US3666470A - Photographic printing element containing fluorescent dye - Google Patents

Photographic printing element containing fluorescent dye Download PDF

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Publication number
US3666470A
US3666470A US838812A US3666470DA US3666470A US 3666470 A US3666470 A US 3666470A US 838812 A US838812 A US 838812A US 3666470D A US3666470D A US 3666470DA US 3666470 A US3666470 A US 3666470A
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US
United States
Prior art keywords
photographic
water
printing element
vinyl
layer
Prior art date
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Expired - Lifetime
Application number
US838812A
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English (en)
Inventor
Nobuo Tsuji
Takushi Miyazako
Fumihiko Nishio
Tatsuya Tajima
Yoshinori Tsuchiya
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • 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
    • G03C1/81—Photosensitive materials characterised by the base or auxiliary layers characterised by anticoiling means
    • 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
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G03C1/8155—Organic compounds therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/134—Brightener containing

Definitions

  • the present invention relates to a photographic printing element and in particular to a photographic printing element having improved whiteness in the absence of a matt surface.
  • the conventional method of incorporating a fluorescent whitening dye has the drawback that, since the fluorescent whitening dye is not absorbed on the colloidal component of photographic layers, such as gelatin, although the fluorescent dye has a direct dyeing afiinity to fibers, the intensity of fluorescence emitted from the fluorescent whitening agent incorporated in photographic layers is weaker than the case where the same fluorescent dye is absorbed on fibers, and suflicient whitening effect is not obtained. Furthermore, the greater part of the fluorescent whitening dye present in the photographic layer is removed in the water-washing stage after development, which severely weakens the whitening effect.
  • the aforesaid method of incorporating water-soluble poly-N-vinyl-S-methyl-Z-oxazolidine or water-soluble polyvinyl pyrrolidone in the photographic layer has the drawback that, although the whitening effect is higher as the degree of polymerization of the polymer to be employed is higher, when a polymer having a high degree of polymerization is employed, the surface of the photographic printing element is matted.
  • an object of the present invention is to pro* vide a photographic printing element having improved whiteness by employing a water-soluble fluorescent whitening dye without the accompaniment of the aforesaid drawbacks.
  • Another object of the present invention is to provide a water-soluble high molecular weight compound to be employed together with a fluorescent'whitening dye for improving the whiteness of a photographic printing element by being incorporated in a photographic layer of the element without being accompanied by the aforesaid drawbacks.
  • a photographic printing element such as, a baryta layer, an undercoating, a light-sensitive emulsion layer, a protective layer, or a diffusion transfer imagereceiving layer applied on a support.
  • the water-soluble fluorescent whitening dye (or fluorescent brightening agent) to be employed in the present invention is one which emits a blue-purple fluorescence (of wavelengths of 43 0-470 mu.) by absorbing ultraviolet rays.
  • fluorescent whitening dyes which may be employed in the present invention, there may be mentioned those known water-soluble fluorescent dyes having a direct dyeing aflinity, such as diaminostilbene dyes, benzidine dyes, triazole dyes, imidazole dyes, and imidazolone dyes. Specific examples of such fluorescent whitening'dyes are as follows:
  • Diaminostilbene fluorescent dyes (a) Compounds of the formula QCEECH-QNHQIE] wherein X, Y, X, and Y each represents -NHC H --NHC H SO Na, 0H, NH NHCH CH SO Na, --OCH CH OH, or -OC,H and n. represents 5 to 100.
  • A represents an alkylene group having 4-5 carbonatoms Compounds of the formula or an alkylene group having a hetero atom or hetero N N atomic group; Y represents an alkylene group having 2-10 carbon atoms, a substituted alkylene group, an alkylene C @343; group having 6-18 carbon atoms, or a substituted alkylene group; Z represents adivalent hetero armor.
  • R represents a halogen vinylpyn'olidone, N m l l idi i i g ql atom, CR, SR, I tam, N-vinyl-5-methyl-2-oxazolidinone, vinyl acetate,
  • N-vinyla mide:compoundrepresented by 35 the above general formula may be easily prepared by IQ? acting the corresponding N-alkylacyl compound represented by the general formula R CONHR and acetylene in an autoclave in the presence of an alkali catalyst.
  • N-vinylamide compound there may be mentioned N-vinyl-N-methylformamide (boiling point 73 C. at a pressure of 50 mm. Hg), N-vinyl-N- methyl acetamide (boiling point 63 C./ 17 mm. Hg), N- vinyl-N-methylpropionamide (boiling point 75 C./ 17 mm. Hg), N-vinyl-N-ethylformamide (boiling point 81 C./50 mm. Hg), and the like.
  • the desired polymer may be obtained by dissolving the above N-vinylamide compound in a solvent such as water, an alcohol, benzene, ligroin or the like and conducting the polymerization in a nitrogen gas stream at a temperature of about 40-100 C. in the presence of a catalyst such as hydrogen peroxide, potassium persulfate, 2,2-azobisbutyronitrile, or the like.
  • a solvent such as water, an alcohol, benzene, ligroin or the like
  • a catalyst such as hydrogen peroxide, potassium persulfate, 2,2-azobisbutyronitrile, or the like.
  • the proportion of the aforesaid comonomer be less than 20 mole percent of the total amount of copolymer.
  • the molecular weight is preferably in the range of about 50,000500,000 (intrinsic viscosity 0.2-1.5 in an aqueous solution at 30 C.). Particularly useful are polymers having a molecular weight of about 100,000400,000 (intrinsic viscosity 0.5-1.2 in an aqueous solution at 30 C.). However, polymers possessing molecular weights above and below these ranges may be employed.
  • the aforesaid conventional N-vinylpyrrolidone polymer When using the aforesaid conventional N-vinylpyrrolidone polymer, if the molecular weight thereof is higher than 100,000, and particularly if it approaches about 360,000, the miscibility of the polymer with gelatin is degraded, whereby the surface of the photographic printing paper tends to be severely matted.
  • the aforesaid N-vinylamide polymer of this invention having a molecular weight of higher than 100,000 shows a good miscibility with gelatin and moreover even if the molecular weight thereof is over 300,000, very little lack of miscibility occurs, provided the amount of the polymer employed is not excessive, that is, not more than about 60% by weight.
  • the amount of of the N-vinylamide polymer or copolymer of the present invention provided sufficient polymer is present to obtain the desired whitening effect.
  • at least by weight of the polymer based upon the total weight of polymer and gelatin binder is desirable to obtain significant whitening eifect.
  • the preferred amount of polymer employed is about 5-40% by weight. Most preferably, the amount employed is about 15-25% by weight.
  • the photographic layers of the photographic printing element of this invention include any of a silver halide emulsion layer, a baryta layer, an undercoating, a protective layer applied to a support such as paper, synthetic resin film, a glass plate or a metal plate and an image receiving layer for a diffusion transfer printing element applied to the support.
  • the fluorescent whitening dye and the water-soluble high molecular weight compound may be incorporated in any one of the above photographic layers to provide the desired effect. Further, the water-soluble high molecular weight material may be incorporated in a different photographic layer than the layer containing the fluorescent whitening dye.
  • the invention has been exemplified above in terms of using gelatin as the binder.
  • binders such as synthetic resins may be similarly employed in the present invention.
  • a photographic printing element providing the same or a superior effect than con ventional photographic elements containing an N-vinylpyrrolidone polymer or an N-vinyl-S-methyloxazolidione polymer is provided without resulting in the matting of the surface encountered in the conventional methods.
  • the resulting silver halide emulsion was applied to a photographic baryta paper of g./sq. meter to provide a photographic paper.
  • the photographic paper thus prepared was processed in a developer and a fixing solution having the following compositions respectively;
  • the sample was washed with running water of 15 C. for 1, 5, or 24 hours.
  • the intensity of fluorescence of the photographic papers of this invention was remarkably higher than the result of the control sample shown by curve (a) and among the photographic papers of this invention, the sample having the water-soluble high molecular Weight material having a higher molecular weight gave higher intensity of fluorescence. Moreover, even though the watersoluble high molecular weight compound having a higher molecular weight was employed, the surface properties of the photographic paper were not injured. Also, very little reduction in whiteness by water washing was observed.
  • the baryta coating composition was applied to a paper in a thickness of 100 g./ sq. meter.
  • a gelatino silver halide emulsion containing 50 g. of gelatin and 20 g. of silver chloride and having added thereto formaldehyde as a hardening agent and saponin as a wetting agent followed by drying.
  • the photographic paper thus prepared was processed as in Example I and the result was compared with a control paper wherein no -N-vinyl-N-methylformamide polymer was incorporated in the baryta layer.
  • the results showed that the whiteness of the surface of the photographic paper of this invention was much better than the control case. Moreover, the whitetness of the photographic paper of this invention was not reduced by water washing.
  • EXAMPLE HI After adding formaldehyde as a hardening agent and saponin as a wetting agent to a gelatino silver halide emulsion containing 20 g. of silver chlorobromide (60 mole percent silver bromide) per 50 g. of gelatin, the resulting silver halide emulsion was applied to a baryta coated paper of 150 g./sq. Before drying the silver halide emulsion layer, an aqueous solution containing 0.7 g. of Whitex BF (trade name of Sumitomo Chemical Industries Co.) as a fluorescent whitening dye, 8 g.
  • Whitex BF trade name of Sumitomo Chemical Industries Co.
  • N-vinyl-N-methylpropionamide polymer having an intrinsic viscosity of 0.98, 3 ml. of an aqueous 30% solution of formalin, 6 ml. of a 6% methanol solution of saponin, and one liter of water followed by drying to provide a protective layer.
  • the photographic paper thus prepared was processed and dried as in Example I and the results were compared with a control having no added N-vinyl-methylpropionamide polymer in the protective layer.
  • the results showed that the whiteness of the surface of the photographic paper of the present invention was much better than'in the control. Moreover, the whiteness was not reduced by water washing after processing.
  • the photographic paper thus prepared was processed and dried as in Example I and the results were compared with a control having no added N-vinyl-tN-methylform amide polymer.
  • the whiteness of the photographic paper of this invention was much better than the control and also was not reduced by water washing after processing.
  • the photographic paper thus prepared was processed and dried as in Example I and the results were compared with a control wherein the aforesaidc'opolymer was not incorporated in the emulsionflayenThe results showed that the whiteness of the surface of the photographic paper of this invention was much better than the "control case and was not reduced by water washing after processmg. p
  • EXAMPLE VII To one liter of a aqueous 5% gelatin solution containing colloidal nickel sulfite were aded 0.5 g. of .Tinopal G (trade name of Sandoz A. G.) as a fluorescent whitening dye and 1 2 g. of a copolymer hayinga mole ratio of N-vinyl-N-methylformamide "to methacrylamide of 9:1 and an intrinsic viscosity of 0:75 andthe' resulting solution was applied to a paper of g. /sq. meter. On the layer thus formed was applied a stripping layermainly consisting of sodium alginate, to' provide a diifusion transfer image receiving element.
  • a stripping layer mainly consisting of sodium alginate, to' provide a diifusion transfer image receiving element.
  • the image receiving element thus prepared was closely placed on a light-sensitive layer having a silver halide emulsion layer which had been exposed.
  • the assembly was passed through a diffusion transferring deviceand a developer and the image receiving element was stripped from the light-sensitive elemen't after- 30 seconds;
  • the results were compared with 'a control wherein the aforesaid copolymer was not employed.
  • the results showed that the whiteness of the white background. portions of the positive image was better than the control.
  • said water-soluble fluorescent whitening dye is selected from the group consisting of a diaminostilbene fluorescent dye, a benzidine fluorescent dye, a triazole fluorescent dye, an imidazole fluorescent dye and an imidazolone fluorescent dye.
  • the photographic printing element as claimed in claim 1 wherein said compound is selected from the group consisting of N-vinyl-N-methylformamide, N-vinyl-N- methylacetamide, N-vinyl N-methylpropionamide, and N vinyl-N-ethylformamide.
  • photographic printing element as claimed in claim 1 wherein said photographic layer is selected from the group consisting of a baryta layer, an undercoating layer, a light-sensitive silver halide emulsion layer and a protective layer.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US838812A 1968-07-04 1969-07-03 Photographic printing element containing fluorescent dye Expired - Lifetime US3666470A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP43046708A JPS4831842B1 (enrdf_load_stackoverflow) 1968-07-04 1968-07-04

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US3666470A true US3666470A (en) 1972-05-30

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US838812A Expired - Lifetime US3666470A (en) 1968-07-04 1969-07-03 Photographic printing element containing fluorescent dye
US00118990A Expired - Lifetime US3779766A (en) 1968-07-04 1971-02-25 Method for developing photographic elements

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Application Number Title Priority Date Filing Date
US00118990A Expired - Lifetime US3779766A (en) 1968-07-04 1971-02-25 Method for developing photographic elements

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US (2) US3666470A (enrdf_load_stackoverflow)
JP (1) JPS4831842B1 (enrdf_load_stackoverflow)
BE (1) BE735486A (enrdf_load_stackoverflow)
DE (1) DE1933844A1 (enrdf_load_stackoverflow)
FR (1) FR2012272A1 (enrdf_load_stackoverflow)
GB (1) GB1242020A (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873317A (en) * 1972-05-11 1975-03-25 Fuji Photo Film Co Ltd Image receiving materials with whitening agents for a silver salt diffusion transfer process and method of preparing the same
US4526853A (en) * 1982-10-15 1985-07-02 Konishiroku Photo Industry Co., Ltd. Method of providing an increased brightening effect and silver halide photographic material having increased brightening effect
US6329438B1 (en) 1994-10-06 2001-12-11 Medtronic Xomed, Inc. High density sponge and method and apparatus for rinsing a high density sponge
US20130216947A1 (en) * 2012-01-18 2013-08-22 Tatsuya Susuki Chemical coating composition for forming a laser-markable material and a laser-markable material
US9029441B2 (en) 2011-12-15 2015-05-12 Fujifilm Hunt Chemicals Us, Inc. Low toxicity solvent system for polyamideimide and polyamide amic acid resins and coating solutions thereof
US9725617B2 (en) 2014-04-17 2017-08-08 Fujifilm Hunt Chemicals U.S.A., Inc. Low toxicity solvent system for polyamideimide and polyamide amic acid resin coating
US9751986B2 (en) 2011-12-15 2017-09-05 Fujifilm Hunt Chemicals Us, Inc. Low toxicity solvent system for polyamideimide resins and solvent system manufacture
US9815941B2 (en) 2014-04-17 2017-11-14 Cymer-Dayton, Llc Low toxicity solvent system for polyamdieimide and polyamide amic acid resin manufacture

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115124A (en) * 1974-09-06 1978-09-19 Eastman Kodak Company Method of immobilizing optical brighteners
JPS5222666U (enrdf_load_stackoverflow) * 1975-08-05 1977-02-17
JPS5862652A (ja) * 1981-10-08 1983-04-14 Konishiroku Photo Ind Co Ltd 直接ポジカラ−画像の形成方法
JPS60170847A (ja) * 1984-02-16 1985-09-04 Fuji Photo Film Co Ltd 受像材料
JPH07117740B2 (ja) * 1987-12-11 1995-12-18 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
US20050025741A1 (en) 2003-05-15 2005-02-03 Lau Aldrich N.K. Poly and copoly(N-vinylamide)s and their use in capillary electrophoresis

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3628957A (en) * 1966-03-22 1971-12-21 Ferrania Spa Gelatino-silver halide emulsions containing water-soluble acrylamide copolymers

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873317A (en) * 1972-05-11 1975-03-25 Fuji Photo Film Co Ltd Image receiving materials with whitening agents for a silver salt diffusion transfer process and method of preparing the same
US4526853A (en) * 1982-10-15 1985-07-02 Konishiroku Photo Industry Co., Ltd. Method of providing an increased brightening effect and silver halide photographic material having increased brightening effect
US6329438B1 (en) 1994-10-06 2001-12-11 Medtronic Xomed, Inc. High density sponge and method and apparatus for rinsing a high density sponge
US9029441B2 (en) 2011-12-15 2015-05-12 Fujifilm Hunt Chemicals Us, Inc. Low toxicity solvent system for polyamideimide and polyamide amic acid resins and coating solutions thereof
US9751986B2 (en) 2011-12-15 2017-09-05 Fujifilm Hunt Chemicals Us, Inc. Low toxicity solvent system for polyamideimide resins and solvent system manufacture
US20130216947A1 (en) * 2012-01-18 2013-08-22 Tatsuya Susuki Chemical coating composition for forming a laser-markable material and a laser-markable material
US9725617B2 (en) 2014-04-17 2017-08-08 Fujifilm Hunt Chemicals U.S.A., Inc. Low toxicity solvent system for polyamideimide and polyamide amic acid resin coating
US9815941B2 (en) 2014-04-17 2017-11-14 Cymer-Dayton, Llc Low toxicity solvent system for polyamdieimide and polyamide amic acid resin manufacture

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Publication number Publication date
BE735486A (enrdf_load_stackoverflow) 1969-12-16
US3779766A (en) 1973-12-18
DE1933844A1 (de) 1970-05-27
GB1242020A (en) 1971-08-11
FR2012272A1 (enrdf_load_stackoverflow) 1970-03-20
JPS4831842B1 (enrdf_load_stackoverflow) 1973-10-02

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