CZ27596A3

CZ27596A3 - Mutable composition and processes for preparing thereof

Info

Publication number: CZ27596A3
Application number: CZ96275A
Authority: CZ
Inventors: Ronald Sinclair Nohr; John Gavin Macdonald; Vincent Daniel Mcginniss; Robert Samuel Whitmore
Original assignee: Kimberly Clark Co
Priority date: 1993-08-05
Filing date: 1994-07-29
Publication date: 1996-08-14
Also published as: BR9407181A; FI960483A; CA2168727A1; SK15296A3; RU2152636C1; NO960455L; HU9600241D0; JPH09502031A; HUT73681A; CN1131468A; EP0712506A1; DE712506T1; AU7517394A; FI960483A0; PL312835A1; ES2107396T1; WO1995004955A1; NO960455D0

Abstract

A colored composition which includes a colorant and an ultraviolet radiation transorber. The colorant, in the presence of the ultraviolet radiation transorber, 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 colored composition can be incorporated into a toner adapted to be utilized in an electrophotographic process. The toner includes the colorant, ultraviolet radiation transorber, 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 ultraviolet radiation is incoherent, pulsed ultraviolet radiation produced by a dielectric barrier discharge excimer lamp. In another embodiment, the colored composition which comprises a colorant and an ultraviolet radiation transorber may also contain a molecular includant having a chemical structure which defines at least one cavity. Each of the colorant and ultraviolet radiation transorber is associated with the molecular includant. In some embodiments, the colorant is at least partially included within a cavity of the molecular includant and the ultraviolet radiation transorber is associated with the molecular includant outside of the cavity. In other embodiments, the ultraviolet radiation transorber is covalently coupled to the molecular includant.

Description

Technical field. BACKGROUND OF THE INVENTION The present invention relates to a mutable color composition that may in some embodiments be used in an electrographic toner, such as a toner used in a photocopier, which is based on transfer xerography.

Electrophotography is generally defined as the process by which photons are captured to form an electrical analog of the original image. The electric analog is then processed in a series of degrees, resulting in a physical image. The most common form of electrophotography currently used is called transfer xerography. This process, although first demonstrated by C. Carlson in 1938, was only slowly gaining popularity. Now, however, transfer xerography is the foundation of a multi-billion dollar industry,

The heart of the process is a photoreceptor, which is usually a moving element of a process that typically has the shape of either a drum or an endless seamless strip. The corona discharge device stores gaseous ions on the photoreceptor surface. These ions form a homogeneous electric field across the photoreceptor and a uniform charge layer on its surface. The illuminated original image is transmitted through a set of lenses and focused on the photoreceptor. Impinging light on the charged photoreceptor surface results in increased conductivity "across the photoreceptors" SE "Current ~ ^_ neutralization of surface charges. They retain their charge for photoreceptor areas. The resulting surface charge pattern is a latent electrostatic image.

The proximity of the photoreceptor is indicated by a thermoplastic pigmented powder or toner, the particles of which carry an opposite charge to the surface charges on the photoreceptor, thereby allowing the toner particles to be attracted to the charged regions on the photoreceptor surface: The result is a physical image on the photoreceptor surface formed by electrostatically maintained toner particles.

A blank sheet of paper is introduced into the physical contact with the toner-carrying photoreceptor. The charge applied to the back of the paper causes the toner image to be pulled onto the paper. The resulting image is a positive image of the original. The paper is then delayed by the photocopiers? the toner image adheres to it by electrostatic attraction. The toner image is permanently melted onto the paper by a suitable heating device such as a hot pressure roller or a radiant heating device.

Because toner is poorly transferred to the paper, the photoreceptor surface needs to be cleaned of the remaining toner. Toner wipes with a brush, cloth or knife. Toner removal is aided by corona discharge or inverted polarity; Then, the photoreceptor is flooded with a uniform light source to remove any residual charge from the previous 'image' cycles, thereby 'perfectly' erasing the previous electrostatic image and preparing the photoreceptor surface for the next cycle.

Typically, the toner is thermoplastic powder particles having an average particle size of 1 to 15 µm. Black toner typically contains 5 to 10% by weight of carbon black particles less than 1 μηη dispersed in a thermoplastic powder. For toners used in color xerography, the carbon black may be replaced by cyan, fuchsin, or yellow pigments. The concentration and dispersion of the pigment must be adjusted to provide the toner with the appropriate conductivity for the respective developing system. For most development processes, toner is required to be left over for a long period of time by electrode contact. The thermoplastic used in toner is generally chosen based on its melt behavior. This thermoplastic must melt in a relatively narrow temperature range, and must be stable to storage and capable of withstanding intensive mixing occurring in the xerographic development chambers.

The success of electrophotography and especially transfer xerography is undoubtedly an important factor in the efficient distribution of information that has become necessary on a global scale. However, it also contributes to the creation of an enormous amount of paper that must be either disposed of or recycled at the end. Although paper recycling technology exists, it is costly, time consuming and generates waste that needs to be disposed of properly. A conventional paper recycling method involves converting the paper into a slurry and treating the slurry to remove ink, toner, and other colorants, i.

discoloration of paper, which is an expensive and not always quite successful operation. In addition, dyeing yields sludge, which is most often disposed of in landfills. The resulting bleached paper slurry is then used, often with the addition of at least some fresh paper pulp, to produce paper, cardboard, cellulosic packaging materials and the like.

The purest form of recycling, however, would be to reuse the paper intact, i.e., without having to ¹ * crushing .. To this slurry účelem'byly described toners for copy machines which discolour on exposure to near infrared or infrared radiation.

Although its lower limit ends at a wavelength of about 375 nm, the solar radiation spectrum has a significant infrared component at the upper end of the spectrum. Therefore, such toners have a serious disadvantage in that they are transient in the presence of environmental factors such as sunlight and heat. This result is unsatisfactory because documents can become unreadable before their function or purpose ends. Thus, there is a need for toners for copiers that allow the recycling of intact paper but which are stable to normally occurring environmental factors.

SUMMARY OF THE INVENTION

The invention addresses the need for a simple, economically efficient and environmentally friendly way to recycle paper and reuse multiple photocopiers.

The invention generally provides a dyeing system that is mutable when exposed to radiation. The subject of the invention is a composition comprising a colorant which is mutable in the radiation transorber. The radiation transorber is capable of absorbing radiation and interacting with the dye to induce dye mutation. In addition, it is desirable that the dye mutation is irreversible.

The composition of the invention includes a dye and an ultraviolet radiation transorber. The dye in the presence of the ultraviolet radiation transorber is adapted to be mutable when exposed to the ultraviolet radiation. The ultraviolet transorber is adapted to absorb ultraviolet light and interact with the dye to produce irreversible dye mutation. It is desirable that the ultraviolet transorber absorb ultraviolet radiation at a wavelength of about 4 to about 400 nm. It is even more desirable that the ultrafine transorber transducer and the absorbent silicon tetrafluoride are irradiated with a wavelength of < RTI ID = 0.0 > 0O0- < / RTI >^;

In another embodiment of the invention, the color composition comprising the colorant and the ultraviolet radiation transorber may also comprise a molecular includant whose chemical structure defines at least one cavity. Such molecular includants include, but are not limited to, clathrates, zeolites, and cyclodextrins. Both the dye and the ultraviolet radiation transorber are associated with one or more molecular includants. In some embodiments, the dye is at least partially incorporated in the molecular-integrating α-transorber-ultraviolet radiation by the molecular includant outside the cavity. In some embodiments, the ultraviolet transorber is covalently bound to the exterior of the molecular includant,

The invention also relates to a method of mutating a dye in a composition of the invention. The method comprises irradiating the composition comprising the mutable dye and the ultraviolet radiation transorber with ultraviolet radiation sufficient to mutate the dye. As noted above, in some embodiments, the composition further comprises a molecular includant. In another embodiment, the composition is applied to the substrate prior to ultraviolet irradiation. It is desirable that the mutated dye be stable. The invention also relates to a substrate on which the image is composed of a composition according to the invention.

The invention also relates to an electrophotographic method which allows multiple use of a substrate as photocopier paper. The method comprises exposing the image to a substrate obtained by the above method to ultraviolet radiation at a dose sufficient to irreversibly mutate the dye. Next, a second image is formed on the photoreceptor surface and a second toner is applied to the photoreceptor surface to form a toner image that replicates the second image. Then, the second toner image of the second image is transferred to the substrate and the second toner image is fixed to the substrate. If the second toner comprises a dye and an ultraviolet transorber according to the invention, the dye in the second image may also be mutated by exposure to ultraviolet radiation, allowing the substrate to be reused to fix the third image to the substrate.

The detailed description of the subject matter, features and advantages of the invention will be apparent from the description of the embodiments and the appended claims.

The invention generally relates to a dyeing system that is mutable when exposed to irradiation. The invention relates to a composition comprising a dye that is mutable in the presence of a radiation transorber. The radiation transorber is capable of absorbing radiation and interacting with the dye to produce a dye mutation.

In particular, the composition of the invention includes a dye and an ultraviolet radiation transorber. The dye in the presence of the ultraviolet radiation transorber is adapted to be mutable when exposed to the ultraviolet radiation. The ultraviolet transorber is adapted to absorb ultraviolet radiation and interact with the dye to induce an irreversible dye mutation. The term composition and ^f,! Such variations as the color composition are used herein to mean a dye and an ultraviolet radiation transorber. When referring to a color composition that is adapted for a particular application, such as toner for use in an electrographic process, then the composition-based term is used to indicate that the material, such as toner, includes a dye, an ultraviolet transorber, and optionally a molecular includant. .

The term dye, as used herein, is intended to include, without limitation, any material which, in the presence of an ultraviolet radiation transorber, is adapted to be mutable when exposed to ultraviolet radiation. The dye is typically an organic substance such as an organic dye or pigment, including toners and lacquers. It is desirable that the dye be substantially transparent to the ultraviolet radiation to which it is exposed, i. not to interact with it significantly. The term is intended to include a single substance or a mixture of two or more substances.

Exemplary groups of organic dyes include, but are not limited to, triarylmethyl-dyes, carbiniums, may have little chromium dyes, {4- [4- (dimethylamino) - [4- (dimethylamino) amino] ) phenyl] -a-phenylbenzene-methanol}, carboline hydrocarbon chloride malachite green [N-4 - [[44-dimethylamino) phenyl] phenylmethylene] -2,5-cyclohexyldien-1-ylidene] -N-methylmethanamine chloride or bis [] ( dimethylamino} phenyl] phenylmethyl chloride and malachite green oxalate [N-4 - [[4- (dimethylamino) phenyl] phenylmethylene] -2,5-cyclohexyidin-1-ylidene] -N-methylmethanaminium chloride or bis [p- (dimethylamino) phenyl] monoazo dyes, such as cyanine black, chrysoidine [Basic Orange 2; 4- (phenylazo) -1,3-benzenediamine monohydrochloride.] .beta.-naphthol orange; triazine dyes such as double salt of methylene green with zinc chloride [double salt of 3,7-bis (dimethylamino) -6-nitrophenothiazine-5-ium chloride --žiňěena'tý ^{^r],;} oxazihova colorant, -ja is a Lumichrorne- (7,8-dimethylaloxazin) phosphate dye such as Lucifer Yellow CH (dilithium salt of 6-amino-2 - [(hydrazinocarbonyl) amino] 2,3-dihydro-1 3-dioxo-1H-benz [de] isoquinoline-5,8-disulfonic acid}; azine dyes, such as Janus green B [3- (diethylamino) -7 - [[4- (dimethylamino) phenyl] azo] -5-phenylphenazinium chloride}; cyanine dyes such as indocyanine green [Cardio-Green or Fox Green; 2- [7- [1,3-dihydro-1,1-dimethyl-3- (4-sulfobutyl) -2H-benz [e] indol-2-ylidene] -1,3,5-heptatrienes sodium salt, sodium salt 1,11-dimethyl-3- (4-sulfobutyl) -1H-benz [e] indolium hydroxide; 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-3-one J; coumarin dyes such as 7-hydroxy-4-methylcoumarin (4-methylumbelliferone); benzimidazole dyes such as HoecH33 33258 [bisbenzimide or 2- (4-hydroxyphenyl) -5- (4-methyl-1-piperazinyl) -2,5-bi-1H-benzimidazoline hydrochloride pentahydrate]; parachinoid dyes such as hematoxylin {Natural Black 1,7,11b-dihydrobenz [b] indeno [1,2-d] pyran-3,4,6a, 9,10 (6H) -pentol}; fluorescein dyes such as fluoresceinamine (5-aminofluorescein); diazonium salts such as diazonium red RC (Azoic Diazo # 10 or Fast Red RC salt; double salt of 2-methoxy-5-chlorobenzenediazonium chloride, zinc chloride), azodiazo dyes such as Fast Blue BB (Azoic Diazo # 20; 4-benzoylamino double salt) -2,5-diethoxybenzenediazonium chloride, zinc chloride), phenylenediamine dyes, such as disperse yellow 9 [N- (2,4-dinitrophenyl) -1,4-phenylenediamine or Solvent Orange 53]; Orange 52; 1-phenylazo-4- (4-hydroxyphenylazo) naphthalene] anthraquinone dyes such as dispersion blue 3 [Celliton Fast Blue FFR; 4- (2-hydroxyethylamino) -9,10-anthraehinone], disperse blue 14 [Celliton

Fast Blue B; 1,4-bis- (methylamino) -9,10 * anthraquinone] and alizarin blue-black B- (Mordant-Black-1,2-trisazo dyes, such as} ρπωέ-Εηο0Γ_7_1- [Βθηζο-Ι; ί9Ηΐ- Blue-FFtrnebó

Sirius Light Blue BRR; tetrasodium salt of 3j (4 - [(4 - [(6-amino-1-hydroxy-3-sulfonaphthalenyl) azo] -6-sulfo-1-naphthalenyl) -azo] -1-naphthalenyl) azo] -1, 5-naphthalenedisulfonic acid}; xanthene dyes such as 2,7-dichlorofluorescein; proflavin dyes such as 3,6-diaminoacridine hemisulphate (proflavin); sulfonaphthaline dyes such as cresol red (o-cresolsufonaphthaine); phthalocyanine dyes such as copper phthalocyanine (Pigment Blue 15; (SP-4-1} - (29H-31H _L ftalocyanato (2 -) - N ^29, N ³⁰ IN ³ ', N ^32] copper}; karatenoidová dyes, such as trans-beta-carotene (Food Orange 5); carmine-based dyes such as carmine, aluminum or calcium-aluminum carmine lacquer (7-α-Dglucopyranosyl-9,10-dihydro-3,5,6,8-tetrahydroxy-1-methyl'9,10-dioxo) Azuric dyes, such as A [3-amino-7- (dimethylamino) phenothiazine-5-ium chloride or 7Xdimethylamino) -3-imino-3H-phenothiazine hydrochloride, and acridine dyes such as acridine orange [Basic Orange 14; 3,8-bis- 7 (dimethylamino) acidin hydrochloride hydrochloride, zinc chloride] and acriflavine (Acriflavine neutral;

a mixture of 3,6-diamino-10-methylacridinium chloride with 3,6-acridinediamine).

The term mutable in relation to the dye is used in such a way that the absorption maximum of the dye in the visible region of the electromagnetic spectrum is capable of mutation or alteration by exposure to ultraviolet radiation in the presence of ultraviolet transorber I:

Generally, it is only necessary that this absorption maximum be mutated to an absorption maximum that is different from the absorption maxima of the dye before exposure to ultraviolet radiation, and that the mutation is irreversible. Thus, the new absorption maximum may be within or outside the visible range of the electromagnetic spectrum. In other words, the dye can mutate to a different color or become colorless. Of course, this latter eventuality is desirable when using a dye in a color composition adapted to be used as a toner in an electrophotographic process wherein an electrophotographic copy is recycled so that the color composition is first bleached and then a new image is placed thereon.

The term irreversible ^-1, as used herein, means that the colorant will not return to its original color, ceases to be exposed to ultraviolet radiation. It is desirable for the mutated dye to be stable, i.e. not to be noticeably adversely affected by radiation normally found in the environment, such as natural or artificial radiation.

light and heat. It is therefore desirable that the dye after the discoloration remains for an undefined period of time.

The term ultraviolet transorber is used herein to mean any material that is adapted to absorb ultraviolet radiation and interact with the dye to induce a mutation of the dye. In some embodiments, the ultraviolet transorber may be an organic compound. The term compound is intended to include a single substance or a mixture of two or more substances. If two or more substances are used, it is not necessary for all of them to absorb ultraviolet radiation of the same wavelength.

The invention includes individual compounds which are capable of absorbing ultraviolet radiation in a narrow wavelength range. The compounds are synthesized by combining a wavelength selective sensitizer and a photoreactor. Photoreactors often do not effectively absorb high energy radiation. When combined with seňž'itÍ2atórerň ~ ^_ ~ špe'čifičkýriT'na wavelength is formed at a compound specific wavelength and efficiently absorbs a very narrow spectrum of radiation. Examples of ultraviolet radiation transorber are shown in Examples 5 and 9.

Although the mechanism of interaction of the ultraviolet radiation transorber with the dye is not fully understood, it is believed that the transorber may interact with the dye in various ways. For example, the ultraviolet radiation transorber may be converted to one or more free radicals that interact with the dye by absorbing ultraviolet radiation. These compound-forming free radicals are typically "hindered" ketones, some of which include, but are not limited to: benzildimethyl ketal (commercially available as Irgacure® 651, Ciba-Geigy Corporation, Hawthorne, New York); 1-hydroxycyclohexylphenyl ketone (Irgacure® 500); 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one] (Irgacure® 907); 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure® 369) and 1-hydroxycyclohexylphenyl ketone (Irgacure® 184). -. .

Alternatively, ultraviolet radiation may induce electron transfer or a redox oxidation reaction between the ultraviolet radiation transorber and the dye. In this case, it can be an ultraviolet radiation transorber, but without. limited to them, Michler's ketone (p-dimethylaminophenyl ketone) or benzyltrimethylstannate. Alternatively, a cationic mechanism may be involved, in which case the ultraviolet transorber may be, for example, bis [4- (diphenylsulfonio) phenyl] sulfidbis (hexafluorophosphate) (Degacure® KI85, Ciba-Geigy Corporation, Hawthorne, New York); Cyracure® LIV9

6990 (Ciba-Geigy Corporation) which is a mixture of bis [4- {diphenylsulphonio) phenyl] sulfídbis (hexafluorophosphate) 's''prih'ÍJŽhýmimonošulfonTúmhexafluorofosfátovýmt-solemÍ7-a-5-2 -, - 4 ^and (cyklcř --- pentadienyl) [1,2,3,4,5,6- (methylethyl) benzene] iron (II) hexafluorophosphate (Irgacure® 261).

The term ultraviolet radiation is used herein to refer to electromagnetic radiation having a wavelength in the range of about 4 to about 400 nm. A particularly desirable range of ultraviolet radiation according to the invention is between about 100 and 375 nm. Thus, the term includes regions commonly referred to as ultraviolet and vacuum ultraviolet. The wavelengths typically associated with these two regions are about 180 to about 400 nm and about 100 to about 180 nm, respectively.

In some embodiments, the molar ratio of the ultraviolet radiation transorber to dye is generally greater than or equal to about 0.5. Typically, the more ultraviolet radiation transorber is more effective at absorbing ultraviolet radiation and interacting with the dye, i.e., transferring absorbed energy to the dye to induce irreversible mutation of the dye, the lower the ratio may be. Current theories of molecular photochemistry indicate that the lower limit of this ratio is 0.5 based on the formation of two free radicals on the photon. In practice, however, ratios higher than 1, possibly up to 10 are likely to be required. However, the invention is not limited to any particular molar ratio range. An important characteristic is that the transorber is present in an amount sufficient to cause dye mutation.

In practice, both the dye and the ultraviolet radiation transorber are likely to be solids. However, any of these may also be liquid. In an embodiment where the color composition of the invention is solid, the efficiency of the ultraviolet radiation transorber is improved when the dye with the ultraviolet transorber is in intimate contact. To this end, it is desirable to thoroughly mix the two components together with other ingredients which may optionally be present. This mixing is usually carried out by any method known to the person skilled in the art. If the color composition comprises a polymer, mixing is facilitated if the dye and the ultraviolet radiation transorber are at least partially soluble in the softened or molten polymer. In this case, the composition is readily prepared by, for example, a two-roll kneader. Alternatively, the color composition may be liquid because one or more of its components are liquid.

For some applications, the color composition of the present invention will typically be used in a non-particulate-other application should be a particle-composition, for example, a color composition particle adapted to be used as a toner in an electrophotographic process. they are typically composed of particles of an average size of 7 to 15 µm; however, smaller or larger particles may be used. It is important that the particles are as uniform as possible. Methods for making such particles are known to those of ordinary skill in the art.

Photochemical processes include absorption of light or photon by a molecule, such as an ultraviolet radiation transorber, to induce a highly reactive electron ......

excited state. However, the energy of the photons, which is proportional to the wavelength of the radiation, cannot be absorbed by the molecule until it matches the difference in energy between the non-excited

If the direct wavelength range of the ultraviolet radiation to which the color composition is exposed, at least a portion of the radiation must have a wavelength. that provides the necessary energy to increase the ultraviolet transorber to an energy level that is capable of interacting with the dye.

Thus, ideally, the absorption maximum of the ultraviolet radiation transorber will be adapted to the wavelength range of the ultraviolet radiation in order to increase the efficiency of the dye mutation. This efficiency is also increased when the wavelength range is relatively low, with the maximum being transorber. ultraviolet radiation to this range. For these reasons, a particularly suitable ultraviolet radiation has a wavelength of about 10 to about 375 nm. Ultraviolet radiation within this range may advantageously be incoherent, pulsed ultraviolet radiation from a dielectric barrier excimer lamp.

The term incoherent, pulsed ultraviolet radiation refers to radiation emitted by a dielectric barrier excimer lamp (hereinafter called an excimer lamp). Such a lamp is described, for example, in U. 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 originally developed by ABB Infocom Ltd., Lenzburg, Switzerland. The excimer lamp technology was then adopted by Haráus Noblelight AG, Hanau, Germany.

The excitation lamp emits radiation with a very narrow bandwidth, ie radiation, in which half the width is of the order of 5 to 5 nm-mercury-radiation-non-coherent-and pulse, whereas the pulse frequency is dependent on the frequency of the AC voltage source, which is typically in the range of about 20 to about 300 kHz. The excitation lamp is typically referred to by the wavelength at which the maximum radiation intensity occurs and this convention is followed in this description. Compared to most commercially usable ultraviolet radiation sources that typically emit throughout the ultraviolet spectrum and even into the visible region, the radiation of the excimer lamp is substantially monochromatic.

Éxcimers are unstable molecular complexes that occur only under extreme conditions, such as temporarily found in special types of gas discharge. Typical examples are molecular bonds between two noble gas atoms or between a noble gas atom and a halogen atom. Excimer complexes decompose in less than microseconds and release their binding energy during ultraviolet radiation during decomposition. Known excimers generally emit in the range of about 125 to about 360 nm depending on the excimer gas mixture. -3

Although the dye and ultraviolet transorber have been described as single _t compounds, they may form part of the same molecule. For example, they can be covalently linked to each other, either directly or indirectly via a relatively small molecule, the so-called spacer.

arm. As an alternative, the dye and ultraviolet transorber may be covalently bonded to a large molecule, such as an oligomer or polymer, especially when the solid color composition of the invention is adapted to be used as a toner in an electrophotographic process. Further, the dye and ultraviolet transorber may be associated with a large molecule, including van der Waals forces and hydrogen bonds. Other variations are obvious to the skilled artisan.

For example, in one embodiment, the composition of the invention further comprises a molecular includant. The term molecular includant is used herein to include any chemical whose chemical structure defines at least one cavity. Thus, this molecular includant has a void-containing structure. The term cavity herein means that it includes any opening or space of sufficient size to accommodate at least a portion of the dye or ultraviolet transorber, or both. Thus, the cavity may be a tunnel through a molecular includant or a cavity in a molecular includant. The cavity may be isolated or connected to one or more other cavities. The molecular includant may be inorganic or organic in nature. In certain embodiments, the chemical structure of the molecular includant is adapted to form a molecular inclusion complex. Examples of molecular ingestion agents include, but are not limited to, clathrates or intercalates, zeolites, and cyclodextrins. Examples of cyclodextrins include, but are not limited to, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropyl-β-cyclodextrin, hydroxyethyl-β-cyclodextrin, sulfate-β-cyclodextrin and sulfated γ-cyclodextrin (American-Products Company, Hammond, Indiana). In some embodiments, the molecular _includant: a cyclodextrin. In particular, in some embodiments, the molecular includant is a cyclopyrrolidine other than the one described below, without the intention to be bound by the following theory, it is believed that the closer the transorber molecule to the mutant dye is on the molecular includant, the more effective the interaction with dye causing dye mutation. Thus, molecular inclusion substances with functional groups that can react with and bind to the transorber molecule are more desirable, and are close to the mutable dye binding site.

The ultraviolet radiation dye and transorber are associated with the molecular includant. The term "associated" in its broadest sense means that the dye and the "ultraviolet radiation transorber" are at least in close-proximity-molecular-inclusion materials. The dye and / or the ultraviolet radiation transorber may be maintained in close proximity to the molecular includant by, for example, hydrogen bonds, van der Waals forces and the like. Alternatively, either the dye or ultraviolet transorber or both may be covalently bonded to the molecular includant. In certain embodiments, the dye will be associated with the molecular includant using hydrogen bonds and / or van der Waals forces, and the like, while the ultraviolet transorber is covalently bound to the molecular includant. In other embodiments, the dye is at least partially incorporated in the molecular includant cavity and the ultraviolet transorber is located outside the molecular includant cavity.

In one embodiment, where the dye and the ultraviolet radiation transorber are associated with a molecular includant, the dye crystal violet, the ultraviolet radiation transorber is dehydrated with phthalylglycine-2959 and the molecular includant

In another embodiment, where the dye and the adsorption of the radiation are associated with the molecular includant, the dye crystal violet is the transverse ultraviolet radiation transducer. - (4-hydroxyphenyl) -butan-2-one-2959 (chlorine substituted) and the molecular includant is β-cyclodextrin.

In another embodiment, where the dye and the ultraviolet radiation transorber are associated -. with a molecular includant, is a malachite green dye, the ultraviolet transorber is Irgacure 184, and the molecular includant is a β-cyclodextrin, as shown in Figure 1. In yet another embodiment where the dye and ultraviolet transorber are associated with the molecular includant , is a dyeing Victorian pure blue BO, the ultraviolet transorber is Irgacure 184 and the molecular includant is β-cyclodextrin, as shown in Figure 2.

Examples 5 to 9 describe the preparation and association of these dyes and transorbers

S1 of ultraviolet radiation with β-cyclodextrins. The procedures described in Examples 5 to 9 are intended to represent only one method of preparation and association of these components, and many other methods known in the art of chemistry can be used. Other methods for preparing and associating these components or any other components that may be used in the present invention will be apparent to those of ordinary skill in the art upon selection of particular components.

In practice, it is likely that the dye, ultraviolet transorber, and molecular includant will be solids. However, any of these may be liquid. The color composition can be liquid either because one or more of its constituents is liquid, or if the molecular includant is organic, a solvent is used. Suitable solvents include, but are not limited to, amides such as Ν, β-dimethylformamide; sulfoxides such as dimethyl sulfoxide; ketones such as acetone, methyl ethyl ketone and methyl butyl ketone; aliphatic and aromatic hydrocarbons such as hexane, octane, benzene, toluene and xylenes; esters such as ethyl acetate; water; and the like. If the molecular includant is cyclodextrin, amides and sulfoxides are particularly suitable solvents.

The invention also relates to a dye mutation method in a composition of the invention. Briefly, the method comprises irradiating the composition comprising the mutable dye and the ultraviolet radiation transorber with ultraviolet radiation at a dose sufficient to mutate the dye, As noted above, in one embodiment, the composition further comprises a human substance: another embodiment. the ultraviolet radiation is applied to the substrate by pre-UV-radiation.

The amount or amount of ultraviolet radiation to which the inventive dye is exposed generally corresponds to the amount required to mutate the dye. The amount of ultraviolet radiation required to mutate the dye can be determined by one of ordinary skill in the art by routine experimentation. Energy density is a measure of the amount of emitted electromagnetic energy passing through the area unit, and is usually expressed in watts per centimeter-square (W / cm ² ). The energy density ranges between approximately 5 mW / cm ² and 15 mW / cm ² , in particular 8-10 mW / cm ² . Furthermore, the dose size is typically a function of the exposure time and the intensity or flow of the radiation source that it irradiates

The color of the composition can be varied according to the distance of the light, depending on the wavelength range of the ultraviolet radiation. atmosphere between the radiation source and the composition. Thus, in some cases, it may be appropriate to expose the composition to a controlled atmosphere or vacuum, but this is generally not desirable.

For example, in one embodiment, the dye of the invention is mutated by exposure to 222 nm excimer lamps. Specifically, the crystal violet dye is mutated by exposure to excimer lamps of 22 nm. More specifically, the crystal violet dye is subjected to exposure to excimer lamps 222 ηηχ located about 5 to 6 cm from the dye, wherein the lamps are arranged in four parallel columns of about 30 cm in length, as shown in Figures 3 and 4. that in this aspect of the invention it is not critical. Thus, one or more lamps may be arranged in any configuration and at any distance that results in mutation of the dye upon exposure to ultraviolet, lamp radiation. One of ordinary skill in the art is able to determine routinely which configurations and which distances are appropriate. It is also to be understood that different excimer lamps must be used for the various ultraviolet radiation transorber. The excimer lamp used to mutate the dye associated with the ultraviolet radiation transorber should produce ultraviolet radiation of wavelength that is absorbed by the ultraviolet radiation transorber.

The color composition of the invention may be used on any or any substrate. However, if the composition is present in the substrate, the substrate should be substantially transparent to the ultraviolet radiation used to mutate the dye. This means that the ultraviolet radiation is not absorbed or substantially absorbed by the substantially non-interfering material. In practice, the composition is usually placed on a substrate, with paper being the most common substrate. However, other substrates may be used including, but not limited to, woven and nonwoven fabrics or webs, and the like.

Another aspect of the invention is a substrate having an image thereon formed by a composition of the invention. Although the invention relates to any substrate capable of fixing a color image, paper is a desirable substrate. Particularly desirable substrates include, but are not limited to, photocopy paper and fax paper.

As an example, the composition of the invention may be incorporated into a toner adapted for use in an electrophotographic process. The toner includes a dye, an ultraviolet transorber, and a carrier. The carrier may be a polymer and the toner may further comprise a charge carrier. Briefly, the photophotographic process includes the steps of forming an image on the photoreceptor surface, applying toner to the photoreceptor surface to form a toner image that replicates the image, transferring the toner image to the substrate, and fixing the toner image to the substrate. After fixing the toner to the substrate, the dye in the composition is mutated by irradiating the substrate with ultraviolet radiation at a dose sufficient to irreversibly mutate the dye. In some embodiments, the ultraviolet radiation used in this method will have a dye mutation of about 100 to about 375 nm. In other embodiments, incoherent, pulsed ultraviolet radiation produced by a dielectric barrier excimer lamp is used. In another embodiment, the toner may further comprise a molecular includant.

If the color composition is adapted to be used as a toner in an electrophotographic process, the composition will also contain a carrier known to the person skilled in the art. For many applications, the carrier will be a polymer, typically a thermoset or thermoplastic polymer, the latter being more common.

Other examples of thermoplastic polymers include, but are not limited to: end cap polyacetals such as poly (oxymethylene) or polyformaldehyde, poly (trichloroacetaldehyde), poly (n-valeraldehyde), poly (acetaldehyde), poly (propionaldehyde) and the like; acrylic polymers such as polyacrylamide, 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), and the like. copolymers of ethylene (III) trifluoroethylene (7) (see also Trifluoroethyl) 7 (vinyl fluoride) and the like; epoxy resins such as condensation products of epichlorohydrin and bisphenol A; polyamides such as poly (6-aminocaproic acid) or poly (ε-caprolactam), poly (hexamethylenadipamide), poly (hexamethylenebasamide), poly (11-aminoundecanoic acid) and the like; polyaramides such as poly (imino-1,3-phenylenimino-phthaloyl) or poly (menylene isophthalamide and the like; parylenes such as poly-p-xylylene, poly (chloro-p-xylene) and the like; polyaryl ethers such as poly (oxy-) 2,6-dimethylH, 4-phenylene) or poly (p-phenylene oxide) and the like; polyarylsulfones such as poly (oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1-phenylenesopropylidene-1,4-phenylene), poly (sulfonyl-1, 4-phenyleneoxy-1-phenylene sulfonylPtB-phenylene) and the like; polycarbonates such as poly (bisphenol A) or poly (carbonyldioxy-1,4-phenylene). polymers, poly (ethylene terephthalate), poly (cyclohexylene-1,4-dimethylenteraphthalate) or poly (oxymethylene) or poly (tetramethylene terephthalate); 1,4-cyclohexylenemethyleneoxy terephthaloyl) and the like; polyaryl sulfides such as poly (p-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. is polyethylene, polypropylene, poly (1-butene), poly (2-butene), poly (1-pentene), 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 acryionitrile-butadiene-styrene copolymers (βB5), styrene-n-butyl-orthacrylate copolymers, copolymers, and the like.

Some of the more commonly used thermoplastic polymers include copolymers styrene-n-butyl methacrylate, polystyrene, copolymers styrene-n-butyl acrylate, copolymers styrene-butadiene, polycarbonates, poly (methyl methacyl acetate), poly (vinylidene fluoride), polyamides (nylon-12), polyethylene , polypropylene, copolymers of ethylene-vinyl acetate and epoxy resins.

Examples of thermosetting polymers include, but are not limited to, alkyd resins such as phthalanhydride-glycerol resins, maleic anhydride-glycerol resins, adipic acid-glycerol resins, and phthalic anhydride-pentaerythritol resins; allylic resins in which monomers such as diallyl phthalate, dialyl isophthalate, diallyl maleate and diallyl chlorendate serve as non-volatile crosslinking agents in polyester blends;

amino resins, such as aniline formaldehyde resins, ethylene urea resins, formaldehyde resins, dicyandiamide formaldehyde,. resin - melamine-formaldehyde. sulfonamide-formaldehyde resin and urea-forrhaldehyde resin; epoxy resins such as crosslinked epichlorohydrin-bisphenol A resins; phenolic. resins such as phenol formaldehyde resins, including novoaks and resols; and thermosetting polyesters, silicones and urethanes.

In addition to the dye and the ultraviolet radiation transorber and optionally the carrier, the colored composition of the invention may also contain other components depending on the application for which it is intended. For example, a composition that is intended to be used as a toner in an electrophotographic process may optionally include, for example, charge carriers, heat oxidation stabilizers, viscoelastic modifiers, crosslinking agents, plasticizers, and the like. process, optionally containing charge control additives such as quaternary ammonium salt; flow control additives such as hydrophobic silica, zinc stearate, calcium stearate, lithium stearate, polyvinyl stearate and polyethylene powder; and fillers, such as calcium carbonate, clay and talc, in addition to other additives used by those of ordinary skill in the art. For some applications, the hub will be the main toner component. Charge carriers are, of course, known to the person skilled in the art and typically are metal particles with a polymer coating. The identity and amount of such other additives is known to the person skilled in the art. The toner of the invention may further comprise a molecular includant as described above.

When the color composition is used as a toner for an electrophotographic process, various variations within the scope of the invention are possible. For example, composition-based toner may be used to form a first image on an unused sheet of paper. The sheet can then. to be recycled by exposure to ultraviolet radiation according to the invention to discolor the dye and consequently the composition. Then a second image can be created on the sheet. The second image may be formed from a standard known toner or a composition-based toner that is either the same or different from the composition-based toner used to form the first image. When composition-based toner is used to form the second image, the sheet can be recycled again, the number of cycles being limited by the formation of a now colorless composition on the paper surface. Furthermore, no more image can be placed on either side of the sheet. That is, it is not necessary for the second image to be created, on the same side as the first image1.

Furthermore, the conversion of the composition-based toner image into a colorless form does not need to take place on the sheet. For example, sheets of images formed from composition-based toners can be recycled in a traditional manner. Instead of the usual bleaching, however, the leaves are either exposed to ultraviolet radiation either before or after slurrying. One of ordinary skill in the art will recognize that when the leaves are exposed to ultraviolet radiation after slurry, no slurry component will interfere with the ability of the ultraviolet radiation transorber to mutate the dye upon exposure to ultraviolet radiation. Thus, the colorless toner is simply incorporated into the paper formed from the resulting slurry.

FIG. 1 depicts an ultraviolet / mutable dye / molecular includant transorber complex, wherein the mutable dye is malachite green, the ultraviolet transorber is Irgacure 184 (1-hydroxycyclohexylphenyl ketone) and the molecular includant is 3 ' clodextrin.

FIG. 2 shows a complex of an ultraviolet radiation transorber / mutable - -barvivo / molekulárnrinkludujícrlátka wherein mutabiíním'barvivem ^_ je'viktoriánská'čistá'modř

BO (Basic Blue 7), the ultraviolet transorber is Irgacure 184 (1-hydroxycyclohexylphenyl ketone) and the molecular includant is β <yklodextrin.

FIG. 3 illustrates several 222 nm excimer lamps arranged in four parallel columns, wherein the twelve digits are positions in which twelve intensity measurements of about 5.5 cm from excimer lamps have been made.

FIG. 4 depicts a plurality of 222 nm excimer lamps arranged in four parallel columns, wherein the nine digits are positions in which nine measurements of intensity of about 5.5 cm from the excimer lamps have been made.

Fig. 5 shows a number of 222 nm excimer lamps arranged in four parallel columns where the position of the digit Ί represents the position in which ten intensity measurements were made from the increasing distance from the lamps. (Measurements and their distances from lamps are summarized in Table.7.) ___________________________________ _: _________________

The invention is described in more detail by way of examples. However, these examples do not limit the invention in any way. All parts exemplified are by weight unless otherwise indicated.

Example 1

This example illustrates the preparation of films consisting of a dye, an ultraviolet transorber, and a thermoplastic polymer. The dye and ultraviolet transorber were ground separately in a mortar. The desired amount of milled components was weighed and placed in an aluminum dish along with a weighed amount of thermoplastic polymer. The dish was placed on a heating plate set at 150 ° C, and the dish in the dish was stirred until melted. Several drops of the molten mixture were poured onto a steel plate and smeared using a thin film microscope slide. The steel plates were 3 x 5 inches (7.6 cm x 12.7 cm) and were obtained from QPanel Company, Cleveland, Ohio. The film thickness on the steel plate was estimated on the order of 10-20 µm.

In each case, the malachite oxalate dye was green (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin), referred to herein as dye A. The ultraviolet transorber (UVR) was comprised of one or more Irgacure® 500 products (IRR A), Irgacure ® 651 (UV B) and Irgacure ® 907 (UVR C), described above and available from Ciba-Geigy Corporation, Hawthorne, New York. One of the following was used as polymer: epichlorohydrinbisphenol A epoxy resin (polymer A), Epon 1004F (Shell Oil Company, Houston, Texas); poly (ethylene glycol) having a weight average molecular weight of about 8,000 (polymer B), Carbowax 8000 (Aldrich Chemical Company); and poly (ethylene glycol) having a weight average molecular weight of about 4600 (polymer C), Carbowax 4600 (Aldrich Chem icaf-Com pan) -. -I-prepared film -kontrolní- ·, -Which was ^- formed poíjžě ^_ J báTvívem polymer. The composition of the films is summarized in Table 1.

Table 1. Composition of Films Containing Dye and Ultraviolet Transorber (UVR)

dye U.VRI polymer film- type parts - type ' parts' /type days - AND AND 1 AND 6 AND 90 C 4 δΒ; _ _... —Ao- '-1 ------- · '·· - a- - - · - • -12- · '. '--- 90' - C 8 C. AND 1 AND 18 AND 90 C 12 D AND 1 AND 6 AND 90 B 4 E AND 1 B 30 t. AND 70 F AND 1 - - AND 100 G AND 1 AND 6 B 90

C 4

HA 1 B 10 C 90

Even on a steel plate, each film was exposed to ultraviolet radiation. In any case, she was. the steel plate is placed on the surface of the moving conveyor belt with variable speed control with a film sample on the surface. Three different sources of ultraviolet radiation or lamps were used. Lamp A consisted of an excitation lamp 222 nm and a lamp B of an excitation lamp 308 nm, which have already been described. Lamp C was a lamp bulb fusion system D (Fusion Systems Corporation, Rockvill, Maryland). Excimer lamps were arranged in. about 30 cm in length, the lamps being oriented normally with respect to the direction of movement of the web. The lamps were cooled by circulating the water through a centrally located or internal lamp tube and consequently operated at a relatively low temperature, i.e. about 50 ° C. Energy density at the outer surface-iampyje-typicallyVrozrhežrašříáz ^ šrzOI / m ² ? ^: '

In fact, this range merely reflects the potential of current excimer lamps as energy sources; in the future, higher energy densities may be appropriate for practice. For lamps A and B, the distance from the lamp to the film sample was 4.5 cm and the band was set at a speed of 20 ft / min (0.1 m / s). For lamp C, the belt speed was 14 ft / min (0.07 m / s) and the lamp to sample distance was 10 cm. Ultraviolet radiation sample exposure results are summarized in Table 2. In addition to film F, the table records the number of passes under the lamp required to discolour the film. Film F shows the number of passes made, with the film in each case remaining color (no change).

Table 2, Exposure Results of Films Containing Dye and Ultraviolet Transorber (UV) ultraviolet light film lamp A lamp B

AND

B

C

D

E

F

G

H

Example 2

This example describes the preparation of solid color compositions adapted to be used as toners in the electrophotographic process. In each case, the toner included the dye A described in Example 1; DER 667 polymer, epichlorohydrin 22 bisphenol A epoxy resin (polymer D), Epon 1004F (Dow Chemical Company, Midland, Michigan); and Resin "náboje7 ^ nostč A7T ~ <~ was ~ tery-formed velmt- · finely-minced" ^_ kove'rn spolýmeřriím coating. The ultraviolet transorber (UVR) was comprised of one or more UVR B products of Example 1, Irgacure® 369 (UVR D) and Irgacure® 184 (UV E); . the last two transorberes have been previously described and are available from Ciba-Geigy Corporation, Hawthorne, New York. In one instance, a second polymer, styrene acrylate 1221, styrene-acrylic acid copolymer (Hercules Incorporated, Wilmington, Delaware) was further present.

To prepare the toner, the dye, the ultraviolet transorber and the polymer in the 3VV 800E, 3 x 7 inch (7.6 cm x 2 inch) twin roll mixer were melt blended in the melt.

... 17.8 cm) (Farrel Corporation, Ansonia, Connecticut). ^{'Mlýňě'šdiágóhálriím} hammer through a 0.010 in (r. B. KÍeinfelďt, Cincinnati, Ohio) and then sieved to the desired particle size in an air micronizer dvouplacovém Sturtvant (RD Kleinfeldt) to give a product which is referred to herein as pretoner. The charge carrier was then added to the pretoner and mixed thoroughly. Table 3 summarizes the composition of the pretoners and, in Table 4, the composition of the toners.

Table 3. Pretoner composition overview

dye JJVRI polymer _ pretoner A (g) type G type G AND 1 D 20 D 80 B 1 B 20 D 80 C 1 B 10 D 80 D 10 D 1 B 6.9 D 40 D 6.6 E 40 E 6.6

'Table 4. Toner Cartridge Overview hub carrier pretoner toner type 9 (9) AND AND 8.4 210 B B 8.4 ²¹⁰ C C 8.4 210 D D 8.4 210

Each toner was separately inserted into the Sharp ZT-50TD1 toner cartridge and installed either on a Sharp xerographic copier, model Z-76 or Sharp model Z-77 (Sharp Electronics Corporation, Mahwah, New Jersey). Images were created in the usual way on bank paper (Neenah Bond). The sheets carrying the image were then exposed to the ultraviolet radiation of lamp B described in Example 1. In each case, the image was bleached one pass.

Example 3

This example describes the preparation of β-cyclodextrin as a molecular includant, having (1) an ultraviolet transorber covalently bound to a cyclodextrin outside the cyclodextrin cavity, and (2) a cyclodextrin-associated dye through hydrogen bonds and / or van der Waals forces,

A. Friedei-Crafts acylation transorber

A 250 mL three-necked round bottom reaction flask was fitted with a condenser and a pressure equalizing dropping funnel fitted with a nitrogen inlet tube. A magnetic stir bar was placed in the flask. Under a stream of nitrogen, 10 g (0.05 mol) of 1-hydroxycyclohexylphenyl ketone (Irgacure® 184, Ciba-Geigy Corporation, Hawthorne, New York), 100 ml of anhydrous tetrahydrofuran (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin) were charged into the flask and 5 g (0.05 mol) of succinic anhydride (Aldr). To the continuously stirred contents of the flask were then added 6.7 g-anhydrous " hexafluoride " to give an ice bath at about 0 DEG C. and then allowed to warm to room temperature for 2 hours. room. Then the reaction mixture was poured onto a mixture of 500 ml of ice water and 100 ml of diethyl ether. The ether layer was removed after addition of a small amount of sodium chloride to the aqueous phase to facilitate phase separation. The ether layer was dried over anhydrous magnesium sulfate. Removal of ether under reduced pressure gave 12.7 g (87%) of a white crystalline powder. Nuclear Magnetic Resonance Analysis revealed that it was 1-hydroxy-cyclohexyl-4- (2-carboxyethyl) carbonylphenyl ketone ...........

B. Preparation of Acyl Chloride Acylated Transorber 12.0 g of 1-hydroxycyclohexyl-4- (2'-carboxyethyl) carbonylphenyl ketone (0.04 mol), 5, were introduced into a round bottom flask equipped with a condenser. 95 g (0.05 mol) of thionyl chloride (Aldrich) and 50 ml of diethyl ether. The resulting reaction mixture was stirred for 30 min at 30 ° C _r solvent was then removed under reduced pressure. The white solid residue was kept at 0.01 to about 30 min for 30 min to remove solvent residues and excess thionyl chloride to give 12.1 g (94%) of 1-hydroxycyclohexyl-4- (2-chloroformylethyl) carbonyl phenyl ketone.

C. Covalent binding of acylated transorber to cyclodextrin

To a 250 ml three-necked round bottom reaction flask containing a magnetic stir bar and equipped with a thermometer, condenser and dropping funnel with. 10 g (9.8 mmol) of? -cododextrin (American Maize-Products Company, Hammond, Indiana), 31.6 g (98 mmol) of 1-hydroxycyclohexyl-4? 2-oroformylethyl) carbonylphenyl ketone and 100 ml of Ν, Ν-dimethylformamide. The mixture was heated to 50 C and 0.5 mL of triethylamine was added. The reaction mixture was kept at 50 ° C for 1 h and allowed to cool to room temperature. It has not been attempted in this preparation to isolate the product, β-cyclodextrin, to which the ultraviolet radiation transorber has been covalently bonded (referred to herein as β-cyclodextrin transorber).

The above procedure was repeated to isolate the reaction product. Finally, the reaction mixture was concentrated on a rotary evaporator to about 10% of the original volume. The residue was poured onto ice with water, to which was added sodium chloride to precipitate the product from solution. The resulting precipitate was isolated by filtration and -promylethylether. .FevnýψodíUbyl · -sušenza-sníŽenéhcΓtlak ^ J ^_ apóškytΓ24; 8 g of white powder. In the third preparation, the rotary evaporator residue was fed on top of a column of about 7.5 cm containing about 15 g of silica gel, the residue was eluted with N, N -dimethylformamide, while the eluent was monitored with Whatman® Flexible-Backed TLC plates (catalog no. 05-713 -161, Fisher Scientific, Pittsburgh, Pennsylvania). The eluted product was isolated by evaporation of the solvent. The structure of the product was confirmed by nuclear magnetic resonance analysis.

D. Dye association with cyclodextrin-transorber preparation of color composition

To a solution of 10 g (estimated as about 3.6 mmol) of the β-cyclodextrin transorber in 150 ml of Ν, ml-dimethylformamide in a 250 ml round bottom flask was added 1.2 g (3.6 mmol) of ) malachite green oxalate (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin), referred to herein as dye

A. The reaction mixture was stirred with a magnetic stir bar for 1 h at room temperature. Most of the solvent was then removed by rotary evaporation and the residue was eluted from the silica gel column as above. The βcyclodextrin-transorber and dye A inclusion complex passed through the first column and separated cleanly from both the free dye A and the β-cyclodextrin transorber. The complex-containing eluent was. collected and the solvent removed on a rotary evaporator. The residue was subjected to a reduced pressure of 0.01 torr to remove residual solvent and afforded a blue-green powder.

E. Color composition mutations

The inclusion complex of the β-cyclodextrin-transorber and dye A was exposed to ultraviolet radiation from two different lamps, lamps A and B. Lamp A consisted of 222 nm excimer lamps arranged in groups of four cylindrical lamps about 30 cm long. The lamps were cooled by circulating water through a centrally located or internal lamp tube and consequently operated at a relatively low temperature, i.e. about 50 ° C. Typically, the energy generation density on the outer surface of the lamp is in the range of about 4 to about 20 J / m ² . However, this range actually only reflects the possibilities of current excimer lamps as energy sources; in the future, higher energy densities may be required in practice. The distance from the lamp to the irradiated sample was 4.5 cm. Lamp B consisted of Hanovia 500 W medium pressure mercury lamp (Hanovia Lamp Co., Newark, New Jersey.) .'_ Plamp DistanceYour PaintedTulkbybaiah 15'cm: ------------ Several drops of Ν, Ν-dimethylformamide solution inclusion A complex of β-cyclodextrinrtransorber with dye A was applied to a TLC plate and a small polyethylene weighing bottle. Both samples were exposed to lamp A and stained (i.e., mutated to colorless) within 15-20 seconds. Similar results were obtained with lamp B in 30 s.

The first control sample, consisting of a solution of dye A and β-cyclodextrin in Ν, ethyldimethylformamide, was not discolored by lamp A. A second control sample consisting of Dye A and 1-hydroxycyclohexylphenyl ketone in N, N, dimethylformamide was a lamp A of 60 s; However, when standing, the color began to reappear within 1 hour.

In order to evaluate the effect of the solvent on the decolourisation, 50 mg of the inclusion complex of β-N, N-hexane with dye A was dissolved in 1 ml of solvent. The resulting solution was placed on a microscope slide and exposed to lamp A for 1 min. The decolorization rate, ie, the time to decolorization of the sample, was directly proportional to the complex solubility in the solvent as summarized below.

solvent solubility decolourizing time N, N-dimethylformamide bad 1 min dimethylsulfoxide soluble <10s acetone soluble <10s hexane insoluble - ethyl acetate bad 1 min

Finally, 10 mg of the β-cyclodextrin-transorber inclusion complex with dye A was placed on a microscope slide and crushed with a pestle. The resulting powder was exposed to 10 with lamp A. The powder was bleached. Similar results were obtained with lamp 6, but at a slower rate.

Example 4

In view of the possibility that the acyl chloride of the acylated transorber at least partially occupies the cyclodextrin cavity at least partially at the expense of the dye in preparing the color composition described in Example 3, a modified preparative procedure was performed. Thus, this example describes the preparation of a β-cyclodextrin molecular includant having (1) a dye at least partially incorporated in the cyclodextrin cavity and associated with it via hydrogen bonds and / or van der Waals forces, and (2) an ultraviolet transorber covalently bound to cyclodextrin outside the cavity cyclodextrin.

A. Dye association with cyclodextrin

To the solution. 10.0 g (9.8 mmol) of β-cyclodextrin in 150 ml of Ν-dimethylformamide was added with 3.24 g (9.6 mmol) of dye A. The resulting solution was stirred at room temperature for 1 h. The reaction solution was concentrated under reduced pressure on a rotary evaporator to about one tenth of the original volume. The residue was applied to a silica gel column as described in part C of Example 1. The solvent in the eluent was removed by rotary evaporation under reduced pressure to obtain 12.4 g of a blue-green β-cyclodextrin inclusion complex powder and A. dye.

B. Covalent bonding of acylated transorber to inclusion complex of cyclodextrin and dye - preparation of color composition

10 g (9.6 mmol) of the β inclusion complex were introduced into a 250 mL round bottom three-neck reaction flask containing a magnetic stir bar and equipped with a thermometer, condenser, and pressure-equalizing dropping funnel fitted with a nitrogen feed pipe. cyclodextrin and dye A, 31.6 g (98 mmol) of 1-hydroxycyclohexyl-4- (2-chloroformylethyl) carbonylphenyl ketone, prepared as in Part B of Example 1, and 150 ml of Ν, β-dimethylformamide. The reaction mixture was heated to 50 ° C and 0.5 mL of triethylamine was added. The reaction mixture was kept at 50 ° C for 1 h and then allowed to cool to room temperature. The reaction mixture was treated as in Part A above and were recovered ^two 44; -2- G tnkluzního ^- complex ^- β-cyclodextrin-transorber dyes I "blue-green powder.

C. Color composition mutations

The procedures described in Part E of Example 1 were repeated with the inclusion complex of the βcyclodextrin-transorber and dye A prepared in Part B, essentially with the same results.

Example 5

This example describes a process for preparing an ultraviolet transorber, termed phthaloylglycine-2959.

In a 250 ml, three-necked round bottom flask equipped with a Dean & Stark adapter with condenser and two glass stoppers, 20.5 g (0.1 mol) of a wavelength sensitive sensitizer, phthaloylglycine (Aldrich) were mixed; 24.5 g (0.1 mol) of a photoreactor, DARCUR 2959 (Ciba-Geigy, Hawthorne, NY); 100 ml benzene (Aldrich); and 0.4 g of p-toluenesulfonic acid (Aldrich). The mixture was heated to reflux for 3 h, after which time 1.8 mL of water was collected. Evaporation of the solvent under reduced pressure gave 43.1 g of a white powder. Powder by! recrystallized from 30% ethyl acetate in hexane (Fisher) to give 40.2 g (93%) of a white crystalline powder with a melting point of 153154 ° C. The reaction is summarized as follows:

O

benzene acid

The resulting product, phthaloytglycine-2959, had the following physical parameters:

IR [Nujol Muu] ν _max 3440, 1760, 1740, 1680, 1600 cm -1 ¹ H NMR [CDCl ₃ ] δ ppm 1.64 [s], 4.25 [m], 4.49 [m], 6 , 92 [m], 7.25 [m], 7.86 [m], 7.98 (m), 8.06 [m] ppm.

Example 6

This example describes the method of dehydration of phthaloylglycine-2959 produced in Example 5.

In a 250 ml round bottom flask equipped with a Dean & Sticker Adapter with Cooler, 21.6 g (0.05 mol) of phthaloylglycine-2959 were mixed; 100 ml of anhydrous benzene (Aldrich); and 0.1 g of p-toluenesulfonic acid (Aldrich). The mixture was heated to reflux for 3 h. After 0.7 ml of water was collected in the receiver, the solution was evaporated under reduced pressure to give 20.1 g (97%) of a white solid. The solid was used without further purification. The reaction is summarized as follows:

toluenesulfonic acid

In benzene

+ H ₂ O

The product obtained had the following physical parameters:. IR (NUJOL) at _max 1617 cm ^-1 (C = C = O)

Example 7

This example describes a method for producing β-cyclodextrin with covalently bonded dehydrated phthalylglycine-2959 groups from Example 6.

In a 100 ml round bottom flask, 5.0 g (4 mmol) of β-cyclodextrin (American Maize Product Company, Hammond, Indiana) (referred to as beta-CD in the following reaction scheme) were mixed; 8.3 g (20 mmol) of dehydrated phthaloylglycine-2959; 50 ml of anhydrous DMF; 20 mh benzene; and 0.01 g of p-toluenesulfonyl chloride (Aldrich). The mixture was cooled in a salt / ice bath and stirred for 24 h. The reaction mixture was poured into 150 mL of a weak sodium bicarbonate solution and extracted three times with SO-mL-ethyl ether; -Water--vrštva ^then: -It -odfiltrována-and--is obtained -White solid comprising 0-cyclodextrin with phthaloylglycine-connected group 2959th A yield of 9.4 g was obtained. Reversed phase TLC chromatography using a 50:50 DMF: acetonitrile mixture showed a new product peak compared to the starting materials.

Beta-CD o

II o

Of course, the β-cyclodextrin molecule has several primary and secondary alcohol groups with which phthaloylglycine-2959 can react. Said reaction scheme shows for illustration only one phthaloylglycine-2959 molecule.

Example 8

This example describes a process for associating the dye and the ultraviolet transorber

I radiation with a molecular includant. Specifically, this example describes a method of associating a crystal violet dye with a molecular inclusion substance β-cyclodextrin covalently bound to the ultraviolet transorber phthaloylglycine-2959 of Example 7.

4.0 g of β-cyclodextrin with dehydrated phthaloylglycine-2959 and 50 ml of water were introduced into a 100 ml beaker. The water was heated to 70 ° C at which point the solution was clarified. Next, 0.9 g (2.4 mmol) of crystal violet (Aldrich Chemical Company, Milwaukee, WI) was added and the solution was stirred for 20 min. After the solution was filtered, the filtrate was washed with the filtrate and then dried in a vacuum oven at 84 ° C. A purple-blue powder was obtained with a yield of 4.1 g (92%). The reaction product obtained had the following physical parameters:

UV spectrum DMF λ _φ3Χ 610 nm (cf _j X _max 604 nm)

Example 9

This example describes a process for preparing a chlorine-substituted 4- (4-hydroxyphenyl) butan-2-one-2959 ultraviolet transorber.

In a 250 ml round bottom flask equipped with a condenser and a magnetic stir bar, the following were mixed: 17.6 g (0.1 mol) wavelength selective sensitizer, 4- (4-hydroxyphenyl) butan-2-one (Aldrich) Chemical Company, Milwaukee, WI); 26.4 g (0.1 mol) of a photoreactor, chlorosubstituted DARCUR 2959 (Ciba-Geigy Corporation, Hawthorne, New York); 1.0 ml pyridine (Aldrich Chemical Company, Milwaukee, WI); and 100 ml of anhydrous tetrahydrofuran (Aldrich Chemical Company, Milwaukee, WI). The mixture was heated to reflux for 3 h and the solvent was partially removed under reduced pressure (60% collected). The reaction mixture was then poured into ice-water and extracted with two 50-ml aliquots of diethyl ether. After drying over anhydrous magnesium sulfate and removing the solvent, 39.1 g of white solid remained. Recrystallization of this white powder from 30% ethyl acetate in hexane gave 36.7 g (91%) of a white powder with a melting point of 142-143 ° C. The reaction is summarized as follows:

The reaction product obtained had the following physical parameters:

IR [Nujo] Muu] v _max 3460, 1760, 1700, 1620, 1600 cm -1 ¹ H [CDCl 3] δ ppm 1.62 [s], 4.2 [m], 4.5 [m], 6.9 [m] ppm.

The ultraviolet transorber produced in this example, 4- (4-hydroxyphenyl) butan-2-one-2959 (chlorosubstituted), may be associated with β-cyclodextrin and a dye such as crystal violet by the methods described in Examples 6 to 8 above, wherein replacing said dehydrated phthaloyl glycine-2959 with 4- (4-hydroxyphenyl) butan-2-one-2959 (chlorosubstituted).

Example 10

This example demonstrates that the 222 nm excimer lamps shown in Figure 3 produce a uniform intensity reading on the substrate surface at a distance of 5.5 cm from the numbered lamps in an amount sufficient to mutate the dye in the present compositions present on the surface. substrate. The lamp 10 includes a housing 15 with four excimer flasks 20 disposed parallel, the excimer flasks 20 having a length of about 30 cm. The lamps are cooled with water circulating through a centrally located or inner tube (not shown) and consequently the lamps * operate at a relatively low temperature, i.e. about 50 ° C. The power density at the lamps outer _povrchu jeLtypicky rezmezí-in-Asr-up asrZQt / cm ^2: ------------------------ Table 5 summarizes the intensity reading. which was obtained by a measuring device on the substrate surface. Readings 1, 4, 7, and 10 were placed approximately 7.0 cm from the left edge of the column shown in Figure 3. The readings 3, 6, 9, and 12 were positioned approximately 5.5 cm from the right edge of the column shown on Fig. 3. The readings marked 2, 5, 8 and 11 were centrally located approximately 17.5 cm from each edge of the column shown in Fig. 3.

Table 5 background (pW) reading (mW / ciri ² )

24.57 9.63 19.56 9.35 22.67 9.39 19.62 9.33 17.90 9.30 19.60 9.30 21.41 9.32 17.91 9.30 23.49 9.30 19.15 9.36 17.12 9.35 21.44 9.37

Example 11

This example demonstrates that the 222 nm excimer lamps shown in Figure 4 produce a uniform intensity reading on the substrate surface of 5.5 cm from the numbered lamps in an amount sufficient to mutate the dye in the compositions of the invention that are present on the substrate surface. IQ Excimer Lamp. includes a housing 15 with four excimer flasks 20 disposed in parallel, wherein the excimer flasks -ZO-coarse-viscosity-located or inner tube (not shown) and consequently the lamps operate at a relatively low temperature, ie about 50 ° C. The power density at the lamps outer surface typically is in the range of about 4 to about 20 J / ^cm.

Table 6 summarizes the reading of the intensity obtained by the measurement device on the substrate surface. Readings 1, 4, and 7 were placed approximately 7.0 cm from the left edge of the columns shown in FIG. 4. The readings 3, 6, and 9 were positioned approximately 5,55.5 cm from the right edge of the columns shown in FIG. 4? Readings 2, 5, and 8 were centrally located approximately 17.5 cm from each of the columns of Figure 4.

Table 6

background (pW) reading (mW / cm ² ) 23.46 9.32 16,12 9.31 17.39 9.32 20.19 9.31 66,45 ______ _ . 9,29- ... ___________ _____ 20.42 9.31 18.33 9.32 15.50 9.30 20.90 9.34

Example 12

This example demonstrates the intensity produced by the 222 nm excimer lamps shown in Figure 5 on the substrate surface as a function of surface distance from lamps, which intensity is sufficient to mutate the dye in the compositions of the invention that are present on the substrate surface. The excimer lamp 10 includes a housing 15 with four excimer flasks 2Ώ disposed parallel to each other, wherein the excimer flasks 20 have a length of about 30 cm 3 / cm 2 in a water-circulating tube centrally located or inner tube (not shown) and consequently the lamps operate at relatively low temperature, i.e. about 50 ° C. Developmental density, energy on the outer surface of the lamp is typically in the range of about 4 to about 20 J / cm ² .

Table 7 summarizes the reading of the intensity obtained by the measurement device on the substrate surface at position 1 shown in Figure 5. Position 1 was centrally located approximately 17 cm from each edge of the column shown in Figure 5.

Table 7.

distance (cm) - background (pW) reading (mW / cm ² )

5.5 18.85 9.30 6.0 15.78 9.32 10 18.60 ' 9.32 15 20.90 9.38 20 21.67 9.48 25 19.86 9.69 30 22.50 11.14 35 26.28 9.10 40 24.71 7.58 50 26.95 . 5.20

Variations and modifications not exceeding the spirit or scope of the invention will be apparent to those of ordinary skill in the art from this disclosure.

Claims

PATENT CLAIMS

1/4

FIG.

4V

A color composition comprising a mutable dye and an ultraviolet radiation transorber.

2/4 o

(D. ^Cis

AND

CH, c = o

FIG. 2 pl · '2-7

2. A color composition according to claim 1, further comprising: a molecular includant.

The color composition of claim 2, wherein the molecular / inclusion substance is selected from the group consisting of citrates, zeolites, and cyclodextrins. ~

The color composition of claim 2, wherein the mutable dye and the ultraviolet radiation transorber are associated with the molecular includant.

The color composition according to claim 4, wherein the dye is at least partially incorporated in the cavity of the molecular includant.

The color composition of claim 4, wherein the ultraviolet radiation transorber is associated with a molecular includant outside the cavity.

The color composition according to claim 6, characterized in that the ultraviolet transorber is covalently bound to the molecular includant.

8. A method of mutating a color composition, wherein the color composition comprises a mutable dye and an ultraviolet radiation transorber, the method comprising the step of irradiating the color composition with ultraviolet radiation at a dose sufficient to irreversibly mutate the dye.

9. The method of claim 8 wherein the color composition further comprises a molecular encapsulation substance.

The method of claim 9, wherein the dye and the ultraviolet radiation transorber are associated with the molecular includant.

11. The method of claim 8, further comprising the step of applying the color composition to the substrate prior to irradiating the color composition with ultraviolet radiation.

»

12. The method of claim 11 wherein the mutated dye is stable.

13. The method of claim 10, further comprising the step of applying the color composition to the substrate prior to irradiating the color composition with ultraviolet radiation.

14. The method of claim 13 wherein the mutated dye is stable.

Toner in an electrophotographic process comprising a mutable dye, an ultraviolet transorber and a dye carrier and an ultraviolet transorber.

Toner according to claim 15, characterized in that the carrier comprises a polymer.

The toner of claim 15 wherein the composition further comprises a charge carrier.

T8. Toner according to claim 15, characterized in that the ultraviolet radiation transorber absorbs ultraviolet radiation with a wavelength of about 100 to about 375 nm.

The solid color composition of claim 18, wherein the ultraviolet radiation is incoherent, pulsed ultraviolet radiation from a dielectric barrier excimer lamp.

Toner according to claim 15, characterized in that _; includes a molecular includant.

The toner of claim 20, wherein the mutable dye and the ultraviolet radiation transorber are associated with the molecular includant.

Toner according to claim 21, characterized in that the mutable dye is at least partially included in the molecular includant cavity.

..... ~ - “

23. The method of claim 2, wherein the ultraviolet transorber is covalently bound to the molecular includant.

An electrophotographic process comprising the steps of forming a photoreceptor surface image, applying toner to a photoreceptor surface to produce a toner image that replicates an image, the toner comprising a mutable dye, an ultraviolet transorber, and a carrier, transferring the toner image to substrate and fixation of the toner image to the substrate.

25. The electrophotographic process of claim 24 wherein the carrier comprises a polymer. ___________________________

26, The electrophotographic process of claim 24, wherein the composition further comprises a charge carrier.

27. The electrophotographic process of claim 24, wherein the ultraviolet radiation transorber absorbs ultraviolet light at a wavelength of about 100 to about 375 nm.

28. The electrophotographic process of claim 27, wherein the ultraviolet radiation is a non-coherent, pulsed ultraviolet radiation of a dielectric barrier emitting diode lamp.

29. The electrophotographic process of claim 24, wherein the toner further comprises a molecular includant.

30. The electrophotographic process of claim 29, wherein the mutable dye and the ultraviolet radiation transorber are associated with the molecular includant.

31. The electrophotographic process of claim 30, wherein the mutable dye is at least partially included in the molecular includant cavity.

32. The electrophotographic process of claim 30 wherein the ultraviolet transorber is covalently bound to the molecular includant.

_tt

33. An electrophotographic process comprising the steps of forming a first image substrate comprising a first toner comprising " 1 " _ "

a mutable dye, an ultraviolet radiation transorber and a dye carrier and an ultraviolet radiation transorber; exposing the first image to the ultraviolet radiation at a dose sufficient to irreversibly mutate the dye; photoreceptor surface, ............

applying a second toner to the photoreceptor surface to form a toner image that replicates the second image, transferring the second toner image of the second image to the substrate and fixing the second toner image to the substrate.

34. The electrophotographic process of claim 33 wherein the carrier is a polymer.

35. The electrophotographic process of claim 33, wherein the first toner is charged with a charge emitter. * •

36. The electrophotographic process of claim 33, wherein the first toner further comprises a molecular includant.

37. The electrophotographic process of claim 33, wherein the ultraviolet radiation transorber absorbs ultraviolet radiation of about 100 to about 375 nm.

38. The electrophotographic process of claim 37, wherein the ultraviolet radiation is incoherent, pulsed ultraviolet radiation from a dielectric barrier excimer lamp.

-------

39, wherein the second toner comprises a second mutable dye, a second ultraviolet radiation transorber, and the like.

a second carrier for the second dye and a second ultraviolet radiation transorber.

40. The electrophotographic process of claim 39 wherein the second carrier is a polymer.

*

41. The electrophotographic process of claim 39, wherein the second toner comprises a charge carrier.

42. The electrophotographic process of claim 39, wherein the second toner further comprises a molecular contaminant.

43. An electrophotographic process according to claim 39, wherein the ultraviolet process. the radiation has a wavelength of about 100 to about 375 nm.

44. The electrophotographic process of claim 43, wherein the ultraviolet radiation transorber absorbs ultraviolet radiation at about 100 to about 375 nm.

45. A substrate having an image thereon which is formed from a color composition, wherein the color composition comprises a mutable dye and an ultraviolet radiation transorber.

46. The substrate of claim 45, wherein the color composition further comprises a molecular nucleating agent ^. -----

47. The substrate of claim 46, wherein the molecular includant is selected from the group consisting of clathrates, zeolites, and cyclodextrins.

48. The substrate of claim 46, wherein the stable dye and the ultraviolet radiation transorber are associated with a molecular damper. substance .........

49. Substrate characterized by by doing so. that it comprises an image formed by electrophoretic toner, wherein the electrophoretic toner comprises a mutable dye, an ultraviolet transorber and a dye carrier and an ultraviolet transorber.

50. The substrate of claim 49 wherein the carrier comprises a polymer.

The substrate of claim 49, wherein the toner further. includes a carrier

The substrate of claim 49, wherein the toner further comprises a molecular includant.

The substrate of claim 52, wherein the molecular includant is selected from the group consisting of clathrates, zeolites and cyclodextrins.

The substrate of claim 52, wherein the mutable dye and the ultraviolet radiation transorber are associated with the molecular includant.

55. An ultraviolet transorber comprising, in combination, a wavelength selective sensitizer and a photo-reactor ^.

The ultraviolet transorber of claim 55, wherein the wavelength selective sensitizer is covalently bonded to the photoreactor.

57. The ultraviolet transorber of claim 55, wherein the wavelength selective sensitizer absorbs ultraviolet radiation of about 100 to about 375 nm.

58. The ultraviolet transorber of claim 57, wherein the ultraviolet radiation is incoherent, pulsed ultraviolet radiation from the dielectric barrier excimer lamp.

59. The ultraviolet transorber of claim 55, wherein the wavelength selective sensitizer is selected from the group consisting of phthaloylglycine and Φ (4-oxyphenyl) 2-butanone.

60. The ultraviolet transorber of claim 55 wherein the photoreactor is selected from the group consisting of [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one and cyclohexylphenylketonester.

The ultraviolet transorber according to claim 55, which is phthaloylglycyl-1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpyridin-1-one.

The ultraviolet transorber of claim 55, which is phthaloylglycylcyclohexylphenylketonester.

The ultraviolet transorber of claim 55, which is 4- (4-oxyphenyl) -2-butene-3'-N - [(2-methoxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one. '—---- -------- ₂ _2_

The ultraviolet transorber of claim 55 which is 4 (4-oxyphenyl) -2-butanone cyclohexylphenyl ketonester.

rv ύπ

3/4

FIG. 5