|Publication number||US3284205 A|
|Publication date||8 Nov 1966|
|Filing date||17 Sep 1963|
|Priority date||17 Sep 1963|
|Also published as||DE1282449B|
|Publication number||US 3284205 A, US 3284205A, US-A-3284205, US3284205 A, US3284205A|
|Inventors||Lewis James M, Sprague Robert H, Stewart John A|
|Original Assignee||Horizons Inc|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (3), Referenced by (62), Classifications (5)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3 284,205 BENZOTRIAZOLE AI ID HETEROCYCLIC KETI- MIDE ACTIVATORS FOR LEUCO COMPOUNDS Robert H. Sprague, Chagrin Falls, John A. Stewart, Parma, and James M. Lewis, Cleveland, Ohio, assignors to Horizons Incorporated, Cleveland, Ohio, a corporation of New Jersey No Drawing. Filed Sept. 17, 1963, Ser. No. 309,407 11 Claims. (CI. 96-90) This invention relates to non-silver photosensitive compositions which print-out an image directly upon exposureto a suitable dosage of visible light, and to the use of such compositions as thin films in photographic processes. More particularly this invention relates to photosensitive compositions comprising at least one colorless leuco compound which when intimately admixed wit-h one or more colorless activator compounds, yields a mixture which when exposed to visible light prints out a visible image directly at speeds which are of practical significance, and to the processing of such compositions to yield a permanent useful image.
1. The leuco compounds The leuco compounds which may be utilized in accordance with the present invention comprise two recognized classes of dye forming colorless com-pounds, namely leuco base of diand triaryl-methane dyes and a second class of leuco compounds, namely leuco Xanthenes, leuco thioxantlhenes, leuco selenoxanthenes and leuco ac-nidenes.
The leuco bases of diand triarylmethane dyes which are usitable in the compositions about to be described more :fully are those represented by the general formula wherein each R is selected from the group consisting of H, lower alkyl and aryl and the several Rs may be the same or different, and R is selected from the group consisting of H, aryl, alkyl and particularly wherein each of the Rs is selected from the group consisting of H, alkyl and aryl.
Leuc-o dyes represented by the above formula which have been found suitable include:
leuco crystal violet leuco opal blue leuco malachite green leuco rosaniline leuco pararosaniline p,p,p"-trimethyl leuco opal blue p,p,p-trichloro leuco opal blue and other compounds of a similar nature.
The other class of leuco compounds which are suitable in the composition about to be described more fully, are generally similar to the leuco triaryl-methane dyes except that they are characterized by the presence of one or more bridging hetero atoms and therefore are ice compounds which may be represented by the general formulas RQ/ H wherein each R is selected from the group consisting of H, lower alkyl and aryl and may be the same or different and R is selected from the group consisting of H, alkyl and aryl, including particularly and wherein Z represents a member selected from the group consisting of O, S, Se and -NH.
As indicated, the preferred leuco compounds of this class are substituted in the 3,6 positions and include 3,6 bis (dimethylamino) 9 (p-dimethylaminophenyl) xanthene 3,6 bis (diethylamino) 9 (p dimet'hylaminopihenyl) xant hene 3,6 bis (diethylamino) 9 (p diethylarnin-oplie-nyl) 'xant hene 3,6 bis (dimeflhylamino) 9 (p-dimethylaminophenyl) thioxanthene 2. The activators A diverse group of colorless nitrogen-containing organic compounds have been founduseful in the present invention. In general these compounds fall into either of the two following groups:
A. Triaz-oles, i.e. heterocyclic compounds wherein there are three nitrogen atoms in a 5 membered heterocyclic nucleus.
B. Heterocyclic ketimides, i.e. compounds wherein an imide nitrogen (=NH) is attached to a ring carbon in a 5 or 6 membered heterocyclic nucleus.
While not wishing to be bound :by any specific theory it appears that the ketimide activators in the present invention are compounds capable of existence in two tutomeric forms of which the signfiicant fragment of the structure may center on the imide group, viz.
Hegero Nucleus G=NH Hetero O-NHr Nucleus In the results which follow the activators were: A. 3-naphthylisoxazolone imide 3. Evaluation procedure and results The data reported in the table which follows is the result of tests demonstrating the effect of visible light on mixtures of various leuco base and activators. In each of the five (5) compositions for which results are reported, the leuco compound was 3,6-bis-(dimethylamino) -9- (p-dimethylarnin-ophenyl xanthene hereinafter identified as D-l79. I
For each composition, equal volumes of acetone and a 10% by weight solution of polystyrene in benzene were mixed and then the indicated weight of the specified activator and an equal weight of D179 Were dissolved in the mixture. The resulting composition was coated by means of a Bird applicator on 500-D Mylar polyester in a coating having a wet thickness of 0.0015 inch. The coating was permitted to dry in air. Thereafter the com position was exposed (1) either to a General Electric No. 2 Reflector Photo Flood Lamp (RFL 2) through a step tablet or (2) using an Eastman Kodak No.10l Sensitomete with the light converted to equal mean noonday sun by means of a suitable filter (Eastman No. 78AA).
When the composition wa exposed to a General Electric 500 watt RFL2 Photofiood lamp exposure was through a #2 silver step wedge for a 5 minute interval at a distance of 12 inches from lamp to test materials. The density and number of steps visible in the image were read, after fixing the image by solvent wash or by heat.
When the composition was exposed on an Eastman Kodak No. 101 Sensitometer the light was converted by the use of a 78AA Filter, to equal mean noon day light. The resulting image was fixed by a solvent wash or by exposure to heat. Thereafter the density of the image was read and the LES. Was computed as described below.
The exposed material was stabilized by two or more successive rinses in a mixture of 1 part acetone and 4 parts petroleum ether, or by being maintained at 125 C. in a convention type oven for four (4) minutes. The stabilized material was reexposed 4 minutes to the RFLZ with no darkening. The densities in the resulting step wedge were read with an Eastman No. 1 Color Densitometer using the Green Filter, with the results reported below.
L.E.S. (abbreviation for Light Exposure Speed) refers to a speed rating system developed at the Wright Air Development Division of Air Research and Development Command (USAF), and is defined as the reciprocal of the exposure in meter candle seconds which is required to produce a double diffuse reflection density of 0.2 density units above base plus fog. As in the more conventional ASA system used to rate silver halide films, the higher the LES. number faster the film is.
Similarly, exposure to visible light of a mixture of leuco Crystal Violet and S-chlorobenzotuiazole gives a visible image and exposure to visible light of a mixture of leuco Crystal Violet and 3-naphthylisoxazolone imide gave a blue image of comparable density.
4 4. Fixing After exposure, the colored image produced may be fixed or stabilized either by a solvent rinse as described above or by mild heating.
The method of stabilization selected in any specific instance will depend to some extent upon the materials being used and it is to be noted that many of the slower compositions may be preferable to some of the faster compositions because some of the latter are less susceptible to heat or dry fixing than some of the former.
While not wishing to be bound by any specific theory as to the manner in which the exposure to visible light to an intimate mixture comprising two or more originally colorless compounds produced a colored image, it is believed that the final colored image Which forms in the light struck areas is always the dye which forms as a result of oxidation of the leuco base. Furthermore it appears that when the photosensitive mixtures is prepared, on mixing the compounds which are colorless, a weakly tinted mixture is formed.
It is also considered possible that the real active ingredient in the mixture is that very minute amount of an oxidized product which results when the leuco base is exposed to oxygen e.g. in the ordinary atmosphere.
Whatever the true mechanism each of the activators listed above, or mixtures of the same, bring about oxidation of the leuco compound upon exposure to a suitable dose of visible light and as a result form a direct visible print-out image in the light struck areas.
5. Proportions The relative proportions of the leuco dye bases and the activators for the same may be varied considerably from the weight proportions given by Way of illustration in the examples and are preferably within the range between 10 to 1 and 1 to 10 parts by weight.
As with other photosensitive compositions if not used at the time they are prepared the compositions of the present invention would be stored in cool dark relatively dry surroundings.
Having now described the invention in accordance With the patent statutes it is not intended that it be limited except as may be required by the appended claims.
1. A composition which prints out a visible image directly as a result of exposure to visible light said composition comprising an intimate mixture consisting essentially of:
(1) at least one leuco compound selected from the group consisting of leuco compounds represented by one of the following general formulas R\ III R R R2 R wherein each R is a monovalent radical selected from the group consisting of H, lower alkyl and aryl and not all of the Rs need be the same and R is a monovalent radical selected from the group consisting of H, lower alkyl and aryl: and
wherein each R has the same meaning as indicated above and Z represents a member selected from the group consisting of O, S, Se and NH, and R is a monovalent radical selected from the group consisting of H, alkyl and aryl; and
(2) at least one colorless nitrogen-containing organic compound selected from the group consisting of henzotriazoles and heterocyclic ketimides in which the imide nitrogen is attached to a ring carbon in a 'heterocyclic nucleus having at least 5 and not more than 6 atoms.
2. The composition of claim 1 wherein the leuco compound is a leuco base of a triphenylmethane dye.
3. The composition of claim 1 in which the nitrogencontaining compound is benzotriazole.
4. The composition of claim 1 wherein the nitrogencontaining compound is an isoxazolone imide.
5. The composition of claim 1 wherein the leuco base is 3,6-b-is(dimethylamtino)9-(p-dimethylamino phenyl) Xanthene.
6. A dry film consisting of a composition according to claim 1 dispersed in a thin layer on an inert support.
7. The film of claim 2 wherein the support is a film forming plastic.
8. The film of claim 2 wherein the binder is a cellulose 6 compound selected from the group consisting of cellulose and cellulose derivatives.
9. The film of claim 2 wherein the 'suppomt is transparent.
10. The process of producing a direct print-out image from originally colorless compounds which comprise prepaving the composition of claim 1 in the form of a thin layer, exposing said layer to visible light and fixing the image which prints out directly as a result of said exposure. 1
11. The composition of claim 1 wherein the heterocyclic ketimide has a five member heterocyelic nucleus.
References Cited by the Examiner UNITED STATES PATENTS 2,895,892 7/1959 Chalkley 9690 X 2,927,025 3/ 1960 Ryskiewicz 969O 2,981,622 4/1961 Chalkey 9()90 X J. TRAVIS BROWN, Acting Primary Examiner.
NORMAN G. TORCHIN, Examiner.
D. D. PRICE, Assistant Examiner.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2895892 *||10 Aug 1954||21 Jul 1959||Lyman Chalkley||Photochemical process|
|US2927025 *||23 Oct 1956||1 Mar 1960||Ibm||Photosensitive materials and recording media|
|US2981622 *||13 Jul 1959||25 Apr 1961||Lyman Chalkley||Photographic process|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3359109 *||29 Apr 1964||19 Dec 1967||Du Pont||Leuco dye-n, n. o-triacylhydroxylamine light-sensitive dye former compositions|
|US3360370 *||29 Apr 1964||26 Dec 1967||Du Pont||Leuco dye-aromatic bitriazole lightsensitive dye former compositions|
|US3364030 *||29 Apr 1964||16 Jan 1968||Du Pont||Leuco dye-diacylazino light-sensitive dye former compositions|
|US3390994 *||17 Feb 1966||2 Jul 1968||Du Pont||Photodeactivatable light-sensitive color-forming composition|
|US3390997 *||29 Apr 1964||2 Jul 1968||Du Pont||Photosensitive composition comprising a triphenylemethane derivative and a nitrogen-containing photo-oxidant|
|US3395018 *||29 Apr 1964||30 Jul 1968||Du Pont||Light-sensitive color-forming composition|
|US4962011 *||17 May 1988||9 Oct 1990||Basf Aktiengesellschaft||Photopolymerizable recording materials containing a triazole sensitizer and photoresist layers and lithographic printing plates based thereon|
|US5616443 *||1 Jun 1995||1 Apr 1997||Kimberly-Clark Corporation||Substrate having a mutable colored composition thereon|
|US5643356 *||5 Jun 1995||1 Jul 1997||Kimberly-Clark Corporation||Ink for ink jet printers|
|US5643701 *||1 Jun 1995||1 Jul 1997||Kimberly-Clark Corporation||Electrophotgraphic process utilizing mutable colored composition|
|US5645964 *||5 Jun 1995||8 Jul 1997||Kimberly-Clark Corporation||Digital information recording media and method of using same|
|US5681380 *||19 Dec 1996||28 Oct 1997||Kimberly-Clark Worldwide, Inc.||Ink for ink jet printers|
|US5683843 *||22 Feb 1995||4 Nov 1997||Kimberly-Clark Corporation||Solid colored composition mutable by ultraviolet radiation|
|US5700850 *||5 Jun 1995||23 Dec 1997||Kimberly-Clark Worldwide||Colorant compositions and colorant stabilizers|
|US5709955 *||16 Oct 1996||20 Jan 1998||Kimberly-Clark Corporation||Adhesive composition curable upon exposure to radiation and applications therefor|
|US5721287 *||5 Jun 1995||24 Feb 1998||Kimberly-Clark Worldwide, Inc.||Method of mutating a colorant by irradiation|
|US5733693 *||2 Jan 1997||31 Mar 1998||Kimberly-Clark Worldwide, Inc.||Method for improving the readability of data processing forms|
|US5739175 *||5 Jun 1995||14 Apr 1998||Kimberly-Clark Worldwide, Inc.||Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer|
|US5747550 *||5 Jun 1995||5 May 1998||Kimberly-Clark Worldwide, Inc.||Method of generating a reactive species and polymerizing an unsaturated polymerizable material|
|US5773182 *||5 Jun 1995||30 Jun 1998||Kimberly-Clark Worldwide, Inc.||Method of light stabilizing a colorant|
|US5782963||27 Nov 1996||21 Jul 1998||Kimberly-Clark Worldwide, Inc.||Colorant stabilizers|
|US5786132||29 May 1996||28 Jul 1998||Kimberly-Clark Corporation||Pre-dyes, mutable dye compositions, and methods of developing a color|
|US5798015 *||5 Jun 1995||25 Aug 1998||Kimberly-Clark Worldwide, Inc.||Method of laminating a structure with adhesive containing a photoreactor composition|
|US5811199 *||5 Jun 1995||22 Sep 1998||Kimberly-Clark Worldwide, Inc.||Adhesive compositions containing a photoreactor composition|
|US5837429||5 Jun 1996||17 Nov 1998||Kimberly-Clark Worldwide||Pre-dyes, pre-dye compositions, and methods of developing a color|
|US5849411 *||5 Jun 1995||15 Dec 1998||Kimberly-Clark Worldwide, Inc.||Polymer film, nonwoven web and fibers containing a photoreactor composition|
|US5855655||15 Apr 1997||5 Jan 1999||Kimberly-Clark Worldwide, Inc.||Colorant stabilizers|
|US5858586||16 May 1997||12 Jan 1999||Kimberly-Clark Corporation||Digital information recording media and method of using same|
|US5865471 *||21 Dec 1994||2 Feb 1999||Kimberly-Clark Worldwide, Inc.||Photo-erasable data processing forms|
|US5885337||31 Oct 1997||23 Mar 1999||Nohr; Ronald Sinclair||Colorant stabilizers|
|US5891229||31 Jul 1997||6 Apr 1999||Kimberly-Clark Worldwide, Inc.||Colorant stabilizers|
|US5908495||24 Sep 1997||1 Jun 1999||Nohr; Ronald Sinclair||Ink for ink jet printers|
|US6008268||22 Jan 1998||28 Dec 1999||Kimberly-Clark Worldwide, Inc.||Photoreactor composition, method of generating a reactive species, and applications therefor|
|US6017471||23 Apr 1997||25 Jan 2000||Kimberly-Clark Worldwide, Inc.||Colorants and colorant modifiers|
|US6017661||8 Oct 1997||25 Jan 2000||Kimberly-Clark Corporation||Temporary marking using photoerasable colorants|
|US6033465||5 Apr 1996||7 Mar 2000||Kimberly-Clark Worldwide, Inc.||Colorants and colorant modifiers|
|US6054256||3 Dec 1998||25 Apr 2000||Kimberly-Clark Worldwide, Inc.||Method and apparatus for indicating ultraviolet light exposure|
|US6060200||3 Feb 1998||9 May 2000||Kimberly-Clark Worldwide, Inc.||Photo-erasable data processing forms and methods|
|US6060223||3 Dec 1998||9 May 2000||Kimberly-Clark Worldwide, Inc.||Plastic article for colored printing and method for printing on a colored plastic article|
|US6063551||16 Nov 1998||16 May 2000||Kimberly-Clark Worldwide, Inc.||Mutable dye composition and method of developing a color|
|US6066439||3 Dec 1998||23 May 2000||Kimberly-Clark Worldwide, Inc.||Instrument for photoerasable marking|
|US6071979||26 Dec 1997||6 Jun 2000||Kimberly-Clark Worldwide, Inc.||Photoreactor composition method of generating a reactive species and applications therefor|
|US6090236||31 Dec 1997||18 Jul 2000||Kimberly-Clark Worldwide, Inc.||Photocuring, articles made by photocuring, and compositions for use in photocuring|
|US6099628||23 Jan 1997||8 Aug 2000||Kimberly-Clark Worldwide, Inc.||Colorant stabilizers|
|US6120949||3 Dec 1998||19 Sep 2000||Kimberly-Clark Worldwide, Inc.||Photoerasable paint and method for using photoerasable paint|
|US6127073||3 Dec 1998||3 Oct 2000||Kimberly-Clark Worldwide, Inc.||Method for concealing information and document for securely communicating concealed information|
|US6168654||6 Apr 1999||2 Jan 2001||Kimberly-Clark Worldwide, Inc.||Colorant stabilizers|
|US6168655||15 Dec 1998||2 Jan 2001||Kimberly-Clark Worldwide, Inc.||Colorant stabilizers|
|US6211383||10 Feb 1998||3 Apr 2001||Kimberly-Clark Worldwide, Inc.||Nohr-McDonald elimination reaction|
|US6228157||20 Jul 1999||8 May 2001||Ronald S. Nohr||Ink jet ink compositions|
|US6235095||1 Jun 1999||22 May 2001||Ronald Sinclair Nohr||Ink for inkjet printers|
|US6242057||29 Apr 1998||5 Jun 2001||Kimberly-Clark Worldwide, Inc.||Photoreactor composition and applications therefor|
|US6265458||28 Sep 1999||24 Jul 2001||Kimberly-Clark Worldwide, Inc.||Photoinitiators and applications therefor|
|US6277897||3 Jun 1999||21 Aug 2001||Kimberly-Clark Worldwide, Inc.||Photoinitiators and applications therefor|
|US6294698 *||16 Apr 1999||25 Sep 2001||Kimberly-Clark Worldwide, Inc.||Photoinitiators and applications therefor|
|US6331056||24 Feb 2000||18 Dec 2001||Kimberly-Clark Worldwide, Inc.||Printing apparatus and applications therefor|
|US6342305||28 Dec 1999||29 Jan 2002||Kimberly-Clark Corporation||Colorants and colorant modifiers|
|US6368395||12 May 2000||9 Apr 2002||Kimberly-Clark Worldwide, Inc.||Subphthalocyanine colorants, ink compositions, and method of making the same|
|US6368396||19 Jan 2000||9 Apr 2002||Kimberly-Clark Worldwide, Inc.||Colorants, colorant stabilizers, ink compositions, and improved methods of making the same|
|US6486227||19 Jun 2001||26 Nov 2002||Kimberly-Clark Worldwide, Inc.||Zinc-complex photoinitiators and applications therefor|
|US6503559||3 Jun 1999||7 Jan 2003||Kimberly-Clark Worldwide, Inc.||Neonanoplasts and microemulsion technology for inks and ink jet printing|
|US6524379||12 Jan 2001||25 Feb 2003||Kimberly-Clark Worldwide, Inc.||Colorants, colorant stabilizers, ink compositions, and improved methods of making the same|
|U.S. Classification||430/332, 430/343|