Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.


  1. Advanced Patent Search
Publication numberUS2346090 A
Publication typeGrant
Publication dateApr 4, 1944
Filing dateAug 19, 1942
Priority dateAug 19, 1942
Publication numberUS 2346090 A, US 2346090A, US-A-2346090, US2346090 A, US2346090A
InventorsStaehle Henry C
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Photographic bleach-out layer
US 2346090 A
Abstract  available in
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

Patented Apr. 4, 1944 UNITED STATES PATENT OFFICE I PHOTOGBAPHIC BLEACH-OUT LAYER Henry 0. Staehle, Rochester, N. E, minor to Eastman Kodak Company,

corporation of New Jersey Claims.

My invention relates to light-sensitive layers for photography, and more particularly to lightsensitive layers for the so-called bleaching out" process of photography.

As is well known, the bleaching-out. process of photography primarily consists of exposing to light a layer containing a. dye capable of being decolorized under influence of light. Various substances have been used in this process for the purpose of speeding up the printing of the photographic layer and the bleaching of the dye therefrom. For instance, hydrogen peroxide has been used to accelerate the bleaching, but due to the fact that it rapidly decomposes into oxygen and water, it is of little or no use. Similarly, metal peroxides such as barium peroxide have been tested'as bleaching accelerators, but have been found to beof little or no use.

In a bleaching-out process in. which the accelerator is incorporated in the photographic layer along with the dye, the special characteristics which the bleaching accelerator must have are thatit will keep indefinitely in intimate contact with the dye without adverse eiiects upon the dye, and yet is or may be caused to be available when required for bleaching. To meet these requirements, the accelerator should be relatively stable and non-volatile. Moreover, after the accelerator hasserved its purpose, it should be readily removable from the layer to prevent further bleaching of the dye in the unexposed area of the layer. It is now apparent why a relatively unstable peroxide such as hydrogen peroxide is unsuitable for the purpose.

Peroxide compounds relatively more stable than hydrogen peroxide, such as solid peroxides, would be suitable for use in the process since they have relatively low vapor pressures and are, therefore. substantially non-volatile under ordinary conditions.

One object of the present invention is to provide a photographic material for use in the bleaching-out process of photography.

Another object is to provide bleaching accelerator compounds of particular use in bleachins-out layers.

I have discovered a class otperoxide compounds, namely, solid organic peroxides which are eminently suitable for use in the bleaching- I out process and especially suitable for incorporation into bleaching-out layers. Typical solid organic peroxides which are found to besuitable for use in my invention are, ior example, benzoyl acetyl peroxide, and tetralin peroxideI-Ielv. Chim. Acta 15, 1390 (1932), and others.

These peroxides, especially benzoyl peroxide, have the property of being relatively stable in the dry state; however, upon treatment with moisture they gradually'decompose into ouanic acid and hydrogen peroxide. This property is especially useful in my process as will be apparent from the following description.

In the manner of my invention the peroxide compound is incorporated into the photographic layer along with the dye and the layer kept in the dry state until it is desired to make an exposure, then the layer is first moistened, then exposed, and finally treated with further moisture in the absence .of strong light to decompose the residual peroxide compound.

The photographic layer may contain as the hindingagent a high molecular weight colloidal material such as natural or synthetic resins, cellulose esters and the like. For example, cellulose nitrate or acetate, cellulose mixed esters, such as cellulose acetate propionate, resins such as polyvinyl acetate, cellulose others, etc. are


The following examples illustrate my invention.

Example 1 ii baryta paper is coated with a solution oi the following composition:

After curing the paper it is stored in a dry place until required for use. The cellulose nitrate used in the above formula is a low viscosity highly alcohol soluble nitrate of nitrogen content of about 11 per cent. Before exposure the paper is moistened by exposure to humid air and following this exposed to strong light under asuitable pattern and finally exposed further to moist air to decompose the peroxide compound remaining in the layer. The paper is then dried. Where the colored layer has been exposed to light, the dye will be markedly destroyed. The

unexposed portions will be relatively unaffected.

The principal function of the peroxide is to inperoxlde, acetyl benzoyl peroxide, ascaridol, crease the rate of bleaching, that is. y having the peroxide present, the dye is bleached in a fraction oi the time required when no peroxide is used.

' Example 2 Grams Polyvinyl acet Methyl alonhnl Methylene Blue Benzoyl pernxifln If desired, the paper may first be coated with the composition of Example 1, minus either the dye or peroxide compound, followed by a coating from the solution of Example 2 containing either dye or peroxide compound depending upon which was used in the undercoat. After curing, the paper is stored in a dry place. The bleaching-out paper thus prepared may be processed as described in Example 1.

Example "3 A baryta paper is coated with a subbing layer from a composition such as shown in Example 1, preferably containing no dye or peroxide compound. This subbing layer is then overcoated with a bleaching-out'layer containing cellulose acetate 38 per cent acetyl, as the binding agent, from the following solution.

Grams In theproduction of other bleaching-out papers prepared in a manner similar to that shown in the preceding examples, other organic peroxide compounds may be used in place of benzoyl peroxide, and similarly, other dyes maybe substituted for the particular dye of the examples. In addition, it it is so desired, instead of coating a baryta paper one may use "for the supp rt a cellulose ester as, tor example, cellulose nitrate and coat this support with a' solution or dye, organic peroxide compound and cellul'osic or resin binder from a solvent combination such as shown in Example 1. It is not necessary that the coating composition be entirely free from water since peroxides are slowly decomposed in water. A-

cordingly, other binding agents which can be coated from aqueous organic solvent solution are suitable for use in the layers of my invention.

Other dyes suitable for use in the bleaching-out layers or my invention may for example be Rhodamine, Curcumin, Brilliant Green, Pyronine G, Rosinduline, etc.

Obviously, my invention is not limited to the foregoing examples or the described methods given therein, and Kris tobe understood that the agent, a bleaching-out dye, and a solid organic peroxide compound as an accelerator for bleaching said dye, and coating a layer from the composition.

2. The method of forming a photographic layer for the bleaching-out process which comprises dissolving in organic solvent medium substantially free of water, a binding agent, a bleachingout dye, and a solid organic peroxide compound as an accelerator for bleaching said dye, and coating a layer from the composition.

3. The method of forming a photographic layer for the bleaching-out process'which comprises dissolving in organic solvent medium a binding agent, a bleaching-out dye, and benzoyl peroxide as an accelerator for bleaching said dye, and coating a layer from the composition.

4. The method of forming pictures in the bleaching-out process of photography which comprises moistening a photographic layer having a binding agentand uniformly dispersed therein a bleaching-out dye and a solid organic peroxide as an accelerator tor bleaching said dye, exposing said layer througha pattern, and treating.

.layer through a pattern, and treating said layer with additional moisture to decompose any undecomposed peroxide in the layer.

HENRY c. srAnr-nn.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2518710 *Mar 27, 1948Aug 15, 1950Gen Aniline & Film CorpLumazines and alloxazines as catalysts in dye bleach baths for color photography
US2844465 *Mar 17, 1954Jul 22, 1958Lyman ChalkleyPhotographic process
US3765890 *Nov 15, 1971Oct 16, 1973Agfa Gevaert AgOrganic hydrogen peroxide addition compounds for vesicular image formation processes
US3892569 *Dec 4, 1972Jul 1, 1975Gen Film Dev CorpPhotosensitive sheets comprising organic dyes and sensitizers
US5185233 *Apr 30, 1991Feb 9, 1993Canon Kabushiki KaishaLight absorption; thermal decomposition, fading of dye compound
US5616443 *Jun 1, 1995Apr 1, 1997Kimberly-Clark CorporationToner for electrography
US5643356 *Jun 5, 1995Jul 1, 1997Kimberly-Clark CorporationUnsaturated ketone sensitizer bonded to radiation transorber with color, molecular includent and vehicles
US5643701 *Jun 1, 1995Jul 1, 1997Kimberly-Clark CorporationElectrophotgraphic process utilizing mutable colored composition
US5645964 *Jun 5, 1995Jul 8, 1997Kimberly-Clark CorporationStabilizers
US5681380 *Dec 19, 1996Oct 28, 1997Kimberly-Clark Worldwide, Inc.Ink for ink jet printers
US5683843 *Feb 22, 1995Nov 4, 1997Kimberly-Clark CorporationSolid colored composition mutable by ultraviolet radiation
US5685754 *May 19, 1995Nov 11, 1997Kimberly-Clark CorporationMethod of generating a reactive species and polymer coating applications therefor
US5686503 *Jan 22, 1996Nov 11, 1997Kimberly-Clark CorporationPhotoinitiators
US5700850 *Jun 5, 1995Dec 23, 1997Kimberly-Clark WorldwidePhotostability; colorant and radiation absorber
US5709955 *Oct 16, 1996Jan 20, 1998Kimberly-Clark CorporationLamination, photoreactor with wavelength-specific sensitizer bonded to photoinitiator
US5721287 *Jun 5, 1995Feb 24, 1998Kimberly-Clark Worldwide, Inc.Radiating in presence of transorber
US5733693 *Jan 2, 1997Mar 31, 1998Kimberly-Clark Worldwide, Inc.Method for improving the readability of data processing forms
US5739175 *Jun 5, 1995Apr 14, 1998Kimberly-Clark Worldwide, Inc.Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US5747550 *Jun 5, 1995May 5, 1998Kimberly-Clark Worldwide, Inc.Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US5773182 *Jun 5, 1995Jun 30, 1998Kimberly-Clark Worldwide, Inc.Method of light stabilizing a colorant
US5782963 *Nov 27, 1996Jul 21, 1998Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US5786132 *May 29, 1996Jul 28, 1998Kimberly-Clark CorporationPre-dyes, mutable dye compositions, and methods of developing a color
US5798015 *Jun 5, 1995Aug 25, 1998Kimberly-Clark Worldwide, Inc.Exposing a photoreactor composition to radiation in which the photoreactor composition comprises a wavelength-specific sensitizer associated with a reactive-species generating photoinitiator
US5811199 *Jun 5, 1995Sep 22, 1998Kimberly-Clark Worldwide, Inc.Exposing photoreactor to radiation; photoreactor comprises wavelength specific sensitizer
US5837429 *Jun 5, 1996Nov 17, 1998Kimberly-Clark WorldwideDye covalently bound to radiation transorber that is colorless and will form color when irradiated
US5849411 *Jun 5, 1995Dec 15, 1998Kimberly-Clark Worldwide, Inc.Polymer film, nonwoven web and fibers containing a photoreactor composition
US5855655 *Apr 15, 1997Jan 5, 1999Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US5858586 *May 16, 1997Jan 12, 1999Kimberly-Clark CorporationDigital information recording media and method of using same
US5865471 *Dec 21, 1994Feb 2, 1999Kimberly-Clark Worldwide, Inc.For use with photo-sensing apparatus
US5885337 *Oct 31, 1997Mar 23, 1999Nohr; Ronald SinclairComprising a reducing agent and/or a molecular inclusion compound for inhibiting discoloration when exposed to sunlight or artificial light
US5891229 *Jul 31, 1997Apr 6, 1999Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US5908495 *Sep 24, 1997Jun 1, 1999Nohr; Ronald SinclairColorant; a modified photoreactor; and a liquid vehicle wherein the colorant is rendered light-stable in the mixture
US6008268 *Jan 22, 1998Dec 28, 1999Kimberly-Clark Worldwide, Inc.A photoreactor compound comprising a wavelength-specific sensitizer moiety covalently bonded to two reactive species-generating photoinitiator moieties; photopolymerization; photocuring; low-energy lamps
US6017471 *Apr 23, 1997Jan 25, 2000Kimberly-Clark Worldwide, Inc.Colorants and colorant modifiers
US6017661 *Oct 8, 1997Jan 25, 2000Kimberly-Clark CorporationSubstrate surface attached to merchandise and labeled with indicia comprising a mutable colorant, molecular includant and a transorber which irreversibly decolors colorant upon exposure to ultraviolet radiation
US6033465 *Apr 5, 1996Mar 7, 2000Kimberly-Clark Worldwide, Inc.Colorants and colorant modifiers
US6054256 *Dec 3, 1998Apr 25, 2000Kimberly-Clark Worldwide, Inc.Colorimetric analysis; detecting dosage radiation
US6060200 *Feb 3, 1998May 9, 2000Kimberly-Clark Worldwide, Inc.Photo-erasable data processing forms and methods
US6060223 *Dec 3, 1998May 9, 2000Kimberly-Clark Worldwide, Inc.Plastic article for colored printing and method for printing on a colored plastic article
US6063551 *Nov 16, 1998May 16, 2000Kimberly-Clark Worldwide, Inc.A leuco dye associated with a radiation transorber where the radiation transorber comprises a wavelength-selective sensitizer covalently bonded to a reactive species-generating photoreactor; phthaloylglycine; 4-(4-hydroxyphenyl)but-2-one
US6066439 *Dec 3, 1998May 23, 2000Kimberly-Clark Worldwide, Inc.Instrument for photoerasable marking
US6071979 *Dec 26, 1997Jun 6, 2000Kimberly-Clark Worldwide, Inc.To generate photoinitiators for polymerizing unsaturated monomers and curing an unsaturated oligomer/monomer mixture
US6090236 *Dec 31, 1997Jul 18, 2000Kimberly-Clark Worldwide, Inc.Photocuring, articles made by photocuring, and compositions for use in photocuring
US6099628 *Jan 23, 1997Aug 8, 2000Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US6120949 *Dec 3, 1998Sep 19, 2000Kimberly-Clark Worldwide, Inc.A temporary markings comprising a colorant, a mutable colorant and an ultraviolet radiation transorber, when irradiating with ultraviolet radiation, and changing the colorant to colorless
US6127073 *Dec 3, 1998Oct 3, 2000Kimberly-Clark Worldwide, Inc.Method for concealing information and document for securely communicating concealed information
US6168654Apr 6, 1999Jan 2, 2001Kimberly-Clark Worldwide, Inc.Porphine imparts light-stability to the colorant so that the colorant does not fade
US6168655Dec 15, 1998Jan 2, 2001Kimberly-Clark Worldwide, Inc.Phenol derivatives
US6211383Feb 10, 1998Apr 3, 2001Kimberly-Clark Worldwide, Inc.Reacting the compound in a non-aqueous non-polar solvent in the presence of a transition metal salt such that the hydroxy group is dehydrated
US6228157Jul 20, 1999May 8, 2001Ronald S. NohrInk jet ink compositions
US6235095Jun 1, 1999May 22, 2001Ronald Sinclair NohrInk for inkjet printers
US6242057Apr 29, 1998Jun 5, 2001Kimberly-Clark Worldwide, Inc.Photoreactor composition and applications therefor
US6265458Sep 28, 1999Jul 24, 2001Kimberly-Clark Worldwide, Inc.Photoinitiators and applications therefor
US6277897Jun 3, 1999Aug 21, 2001Kimberly-Clark Worldwide, Inc.Photoinitiators and applications therefor
US6294698Apr 16, 1999Sep 25, 2001Kimberly-Clark Worldwide, Inc.Photoinitiators and applications therefor
US6331056Feb 24, 2000Dec 18, 2001Kimberly-Clark Worldwide, Inc.Printing apparatus and applications therefor
US6342305Dec 28, 1999Jan 29, 2002Kimberly-Clark CorporationColorants and colorant modifiers
US6368395May 12, 2000Apr 9, 2002Kimberly-Clark Worldwide, Inc.Colorfastness; photostability
US6368396Jan 19, 2000Apr 9, 2002Kimberly-Clark Worldwide, Inc.Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6486227Jun 19, 2001Nov 26, 2002Kimberly-Clark Worldwide, Inc.Zinc-complex photoinitiators and applications therefor
US6503559Jun 3, 1999Jan 7, 2003Kimberly-Clark Worldwide, Inc.Neonanoplasts and microemulsion technology for inks and ink jet printing
US6524379Jan 12, 2001Feb 25, 2003Kimberly-Clark Worldwide, Inc.Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
U.S. Classification430/332, 430/339
International ClassificationG03C7/02
Cooperative ClassificationG03C7/02
European ClassificationG03C7/02