US2049005A - Color-photographic bleach out dyestuff layers - Google Patents

Color-photographic bleach out dyestuff layers Download PDF

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Publication number
US2049005A
US2049005A US649442A US64944232A US2049005A US 2049005 A US2049005 A US 2049005A US 649442 A US649442 A US 649442A US 64944232 A US64944232 A US 64944232A US 2049005 A US2049005 A US 2049005A
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color
photographic bleach
layers
acid
blue
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US649442A
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Gaspar Bela
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Gaspar Bela
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/02Direct bleach-out processes; Materials therefor; Preparing or processing such materials

Description

Patented July 28, 1936 PATENT OFFICE COLOR-PHOTOGRAPH) BLEACH OUT DYESTUFF LAYERS Bla Gaspar, Brussels, Belgium No Drawing. Application December 29, 1932,

Serial No. 649,442. 1932 '7 Claims.

This invention relates to a method of producing color-photographic bleach-out dyestufi layers. Attempts to produce color photographic images by bleaching processes are very old, and

5 innumerable variations of this process have been proposed. Very appreciable results have been obtained in this direction, but notwithstanding it has not been possible to make the finished images correspondingly durable. In particular 10 there have been used for this purpose practically without exception basic dyestuffs. Reference is certainly contained in the literature to the effect that on occasion substantive or acid dyestuffs have also been investigated for the-pur- 15 pose in question, thus for example by Valenta in the Photographische Rundschau, 1911, page 56 etc.-, but the results obtained were not of a useful kind, because the bleaching action was too slow. Indications have also been furnished from other sources, but these related in themselves to dyestuffs extremely unfast in light.

The surprising fact has been discovered that the bleaching, i. e. the light-sensitiveness of acid dyestuffs, which in themselves are lasting in light, 25 may be very considerably increased if in addition to a desired sensitizer there is also introduced into the layer a suitable auxiliary body, which activates the sensitizer. As auxiliary body there are employed the acid salts of multi-base acids, organic or inorganic acids or acid or reducing substances, such as phenols. or aminophenols, and more particularly those which are suitable as photographic developers. An extremely high sensitiveness to light is obtained, if a durable double compound of hypo-sulfurous acid is employed, for example sodium formaldehyde sulfo oxalate or its double metal salts. These compounds may be employed either alone as sensitizers or also admixed with other sensitizers. As additional auxiliary bodies there are employed metal salts having a catalytical action, for example vanadium or titanium salts. Inorganic sulfur compounds, such as sulfides or sulfites may be incorporated'in the layer.

Example 1 In Germany January 4,

tion is apparent after approximately 10 minutes, which action continues up to complete bleaching.

Example 2 Tartrazine is mixed with thiosinamine and sul- 5 A. 100 grammes water 5 grammes thiosinamine 25 grammes 20% sodium bisulfate solution- The sensitizing effect, which in itself is of a powerful kind, may be further increased by the addition of 1 gramme monomethyl paramidophenol sulfate. Y

B. 200 grammes water 5 grammes rongalite 5 grammes thiocarbamide There are employed for 4 com. gelatine 4%, approximately com. 1% dyestuif solution and A; com. sensitizer to 1 qdm.

Example 3 For a three-color image there are employed I for example Tartrazine, Patent Blue A, Fast Red D in mixture with a colloid, for example gelatine, in conjunction with one of the sensitizers set forth above.

The process according to the invention reveals the particular advantage, that, as compared with the dyes hitherto in use, dyestuffs may be employed which are extremely fast in light, and after the fixing an additional bleaching of the dyestuff does not take place. The dyestuffs employed in accordance with the invention possess the advantage that the substantive dyestuffs remain adhering to the fibres of the paper, or single substantive dyestufl's and also the acid dyestuffs impregnate the gelatine in such fashion 5 that the same cannot be-washed out or only with extreme difficulty. The fixing of the bleached images is accordingly very simple. The images are washed subsequently in water, as a result of which the sensitizer is dissolved away and them dyestufi remains adhering to the backing or support or in the binding agent (for example in the gelatine), and cannot be washed out-or at least only with extreme dificulty. There may also be performed subsequently a short aftertreatment in copper sulfate or alum or in another mordant forming means for the purpose of increasing the fastness in light.

The dyestufis may be employed in mixture or also poured in the known manner on to superimposed layers. For copying purposes there are employed either tripack images or other master images or color-screen images as desired.

It has been found that large-grain screen images may be copied particularly well, as in this case parallactic errors and whitening of the colors are unable to occur.

Suitable dyestuffs are, for example, Diamine Pure Blue FF, Tartrazine, New Patent Blue, Phloxine B B N, Xylene Light Green 63, Patent Blue, Chromium Green GD extra, Guinea Blue, Fast Red D, Chloramine Light Red 7 BL, Chromium Fast Red BD paste, Geranine, Complementary Red D, Pinatype Blue D, Xylene Fast Blue FF.

The index numbers of the dyes quoted in the foregoing examples are set forth in Schultz Dyestufi! Tables, Berlin, 5th Ed., 1920, as follows:-

Chloramine Light Red 73L No number found (manuiactured by Sandor, Basel, Swi mrland). Tartraziue 23 Patent Blue 545 Fast Red D 168 Diamine Pure Blue FF 424 New Patent Blue 663 Phloxine 596 Chromium Fast Red BD Schultz, page 379 (no number). Geranine 118 Complementary Red Mentioned in the "Pine Handbuch" oi the I. G. Farbenindustrie A.-G. l 'inatype Blue Do. Xylene Light Green GB No number (manufactured by Sandor, Basel). Xylene Fast Blue 0. Chromium Green GD extra 609 Guinea Blue It will be understood that no restriction is made to the particular examples described in the above or to the specific samples quoted, and that numerous modifications and substitutions are quite possible within the meaning of the above description and the annexed claims without departing from the spirit of the invention.

I claim:--- 1. Photographic bleach-out layers comprising a colloidal carrier fastly dyed by at least one acid azo-dyestuff and having incorporated in addition a sensitizer and an agent activating the said sensitizer, one at least of the additions being dischargeable.

2. Photographic bleach-out layers comprising a colloidal carrier fastly dyed by at least one acid azo-dyestufl and having incorporated in addition a sensitizer and a substance of acid reaction'activating the said sensitizer, one at least of the additions being dischargeable.

3. Photographic bleach-out layers comprising a colloidal carrier fastly dyed by at least one acid azo-dyestufl and having incorporated in addition a sensitizer and a reducing substance activating the said sensitizer, one at least of the additions being dischargeable.

4. Photographic bleach-out layers comprising a colloidal carrier fastly dyed by at least one acid azo-dyestufl and having incorporated in one at least of the additions being dischargeable. o

'7. Photographic bleach-out layers comprising a colloidal carrier fastly dyed by at'least one acid azo-dyestufl and having incorporated in addition a compound of the thio-urea-group and a substance of acid reaction, one at least of the 45 additions being dischargeable.

BELA GASPAR.

US649442A 1932-01-04 1932-12-29 Color-photographic bleach out dyestuff layers Expired - Lifetime US2049005A (en)

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Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3892569A (en) * 1972-12-04 1975-07-01 Gen Film Dev Corp Photosensitive sheets comprising organic dyes and sensitizers
US5616443A (en) * 1993-08-05 1997-04-01 Kimberly-Clark Corporation Substrate having a mutable colored composition thereon
US5643356A (en) * 1993-08-05 1997-07-01 Kimberly-Clark Corporation Ink for ink jet printers
US5645964A (en) * 1993-08-05 1997-07-08 Kimberly-Clark Corporation Digital information recording media and method of using same
US5681380A (en) * 1995-06-05 1997-10-28 Kimberly-Clark Worldwide, Inc. Ink for ink jet printers
US5686503A (en) * 1994-06-30 1997-11-11 Kimberly-Clark Corporation Method of generating a reactive species and applications therefor
US5700850A (en) * 1993-08-05 1997-12-23 Kimberly-Clark Worldwide Colorant compositions and colorant stabilizers
US5721287A (en) * 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5733693A (en) * 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
US5739175A (en) * 1995-06-05 1998-04-14 Kimberly-Clark Worldwide, Inc. Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US5747550A (en) * 1995-06-05 1998-05-05 Kimberly-Clark Worldwide, Inc. Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US5773182A (en) * 1993-08-05 1998-06-30 Kimberly-Clark Worldwide, Inc. Method of light stabilizing a colorant
US5782963A (en) * 1996-03-29 1998-07-21 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5786132A (en) * 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
US5798015A (en) * 1995-06-05 1998-08-25 Kimberly-Clark Worldwide, Inc. Method of laminating a structure with adhesive containing a photoreactor composition
US5811199A (en) * 1995-06-05 1998-09-22 Kimberly-Clark Worldwide, Inc. Adhesive compositions containing a photoreactor composition
US5837429A (en) * 1995-06-05 1998-11-17 Kimberly-Clark Worldwide Pre-dyes, pre-dye compositions, and methods of developing a color
US5849411A (en) * 1995-06-05 1998-12-15 Kimberly-Clark Worldwide, Inc. Polymer film, nonwoven web and fibers containing a photoreactor composition
US5855655A (en) * 1996-03-29 1999-01-05 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5865471A (en) * 1993-08-05 1999-02-02 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms
US5885337A (en) * 1995-11-28 1999-03-23 Nohr; Ronald Sinclair Colorant stabilizers
US5891229A (en) * 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6008268A (en) * 1994-10-21 1999-12-28 Kimberly-Clark Worldwide, Inc. Photoreactor composition, method of generating a reactive species, and applications therefor
US6017471A (en) * 1993-08-05 2000-01-25 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6017661A (en) * 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
US6033465A (en) * 1995-06-28 2000-03-07 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6071979A (en) * 1994-06-30 2000-06-06 Kimberly-Clark Worldwide, Inc. Photoreactor composition method of generating a reactive species and applications therefor
US6099628A (en) * 1996-03-29 2000-08-08 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
US6242057B1 (en) 1994-06-30 2001-06-05 Kimberly-Clark Worldwide, Inc. Photoreactor composition and applications therefor
US6265458B1 (en) 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6277897B1 (en) 1998-06-03 2001-08-21 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
US6368396B1 (en) 1999-01-19 2002-04-09 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
US6486227B2 (en) 2000-06-19 2002-11-26 Kimberly-Clark Worldwide, Inc. Zinc-complex photoinitiators and applications therefor
US6503559B1 (en) 1998-06-03 2003-01-07 Kimberly-Clark Worldwide, Inc. Neonanoplasts and microemulsion technology for inks and ink jet printing
US6524379B2 (en) 1997-08-15 2003-02-25 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same

Cited By (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3892569A (en) * 1972-12-04 1975-07-01 Gen Film Dev Corp Photosensitive sheets comprising organic dyes and sensitizers
US6060200A (en) * 1993-08-05 2000-05-09 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms and methods
US5643356A (en) * 1993-08-05 1997-07-01 Kimberly-Clark Corporation Ink for ink jet printers
US5643701A (en) * 1993-08-05 1997-07-01 Kimberly-Clark Corporation Electrophotgraphic process utilizing mutable colored composition
US5645964A (en) * 1993-08-05 1997-07-08 Kimberly-Clark Corporation Digital information recording media and method of using same
US6054256A (en) * 1993-08-05 2000-04-25 Kimberly-Clark Worldwide, Inc. Method and apparatus for indicating ultraviolet light exposure
US5683843A (en) * 1993-08-05 1997-11-04 Kimberly-Clark Corporation Solid colored composition mutable by ultraviolet radiation
US5616443A (en) * 1993-08-05 1997-04-01 Kimberly-Clark Corporation Substrate having a mutable colored composition thereon
US5865471A (en) * 1993-08-05 1999-02-02 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms
US5700850A (en) * 1993-08-05 1997-12-23 Kimberly-Clark Worldwide Colorant compositions and colorant stabilizers
US5858586A (en) * 1993-08-05 1999-01-12 Kimberly-Clark Corporation Digital information recording media and method of using same
US5721287A (en) * 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5733693A (en) * 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
US5908495A (en) * 1993-08-05 1999-06-01 Nohr; Ronald Sinclair Ink for ink jet printers
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US5773182A (en) * 1993-08-05 1998-06-30 Kimberly-Clark Worldwide, Inc. Method of light stabilizing a colorant
US6127073A (en) * 1993-08-05 2000-10-03 Kimberly-Clark Worldwide, Inc. Method for concealing information and document for securely communicating concealed information
US6120949A (en) * 1993-08-05 2000-09-19 Kimberly-Clark Worldwide, Inc. Photoerasable paint and method for using photoerasable paint
US6017471A (en) * 1993-08-05 2000-01-25 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6060223A (en) * 1993-08-05 2000-05-09 Kimberly-Clark Worldwide, Inc. Plastic article for colored printing and method for printing on a colored plastic article
US6066439A (en) * 1993-08-05 2000-05-23 Kimberly-Clark Worldwide, Inc. Instrument for photoerasable marking
US6342305B1 (en) 1993-09-10 2002-01-29 Kimberly-Clark Corporation Colorants and colorant modifiers
US6071979A (en) * 1994-06-30 2000-06-06 Kimberly-Clark Worldwide, Inc. Photoreactor composition method of generating a reactive species and applications therefor
US6090236A (en) * 1994-06-30 2000-07-18 Kimberly-Clark Worldwide, Inc. Photocuring, articles made by photocuring, and compositions for use in photocuring
US5709955A (en) * 1994-06-30 1998-01-20 Kimberly-Clark Corporation Adhesive composition curable upon exposure to radiation and applications therefor
US5685754A (en) * 1994-06-30 1997-11-11 Kimberly-Clark Corporation Method of generating a reactive species and polymer coating applications therefor
US6242057B1 (en) 1994-06-30 2001-06-05 Kimberly-Clark Worldwide, Inc. Photoreactor composition and applications therefor
US5686503A (en) * 1994-06-30 1997-11-11 Kimberly-Clark Corporation Method of generating a reactive species and applications therefor
US6008268A (en) * 1994-10-21 1999-12-28 Kimberly-Clark Worldwide, Inc. Photoreactor composition, method of generating a reactive species, and applications therefor
US6017661A (en) * 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
US6235095B1 (en) 1994-12-20 2001-05-22 Ronald Sinclair Nohr Ink for inkjet printers
US5786132A (en) * 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
US5681380A (en) * 1995-06-05 1997-10-28 Kimberly-Clark Worldwide, Inc. Ink for ink jet printers
US5747550A (en) * 1995-06-05 1998-05-05 Kimberly-Clark Worldwide, Inc. Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US5849411A (en) * 1995-06-05 1998-12-15 Kimberly-Clark Worldwide, Inc. Polymer film, nonwoven web and fibers containing a photoreactor composition
US5837429A (en) * 1995-06-05 1998-11-17 Kimberly-Clark Worldwide Pre-dyes, pre-dye compositions, and methods of developing a color
US6063551A (en) * 1995-06-05 2000-05-16 Kimberly-Clark Worldwide, Inc. Mutable dye composition and method of developing a color
US5811199A (en) * 1995-06-05 1998-09-22 Kimberly-Clark Worldwide, Inc. Adhesive compositions containing a photoreactor composition
US5798015A (en) * 1995-06-05 1998-08-25 Kimberly-Clark Worldwide, Inc. Method of laminating a structure with adhesive containing a photoreactor composition
US5739175A (en) * 1995-06-05 1998-04-14 Kimberly-Clark Worldwide, Inc. Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US6033465A (en) * 1995-06-28 2000-03-07 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6168655B1 (en) 1995-11-28 2001-01-02 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5885337A (en) * 1995-11-28 1999-03-23 Nohr; Ronald Sinclair Colorant stabilizers
US6099628A (en) * 1996-03-29 2000-08-08 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5782963A (en) * 1996-03-29 1998-07-21 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5855655A (en) * 1996-03-29 1999-01-05 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5891229A (en) * 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6168654B1 (en) 1996-03-29 2001-01-02 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6524379B2 (en) 1997-08-15 2003-02-25 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6277897B1 (en) 1998-06-03 2001-08-21 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6503559B1 (en) 1998-06-03 2003-01-07 Kimberly-Clark Worldwide, Inc. Neonanoplasts and microemulsion technology for inks and ink jet printing
US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
US6265458B1 (en) 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368396B1 (en) 1999-01-19 2002-04-09 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
US6486227B2 (en) 2000-06-19 2002-11-26 Kimberly-Clark Worldwide, Inc. Zinc-complex photoinitiators and applications therefor

Also Published As

Publication number Publication date
FR748339A (en) 1933-07-01
GB417444A (en) 1934-10-04

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