HUT73681A - Mutable composition and methods of use thereof - Google Patents

Description

BACKGROUND OF THE INVENTION The present invention relates to a colored composition comprising a variable dye, an ultraviolet radiation transducer and optionally an inclusion molecule.

The present invention also relates to a method of changing the color composition comprising exposing the color composition to ultraviolet radiation at a dose sufficient to irreversibly alter the color.

The present invention also relates to a toner for use in an electrophotographic process comprising a variable dye, an ultraviolet radiation transducer, a carrier, optionally a carrier, and optionally an inclusion molecule. The present invention further relates to an electrophotographic method wherein an image is obtained on a photoreceptor surface or on a substrate using the aforementioned toner.

The invention further includes an image-bearing substrate and an ultraviolet radiation transducer.

PUBLICATION LITERATURE

For use in a variable composition and method

BACKGROUND OF THE INVENTION The present invention relates to a variable color composition for use in some embodiments in a toner for use in an electrophotographic toner such as a xerographic transmission copier.

Electrophotography can roughly be defined as the process of capturing photons to produce an electrical image analogous to the original. The electrical analogue is then processed through several steps to produce a physical image. The most common form of electrophotography currently used is the so-called xerographic transmission. This procedure was first introduced by C. Carlson in 1938 but spread slowly. Today, however, xero83242-5147 / SL graphics transfer is the foundation of a multi-billion dollar industry.

The heart of the process is a photoreceptor, which is usually a moving element and can be drum-shaped or continuous, seamless. A crown discharge device delivers gas ions to the photoreceptor surface. The ions form a uniform electric field around the photoreceptor and form a uniform charge layer on its surface. The illuminated original image is projected and focused on the photoreceptor through a lens system. The light impinging on the charged photoreceptor surface enhances the conductivity around the photoreceptor and at the same time neutralizes the surface charge. The irradiated areas of the photoreceptor surface retain their charge. The resulting surface charge pattern is the latent electrostatic image.

In its particles, a thermoplastic pigmented powder or toner which carries a charge opposite to the surface charge of the photoreceptor is placed close to the photoreceptor, so that the toner particles bind to the charge-carrying portions of the photoreceptor surface. The result is a physical image of the photoreceptor surface consisting of electrostatically retained toner particles. The photoreceptor carrying the toner is physically contacted with a sheet of plain paper. The charge applied to the back of the paper causes the tone to bind to the paper. This image is a positive copy of the original. The paper is then separated from the photoreceptor together with the tone pattern bound by electrostatic binding. The tone image is permanently combined with the paper by means of a suitable heating device, such as a hot press roller or radiant heat.

Because transferring the toner to paper is not perfect. the photoreceptor surface should be cleaned of any remaining toner. Such a tone adjuster is wiped off with a brush, cloth or blade. Removal of the tone adjuster is facilitated by crown discharge or reverse polarity. The photoreceptor is then illuminated by a uniform light source to neutralize the charge remaining from the previous imaging cycle, to completely remove the previous electrostatic image, and to prepare the photoreceptor surface for the next cycle.

The toner usually consists of thermoplastic dust particles having an average diameter of 1 to 15 µm. The black toner generally contains from 5 to 10% by weight of black carbon particles having a diameter of up to 1 µm and dispersed in the thermoplastic powder. In the toner used for color xerography, black carbon can be replaced with cyan, magenta, or yellow pigments. By adjusting the concentration and dispersion of the pigment, the tone adjuster can provide a conductivity that corresponds to the imaging system. Most devel- opment processes require the tone adjuster to hold the charge used for electrical contact for an extended period of time. The thermoplastic component used in the toner is generally selected based on its melting properties. It is necessary for the thermoplastic component to melt within a relatively narrow temperature range, but to be stable in storage and to withstand the intense kcvcrc in xerographic development chambers.

Successful electrophotography, and more specifically xerographic transmission, undoubtedly plays an important role in the effective dissemination of information, which is the basis for worldwide distribution. However, it also contributes to the production of large quantities of paper which are subsequently discarded or reused. Paper recycling technology is known, but it is costly, time consuming and requires proper storage. The usual solution for reusing paper is to pulp the paper, properly removing ink, toner and other color materials from the pulp, which is a costly and not always successful operation. In addition, the removal of dye substances produces a sludge which must be stored under appropriate conditions. The resulting bleached pulp is then often used, together with a certain amount of virgin pulp, to produce paper, corrugated paper, cellulose-based packaging material and the like.

However, the simplest form of recycling would be to reuse the paper in its original form, thus avoiding the pulp and process. To this end, a toner adjuster has been developed for use in photocopying equipment that becomes discolored by infrared or near radiation. The low wavelength end of the visible light spectrum is at about 375 nm, and there is a significant amount of infrared components at the high wavelength end of the spectrum. The disadvantage of such tone adjusters is therefore that the above environmental factors, such as visible light and heat, become discolored. The document thus becomes illegible before fulfilling its function or purpose. Thus, there is a need for a toner that can be used in photocopiers that allows the reuse of intact paper but is stable under normal environmental conditions.

It is an object of the present invention to meet the need for simple, economical and environmentally sound paper reuse and multiple uses of photocopier paper.

It is an object of the present invention to provide a color system. which can be changed when exposed to radiation. Accordingly, the present invention relates to a composition comprising dyes that can be varied in the presence of a radiation transistor. The radiation transducer is capable of absorbing radiation and interacting with the dye to induce a change in dye. In addition, it is advantageous if the dye change is irreversible.

The composition of the invention comprises a dye and an ultraviolet radiation transducer. The dye is configured to change in the presence of ultraviolet radiation in the presence of a transistor and its exposure to ultraviolet radiation. The function of the ultraviolet radiation transducer is to absorb the ultraviolet radiation and to interact with the dye to induce irreversible change in the dye. It is preferred that the ultraviolet radiation transducer absorbs ultraviolet radiation having a wavelength of about 4-400 nm. In particular, it is advantageous for the ultraviolet radiation transducer to absorb ultraviolet radiation at a wavelength of 100375 nm.

In one embodiment of the present invention, the color composition further comprises, in addition to the dye and the ultraviolet radiation transducer, an inclusion molecule whose chemical structure defines at least one cavity. The inclusion molecule may be, for example, clathrate, zeolite and / or cyclodextrin. The dye and the ultraviolet radiation transporter are associated with one or more inclusion molecules. In some embodiments, the dye is at least partially located in the cavity of the inclusion molecule, and the ultraviolet radiation transistor is associated with the inclusion molecule, but outside the cavity. In some embodiments, the ultraviolet radiation is covalently bonded to the outer portion of the inclusion molecule by a transporter.

The invention further relates to a process for altering the dye in the composition of the invention. In the process, the composition comprising the variable dye and the ultraviolet radiation transducer is exposed to ultraviolet radiation at a dose sufficient to alter the dye. As noted above, certain embodiments of the composition further comprise an inclusion molecule. In another embodiment, the composition is applied to a substrate prior to exposure to ultraviolet radiation. Preferably, the altered dye is stable. The invention relates to a substrate comprising an image formed by the composition of the invention.

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The present invention also relates to an electrophotographic method which allows multiple use of a substrate such as photocopying paper. The method involves irradiating the image formed on the substrate as described above with ultraviolet radiation at a dose sufficient to irreversibly alter the dye. A second image is then formed on a photoreceptor surface, and a second tone adjuster is applied to the photoreceptor surface to form a tone image that repeats the second image. The second tone image of the second image is then applied to the substrate and the second tone image is fixed on the substrate. If the second toner adjuster comprises a dye according to the invention and an ultraviolet radiation transducer, the dye in the second image may also be changed by irradiation with ultraviolet radiation, so that the substrate can be reused to fix a third image on the substrate.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The invention, its details, embodiments and advantages will be described in the following detailed description.

Figure 1 shows an ultraviolet radiation transporter / variable dye / inclusion molecule complex with the variable dye malachite green, the ultraviolet radiation transducer Irgacure 184 (1-hydroxycyclohexylphenyl ketone), and the inclusion molecule beta-cyclodextrin.

Figure 2 shows an ultraviolet radiation transporter / variable dye / inclusion molecule complex, wherein the variable dye is pure Victorian BO (Vic (I

- 8 toria Pure Blue BO, i.e. Basic Blue 7), the ultraviolet radiation transducer Irgacure 184 (1-hydroxycyclohexylphenyl ketone), and the inclusion molecule beta-cyclodextrin.

Figure 3 shows the arrangement of a plurality of 222 nm excimer lamps in four parallel columns, with twelve circled numbers showing the points where an intensity measurement is made about 5.5 cm from the excimer lamp.

Figure 4 shows the placement of a plurality of 222 nm excimer lamps in four parallel columns, where the nine circled numbers indicate the points where an intensity measurement is made about 5.5 cm from the excimer lamp.

Figure 5 shows the placement of several 222 nm excimer lamps in four parallel columns, with the circled number 1 representing the point where ten intensity measurements are made at increasing distance from the lamp (Measurement results and distance are given in Table 7). .

As mentioned above, the present invention relates to a color system that changes upon exposure to radiation. The composition of the present invention comprises a dye that can be altered in the presence of a radiation transistor. The radiation transducer is capable of absorbing radiation and interacting with the dye to cause a change in the dye.

The composition of the invention thus comprises a dye and an ultraviolet radiation transducer. The dye is configured to change in the presence of ultraviolet radiation in the presence of a transistor and its exposure to ultraviolet radiation. The ultraviolet radiation transducer is configured to absorb ultraviolet radiation and interact with the dye to induce irreversible change in the dye. The terms "composition" and "color composition" thus refer to a dye and an ultraviolet radiation transducer. When referring to a color formulation specifically formulated for use as a toner in an electrophotographic process, the term "formulation based" is used to indicate that the material, such as a toner, is a dye, an ultraviolet radiation transducer, and optionally an inclusion molecule. contain.

The term "dye" is understood to include, without limitation, any material that can be altered in the presence of ultraviolet radiation in the presence of a transistor and exposed to ultraviolet radiation. The dye is usually an organic material, such as an organic dye or pigment, such as a toner or lacquer. Preferably, a substantially transparent dye is used which does not significantly interact with the ultraviolet radiation employed. The dye may be a single substance or a mixture of two or more substances.

Organic dyes include, for example, triarylmethyl dyes such as malachite green carbinol base (4- (dimethylamino) -α- [4- (dimethylamino) phenyl] -α-phenylbenzene methanol), malachite green carbinyl hydrochloride. (N-4 - [[4- (dimethylamino) phenyl] phenylmethylene] -2,5-cyclohexylidene-1-ylidene] -N-methylmethane-amminium chloride or bis [p- (dimethyl) amino) phenyl] phenyl

- 10 methylium chloride) and malachite green oxalate [N-4 - [[4- (dimethylamino) phenyl] phenylmethylene] -2,5-cyclohexylidene-1-ylidene] N-methyl methanamine chloride or bis [p-dimethylamino-phenyl] -phenylmethyl-oxalate; monoazo dyes such as cyanine black, chrysoidin [Basic Orange 2; 4- (phenylazo) -1,3-benzenediamine monohydrochloride] and Beta Naftol Orange; thiazine dyes such as methyl green, zinc chloride double salt [3,7bis (dimethylamino) -6-nitro-phenothiazin-5-ium chloride, zinc chloride double salt]; oxazine dyes such as Lumichrome (7,8-dimethylalloxazine); naphthalimide dye such as Lucifer Yellow CH (6-amino-2 - [(hydrazinocarbonyl) amino] -2,3-dihydro-1,3-dioxo-1H-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 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-heptatrienyl] -1,1-dimethyl-3- (4-sulfobutyl) -1H-benz [e] indolium hydroxide inner salt, sodium salt); an indigo dye 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); coumarin dyes such as 7-hydroxy-4-methylcoumarin (4-methylbelliferone); benzimidazole dye such as Hoechst 33258 (bis-benzimide or 2- (4-hydroxyphenyl) -5- (4-methyl-1-piperazinyl) -2,5-bi-1H-benzimidazole trihydrochloride pentahydrate); a parakinoid dye such as hematoxylin (natural black 1; 7,1 lb-dihydrobenz [b] indeno [1,2-d] pyran-3,4,6a, 9,10 (6H) pentol); a fluorescein dye such as fluorescein amine (5-aminofluorescein); diazonium salt dye, such as diazovar EC (azo diazo # 10 or Fást rt '

- 1 1 Red RC salt; 2-methoxy-5-chlorobenzodiazonium chloride, zinc chloride double salt); azo-diazo dye such as Fás Blue BB salt (azo-diazo 20; 4-benzoylamino-2,5-diethoxybenzene-diazonium chloride, zinc chloride double salt); phenylene diamine dye, such as disperse yellow 9 (N- (2,4-dinitrophenyl) -

1,4-Phenylenediamine or Solvent Orange 53); diazofoam such as disperse orange 13 (Solvent Orange 52; 1-phenylazo-4- (4-hydroxy-phenylazo) -naphthalene); anthraquinone dye such as disperse blue 3 (Celliton Fás Blue FFR, 1-methylamino-4- (2-hydroxyethylamino) -9,10-anthraquinone), dispers blue 14 (Celliton Fás Blue Β; 1,4- bis (methylamino) -9,10-anthraquinone) and alizarin blue-black B (Mordant Black 13); trisazo dye 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-naphthalenyl) azo] -1,5-naphthalene disulfonic acid tetranium salt); xanthene dye such as 2,7-dichlorofluorescein: proflavin dye such as 3,6-diaminoacridine hemisulfate (proflavin); sulfonaphthalene dye such as cresol red (o-cresol sulfonaphthalene); a phthalocyanine dye such as copper phthalocyanine (Pigment Blue 15; (SP-4-1) - [29H, 3H-phthalocyanato- (2-) N ⁹ , N ³⁰ , N ³¹ , N ³² ] copper); carrotenoid dye such as trans-3-carrotene (Food Orange 5), carminic acid dye such as carmin, carinic acid (7-aD-glucopyranosyl-9,1O-dihydro-3,5,5,6,8-tetrahydroxyl) lacquer of methyl-9,10-dioxo-2-anthracenecarboxylic acid, aluminum or calcium-aluminum; azur dyes such as azure A (3-amino-7- (dimethylamino) -phenothiazin-5-ium chloride or 7- (dimethylamino) -3-imino-3H-phenothiazine hydrochloride); and acridine nights such as acridine Orange (Basic Orange 14; 3,8-bis (dimethylamino) acridine hydrochloride, zinc chloride double salt) and acriflavine (acriflavine neutral; 3,6-diamino-10-methyl acridinium). chloride and 3,6-acridine diamine).

The term "variable" used in connection with a dye means that in the visible region of the electromagnetic spectrum, the dye absorption maximum is altered by ultraviolet radiation and the presence of ultraviolet radiation in the presence of a transducer. Generally, it is only necessary to convert said absorption maximum to an absorption maximum that differs from the absorption maximum of the dye before ultraviolet radiation, and this change is irreversible. Thus, the new absorption maximum can be outside or inside the visible region of the electromagnetic spectrum. In other words, the color will change color or color as a result of the change. The latter, of course, is advantageous when the dye is used in a color composition that is used as a tone adjuster in an electrophotographic process that reuses the electrophotographic copy by first decolorizing the color composition and then forming a new image thereon.

The term "irreversible" means that the dye does not return to its original color when ultraviolet radiation is eliminated. It is preferred that the altered dye is stable, that is to say normal to the radiation in the environment, so that it has no adverse effect on natural or artificial light and heat. It means that ··*·

Preferably, the colorless dye remains colorless for an indefinite period.

Ultraviolet radiation transducers are any material which is capable of absorbing ultraviolet radiation and of interacting with the dye and thereby causing the dye to change. In some embodiments, the ultraviolet radiation transducer is an organic compound. The compound may be a single substance or a mixture of two or more substances. When two or more materials are used, it is not necessary for each of them to absorb ultraviolet radiation of the same wavelength.

According to the invention, special compounds are used which are capable of absorbing ultraviolet radiation in the narrow wavelength range. The compounds are prepared by combining a wavelength-selective sensitizing dye and a photochemical reagent. The photochemical reagent is often unable to absorb high-energy radiation effectively. In combination with wavelength-selective sensitizing dye, the resulting compound is a wavelength-specific compound capable of absorbing very narrow-spectrum radiation efficiently. Preferred ultraviolet radiation transors are shown in FIG

Examples 5 and 9.

The interaction between the ultraviolet radiation transducer and the dye is not entirely clear, but it is assumed that the interaction may occur via different pathways. For example, the ultraviolet radiation transorber, by absorbing ultraviolet radiation, delivers one or more free radicals which interact with the dye. Such free radical-releasing compounds are generally inhibited ketones, such as benzyldimethyl ketal (Irgacure 651, Ciba Geigy Corp., Hawthorne, New York, USA); 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 mediates an electron transfer or redox reaction between the ultraviolet radiation transducer and the dye. In such cases, ultraviolet radiation transducers include, for example, Michler ketone (p-dimethylaminophenyl ketone) or benzyltrimethyl stannate. The interaction may be via a cationic mechanism. when ultraviolet radiation can be used as a transporter, for example, bis [4- (diphenylsulfonyl) phenyl] sulfide bis (hexafluorophosphate) (Dagacure KI85, Ciba Geigy Corporation, Hawthorne, New York, USA); Cyracure UVI-6990 (Ciba Geigy Corporation), a mixture of bis [4- (diphenylsulfonyl) phenyl] sulfide bis (hexafluorophosphate) and related monosulfonium hexafluorophosphate salts and 5-2,4- (cyclopentadienyl) - [1,2,3,4,5,6- (methylethyl) benzene] iron (II) hexafluorophosphate (Irgacure 261).

Ultraviolet radiation is electromagnetic radiation in the wavelength range of about 4-400 nm. Ultraviolet radiation with a wavelength of about 100-375 nm is preferred. So the expression is: ·: ··. · '·. : (* ....... ·······

- 15 include regions designated as "ultraviolet" and "vacuum ultraviolet". The wavelength ranges for these two regions are generally about 180-400 nm and about 100-180 nm.

The molar ratio of ultraviolet radiation to the transducer dye is generally about 0.5 or greater. As a general rule, the lower the ratio, the more effective the ultraviolet radiation transducer is in absorbing ultraviolet radiation and in creating an interaction with the dye, i.e., transferring the energy absorbed to induce an irreversible change in the dye. According to recent theory of molecular photochemistry, the lower limit at this ratio is 0.5, which corresponds to the formation of two free radicals per photon. However, from a practical point of view, a molar ratio greater than 1 and up to about 10 molar is set. However, the present invention is not bound to a specific molar ratio range. An important feature is that the transistor is present in an amount sufficient to effect effective dye change.

In practice, the dye and the ultraviolet radiation transducer are preferably used in solid state. However, it is also possible that one or all of the materials are in liquid form. In the case of a solid color preparation, the efficiency of the ultraviolet radiation transducer may be enhanced if the dye and the ultraviolet radiation transducer are in close contact. For this purpose, the two components and, if appropriate, the further components are thoroughly combined

- 16 beat. The mixing can be carried out by any method known to those skilled in the art. If the colored composition contains a polymer, mixing may be facilitated if the dye and the ultraviolet radiation transorber are at least partially soluble in the softened or molten polymer. In such cases, the composition may advantageously be prepared, for example, in a two-cylinder mill. In other cases, the colored composition is liquid because one or more of its ingredients are liquid.

In some applications, the color composition of the invention is generally applied in particulate form. In other applications, it is important that the particle size of the formulation is very small. For example, the color composition used as a toner in the electrophotographic process generally has a particle size of 7-15 µm, although smaller or larger particles may be used. It is important that the particle size be as uniform as possible. Methods for preparing such granules are known to those skilled in the art.

In photochemical processes, the light quantum or photon is absorbed by a molecule, such as an ultraviolet radiation transducer, to form a highly reactive electron excited state. However, the molecule is not capable of absorbing photon energy proportional to the wavelength of radiation if it does not reach the difference between the excited or original state and the excited state. This means that the wavelength range of ultraviolet radiation applied to the colored composition is not directly determinative, but the radiation is at least

- 17 carbons must have a wavelength that provides sufficient energy to increase the energy level of the ultraviolet radiation transistor to a value at which it is able to interact with the dye.

It follows that the transistor absorption maximum of ultraviolet radiation preferably corresponds to the wavelength range of ultraviolet radiation, which enhances the efficiency of changing the dye. This efficiency can be further enhanced if the wavelength range of ultraviolet radiation is relatively narrow and the transistor max of the ultraviolet radiation falls within this range. Accordingly, ultraviolet radiation with a wavelength of about 100-375 nm is preferred. Within the above range, incoherent pulsed ultraviolet radiation from a dielectric transition discharge excimer lamp is particularly preferred.

Inconsistent pulsed ultraviolet radiation is radiation produced by a dielectric transition discharge excimer lamp (hereinafter referred to as an excimer lamp). Such a lamp is described, for example, in U. Kogelschatz, "Silent Discharges for the Generation of Ultraviolet and Vacuum Ultraviolet Excimer Radiation", Pure and Appl. Chem. Excimer Radiation from Dielectric-Barrier Discharges, ”Appl. Phys. B. 46, 299-303 (1988). The excimer lamp was originally developed by ABB Infocom Ltd., Lenzburg, Switzerland, and the technology was purchased by Harus Noblelight AG, Hanau, Germany.

- 18 The excimer lamp emits very narrow bandwidth radiation, where the half-width of the radiation is in the order of 5-15 nm. The emitted radiation is incoherent and pulsating, whereby the frequency of the pulsation depends on the frequency of the AC source used as the energy source, which is generally in the range of about 20-300 kHz. The excimer lamp is generally characterized and identifiable by the wavelength corresponding to the maximum intensity of the emitted radiation, and this approach is followed throughout this specification. Thus, unlike most commercially available ultraviolet radiation sources, which generally emit across the entire ultraviolet spectrum and even in the visible region, the radiation of the cxcimer is essentially monochromatic.

Excimers are unstable molecular complexes that occur only under extreme conditions. Thus they appear temporarily in special gas discharges. A typical example is the molecular bond between the two atoms of the noble gases or between my noble gas and a halogen. Excimer complexes dissociate in less than one microsecond and release their binding energy in the form of ultraviolet radiation. Known excimer emits generally in the range of about 125-360 nm depending on the excimer gas mixture.

In the above description, the dye and the ultraviolet radiation transducer are described as separate compounds, but they may be part of the same molecule. For example, they may be covalently linked to each other directly or indirectly via a relatively small molecule or spacer. Alternatively, the dye and ultraviolet radiation may be covalently bonded to a large molecule, such as an oligomer or polymer, using a transorber, particularly when the solid color composition of the present invention is used as a toner in an electrophotographic process. In addition, the dye and the ultraviolet radiation transducer may be in a state associated with a large molecule, where binding is provided, for example, by weak Waals forces and hydrogen bonds. It will be apparent to those skilled in the art that other variants are possible.

For example, in one embodiment, the composition of the invention further comprises an inclusion molecule. Any material having a chemical structure that defines at least one cavity can be used as a inclusion molecule. The inclusion molecule is thus a molecule of hollow structure. By cavity is meant any aperture or space of sufficient size to accommodate at least a portion of the dye and / or ultraviolet radiation transducer. The cavity may be a passageway through the inclusion molecule or a cavernous space within the inclusion molecule. The cavity may be isolated or independent or may be connected to one or more other cavities.

The inclusion molecule may be inorganic or organic. An inclusion molecule having a chemical structure capable of forming an inclusion molecule complex is preferred. An example of an inclusion molecule is 20 ·· ***. ί * '· · * ·· ··: ·; ··· J ··· ·. ... · \ can be clathrates or intercalates, zeolites and cyclodextrins. Examples of cyclodextrin include alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, hydroxypropyl-beta-cyclodextrin, hydroxyethyl-beta-cyclodextrin, sulfated beta-cyclodextrin, and sulfated gamma-cyclodextrin (American Maize-Products, , Indiana, USA). Cyclodextrin is a preferred inclusion molecule. Alpha-cyclodextrin is particularly preferred as the inclusion molecule, and beta-cyclodextrin in other embodiments. Without wishing to be bound by theory, it is believed that the closer the transporter molecule is to the variable dye on the inclusion molecule, the more effective the interaction with and change in the dye is. This means that it is preferable to include an inclusion molecule which carries functional groups which are reactive with the transporter molecule and which are close to the binding site of the variable dye.

The dye and the ultraviolet radiation transporter occur in a form associated with the inclusion molecule. The term "associated" is used in its widest sense and means that the dye and the ultraviolet radiation transorber are at least close to the inclusion molecule. For example, dye and / or ultraviolet radiation can be maintained in close proximity to the transporter by hydrogen bonds, van Waals forces, and the like. Alternatively, the dye and / or ultraviolet radiation are covalently attached to the inclusion molecule by a transforcer covalent bond. E-

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In 21 cases, the dye is linked to the inclusion molecule by hydrogen bonds and / or vanilla Waals forces, while ultraviolet radiation is covalently bound to the inclusion molecule by a transorber. In other cases, the dye is at least partially located within the cavity of the inclusion molecule and the ultraviolet radiation transporter is located outside the cavity of the inclusion molecule.

In the case where the dye and the ultraviolet radiation transporter are in the state associated with the inclusion molecule, the dye may be, for example, crystal violet, the ultraviolet radiation transporter may be, for example, dehydrated phthaloylglycine-2959, and the inclusion molecule may be beta-cyclodextrin. In the case where the dye and the ultraviolet radiation transducer are associated with the inclusion molecule, another example is a composition wherein the dye is a crystal violet, the ultraviolet radiation transducer is 4- (4-hydroxyphenyl) -but-2-one. 2959 (chlorine-substituted derivative), and the inclusion molecule is beta-cyclodextrin.

In another embodiment, wherein the dye and the ultraviolet radiation transducer are associated with the inclusion molecule, the dye is malachide green, the ultraviolet radiation transducer Irgacure 184, and the inclusion molecule beta-cyclodextrin, as shown in Figure 1. In another embodiment, wherein the dye and the ultraviolet radiation transistor are associated with the inclusion molecule, the dye is pure vicar blue BO, the ultraviolet radiation transducer Irgacure 184,

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- 22 cs of the inclusion molecule beta-cyclodextrin as shown in Figure 2.

5-9. Examples 1 to 5 show the preparation of dye and ultraviolet radiation transducer and their association with beta-cyclodextrin. Note that FIGS. The methods described in Examples 1 to 5 are one possible variant of the preparation and association of the compounds and may be carried out by other methods known in the chemical art. The methods of preparation and association of the present invention and any other applicable component are within the skill of the art after selecting the specific components.

In practice, dyes, ultraviolet radiation transducers, and inclusion molecules are solid. However, any of these materials may be in liquid form. The colored composition may be liquid either because one or more of its components are solid or if it contains an organic inclusion molecule, a solvent is used. Suitable solvents are, for example, amides such as N, N-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 xylene; esters such as ethyl acetate and water. When the inclusion molecule is cyclodextrin, the solvent is preferably an amide or sulfoxide.

The invention further relates to a process for altering the dye in the composition of the invention.

Briefly, the process involves irradiating a composition comprising a variable dye and an ultraviolet radiation transducer with a dose of ultraviolet radiation sufficient to alter the dye. As mentioned above, the composition optionally further comprises an inclusion complex. Alternatively, the composition is applied to a substrate prior to exposure to ultraviolet radiation.

The amount or dose of ultraviolet radiation used to treat the dye of the present invention is generally sufficient to change the dye. The amount of ultraviolet radiation required to change the dye can be determined by one of ordinary skill in the art by routine experimentation. The amount of radiated electromagnetic energy per unit area is measured at an energy density, usually expressed as W / cm. The energy density range is about 5-15 mW / cm, preferably 8-10 mW / cm. However, the dose will generally be a function of the irradiation time and the intensity or flux of the radiation source used to irradiate the colored composition. The latter is influenced by the atmosphere between the source and the composition, depending on the distance of the composition from the source and the wavelength range of ultraviolet radiation. Accordingly, in some cases, irradiation of the composition may be accomplished in a controlled atmosphere or in a vacuum, although this is generally not required.

In one embodiment, for example, the dye is changed by irradiation with a 222 nm excimer lamp. In a preferred embodiment, as a dye

- We use 24 crystal violets, which are changed by irradiation with a 222 nm lamp. In a particularly preferred embodiment, a crystal violet is used which is varied by irradiation with a 222 nm excimer lamp at a distance of about 5 to 6 cm from the dye, arranged in four parallel columns of about 30 cm in length. as shown in FIG. The placement of the lamps is not critical to the practice of the invention. Accordingly, one or more lamps may be used in any configuration and at any distance during which the dye is changed by irradiation with ultraviolet radiation emitted by the lamp. Routine investigations by one skilled in the art can determine which configurations and distances are applicable. Obviously, different excimer lamps are used for different ultraviolet radiation transducers. To change the color of a given UV transistor, an excimer lamp is emitted which emits ultraviolet radiation of wavelength absorbed by the UV transistor.

The color composition of the invention may be applied to any substrate or substrate. When the composition is used in the substrate, it is necessary that the substrate is substantially transparent to ultraviolet radiation, which is used to alter the dye. This means that ultraviolet radiation does not interact or absorb significantly in the substrate.

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In practice, the composition is generally applied to the surface of the substrate, where the substrate is generally paper. Other examples of suitable substrates include woven and nonwoven fabrics, fabrics and films.

The invention relates to a substrate bearing an image produced by the composition of the invention. The invention encompasses any substrate capable of carrying a fixed color image, but the substrate is preferably paper. Particularly preferred substrates are, for example, copying paper and fax paper.

For example, the composition of the invention may be incorporated into a toner for use in an electrophotographic technique. The toner contains a dye, an ultraviolet radiation transducer, and a carrier. The carrier may be a polymer and the toner may contain a carrier as an additional component. Briefly, in the electrophotographic process, an image is formed on a photoreceptor surface, a toner is applied to the photoreceptor surface to form a repetitive tone image, and the tone image is transferred to a substrate. and fixing the tone image on the substrate. After fixing the toner on the substrate, the dye in the composition is changed by irradiating the substrate with ultraviolet radiation at a dose sufficient to irreversibly alter the dye. In some embodiments, ultraviolet radiation of about 100-375 nm is used to change the dye. In other embodiments,

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- Inconsistent pulsed ultraviolet radiation produced by 26 Ichtrometric discharge excimer lamps. In another embodiment, the tonicity adjuster further comprises an inclusion molecule.

When the color composition is used as a toner in an electrophotographic process, the composition further comprises a carrier which may be any carrier known to those skilled in the art. In most cases, the carrier is a polymer, usually a thermosetting or thermoplastic polymer, preferably a thermoplastic polymer.

Preferred thermoplastic polymers are, for example, sealed-end polyacetals such as poly (oxymethylene) or polyformaldehyde, poly (trichloroacetaldehyde), poly (n-valeraldehyde), poly (acetaldehyde) and poly (propionaldehyde); acrylic acid polymers such as polyacrylamides, poly (acrylic acid), poly (methacrylic acid). poly (ethyl acrylate) and poly (methyl methacrylate); fluorocarbon polymers such as polytetrafluoroethylene, perfluorinated ethylene / propylene copolymers, ethylene / tetrafluoroethylene copolymers, polychlorotrifluoroethylene, ethylene / chlorotrifluoroethylene copolymers, polyvinylidene fluoride and poly (vinyl fluoride); condensation products of epoxy resins such as epichlorohydrin and bisphenol A; polyamides such as poly (6-aminocaproic acid), poly (E-caprolactam), poly (hexamethylene adipamide), poly (hexamethylene sebacamide), and poly (11-amino undecanoic acid); polyamides such as polyimino-1,3-phenyleneimino-isophthaloyl and poly (m-phenylene-isophthalamide); parylene, such as poly-p-xylene and poly (chloro-p-xylene); polyaryl ethers such as poly (oxy-2,6-dimethyl-1,4-phenylene) and

27 poly (p-phenylene oxide); polyarylsulfones such as poly (oxy-1,4-phenylene-sulfonyl-1,4-phenyleneoxy-1,4-phenylene-isopropylidene-1,4-phenylene) and poly (sulfonyl-1,4-phenyleneoxy) -

1,4-phenylene-sulfonyl-4,4-biphenylene); polycarbonates such as polybisphenol A and polycarbonyldioxy-1,4-phenylene-isopropylidene-1,4-phenylene; polyesters such as polyethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene-1,4-dimethylene terephthalate, and polyoxymethylene-1,4-cyclohexylene methylene-terephthaloyl; polyaryl sulfides such as poly (p-phenylene sulfide) and poly (thio-1,4-phenylene); polyimides such as poly (pyrrolitamidoimido-1,4-phenylene); polyolefins such as 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, polyvinyl acetate, polyvinylidene chloride and polystyrene; and copolymers thereof, such as acrylonitrile / butadiene-styrene (ABS) copolymers, styrene / n-butyl methacrylate copolymers, and ethylene / vinyl acetate copolymers.

Particularly preferred thermoplastic polymers are styrene / n-butyl methacrylate copolymer, polystyrene, styrene / n-butyl acrylate copolymer, styrene / butadiene copolymer, polycarbonate, poly (methyl methacrylate), polyvinylidene fluoride, -12), polyethylene, polypropylene, ethylene / vinyl acetate copolymer and epoxy resin.

Examples of thermosetting polymers include alkyd resins such as phthalic anhydride / glycerol resins, maleic acid / glycerol resins, adipic acid / glycerol resins, and phthalic anhydride / pentaerythritol resins; alliles resins, • ·

28 comprising dialyl phthalate, diallyl phthalate, diallyl maleate and diallyl chlorendate monomer as non-volatile crosslinking agents in a polyester compound; amino resins such as aniline / formaldehyde resins, ethylene urea / formaldehyde resins, dicyandiamide / formaldehyde resins, melamine / formaldehyde resins, sulfonamide / formaldehyde resins and urea / formaldehyde resins; epoxy resins such as cross-linked epichlorohydrin / bisphenol A resins; phenolic resins such as phenol / formaldehyde resins such as novolac and resole; and thermosetting polyesters, silicones and urethanes.

In addition to the dye, ultraviolet ray transducer and optional carrier, the color composition of the invention may contain additional components depending on the intended use. For example, the tonicity adjusting composition used in the electrophotographic process may further comprise, for example, a carrier, a thermal oxidation stabilizer, a viscoelastic modifier, a crosslinker or a plasticizer. In addition, the composition used as a toner in the electrophotographic process is a charge controlling additive, such as a quaternary ammonium salt; flow agents 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 the usual additives. In some embodiments, the charge carrier is a

yl

- 29 main components of tone control. Suitable fillers are any material known to those skilled in the art, preferably metal coated metal particles. The types and amounts of additives that can be used in the color formulation are known to those skilled in the art. In addition, the tonicity adjuster of the present invention may further comprise an inclusion molecule as mentioned above.

When the color composition is used as a tone adjuster in an electrophotographic process, various variations are possible within the scope of the invention. For example, a composition-based toner can be used to form a first image on an unused sheet of paper. The sheet is then subjected to ultraviolet radiation for reuse, thereby decolorizing the dye and consequently the composition. A second image can then be formed on the arc. The second image may be formed with a conventional known toner or formulation tone adjuster which is the same or different from the formulation-based toner used to form the first image. When using a composition-based toner to form the second image, the arc can be traced again, and the number of reuses depends on how long a colorless composition can be applied to the surface of the paper. In addition, any subsequent image can be applied to any side of the arc. This means that the second image does not need to be formed on the side of the arc to which the first image is applied.

In addition, the conversion of a formulation-based tone on a sheet of paper to a colorless form is not required on the sheet. For example, formulation-based tonic

Sheets with an image formed by 30 adjusters can be reused in the usual way. However, instead of the usual decontamination and decolorization step, the sheets are exposed to ultraviolet radiation before or after conversion to the pulp. If the arcs are treated with ultraviolet radiation after conversion to the pulp, it will be apparent to one skilled in the art that none of the pulp components will affect the ability of the ultraviolet transducer to change the dye when irradiated with ultraviolet radiation. The colorless toner is then simply incorporated into the resulting pulp paper.

The invention is further illustrated by the following examples, which are not to be construed as limiting the scope thereof.

Example 1

This example illustrates the preparation of a film containing a dye, an ultraviolet radiation transducer and a thermoplastic polymer. The dye and ultraviolet radiation transducer are ground in a separate mortar. The required amount of ground components is weighed and placed in an aluminum pan with the weighed amount of thermoplastic polymer. The pan is then placed on a hot plate at 15 ° C and the mixture is stirred until melted. A few drops of the molten mixture are poured onto a steel plate and a thin film is formed with a glass microscope plate. The steel sheet measures 7.6 x 12.7 cm and is manufactured by Q-Panel Company, Cleveland, Ohio, USA. The thickness of the film formed on the steel sheet is estimated to be 10-20 μπι.

The dye used in the example is Malachite Green Oxalate (Aldrich Chemical Company, Inc., Milwaukee, Wisconsin, USA), hereinafter referred to as Dye A. The ultraviolet radiation transducer (UVRT) can be Irgacure 500 (UVRT A), Irgacure 651 (UVRT B) and Irgacure 907 (UVRT C) alone or in any mixture (Ciba Geigy Corporation, Hawthorne, New York, USA). The polymer used is one of the following polymers: Epichlorohydrin / Bisphenol Epoxy Resin (Polymer A), Epon 1004F (Shell Oil Company, Houston, Texas, USA); polyethylene glycol, weight average molecular weight about 8000 (polymer B), Carbowax 8000 (Aldrich Chemical Company); poly (ethylene glycol). with a weight average molecular weight of about 4,600 (polymer C), Carbowax 4600 (Aldrich Chemical Company). A dye and a polymer are formed into a control film. The composition is summarized in Table 1.

• · ♦ · »·

ii

Table 1

Film Dye UVRT Polymer

Type Weight- Type Weight- Type Weight-

section section section THE THE 1 THE 6 THE 90 C 4 B THE 1 THE 12 THE 90 C 8 C THE 1 THE 18 THE 90 C 12 D THE 1 THE 6 THE 90 B 4 E THE 1 B 30 THE 70 F THE 1 - - THE 100 G THE 1 THE 6 B 90 C 4 H THE 1 B 10 C 90

·· · · · ·? ··· ·.

: ·: ···. ··. :

* · · »··· * · · il

- 33 The film on the steel sheet is irradiated with ultraviolet radiation. To do this, a sheet of steel bearing a film pattern on its surface is placed on a variable speed moving conveyor. Three different types of ultraviolet light sources or lamps are used. Lamp A is a 222 nm excimer lamp, lamp B is a 308 nm excimer lamp, lamp C is a fusion lamp system comprising D bulb (Fusion Systerns Corporation, Rockville, Maryland, USA). The excimer lamps are arranged in four cylindrical columns about 30 cm in length so that the lamps are oriented in the direction of the web movement. The lamps are cooled with circulating water through a tube located in the center or inside of the lamp and thus operated at a relatively low temperature, for example about 50 ° C. Energy density of the outer surface of the lamps? usually about 4-20 Joule / m '.

This range of energy reflects the power supply of current excimer lamps, and in practice higher energy densities can be advantageously employed. For lamps A and B, the distance between the lamp and the film sample is 4.5 cm and the web speed is 0.1 m / sec. For Lamp C, the tape speed is 0.07 m / sec and the distance between lamp and sample is 10 cm. The film samples were exposed to ultraviolet radiation and the results are summarized in Table 2. Except for film F, the number in the table is the number of times the film has to be moved under the lamp to level off. For F film, the table shows the number of moves, but the film is always colored (no change).

ιί

Table 2 Movie Excimer lamp Fusion lamp A lamp is a B lamp

THE 3 3 B 2 3 C 1 3 D 1 1 E 1 1 F 5 5 G 3 - H 3

Example 2

This example illustrates the preparation of a solid color composition for use as a toner in an electrophotographic process. In each case, the toner is selected from the dye A of Example 1, a polymer which may be TERR 667, an epichlorohydrin / bisphenol epoxy resin A (polymer D), Epon 1004F (Dow Chemical Company, Midland, Michigan, USA); and a charge carrier (carrier A), which is a metal particle coated with a very finely divided polymer. The ultraviolet radiation transducer (UVRT) was one or more of the UVRT B of Example 1, Irgacure 369 (UVRT D) and Irgacure 184 (UVRT E) (Ciba Geigy Corporation, Hawthorne, New York, USA). In one case, a second polymer is used which is styrene acrylate

• 9

1221, a styrene / acrylic acid copolymer (Hercules Incorporated, Wilmington, Delaware, USA).

To prepare the toner, the dyes, ultraviolet ray transducer, and polymer were melt blended in a Model 3VV 800E 7.6 x 17.8 cm two-cylinder experimental mill (Farrel Corporation, Ansonia, Connecticut, USA). The resulting melt mixture is ground in a Micropul hammer mill using a 0.254 mm herringbone sieve (R.D. Kleinfeldt, Cincinnati, Ohio, USA), and the appropriate particle size is sieved in a Sturtvant air 5.08 cm micronizer (R.D. Kleinfeldt) to pre-mix. Add the carrier to the premix and mix thoroughly. Table 3 shows the composition of the premix and Table 4 the toner composition.

Table 3

Premix The dye is UVRT Polymer

(G) Type g Type g THE 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

Tone Adjuster Primer Mixture Charger

Type g (g)

THE THE 8.4 210 B B 8.4 210 C C 8.4 210 D D 8.4 210

The toner adjusters are individually loaded into a Sharp ZT-50TD1 toner feeder and placed in a Sharp Z76 or Z77 xerographic copier (Sharp Electronic Corporation, Mahwah, New Jersey, USA). Copies are made in the usual way on copy paper (Neenah Bond). The plates carrying the image are exposed to ultraviolet radiation with the lamp B described in Example 1. In all cases, the image will become discolored after passing.

Example 3

The example illustrates the preparation of a beta-cyclodextrin inclusion molecule comprising (1) an ultraviolet radiation transducer covalently bonded to the cyclodextrin outside the cavity and (2) a dye associated with the cyclodextrin by hydrogen bonding and / or van Waal power.

- 37 • · ·· ··· ... · · .. · il

A. Friedel-Crafts acylation of the transistor

Place a magnetic stirrer in a 250 ml three-necked round-bottom flask equipped with a reflux condenser and a pressure-equalizing addition funnel with nitrogen inlet. Flush with nitrogen and then 10 g (0.05 mol) of 1-hydroxycyclohexylphenyl ketone (Irgacure 184, Ciba Geigy Corporation, Hawthorne, New York, USA), 100 ml of anhydrous tetrahydrofuran (Aldrich Chemical Company Inc., Milwaukee, Wisconsin). , USA) and 5 g (0.05 mol) of succinic anhydride (Aldrich). While stirring, 6.7 g of anhydrous aluminum chloride (Aldrich) are added. The resulting reaction mixture was kept in an ice bath at 0 ° C for 1 hour and then allowed to warm to room temperature over 2 hours. The reaction mixture was then poured into a mixture of 500 ml of ice water and 100 ml of diethyl ether. To facilitate phase separation, a small amount of sodium chloride is added to the aqueous phase and the ether phase is separated off. The ether layer was dried over anhydrous magnesium sulfate and the ether removed under reduced pressure to give 12.7 g (87%) of a white crystalline powder. The product was found to be 1-hydroxycyclohexyl-4- (2-carboxyethyl) carbonylphenyl ketone by NMR.

B. Preparation of Acylated Transporter Acid Chloride

In a 250 mL round bottom flask equipped with a condenser, 12.0 g (0.04 mol) of 1-hydroxycyclohexyl-4- (2-carboxyethyl) carbonylphenyl ketone, 5.95 g (0.05 mol) thionyl chloride (Aldrich) and 50 ml of diethyl ether were added. The reaction mixture was 30 µl

After stirring at 30 ° C for 38 minutes, the solvent was removed under reduced pressure. The white solid residue was maintained at 0.01 Torr for 30 minutes to remove solvent residues and excess thionyl chloride. 12.1 g (94%) of 1-hydroxycyclohexyl-4- (2-chloroformyl-ethyl) -carbonyl-phenyl-ketone are obtained.

C. Covalent bonding of the acylated transporter with cyclodextrin

In a 250 mL three-necked round bottom flask equipped with a magnetic stirrer, thermometer, condenser, and nitrogen inlet, 10 g (9.8 mmol) of beta-cyclodextrin (American Maize Products Company, Hammond, Indiana, USA), 31.6 g (98). 1 mmol of 1-hydroxycyclohexyl-4- (2-chloroformyl-ethyl) -carbonyl-phenyl-ketone and 100 ml of Ν, Ν-dimethylformamide are charged under a nitrogen atmosphere. The reaction mixture was heated to 50 ° C and 0.5 ml triethylamine was added. After 1 hour at 50 ° C, it was allowed to cool to room temperature. Beta-cyclodextrin carrying a covalently bonded ultraviolet radiation transducer (hereinafter called beta-cyclodextrin transducer) is not isolated.

To isolate the product, the experiment was repeated and the resulting reaction mixture was concentrated in a rotary evaporator to 10% of its original volume. The residue is poured into ice water and the product is salted with sodium chloride. The precipitate was filtered off and washed with diethyl ether. The solid was dried under reduced pressure to give 24.8 g of a white powder

- We get 39. In a third experiment, the residue in the rotary evaporator was placed on top of a 7.5 cm diameter column filled with 15 g of silica gel. The residue was eluted with N, N-dimethylformamide and the eluent was analyzed on a Whatman Flexible-Backed TLC plate (Cat. No. 05-713-161, Fisher Scientific, Pittsburgh, Pennsylvania, USA). The eluted product is isolated by removing the solvent. The structure of the product was confirmed by NMR analysis.

D. Dye Association on the Cyclodextrin Transporter;

Preparation of Color Preparation of a solution of g (estimated at about 3.6 mmol) of beta-cyclodextrin transporter in 150 mL of N, N-dimethylformamide in a 250 mL round bottom flask at room temperature 1.2 g (3.6 mmol) of malachite green oxalate ( Aldrich Chemical Company Inc., Milwaukee, Wisconsin, USA) (hereinafter referred to as Dye A). The reaction mixture was stirred with a magnetic stirrer for 1 hour at room temperature. The major mass of solvent was removed in a rotary evaporator and the residue was eluted on silica gel as described above. The column first leaves the Beta-Cyclodextrin-Transformer-A dye inclusion complex and separates well from Dye-A and the beta-cyclodextrin-transducer. The eluate containing the complex was collected and the solvent was removed in a rotary evaporator. The residue was removed at 0.01 Torr to remove solvent residues to give a blue-green powder.

yl

- 40 Ε. Changing the color composition

The beta-cyclodextrin-transducer-dye inclusion complex is irradiated with two different lamps (lamps A and B) to ultraviolet radiation. Lamp A is a 222 nm excimer lamp, where the luminaires are arranged in four cylindrical columns about 30 cm long. The lamps are cooled centrally or by recirculating water placed inside the lamp, which results in the lamps operating at a relatively low temperature, i.e., about 50 ° C. The energy density of the outer surface of the lamp is about 4-20 Joules / m. This energy comes from the current supply of excimer lamps, and higher energy densities may be used in the future. The distance between the lamp and the irradiated sample is 4.5 cm. Lamp B is a 500W type Hanovia medium pressure mercury vapor lamp (Hanovia Lamp Co., Newark, New Jersey, USA). The distance between lamp B and the irradiated sample is approximately 15 cm.

A few drops of beta-cyclodextrin-transporter-A dye inclusion solution in Ν, dimet-dimethylformamide are placed on a TLC plate and in a small polyethylene measuring vessel. Both samples are irradiated with lamp A, whereby the samples become discolored (become colorless) within 15-20 seconds. Similar results are obtained with lamp B in 30 seconds.

The first control sample contains a solution of dye A and beta-cyclodextrin in Ν, Ν-dimethylformamide, which does not decay under lamp A. The second

- 41 control samples Contains a solution of the dye and 1-hydroxycyclohexylphenylketone in Ν, Ν-dimethylformamide and decolorises under lamp A in 60 seconds. However, the color returns to 1 hour when stationary.

To test the effect of the solvent on discoloration, 50 mg of beta-cyclodextrin-transporter-dye inclusion complex is dissolved in 1 ml of solvent. The resulting solution or mixture is placed on a glass microscope plate and irradiated with lamp A for 1 minute. The degree of discoloration, i.e. the time required for the sample to decolorize, is directly proportional to the solubility of the complex in the solvent, which is summarized in the following table:

Solvent O Idleness Almost settling time

Ν, Ν-dimethylformamide slightly soluble 1 minute Dimethyl sulfoxide soluble <10 sec acetone soluble <10 sec hexane insoluble - Ethyl acetate slightly soluble 1 minute

Finally, 10 mg of beta-cyclodextrin-transporter-A dye inclusion complex is placed on a glass microscope plate and crushed with a spatula. The resulting powder is irradiated with lamp A for 10 seconds. The powder is discolored. A similar result can be achieved with lamp B, but it takes longer.

Example 4

Since the process of the colored composition described in Example 3 has the potential for the acylated transporter acid chloride to at least partially occupy the cavity of the cyclodextrin and thereby partially or completely exclude the dyes, a modified procedure was performed. Thus, this example describes the preparation of a beta-cyclodextrin inclusion molecule which is (1) at least partially closed in the cavity of the cyclodextrin and dyes associated with the cyclodextrin by hydrogen bonding and / or van Waals forces and (2) covalently bonded to the cyclodextrin outside the cavity. radiation carries a transistor.

A. Dye Association on Cyclodextrin

To a solution of 10.0 g (9.8 mmol) of beta-cyclodextrin in 150 mL of N, N-dimethylformamide is added 3.24 g (9.6 mmol) of dye A. The resulting solution was stirred at room temperature for 1 hour. The mixture is then concentrated in a rotary evaporator to 1/10 of the original volume. The residue was passed through a silica gel column as described in Example 1 (C). Removal of the solvent from the eluate in a rotary evaporator afforded 12.4 g of a beta-cyclodextrin-A dye inclusion complex in the form of a blue-green powder.

B. Covalent Binding of Acylated Transporter to Cyclodextrin Dye Inclusion Complex; color preparation

In a 250 mL three-necked round bottom flask equipped with a magnetic stirrer, thermometer, condenser, and nitrogen inlet, 10 g (9.6 mmol) of beta-cyclodextrin-A dye inclusion complex, 31.6 g (98 mmol) of l-hydroxy-cyclohexyl -4- (2-Chloroformyl-ethyl) -carbonyl-phenyl-ketone (prepared as in Example 1B) was charged with 150 ml of N, N-dimethylformamide under a nitrogen atmosphere. The reaction mixture was heated to 50 ° C and mixed with 0.5 mL of triethylamine. After 1 hour at 50 ° C, it was allowed to cool to room temperature. After working up the reaction mixture as described in A above

14.2 g of a beta-cyclodextrin-transporter-A dye inclusion complex are obtained in the form of a blue-green powder.

C. Changing the Colored Composition

The procedure described in Example 1 (E) is repeated with the beta-cyclodextrin-transporter-A dye inclusion complex prepared according to (B) above, yielding essentially the same results.

Example 5

This example illustrates the preparation of an ultraviolet radiation transforter called phthaloylglycine-2959.

In a 250 ml three-necked round-bottom flask with a Dean-Stark cap fitted with a refrigerator and two glass stoppers

20.5 g (0.1 mol) wavelength selective sensitizing dye phthaloylglycine (Aldrich), 24.6 g (0.1 mol) photochemical reagent DARCUR 2959 (Ciby Geigy Hawthorne, New York, USA), 100 of benzene (Aldrich) and 0.4 g of p-toluenesulfonic acid (Aldrich) were weighed. The mixture was refluxed for 3 hours, during which 1.8 mL of water was collected. Removal of the solvent under reduced pressure gave 43.1 g of a white powder. The powder was recrystallized from 30% ethyl acetate / hexane (Fisher) to give 40.2 g (93%) of a white crystalline powder, m.p. 153-154 ° C. The reaction is illustrated in Scheme A.

The product obtained, named phthaloylglycine-2959, has the following physical parameters:

IR (Nujol Muu) _vmax 3440, 1760, 1740, 1680, 1600

-i cm.

11 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 illustrates the dehydration of phthaloylglycine 2959 of Example 5.

In a 250 mL round bottom flask equipped with a Dean-Stark cap fitted with a condenser, a mixture of 21.6 g (0.05 mol) of phthaloylglycine-2959, 100 mL of anhydrous benzene (Aldrich) and 0.1 g of p-toluenesulfonic acid (Aldrich) Reflux for 3 hours. 0.7 ml of water was collected in the trap and the solution was concentrated in vacuo. 20.1 g (97%) of a white solid are obtained

- 45, which are used without further purification. The reaction is shown in Scheme B.

Physical details of the product:

IR (Nujol) _vmax: 1617 ^cm-1 (C = C = O).

Example 7

This example illustrates the preparation of beta-cyclodextrin with covalently bonded dehydrated phthaloylglycine-2959 residues.

In a 100 mL round bottom flask, 5.0 g (4 mmol) of beta-cyclodextrin (American Maize Products Company, Hammond, Indiana, USA) (beta CD in Scheme C) was 8.3 g (20 mmol) of dehydrated fralooyl glycine-2959, A mixture of 50 ml of anhydrous DMF, 20 ml of benzene and 0.01 g of p-toluenesulfonyl chloride (Aldrich) was cooled in a salt / ice bath and stirred for 24 hours. The reaction mixture was poured into dilute sodium bicarbonate (150 mL) and extracted with ethyl ether (3 x 50 mL). Filtration of the aqueous phase gave 9.4 g of a white solid, which is a beta-cyclodextrin bearing phthaloylglycine-2959 groups. Reverse phase TLC (DMF / acetonitrile 50:50) gives a new product spot along with starting material. The reaction is shown in Scheme C.

Of course, the beta-cyclodextrin molecule contains several primary alcohol and secondary alcohol groups with which phthaloylglycine-2959 can react. Only one phthaloylglycine-2959 molecule is included in the reaction scheme for purposes of illustration.

• · il

Example 8

The example illustrates the association of a dye and an ultraviolet radiation with a transporter inclusion molecule. The example further illustrates the association of a crystal violet dye with a covalently bonded ultraviolet radiation transducer, i.e., the beta-cyclodextrin inclusion molecule carrying phthaloylglycine-2959 of Example 7.

A 100 ml beaker was charged with 4.0 g of beta-cyclodextrin bearing a dehydrated phthaloylglycine-2959 group. The inclusion molecule was diluted with 50 mL of water and dissolved at 70 ° C. Then 0.9 g (2.4 mmol) of crystal violet (Aldrich Chemical Company, Milwaukee, Wisconsin, USA) was added to the solution and stirred for 20 minutes. After filtration, the filtrate was washed with the filtrate and dried in a vacuum oven at 84 ° C to give 4.1 g (92%) of a violet-blue powder, showing the following physical parameters:

UV (DMF) Z _max = 610 nm (cf cv λ _Μίιχ = 604 nn?

Example 9

This example illustrates the preparation of 4- (4-hydroxyphenyl) butan-2-one 2959 (chlorine substituted) as a UV transistor.

In a 250 mL round bottom flask equipped with a condenser and a magnetic stirrer, 17.6 g (0.1 mol) of wavelength-selective sensitizing dye is 4- (4-hydroxyphenyl) -butan-2-one (Aldrich Chemical Company, Milwaukee, Wisconsin, USA). , 26.4 g (0.1 mol) of a photochemical reagent substituted with chlorine

- 47 DARCUR 2959 (Ciba Geigy Corporation, Hawthorn, New York, USA), 1.0 ml of pyridine (Aldrich Chemical Company, Milwaukee, Wisconsin, USA) and 100 ml of anhydrous tetrahydrofuran (Aldrich Chemical Company, Milwaukee, Wisconsin, USA). After refluxing for 3 hours, the solvent was partially removed (60%) in vacuo. The reaction mixture was poured into ice-water and extracted with diethyl ether (2 x 50 mL). It was dried over anhydrous magnesium sulfate and the solvent was removed. The remaining 39.1 g of white solid was recrystallized from 30% ethyl acetate / hexane to give 36.7 g (91%) of a white crystalline powder.

M.p. 142-143 ° C.

The procedure is illustrated in Scheme D.

The physical parameters of the product are as follows:

IR (Nujol Muu) _vmax 3460, 1760, 1700, 1620, 1600

-1 cm -1 η NMR (CDCl ₃ ): δ ppm: 1.62 (s), 4.2 (m), 4.5 (m),

6.9 (m) ppm.

The ultraviolet radiation obtained in this example is a transporter, i.e., 4- (4-hydroxyphenyl) butan-2-one-2959 (chloro substituted) beta-cyclodextrin and a dye such as crystal violet can be associated with the compounds of Examples 6-8. Example 4 wherein the dehydrated phthaloylglycine-2959 used in the Examples uses the 4- (4-hydroxyphenyl) butane-2-one-2959 (chlorine substituted) transporter.

- 48 Example 10

In the example it is shown that the 222 nm excimer lamp of Fig. 3 allows a uniform intensity reading on the substrate surface at a distance of 5.5 cm from the lamp. The amount of radiation measured at the numbered sites is sufficient to change the color of the inventive composition on the surface of the substrate. The lamp 10 consists of a lamp housing 15 in which four excimer lamp lamps 20 each about 30 cm in length are placed in parallel. The lamps are cooled with circulating water through a centrally located or internal channel (not shown) and, as a result, the lamps operate at a relatively low temperature of about 50 ° C. The outer surface of the lamp has a light density of about 4-20 Joules / m.

Table 5 shows the reading intensity obtained with a measuring device located on the substrate surface. Measuring points 1, 4, 7, and 10 are approximately 7.0 cm from the left end of the column, as in

Figure 3. Measuring points 3, 6, 9 and 12 are approx

5.5 cm from the right end of the column, as shown in Figure 3. Measuring points 2, 5, 8 and 11 are centered about 17.5 cm from each end.

- 49 Table 5

Background (pW) Reading (m W / cm 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

In the example it is shown that the 222 nm excimer lamp of Fig. 4 provides a uniform intensity reading at the numbered measuring points on the substrate surface spaced 5.5 cm from the lamp. The radiation dose is sufficient to alter the color of the composition of the present invention on the substrate surface. Lamp 10 comprises a lamp housing 15 housing four excimer lamp bulbs 20 each about 30 cm in length. The lamps are cooled with circulating water, either centrally or internally

- through 50 channels (not shown), and as a result the lamps operate at a relatively low temperature, i.e., about 50 ° C. The energy density of the outer surface of lamps is generally about 4-20 Joules / m ² .

Table 6 shows the reading of the intensity data obtained with a measuring device on the surface of the substrate. Measuring points 1, 4 and 7 are approximately 7.0 cm from the left end of the column, as shown in Figure 4. Measuring points 3, 6 and 9 are located about 5.5 cm from the right end of the column, as shown in Figure 4. Measurement points 2, 5 and 8 are located in the center about 17.5 cm from the two ends of the column.

Table 6

Background (pW) Reading (mW / cm ') 23,46 9.32 16.12 9.31 17.39 9.32 20.19 9.31 16.45 9.29 20.42 9.31 18.33 9.32 15.50 9.30 20.90 9.34

- 51 Example 12

In this example, it is shown that the intensity of the 222 nm excimer lamp of Figure 5 on the substrate surface is a function of the distance between the surface and the lamp, but that the intensity is sufficient to alter the color of the composition of the present invention. The excimer lamp 10 consists of a lamp housing 15 in which four excimer lamp bulbs 20 are arranged in parallel, each about 30 cm in length. The lamps are cooled with circulating water through a centrally located or internal channel (not shown) and, as a result, the lamps operate at a relatively low temperature, i.e., about 50 ° C. The energy density of the outer surface of the lamp is usually about 4-20 Joules / m '.

Table 7 shows the reading of the intensity data obtained with the meter placed on the substrate surface at position 1 in Figure 5. Position 1 is centrally located about 17 cm from the two ends of the column.

Table 7 *

Distance (cm) Background (μΐΐ ⁷ ) Reading (mW / cm ')

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

The present invention is described in detail herein. However, one skilled in the art will recognize that many further changes and modifications are possible without departing from the spirit and scope of the invention.

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Claims

A color composition comprising a variable dye and an ultraviolet radiation transducer.

Claims (24)

yl Claims A color composition comprising a variable dye and an ultraviolet radiation transducer. 2. The colored composition of claim 1, further comprising an inclusion molecule. 3. The colored composition of claim 2, wherein the inclusion molecule is clathrate, zeolite and / or cyclodextrin. Color composition according to claim 2, characterized in that the variable dye and the ultraviolet radiation transorber are associated with the inclusion molecule. The color composition of claim 4, wherein the dye is at least partially located in the cavity of the inclusion molecule. 6. A color composition according to claim 4, wherein the ultraviolet radiation transistor is associated with the inclusion molecule and outside the cavity of the inclusion molecule. * · · The colored composition according to claim 6, characterized in that the ultraviolet radiation is covalently bound to the inclusion molecule by a transforcer covalent bond. 8. A method of changing a color composition, wherein the color composition comprises a variable dye and an ultraviolet radiation transducer, wherein the color composition is irradiated with a sufficient amount of ultraviolet radiation to irreversibly alter the color. 9. The method of claim 8, wherein the colored composition further comprises an inclusion molecule. 10. The method of claim 9, wherein the dye and the ultraviolet radiation transistor are associated with the inclusion molecule. 11. The method of claim 8, wherein the colored composition is applied to a substrate prior to exposure to ultraviolet radiation. The process of claim 11, wherein the altered dye is stable. 13. The method of claim 10, wherein the colored composition is applied to a substrate prior to exposure to ultraviolet radiation. • · * ·· «· ·· ♦. · * · · · · · · · · ······················································································································································································· es it 14. The method of claim 13, wherein the altered dye is stable. 15. A tone adjuster for use in electrophotographic techniques, comprising a variable dye, an ultraviolet radiation transducer, and a carrier for dye and ultraviolet radiation transducer. 16. A toner according to claim 15, wherein the carrier comprises a polymer. 17. The toner according to claim 15, further comprising a carrier. 18. A tone adjuster according to claim 15, wherein said ultraviolet radiation absorbing ultraviolet radiation transistor is at a wavelength of about 100-375 nm. 19. The solid color composition of claim 18, wherein said ultraviolet radiation is an incoherent pulsed ultraviolet radiation emitted from a dielectric transition discharge excimer lamp. 20. The toner according to claim 15, further comprising an inclusion molecule. * ························································• The toner according to claim 20, characterized in that the variable dye and the ultraviolet radiation transistor are associated with the inclusion molecule. 22. The toner according to claim 21, wherein the variable dye is at least partially located in the cavity of the inclusion molecule. 23. A toner according to claim 21, wherein said ultraviolet radiation is covalently bound to a inclusion molecule by a transorber. 24. An electrophotographic method, wherein an image is formed on a photoreceptor surface;