CA2120838A1

CA2120838A1 - Solid colored composition mutable by ultraviolet radiation

Info

Publication number: CA2120838A1
Application number: CA002120838A
Authority: CA
Inventors: Ronald Sinclair Nohr; John Gavin Macdonald; Vincent Daniel Mcginniss; Robert Samuel Whitmore, Jr
Original assignee: Kimberly Clark Corp
Current assignee: Kimberly Clark Corp
Priority date: 1993-08-05
Filing date: 1994-04-08
Publication date: 1995-02-06
Also published as: US5643701A; US5683843A; US5616443A

Abstract

Abstract A solid colored composition which includes a colorant and an ultraviolet radiation transorber. The colorant, in the presence of the ultraviolet radiationtransorber, is adapted, upon exposure of the transorber to ultraviolet radiation, to be mutable. The ultraviolet radiation transorber is adapted to absorb ultraviolet radiation and interact with the colorant to effect the irreversible mutation of the colorant. By way of example, the solid colored composition can be a toner adapted to be utilized in an electrophotographic process. The toner includes the colorant and ultraviolet radiation transorber as just described, and a carrier. The carrier can be a polymer, and the toner may contain a charge carrier. The ultraviolet radiation in general will have wavelengths of from about 100 to about 375 nanometers. Especially useful incoherent, pulsed ultraviolet radiation is produced by a dielectric barrier discharge excimer lamp.

Description

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SOLID COLORED COMPOSITION hIUTABLE
l~Y ULTRAVIOLET ~A~IATION

Field of the Invention The present invention relates to a solid colored composition, which in some embodiments may be employed as an electrophotographic toner, e.g., a toner employed in a photocopier which is based on transfer xerography.
Background of the Invention Electrophotography is broadly defined as a process in which photons are captured to create an electrical image analogue of the original. The electrical analogue in turn is manipulated through a number of steps which result in a physical image. The most commonly used form of electrophotography presently in use is called transfer xerography. Although first demonstrated by C. Carlson in 1938, the process was slow to gain acceptance. Today, however, transfer xerography is the foundation of a multibillion dollar industry.
The heart of the process is a photoreceptor, usually the moving element of the process, which is typically either drum-shaped or a continuous, seamless belt. A corona discharge device deposits gas ions on the photoreceptor surface. The ions provide a uniform electric field across the photoreceptor and a uniform charge layer on its surface. An image of an illuminated original is projected through a lens system and focused on the photoreceptor. Light striking the charged photoreceptor surface results in increased conductivity across the photoreceptor with the concomitant neutralization of surface charges.Unilluminated regions of the photoreceptor surface retain their charges. The resulting pattern of surface charges is the latent electrostatic image.
A thermoplastic pigmented powder or toner, the particles of which bear a charge opposite to the surface charges on the photoreceptor, is brought close to ~he photoreceptor, thereby permitting toner particles to be attracted to the -: ~; . . .
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charged regions on the photoreceptor surface. The result is a physical image on the photoreceptor surface consisting of electrostatically held toner particles.
A sheet of plain paper is brought into physical contact with the toner-bearing photoreceptor. A charge applied to the back side of the paper induces 5 the attraction of the toner image to the paper. The image is a positive image of the original. The paper then is stripped from the photoreceptor, with the toner image clinging to it by electrostatic attraction. The toner image is permanently fused to the paper by an appropriate heating means, such as a hot pressure roll or a radiant heater.
Because there is incomplete transfer of toner to the paper, it is necessary to clean the photoreceptor surface of residual toner. Such toner is wiped off with a brush, cloth, or blade. A corona discharge or reverse polarity aids in the removal of toner. A uniform light source then floods the photoreceptor to neutralize any residual charges from the previous image cycle, 15 erasing the previous electrostatic image completely and conditioning the photoreceptor surface for another cycle.
The toner generally consists of 1-15 micrometer average diameter particles of a thermoplastic powder. Black toner typically contains 5-10 percent by weight of carbon black particles of less than 1 micrometer dispersed 20 in the thermoplastic powder. For toners employed in color xerography, the carbon black may be replaced with cyan, magenta, or yellow pigments. The concentration and dispersion of the pigment must be adjusted to impart a conductivity to the toner which is appropriate for the development system. For most development processes, the toner is required to retain for extended 25 periods of time the charge applied by contact electrification. The thermoplastic employed in the toner in general is selected on the basis of its melting behavior. The thermoplastic must melt over a relatively narrow temperature range, yet be stable during storage and able to withstand the vigorous agitationwhich occurs in xerographic development chambers.

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The success of electrophotography, and transfer xerography in particular, no doubt is a significant factor in the efficient distribution of information which has become essential in a global setting. It also contributes to the generation of mountains of paper which ultimately must either be 5 disposed of or recycled. While paper is recycled, it presently is converted topulp and treated to remove ink, toner, and other colored materials, i.e., deinked, an expensive and not always completely successful operation.
Moreover, deinking results in a sludge which typically is disposed of in a landfill. The resulting deinked pulp then is used, often with the addition of at10 least some virgin pulp, to form paper, cardboard, cellulosic packaging materials, and the like.
The simplest form of recycling, however, is to reuse the paper intact, thus eliminating the need to repulp. To this end, toners for copier machines have been reported which are rendered colorless on exposure to near infrared 15 or infrared radiation. Although the spectrum of sunlight ends at about 375 nanometers, it has a significant infrared component. Hence, such toners have a salient disadvantage in that they are transitory in the presence of such environmental factors as sunlight and heat; that is, such toners become colorless. This result is unsatisfactory because the documents can be rendered 20 illegible before their function or purpose has ended. Accordingly, there is aneed for toners for copy machines which will permit the recycling of paper intact, but which are stable to normally encountered environmental factors.

Summary of the Invention It is an aspect of the present invention to provide a solid colored composition which is adapted to become colorless upon exposure to ultraviolet radiation.

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This and otherasPectSwill be apparent to those having ordinary skill in the art from a consideration of the specification and claims which follow.
Accordingly, the present invention provides a solid colored composition which includes:
(A) a colorant which, in the presence of an ultraviolet radiation transorber, is adapted, upon exposure of the transorber to ultraviolet radiation, to be mutable; and (B) an ultraviolet radiation transorber which is adapted to absorb . .
ultraviolet radiation and interact with the colorant to effect the irreversible mutation of the colorant.
The present invention also provides a solid colored composition adapted to be utilized as a toner in an electrophotographic process, which composition includes:
(A) a colorant which, in the presence of an ultraviolet radiation transorber, is adapted, upon exposure of the transorber to ultraviolet radiation, to be mutable;
(B) an ultraviolet radiation transorber which is adapted to absorb ~:
ultraviolet radiation and interact with the colorant to effect the irreversible mutation of the colorant; and (C) a carrier for the colorant and the ultraviolet radiation transorber.
The present invention additionally provides a method of mutating a solid colored composition which includes:
(A) providing a colorant which, in the presence of an ultraviolet radiation transorber, is adapted, upon exposure of th transorber to ultraviolet radiation, to be mutable;
(B) providing an ultraviolet radiation transorber which is adapted to absorb ultraviolet radiation and interact with said colorant to effect the irreversible mutation of the colorant;
(C) blending the colorant and the ultraviolet radiation transorber: and - :~
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(D) irradiating the solid colored composition with ultraviolet radiation at a dosage level sufficient to irreversibly mutate the colorant.
The present invention further provides an electrophotographic process which includes:
(A) creating an image of a pattern on a photoreceptor surface;
(B) applying a toner to the photoreceptor surface to forrn a toner image which replicates the pattern;
(C) transferring the toner image to a substrate; and (D) fixing the toner image to the substrate;
in which the toner includes a colorant, an ultraviolet radiation transorber, anda carrier as already described.
The present invention still further provides an electrophotographic process which includes:
(A) providing a substrate having a first pattern thereon which is formed by a first toner which includes:
(1) a colorant which, in the presence of an ultraviolet radiation transorber, is adapted, upon exposure of the transorber to ultraviolet radiation, to be mutable;
(2) an ultraviolet radiation transorber which is adapted to absorb ultraviolet radiation and interact with the colorant to effect the irreversible mutation of the colorant; and (3) a calTier for the colorant and the ultraviolet radiation transorber;
(B) exposing the first pattern on the substrate to ultraviolet radiation at a dosage level sufficient to irreversibly mutate the colorant;
(C) creating an image of a second pattern on a photoreceptor surface;
(D) applying a second toner to the photoreceptor surface to form a toner image which replicates the second pattern;

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(F) fixing the second toner image to the substrate.
If desired, the second toner can be similar to the first toner.
In certain embodiments, the ultraviolet radiation will have a wavelength in the range of from about 100 to about 400 nanometers. In other embodi-ments, the ultraviolet radiation is incoherent, pulsed ultraviolet radiation ~rom a dielectric barrier discharge excimer lamp.
Other and further advantages and aspects of the present invention will become more apparent to those skilled in the art in view of the following detailed description.

Detailed DescFiption of the Invention The term "composition" and such variations as "solid colored composi-tion" and "colored composition" are used herein to mean a colorant and an ultraviolet radiation transorber. When reference is being made to a solid colored composition which is adapted for a specific application, such as a tonerto be used in an electrophotographic process, the terrn "composition-based" is used as a modifier to indicate that the material, e.g., a toner, includes a colorant and an ultraviolet radiation transorber.
As used herein, the term "colorant" is meant to include, without limitation, any material which, in the presence of an ultraviolet radiation transorber, is adapted upon exposure to ultraviolet radiation to be mutable. As a practical matter, the colorant typically will be an organic material, such as an organic dye or pigment, including toners and lakes. Desirably, the colorant will be substantially transparent to, that is, will not significantly interact with, the ultraviolet radiation to which it is exposed. The term is meant to include a single material or a mixture of two or more materials.
Organic dye classes include, by way of illustration only, triaryl methyl dyes. such as Malachite Green Carbinol base {4-(dimethylamino)-a-~4-(dimethylamino)phenyl]-~-phenylbenzenemethanol}, Malachite Green Carbinol ~. -f ,; .

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, ` hydrochloride {N-4-~[4-(dimethylamino)phenyl]phenylmethylene]-2,5-cyclo-hexyldien- 1 -ylidene]-N-methylmethanaminium chloride or bis~-(dimethyl-amino)phenyl]phenylmethylium chloride}, and Malachite Green oxalate {N-4-[[4-(dimethylamino)phenyl]phenylmethylene]-2,5-cyclohexyldien- l -ylidene]-S N-methylmethanaminium chloride or bis[l2-(dimethylamino)phenyl]phenyl-methylium oxalate}; monoazo dyes, such as Cyanine Blacl~, Chrysoidine [BasicOrange 2; 4-(phenylazo)- 1 ,3-benzenediamine monohydrochloride], and B-Naphthol Orange; thiazine dyes, such as Methylene Green, zinc chloride double salt [3,7-bis(dimethylamino)-6-nitrophenothiazin-5-ium chloride, zinc 10 chloride double salt]; oxazine dyes, such as Lumichrome (7,8-dimethylallox-azine)7 naphthalimide dyes, such as Lucifer Yellow CH {6-amino-2-[(hydra-zinocarbonyl)amino]-2,3-dihydro-1 ,3-dioxo-lH-benz[de]isoquinoline-5,8-disulfonic acid dilithium salt}; azine dyes, such as Janus Green B {3-(diethylamino)-7-[[4-(dimethylamino)phenyl]azo]-5-phenylphenazinium 15 chloride}; cyanine dyes, such as Indocyanine Green ~Cardi~Green or Fox Green; 2-[7-[1,3-dihydro-1,1-dimethyl-3-(4-sulfobutyl)-2H-benz[e]indol-2-ylidene]-l ,3,5-heptatrienyl]-1, 1-dimethyl-3-(4-sulfobutyl)-lH-benz[e]indolium hydroxide inner salt sodium salt}; indigo dyes, such as Indigo ~Indigo Blue or Vat Blue 1; 2-(1,3-dihydro-3-oxo-2H-indol-2-ylidene)-1,2-dihydro-3H-indol-20 3-one}; coumarin dyes, such as 7-hydroxy-4-methylcoumarin (4-methylumbel-liferone); benzimidazole dyes, such as Hoechst 33258 [bisberlzimide or 2'-(4-hydroxyphenyl)-S-(4-methyl- 1 -piperazinyl)-2,5 ' -bi- 1 H-benzimidazole trihydrochloride pentahydrate]; paraquinoidal dyes, such as Hematoxylin {Natural Black 1; 7,1lb-dihydrobenz[b]indeno[1,2-d]pyran-3,4,6a,9,10(6H)-25 pentol}; fluorescein dyes, such as Flouresceinamine (5-aminofluorescein);
diazonium salt dyes, such as Diazo Red RC (Azoic Diazo No. 10 or Fast Red RC salt; 2-methoxy-S-chlorobenzenediazonium chloride, zinc chloride double salt); azoic diazo dyes, such as Fast Blue BB salt (Azoic Diazo No. 20; 4-benzoylamino-2,5-diethoxybenzene diazonium chloride, zinc chloride double .. .

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salt); phenylenediamine dyes, such as Disperse Yellow 9 [N-(2,4-dinitro-phenyl)-1,4-phenylenediamine or Solvent Orange 53]; disazo dyes, such as Disperse Orange 13 [Solvent Orange 52; 1-phenylazo-4-(4-hydroxyphenylazo)-naphthalene~; anthraquinone dyes, such as Disperse Blue 3 [Celliton Fast Blue FFR; 1-methylamino-4-(2-hydroxyethylamino)-9,10-anthraquinone], Disperse Blue 14 [Celliton Fast Blue B; 1,4-bis(methylamino)-9,10-anthraquinone], and Alizarin Blue Black B (Mordant Black 13); trisazo dyes, such as Direct Blue 71 {Benzo Light Blue FFL or Sirius Light Blue BRR; 3-[(4-[(4-[(6-amino-1-hydroxy-3-sulfo-2-naphthalenyl)azo]-6-sulfo- 1 -naphthalenyl)azo] - 1 -naphtha-lenyl)azo]-l ,5-naphthalenedisulfonic acid tetrasodium salt}; xanthene dyes, such as 2',7'-dichlorofluorescein; proflavine dyes, such as 3,6-diaminoacridine hemisulfate (Proflavine); sulfonephthalein dyes, such as Cresol Red (Q-cresol-sulfonephthalein); phthalocyanine dyes, such as Copper Phthalocyanine {Pigment Blue 15; (SP-4-1)-[29H,31H-phthalocyanato(2-)-N29,N3,N3',N32]-copper}; carotenoid dyes, such as trans-B-carotene (Food Orange 5); carminic acid dyes, such as Carmine, the aluminum or calcium-aluminum lake of carminic acid (7-~-D-glucopyranosyl-9,10-dihydro-3,5,6,8-tetrahydroxy-1-methyl-9,10-dioxo-2-anthracenecarboxylic acid); azure dyes, such as Azure A
[3-amino-7-(dimethylamino)phenothiazin-5-ium chloride or 7-(dimethylamino)-3-imino-3H-phenothiazine hydrochloride]; and acridine dyes, such as Acrid-ine Orange [Basic Orange 14; 3,8-bis(dimethylamino)acridine hydrochloride, zinc chloride double salt] and Acriflavine (Acriflavine neutral; 3,6-diamino-10-methylacridinium chloride mixture with 3,6-acridinediamine).
The terrn "mutable" with reference to the colorant is used to mean that the absorption max~mum of the colorant in the visible region of the electro-magnetic spectrum is capable of being mutated or changed by exposure to ultraviolet radiation when in the presence of the ultraviolet radiation transorb-er. In general, it is only necessary that such absorption maximum be mutated to an absorption maximum which is different from that of the colorant prior ,, ,~ : ~

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to exposure to the ultraviolet radiation, and that the mutation be irreversible.Thus~ the new abso~ption maximum can be within or without the visible region of the electromagnetic spectrum. In other words, the colorant can mutate to a different color or be rendered colorless. The latter, of course, is desirable 5 when the colorant is used in a solid colored composition adapted to be utilized as a toner in an electrophotographic process which reuses the electrophoto-graphic copy by first rendering the colored composition colorless and then placing a new image thereon.
As used herein, the term "irreversible" means only that the colorant will 10 not revert to its original color when it no longer is exposed to ultraviolet radia-tion. Desirably, the mutated colorant will be stable, i.e., not appreciably adversely affected by radiation normally encountered in the environment, such as natural or artificial light and heat. Thus, desirably a colorant rendered colorless will remain colorless indefinitely.
The term "ultraviolet radiation transorber" is used herein to mean any material which is adapted to absorb ultraviolet radiation and interact with the colorant to effect the mutation of the colorant. In some embodiments, the ultraviolet radiation transorber may be an organic compound. The term "compound" is intended to include a single material or a mixture of two or 20 more materials. If two or more materials are employed, it is not necessary that all of them absorb ultraviolet radiation of the same wavelength.
While the mechanism of the interaction of the ultraviolet radiation transorber with the colorant is not totally understood, it is believed that it may interact with the colorant in a variety of ways. For example, the ultraviolet 25 radiation transorber, upon absorbing ultraviolet radiation. may be converted to one or more free radicals which interact with the colorant. Such free radical-generating compounds typically are hindered ketones, some examples of which are benzildimethyl ketal (available commercially as Irgacure~ 651, Ciba-Geigy Corporation, Hawthorne, New York), l-hydroxycyclohexyl phenyl l~etone g "
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(Irgacure~ 500), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-, one] (Irgacure~ 907), 2-benzyl-2-dimethylamino- 1 -(4-morpholinophenyl)butan-1-one (Irgacure~ 369), and l-hydroxycyclohexyl phenyl ketone (Irgacure~
184).
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S Alternatively, the ultraviolet radiation may initiate an electron transfer or reduction-oxidation reaction between the ultraviolet radiation transorber andthe colorant. In this case, the ultraviolet radiation transorber may be Michler's ketone (12-dimethylaminophenyl ketone) or benzyl trimethyl stannate. Or, a cationic mechanism may be involved, in which case the ultraviolet radiation transorber could be, for example, bis[4-(diphenylsulphonio)phenyl)] sulfide bis~hexafluorophosphate) (Degacure~ KI85, Ciba-Geigy Corporation, Hawthorne~
New York); Cyracure~ UVI-6990 (Ciba-Geigy Corporation), which is a mixture of bis[4-(diphenylsulphonio)phenyl] sulfide bis(hexafluorophosphate) with related monosulphonium hexafluorophosphate salts; and ~5-2,4-(cyclopenta-dienyl)[l,2,3,4,5,6-~q-(methylethyl)benzene]-iron(II) hexafluorophosphate (Irgacure~ 261).
The term "ultraviolet radiation" is used herein to mean electromagnetic radiation having wavelengths in the range of from about 100 to about 400 nanometers. Thus, the term includes the regions commonly referred to as 20 ultraviolet and vacuum ultraviolet. The wavelength ranges typically assigned to these two regions are from about 180 to about 400 nanometers and from about 100 to about 180 nanometers, respectively.
In some embodiments, the molar ratio of ultraviolet radiation transor-ber to colorant generally will be equal to or greater than about 0.5. As a 25 general rule, the more efficient the ultraviolet radiation transorber is in ab-sorbing the ultraviolet radiation and interacting with, i.e., transferring absorbed energy to, the colorant to effect irreversible mutation of the colorant. the lower such ratio can be. Current theories of molecular photochemistry suggest tha~
the lower limit to such ratio is 0.5, based on the generation of two free .,;

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radicals per photon. As a practical matter, however, higher ratios are likely to be required, perhaps as high as about 50. At the present time, ratios of about 20 to about 30 appear to be typical. In any event, the present invention is not bound by any specific lower molar ratio range. The important feature 5 is that the transorber is present in an amount sufficient to effect mutation of the colorant.
As a practical matter, both the colorant and the ultraviolet radiation transorber are likely to be solids. However, the colorant and/or the transorber can be liquid. It is only necessary for the composition to be a solid.
Because the solid colored composition of the present invention is a solid, the effectiveness of the ultraviolet radiation transorber in effecting the mutation of the colorant is aided if the colorant and the ultraviolet radiation transorber are in intimate contact. To this end, the thorough blending of the two components, along with other components which may be present, is desirable.
Such blending generally is accomplished by any of the means known to those having ordinary skill in the art. When the colored composition includes a polymer, blending is facilitated if the colorant and the ultraviolet radiation transorber are at least partly soluble in softened or molten polymer. In such case, the composition is readily prepared in, for example, a two-roll mill.
For some applications, the solid colored composition of the present invention should be utilized in particulate form. In other applications, the particles of the somposition should be very small. For example, the particles of a solid colored composition adapted for use as a toner in an electrophoto-graphic process typically consist of 7-15 micrometer average diameter particles, although smaller or larger particles can be employed. Methods of formin~ such particles are well known to those having ordinary skill in the art.Photochemical processes involve the absorption or light quanta, or photons, by a molecule, e.g., the ultraviolet radiation transorber, to produce a highly reactive electronically excited state. However, the photon energy, . ::
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which is proportional to the wavelength of the radiation, cannot be absorbed by the molecule unless it matches the energy difference between the unexcited, or onginal, state and an excited state. Consequently, while the wavelength range of the ultraviolet radiation to which the solid colored composition is S exposed is not directly of concern, at least a portion of the radiation must have wavelengths which will provide the necessary energy to raise the ultraviolet radiation transorber to an energy level which is capable of interacting with thecolorant.
It follows, then, that the absolption maximum of the ultraviolet radiation 10 transorber ideally will be matched with the wavelength range of the ultraviolet radiation in order to increase the eff~ciency of the mutation of the colorant.
Such efficiency also will be increased if the wavelength range of the ultraviolet radiation is relatively narrow, with the maximum of the ultraviolet radiation transorber coming within such range. For these reasons, especially suitable ultraviolet radiation has a wavelength of from about 100 to about 375 nanometers. Ultraviolet radiation within this range desirably may be incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp.
The term "incoherent, pulsed ultraviolet radiation" has reference to the radiation produced by a dielectric barrier discharge excimer lamp (referred to hereinafter as "excimer lamp"). Such a lamp is described, for example, by U. Kogelschatz, "Silent discharges for the generation of ultraviolet and vacuum ultraviolet excimer radiation, " Pure & Appl. Chem., 62, No. 9, pp. 1667-1674 (1990); and E. Eliasson and U. Kogelschatz, "UV Excimer Radiation from Dielectric-Barrier Discharges," Appl. Phys. B, 46, pp. 299-303 (1988).
Excimer lamps were developed originally by ABB Infocom Ltd., Lenzburg, Switzerland. The excimer lamp technology since has been acquired by Haraus Noblelight AG, Hanau, Germany.

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The excimer lamp emits radiation having a very narrow bandwidth, i.e., radiation in which the half width is of the order of 5-15 nanometers.
This emitted radiation is incoherent and pulsed, the frequency of the pulses being dependent upon the frequency of the alternating current power supply S which typically is in the range of from about 20 to about 300 kHz. An excimer lamp typically is identified or referred to by the wavelength at which the maximum intensity of the radiation occurs, which convention is followed throughout this specification. Thus, in comparison with most other commer-cially useful sources of ultraviolet radiation which typically emit over the entire ultraviolet spectrum and even into the visible region, excimer lamp radiation is essentially monochromatic.
Excimers are unstable molecular complexes which occur only under extreme conditions, such as those temporarily existing in special types of gas discharge. Typical examples are the molecular bonds between two rare gaseous atoms or between a rare gas atom and a halogen atom. Excimer complexes dissociate within less than a microsecond and, while they are dissociating, release their binding energy in the form of ultraviolet radiation.Known excimers in general emit in the range of from about 125 to about 360 nanometers, depending upon the excimer gas mixture.
Although the colorant and the ultraviolet radiation transorber have been described as separate compounds, they can be part of the same molecule. For example, they can be covalently coupled to each other, either directly, or indirectly through a relatively small molecule, or spacer. Alternatively, the colorant and ultraviolet radiation transorber can be covalently coupled to a 2~ large molecule, such as an oligomer or a polymer, particularly when the solid colored composition of the present invention is adapted to be utilized as a toner in an electrophotographic process. Other variations will be readily apparent to those having ordinary skill in the art.

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When the solid colored composition is adapted to be utilized as a toner in an electrophotographic process, the composition also will contain a carrier, the nature of which is well known to those having ordinary skill in the art.
For many applications, the carrier will be a polymer, typically a thermosetting 5 or thermoplastic polymer, with the latter being the more common.
Examples of thermoplastic polymers include, by way of illustration only, end-capped polyacetals, such as poly(oxymethylene) or polyformaldehyde, poly(trichloroacetaldehyde), poly(n-valeraldehyde), poly(acetaldehyde), poly(propionaldehyde), and the like; acrylic polymers, such as polya-10 crylamide, poly(acrylic acid), poly(methacrylic acid), poly(ethyl acrylate),poly(methyl methacrylate), and the like; fluorocarbon polymers, such as poly(tetrafluoroethylene), perfluorinated ethylene-propylene copolymers, ethylene-tetrafluoroethylene copolymers, poly(chlorotrifluoroethylene), ethylene-chlorotrifluoroethylene copolymers, poly(vinylidene fluoride), 15 poly(vinyl fluoride), and the like; epoxy resins, such as the condensation products of epichlorohydrin and bisphenol A; polyamides, such as poly(6-aminocaproic acid) or poly(~-caprolactam), poly(hexamethylene adipamide), poly(hexamethylene sebacamide), poly(ll-aminoundecanoic acid), and the 1-ike; polyaramides, such as poly(imino-1,3-phenyleneiminoisophthaloyl) or 20 poly(m-phenylene isophthalamide), and the like; parylenes, such as poly-~xylylene, poly(chloro-12-xylylene), and the like; polyaryl ethers, such as poly(oxy-2,6-dimethyl-1,4-phenylene)orpoly(l2-phenyleneoxide), andthelike;
polyaryl sulfones, such as poly(oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenylene-isopropylidene-1,4-phenylene), poly(sulfonyl-1,4-phenylene-25 oxy-1,4-phenylenesulfonyl-4,4'-biphenylene), and the like; polycarbonates, such as poly(bisphenol A) or poly(carbonyldioxy-l ,4-phenyleneisopropylidene-1,4-phenylene), and the like; polyesters, such as poly(ethylene terephthalate), poly(tetramethylene terephthalate), poly(cyclohexylene-1,4-dimethylene terephthalate) or poly(oxymethylene-1,4-cyclohexylenemethyleneoxytere-., -. , . - . .
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phthaloyl), and the like; polyaryl sulfides, such as poly(l2-phenylene sulfide) or poly(thio- 1 ,4-phenylene), and the like; polyimides, such as poly-(pyromellitimido-1,4-phenylene), and the like; polyolefins, such as polyethyl-ene, polypropylene, poly(1-butene), poly(2-butene), poly(l-pentene), S poly(2-pentene), poly(3-methyl-1-pentene), poly(4-methyl-1-pentene), 1,2-poly-1,3-butadiene, 1,4-poly-1,3-butadiene, polyisoprene, polychloroprene, polyacrylonitrile, poly(vinyl acetate), poly(vinylidene chloride), polystyrene, and the like; and copolymers of the foregoing, such as acrylonitrile-butadiene-styrene (ABS) copolymers, styrene-_-butylmethacrylate copolymers, ethylene-vinyl acetate copolymers, and the like.
Some of the more commonly used thermoplastic polymers include styrene-n-butyl methacrylate copolymers, polystyrene, styrene-n-butyl acrylate copolymers, styrene-butadiene copolymers, polycarbonates, poly(methyl -methacrylate), poly(vinylidene fluoride), polyamides (nylon-12), polyethylene, polypropylene, ethylene-vinyl acetate copolymers, and epoxy resins. -Examples of thermosetting polymers include, again by way of illustration only, alkyd resins, such as phthalic anhydride-glycerol resins, maleic acid-glycerol resins, adipic acid-glycerol resins, and phthalic anhydride-pentaerythritol resins; allylic resins, in which such monomers as diallyl phthalate, diallyl isophthalate diallyl maleate, and diallyl chlorendate serve as nonvolatile cross-linking agents in polyester compounds; amino resins, such as aniline-formaldehyde resins, ethylene urea-formaldehyde resins, dicyandiamide-formaldehyderesins, melamine-formaldehyderesins, sulfonamide-formaldehyde resins, and urea-formaldehyde resins; epoxy resins, such as cross-linked epichlorohydrin-bisphenol A resins; phenolic resins, such as phenol-formalde-hyde resins, including Novolacs and resols; and therrnosetting polyesters, silicones, and urethanes.

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In addition to the colorant, ultraviolet radiation transorber, and optional carrier, the solid colored composition of the present invention also can containadditional components, depending upon the application for which it is intended.
For example, a composition which is to be utilized as a toner in an electro-S photographic process also can contain, for example, charge carriers, stabilizersagainst thermal oxidation, viscoelastic properties modifiers, cross-linking agents, plasticizers, and the like. For some applications, the charge carrier will be the major component of the toner. Charge carriers, of course, are well known to those having ordinary skill in the art and typically are polymer-10 coated metal particles.
The amount or dosage level of ultraviolet radiation in general will bethat amount which is necessary to mutate the colorant. The dosage level, in turn, typically is a function of the time of exposure and the intensity or flux of the radiation source which irradiates the solid colored composition. The 15 latter is effected by the distance of the composition from the source and, depending upon the wavelength range of the ultraviolet radiation, can be effected by the atmosphere between the radiation source and the composition.
Accordingly, in some instances it may be appropriate to expose the composi-tion to the radiation in a controlled atmosphere or in a vacuum, although in 20 general neither approach is desired.
The solid colored composition of the present invention can be utilized on or in any substrate. If the composition is present in a substrate, however, the substrate should be substantially transparent to the ultraviolet radiation which is employed to mutate the colorant. That is, the ultraviolet radiation 25 will not significantly interact with or be absorbed by the substrate. As a practical matter, the composition typically will be placed on a substrate, with the most common substrate being paper. Other substrates, such as woven and nonwoven webs or fabrics, films, and the like, can be used, however.

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'`,' ': . , When the solid colored composition is er~yed as a toner for an electrophotographic process, several variations are possible and come within the scope of the present invention. For example, the composition-based toner can be used to form a first image on a virgin paper sheet. The sheet then can 5 be recycled by exposing the sheet to ultraviolet radiation in accordance with the present invention to render the colorant, and, as a consequence, the composition, colorless. A second image then can be formed on the sheet.
The second image can be formed from a standard, known toner, or from a composition-based toner which is either the same as or different from the 10 composition-based toner which was used to form the first image. If a composition-based toner is used to form the second image, the sheet can be recycled again, with the number of cycles being limited by the build-up of now colorless composition on the sur~ace of the paper. However, any subsequent image can be placed on either side of the sheet. That is, it is not required that 15 a second image be formed on the side of the sheet on which the first image was formed.
In addition, the conversion of the composition-based toner image on the sheet to a colorless form does not have to take place on the sheet. For example, sheets having images formed from composition-based toners can be 20 recycled in the traditional way. In place of the usual deinking step, however, the sheets are exposed to ultraviolet radiation, either before or after being converted to pulp. The colorless toner then simple becomes incorporated into the paper formed from the resulting pulp.
The present invention is further described by the examples which 25 follow. Such examples, however, are not to be construed as limiting in any way either the spirit or scope of the present invention. In the examples~ all parts are parts by weight unless stated otherwise.

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Example 1 This example describes the preparation of films consisting of colorant, ultraviolet radiation transorber, and thermoplastic polymer. The colorant and 5 ultraviolet radiation transorber were ground separately in a mortar. The desired amounts of the ground components were weighed and placed in an aluminum pan, along with a weighed amount of a thermoplastic polymer. The pan was placed on a hot plate set at 150C and the mixture in the pan was stirred until molten. A few drops of the molten mixture were poured onto a 10 steel plate and spread into a thin film by means of a glass microscope slide.Each steel plate was 3 x 5 inches (7.6 cm x 12.7 cm) and was obtained from Q-Panel Company, Cleveland, Ohio. The film on the steel plate was estimated to have a thickness of the order of 10-20 micrometers.
In every instance, the colorant was Malachite Green oxalate (Aldrich 15 Chemical Company, Inc., Milwaukee, Wisconsin), referred to hereinafter as Colorant A for convenience. The ultraviolet radiation transorber (UVRT) consisted of one or more of Irgacure~ 500 (UVRT A), Irgacure~ 651 (UVRT
B), and Irgacure~ 907 (UVRT C), each of which was described earlier and is available from Ciba-Geigy Corporation, Hawthorne, New York. The polymer 20 was one of the following: an epichlorohydrin-bisphenol A epoxy resin (Polymer A), EponX 1004F (Shell Oil Company, Houston, Texas); a poly(ethylene glycol) having a weight-average molecular weight of about 8,000 (Polymer B), Carbowax 8000 (Aldrich Chemical Company); and a poly-(ethylene glycol) having a weight-average molecular weight of about 4,600 25 (Polymer C), Carbowax 4600 (Aldrich Chemical Company). A control film was prepared which consisted only of colorant and polymer. The compositions of the films are summarized in Table l-1.

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Table 1-1 Compositions of Films Contail~ing Colorant and Ultraviolet R:ldiation Transorber (UVRT) ColQrant ~VRT Polymer Eilm~ ~ ~L Parts ~ Parts G A l A 6 B 90 While still on the steel plate, each film was exposed to ultraviolet radiation. In each case, the steel plate having the film sample on its surface was placed on a moving conveyor belt having a variable speed control. Three different ultraviolet radiation sources, or lamps, were used. Lamp A was a 222-nanometer excimer lamp and Lamp B was a 308-nanometer excimer lamp, as already described. Lamp C was a fusion lamp system having a "D'l bulb (Fusion Systems Corporation, Rockville, Maryland). The excimer lamps were organized in banks of four cylindrical lamps having a length of about 30 cm, with the lamps being oriented normal to the direction of motion of the belt.

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The lamps were cooled by circulating water through a centrally located or inner tube of the lamp and, as a consequence, they operated at a relatively low temperature, i.e., about 50C. The power density at the lamp's outer surface typically is in the range of from about 4 to about 20 joules per square meter S (J/m2). However, such range in reality merely reflects the capabilities of current excimer lamp power supplies; in the future, higher power densities may be practical. With Lamps A and B, the distance from the lamp to the film sample was 4.5 cm and the belt was set to move at 20 ft/min (0.1 m/sec).
With Lamp C, the belt speed was 14 ft/min (0.07 m/sec) and the lamp-to-10 sample distance was 10 cm. The results of exposing the film samples toultraviolet radiation are summarized in Table 1-2. Except for Film F, the table records the number of passes under a lamp which were required in order to render the film colorless. For Film F, the table records the number of passes tried, with the film in each case remaining colored (no change).
Table 1~2 Results of Exposing Films Containing Colorant and Ultraviolet Radiation Transorber (UVRT) to Ultraviolet Radiation Excimer Lamp Film Lamp A Lam~ BFusion Lamp E

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Table 1-2, Continued -. .
Excimer Lamp FilmLamp A Lamp B Fusion Lamp Example 2 This example describes the preparation of solid colored compositions adapted to be utilized as toners in an electrophotographic process. In every instance, the toner included Colorant A as described in Example 1; a polymer, DER 667, an epichlorohydrin-bisphenol A epoxy resin (Polymer D), Epon~
1004F (I:~ow Chemical Company, Midland, Michigan); and a charge carrier, 15 Carrier A, which consisted of a very finely divided polymer-coated metal.
The ultraviolet radiation transorber (UVRT) consisted of one or more of UVRT B from Example 1, Irgacure~ 369 (UVRT D), and Irgacure~ 184 (UYRT E); the latter two transorbers were described earlier and are available from Ciba-Geigy Corporation, Hawthorne, New York. In one case, a second 20 polymer also was present, styrene acrylate 1221, a styrene-acrylic acid copolymer (Hercules Incorporated, Wilmington, Delaware).
To prepare the toner, colorant, ultraviolet radiation transorber, and polymer were melt-blended in a Model 3VV 800E, 3 inch x 7 inch (7.6 cm x 17.8 cm) two-roll research mill (Farrel Corporation, Ansonia, Connecticut).
25 The resulting melt-blend was powdered in a Mikropul hammermill with a 0.010-inch herringbone screen (R. D. Kleinfeldt, Cincinnati, Ohio~ and ~hen sieved for proper particle sizes in a Sturtvant, air two-inch micronizer (R. D
Kleinfeldt) to give what is referred to herein as a pretoner. Charge carrier then was added to the pretoner and the resulting mixture blended thoroughly.

Table 2-1 summarizes the compositions of the pretoners and Table 2-2 summarizes the compositions of the toners.

Table 2-1 S Summary of Pretoner Compositions Colorant UVRT Polvmer Pretoner A (g) Type g :~ %

D 1 B 6.9 D 40 D 6.6 E 40 E 6.6 Table 2-2 :
Summary of Toner Compositions Pretoner Charge Toner Type g Carrier (g!
A A 8.4 210 B B 8.4 210 C C 8.~ 210 D D 8.4 210 Each toner was placed separately in a Sharp Model ZT-50TDl toner cartridge and installed in either a Sharp Model Z-76 or a Sha~p Model Z-77 xerographic copier (Sharp Electronics Corporation, Mahwah, New Jersey).

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Images were made in the usual manner on bond paper (Neenah Bond). The image-bearing sheets then were exposed to ultraviolet radiation from Lamp B
as described in Example 1. In each case, the image was rendered colorless with one pass.
Having thus described the invention, numerous changes and modifica-tions hereof will be readily apparent to those having ordinary skill in the art without departing from the spirit or scope of the invention.

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Claims

1. A solid colored composition which comprises:
(A) a colorant which, in the presence of an ultraviolet radiation transorber, is adapted, upon exposure of the transorber to ultraviolet radiation, to be mutable; and (B) an ultraviolet radiation transorber which is adapted to absorb ultraviolet radiation and interact with said colorant to effect the irreversiblemutation of the colorant.

2. A method of irreversibly mutating a solid colored composition which comprises:
(A) providing a colorant which, in the presence of an ultraviolet radiation transorber, is adapted, upon exposure of the transorber to ultravioletradiation, to be mutable;
(B) providing an ultraviolet radiation transorber which is adapted to absorb ultraviolet radiation and interact with said colorant to effect the irreversible mutation of the colorant;
(C) blending the colorant and the ultraviolet radiation transorber; and (D) irradiating said solid colored composition with ultraviolet radi-ation at a dosage level sufficient to irreversibly mutate said colorant.

3. The method of claim 2, in which said colorant and said ultraviolet radiation transorber are in intimate contact.

4. The method of claim 2, in which said colorant is applied to a substrate before being irradiated with ultraviolet radiation.

5. The method of claim 2, in which said mutated colorant is stable.

6. A solid colored composition adapted to be utilized as a toner in an electrophotographic process, which composition comprises:
(A) a colorant which, in the presence of an ultraviolet radiation transorber, is adapted, upon exposure of the transorber to ultraviolet radiation, to be mutable;
(B) an ultraviolet radiation transorber which is adapted to absorb ultraviolet radiation and interact with said colorant to effect the irreversiblemutation of the colorant; and (C) a carrier for said colorant and said ultraviolet radiation transorber.

7. The solid colored composition of claim 6, in which said carrier is a polymer.

8. The solid colored composition of claim 7, in which said composi-tion includes a charge carrier.

9. The solid colored composition of claim 6, in which said ultraviolet radiation has a wavelength of from about 100 to about 375 nanometers.

10. The solid colored composition of claim 9, in which said ultraviolet radiation is incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp.

11. An electrophotographic process which comprises:
(A) creating an image of a pattern on a photoreceptor surface;
(B) applying a toner to said photoreceptor surface to form a toner image which replicates said pattern;
(C) transferring said toner image to a substrate; and (D) fixing said toner image to said substrate;
in which said toner comprises:
(1) a colorant which, in the presence of an ultraviolet radiation transorber, is adapted, upon exposure of the transorber to ultraviolet radiation, to be mutable;
(2) an ultraviolet radiation transorber which is adapted to absorb ultraviolet radiation and interact with said colorant to effect the irreversible mutation of the colorant; and (3) a carrier for said colorant and said ultraviolet radiation transorber.

12. The electrophotographic process of claim 11, in which said carrier is a polymer.

13. The electrophotographic process of claim 12, in which said composition includes a charge carrier.

14. The electrophotographic process of claim 11, in which said ultraviolet radiation has a wavelength of from about 100 to about 375 nanometers.

15. The electrophotographic process of claim 14, in which said ultraviolet radiation is incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp.

16. An electrophotographic process which comprises:
(A) providing a substrate having a first pattern thereon which is formed by a first toner which comprises:

(1) a colorant which. in the presence of an ultraviolet radiation transorber, is adapted, upon exposure of the transorber to ultraviolet radiation, to be mutable;
(2) an ultraviolet radiation transorber which is adapted to absorb ultraviolet radiation and interact with said colorant to effect the irreversible mutation of the colorant; and (3) a carrier for said colorant and said ultraviolet radiation transorber;
(B) exposing said first pattern on said substrate to ultraviolet radiation at a dosage level sufficient to irreversibly mutate said colorant;
(C) creating an image of a second pattern on a photoreceptor surface;
(D) applying a second toner to said photoreceptor surface to form a toner image which replicates said second pattern;
(E) transferring said second toner image of said second pattern to said substrate; and (F) fixing said second toner image to said substrate.

17. The electrophotographic process of claim 16, in which said carrier is a polymer.

18. The electrophotographic process of claim 17, in which said composition includes a charge carrier.

19. The electrophotographic process of claim 16, in which said ultraviolet radiation has a wavelength of from about 100 to about 375 nanometers.

20. The electrophotographic process of claim 16, in which said ultraviolet radiation is incoherent, pulsed ultraviolet radiation from a dielec-tric barrier discharge excimer lamp.

21. The electrophotographic process of claim 16, in which said second toner comprises:
(1) a second colorant which, in the presence of an ultraviolet radiation transorber, is adapted, upon exposure of the transorber to ultraviolet radiation, to be mutable;
(2) a second ultraviolet radiation transorber which is adapted to absorb ultraviolet radiation and interact with said second colorant to effect the irreversible mutation of the second colorant; and (3) a second carrier for said second colorant and said second ultraviolet radiation transorber.

22. The electrophotographic process of claim 21, in which said second carrier is a polymer.

23. The electrophotographic process of claim 22, in which said second toner includes a charge carrier.

24. The electrophotographic process of claim 21, in which said ultraviolet radiation has a wavelength of from about 100 to about 375 nanometers.

25. The electrophotographic process of claim 24, in which said ultraviolet radiation is incoherent, pulsed ultraviolet radiation from a dielec-tric barrier discharge excimer lamp.

26. A substrate having an image thereon which is formed by a solid colored composition which comprises:
(A) a colorant which, in the presence of an ultraviolet radiation transorber, is adapted, upon exposure of the transorber to ultraviolet radiation, to be mutable; and (B) an ultraviolet radiation transorber which is adapted to absorb ultraviolet radiation and interact with said colorant to effect the irreversiblemutation of the colorant.

27. A substrate having an image thereon which is formed by an electrophotographic toner which comprises:
(A) a colorant which, in the presence of an ultraviolet radiation transorber, is adapted, upon exposure of the transorber to ultraviolet radiation, to be mutable; and (B) an ultraviolet radiation transorber which is adapted to absorb ultraviolet radiation and interact with said colorant to effect the irreversiblemutation of the colorant; and (C) a carrier for said colorant and said ultraviolet radiation transorber.