer being at least 1 to 1 by weight; and (c) a silver halide emulsion layer.
6. A photosensitive element as defined in claim 5 wherein said terpolymer comprises by weight about 60% ethyl acrylate, about 36% methyl methacrylate and about 4% acrylic acid.
7. A photosensitive element comprising a polyester film support bearing on one side (a) an immediately adjoining terpolymer layer comprising an opacifier and a polymer selected from the group consisting of gelatin and polyvinyl alcohol, said terpolymer comprising by weight 6 about to ethyl acrylate, about 20 to 40% of methyl methacrylate and about 2 to 6% acrylic acid; (b) a gelatin layer comprising a dye developer adjoining said terpolymer layer; and (c) a silver halide emulsion layer.
8. A photosensitive element as defined in claim 7 wherein said dye developer is dispersed in said gelatin layer as a solution of said dye developer in a water immiscible solvent.
9. A photosensitive element as defined in claim 7 wherein the ratio of opacifier to terpolymer in said terpolymer layer is at least 1 to 1 by Weight and the ratio of dye developer to gelatin in said gelatin layer is at least 1 to 1 by weight.
10. A photosensitive element as defined in claim 8 wherein the ratio of opacifier to terpolymer in said terpolymer layer is at least 1 to 1 by weight and the ratio of dye developer to gelatin in said gelatin layer is at least 1 to 1 by weight.
11. A photosensitive element as defined in claim 19 wherein said gelatin and polyvinyl alcohol are present in said terpolymer in amounts ranging between about 15 to 30% by weight of said terpolymer.
12. A photosensitive element as defined in claim 8 wherein said opacifier is carbon black.
13. A photosensitive element as defined in claim 1b wherein said opacifier is carbon black.
References Cited UNITED STATES PATENTS 2/1959 Smith et a1. 96-87 5/1966 Lynch 117161 XR US. Cl. X.R.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US48877765A | 1965-09-20 | 1965-09-20 |
Publications (1)
Publication Number | Publication Date |
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US3460945A true US3460945A (en) | 1969-08-12 |
Family
ID=23941086
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US488777A Expired - Lifetime US3460945A (en) | 1965-09-20 | 1965-09-20 | Ethyl acrylate,methyl methacrylate and acrylic acid terpolymer adhesive for polyester film supports and gelatin layers |
Country Status (1)
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US (1) | US3460945A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3630741A (en) * | 1968-12-31 | 1971-12-28 | Eastman Kodak Co | Adhesive gelatin-terpolymer materials having at least one conjugated vinylene dicarbonyl compound added to the emulsion polymerization reaction mixture |
US3753765A (en) * | 1971-09-20 | 1973-08-21 | Du Pont | Conductive carbon antistatic backing for photographic film |
US4124395A (en) * | 1973-08-10 | 1978-11-07 | Fuji Photo Film Co., Ltd. | Subbing layer on polyester film for light-sensitive material |
US4187113A (en) * | 1975-11-05 | 1980-02-05 | Imperial Chemical Industries Limited | Voided films of polyester with polyolefin particles |
US4329423A (en) * | 1977-10-03 | 1982-05-11 | Imperial Chemical Industries Limited | Photographic coated film bases |
US4374126A (en) * | 1981-02-23 | 1983-02-15 | Warner-Lambert Company | Film forming antimicrobial material |
US4495273A (en) * | 1980-09-17 | 1985-01-22 | Minnesota Mining And Manufacturing Company | Color photographic elements with improved mechanical properties |
US4883828A (en) * | 1987-05-12 | 1989-11-28 | Ecolab Inc. | Disinfectant polymeric coatings for hard surfaces |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2875056A (en) * | 1958-02-14 | 1959-02-24 | Eastman Kodak Co | Polystyrene photographic element having a resinous terpolymer chromic chloride undercoat |
US3249457A (en) * | 1962-09-28 | 1966-05-03 | Interchem Corp | Flocked article and method of manufacture |
-
1965
- 1965-09-20 US US488777A patent/US3460945A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2875056A (en) * | 1958-02-14 | 1959-02-24 | Eastman Kodak Co | Polystyrene photographic element having a resinous terpolymer chromic chloride undercoat |
US3249457A (en) * | 1962-09-28 | 1966-05-03 | Interchem Corp | Flocked article and method of manufacture |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3630741A (en) * | 1968-12-31 | 1971-12-28 | Eastman Kodak Co | Adhesive gelatin-terpolymer materials having at least one conjugated vinylene dicarbonyl compound added to the emulsion polymerization reaction mixture |
US3753765A (en) * | 1971-09-20 | 1973-08-21 | Du Pont | Conductive carbon antistatic backing for photographic film |
US4124395A (en) * | 1973-08-10 | 1978-11-07 | Fuji Photo Film Co., Ltd. | Subbing layer on polyester film for light-sensitive material |
US4187113A (en) * | 1975-11-05 | 1980-02-05 | Imperial Chemical Industries Limited | Voided films of polyester with polyolefin particles |
US4329423A (en) * | 1977-10-03 | 1982-05-11 | Imperial Chemical Industries Limited | Photographic coated film bases |
US4495273A (en) * | 1980-09-17 | 1985-01-22 | Minnesota Mining And Manufacturing Company | Color photographic elements with improved mechanical properties |
US4374126A (en) * | 1981-02-23 | 1983-02-15 | Warner-Lambert Company | Film forming antimicrobial material |
US4883828A (en) * | 1987-05-12 | 1989-11-28 | Ecolab Inc. | Disinfectant polymeric coatings for hard surfaces |
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