CN1131468A

CN1131468A - Mutable composition and method of use thereof

Info

Publication number: CN1131468A
Application number: CN94193454A
Authority: CN
Inventors: R·S·诺赫; J·G·麦克唐纳; V·D·麦金尼斯; R·S·惠特莫尔
Original assignee: Kimberly Clark Corp
Current assignee: Kimberly Clark Worldwide Inc
Priority date: 1993-08-05
Filing date: 1994-07-29
Publication date: 1996-09-18
Also published as: CA2168727A1; HU9600241D0; WO1995004955A1; CZ27596A3; BR9407181A; AU7517394A; DE712506T1; JPH09502031A; ES2107396T1; NO960455L; NO960455D0; HUT73681A; FI960483A0; FI960483A; RU2152636C1; SK15296A3; PL312835A1; EP0712506A1

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

Mutable composition and using method thereof

The cross reference of related application

The application also is the part continuation application of No. the 08/103.503rd, U.S. Patent application (applying on August 5th, 1993) for the part continuation application of U.S. Patent application No. 08/119.912 (applying on September 10th, 1993).

Technical field

The present invention relates to a kind of composition of mixing colours, in some embodiment, it can be used in a kind of toner of electrophotographic image forming, for example is used as toner in the duplicate based on the transfer-type Xeroxing.

Background of invention

Electrophotographic image forming is a kind of process that produces the electron image identical with original paper by the seizure photon in broad terms.This electron image can form a physics image after multistep is handled.Present modal electrophotographic image forming technology is the transfer-type xerox.Though this technology was just proposed by C.Carlson first as far back as 1938, its obtain process that people accept to admit still be suitable slowly.Yet today, the transfer-type xerox has developed into a kind of tens yuan industry.

The xerographi core of transfer-type is a photoreceptor, and it is the basic element of character of a motion in the duplicating process usually, both can be cydariform, also can be a tape loop.Gas ion is deposited on the surface of photoreceptor by corona discharge assembly.These ions form a uniform electric field along photoreceptor, also form the layer of even charge layer on its surface.The image of the original paper that is illuminated focuses on the surface of photoreceptor through the lens combination projection.Light shines the surface of the photoreceptor that is recharged, and making along the conductivity of photoreceptor increases, thereby makes the charging neutrality on surface.The zone that the surface is not illuminated then still keeps its surface charge.The pattern of formed like this surface charge is called as electrostatic latent image.

With a kind of thermoplastic pigment powder or toner, its particle has and the opposite electric charge of the positive negativity of photoreceptor surface charge, take place to, because of these granules of pigments of electrostatic interaction are adsorbed to zone still charged on the photoreceptor surface near the photoreceptor surface.On the surface of photoreceptor, just formed the physical image of forming by the granules of pigments of static electrification like this.

A plain pape is contacted with the photoreceptor physics that has pigment, charge at the back side of paper, thereby the pigment image is adsorbed onto on the paper.This image is the erect image of original paper.Then paper is peeled off from photoreceptor, adhered to pigment image on it with regard to having because of electrostatic attraction on the paper.Through suitable thermal treatment means, for example roll hot pressing or radiation heating, this pigment image just can melt muchly and be attached on the paper.

Because the incomplete transfer of granules of pigments on paper need be removed pigment residual on the photoreceptor surface.Available soft brush, flannelette or scraper are removed pigment residue.Adopt the neutralization of discharge or opposite charges to help to remove.Any residual charge that has with the image last time of neutralizing with the inswept photoreceptor of uniform illumination is eliminated electrostatic latent image last time fully then, uses again after making photoreceptor surface recovery cleaning.

Used toner (being pigment) is made up of by the thermoplastic powder of 1-15 micron mean diameter.In black toner, there is the carbon black granules of 5-10% to be scattered in the thermoplastic powder less than 1 micron.In the used toner of color photocopying, replace carbon black with cyano group pigment, magenta or yellow uitramarine.It is suitable that the concentration of pigment and dispersion degree must be regulated, so that toner has suitable conduction, thereby satisfies the requirement of developing.Concerning most developing process, toner should be able to maintain for a long time (contact electrification generation electric charge).The selection of thermoplastic body generally is based on its melting behavior in the toner.The fusing of thermoplastic body must be in the temperature range of a relative narrower, must be stable storage and also can be in duplicating developer anti-strong agitation.

Electrophotographic image forming, especially transfer printing or xerographi success have promoted the information of global range to propagate undoubtedly greatly, and the production quantity of paper is increased greatly.Paper after the use must be handled or reclaim.Though the existing now technology that reclaims paper, its cost height, consuming time, and also the discarded object that produces also must carry out suitable processing.The method of recovery paper commonly used comprises paper is converted into paper pulp, removes ink, pigment or other coloring matter in the paper pulp then, is about to paper " deinking ", this be a costliness but frequent halfway process.The mud shape thing that forms after the deinking is generally buried processing through soil.The paper pulp that took off China ink generally just can be reused for after adding some original paper pulp produces paper, cardboard material, plastic packaging material or other similar products.

Yet the simplest recovery method should be to utilize complete paper again, so just can save once more the process of pulping.Reported that now some can reach the duplicating machine toner of this purpose, they be subjected to can be changed under near infrared or the infrared irridiation colourless.Be limited to 375 nanometers under the low wavelength of sunshine spectrum, but comprised considerable infrared composition in its long wavelength's scope.Under the environment as daylight or heat, just there is outstanding weak point in the toner of these reports so, and promptly they are variable, can become colorless.A file will become before finishing its mission that the handwriting is blurred, and difficulty is debated, and that yes is unsafty for this.Therefore, need the toner of new duplicating machine, can satisfy the requirement of intactly reclaiming paper, can under normal environmental baseline factor, keep its stability again.The present invention's general introduction

The present invention has satisfied the method for recovery paper simple economy, that meet environmental protection requirement and has repeatedly used the demand of the method for copy paper.

Generally speaking, the invention provides a kind of can photochromic toner system.More particularly, the invention provides a kind of composition that contains colorant, it can change its color in the presence of the radiative transfer absorbing agent.This transfer absorbed agent can the absorbing light radiation and is made it produce change color with the colorant effect.In addition, the change color of this colorant is irreversible.

Colorant and ultraviolet transfer absorbed agent have been comprised in the composition of the present invention.In the presence of ultraviolet transfer absorbed agent, the transfer absorbed agent is through UV-irradiation, and this colorant can change its color.This ultraviolet ray transfer absorbed agent can absorb ultraviolet ray and make it produce irreversible change color with the colorant effect.The ultraviolet wavelength that this ultraviolet ray transfer absorbed agent is absorbed is advisable to about 400 nanometers with about 4, is preferably 100 to 375 nanometers.

Another embodiment of colored composition of the present invention is that it is the molecule occlusion body that comprises colorant, ultraviolet transfer absorbed agent and have the chemical constitution that is limited to a rare cavity.This molecule occlusion body comprises (but being not limited only to) cage compound, zeolite and cyclodextrin.Each colorant and ultraviolet transfer absorbed agent molecule all are connected with one or more molecule occlusion bodies.In some embodiment, colourant molecule is at least partially contained among the cavity of molecule occlusion body, and ultraviolet transfer absorbed agent links to each other with the molecule occlusion body in the cavity outside.In some embodiments, ultraviolet transfer absorbed agent is from outside and its covalent bonding of molecule occlusion body.

The present invention also relates to a kind of method that makes the colorant change color in the composition.This method be exactly will include the composition of changeable colour colorant and ultraviolet transfer absorbed agent carry out irradiation with the ultraviolet ray of the dosage that is enough to make colorants change color.As mentioned above, in some embodiment, said composition also comprises the molecule occlusion body.In another embodiment, said composition is used for a kind of substrate, then by ultraviolet irradiation.The colorant of this variable color should be stable.The present invention relates to have substrate thereon by the formed image of composition of the present invention.

The invention still further relates to the electrophotographic image forming method that substrate such as copy paper can repeatedly be reused.This method comprises earlier carries out the ultraviolet ray irradiation of sufficient dosage so that colorants change color wherein with the image as preceding generation on the substrate.Then, produce second image on the surface of photoreceptor, and carry out the colouring second time to form second toner image on the photoreceptor surface, this image is the duplicate of second image.Then, gained second toner image is transferred on the substrate, and on substrate, second toner image is fixed.Contain colorant of the present invention and ultraviolet transfer absorbed agent in the toner of colouring for the second time, therefore under ultraviolet irradiation, colorant in second toner image also can produce variable color, and so just just substrate is reused for and fixes the 3rd image thereon.

Behind disclosed embodiment of having read following detailed description and appending claims, cited and other purpose, feature and advantage more than the present invention will be known more.

Brief description of drawings

Fig. 1 is the structural drawing of the colorant/molecule occlusion body compound of a ultraviolet transfer absorbed agent/changeable colour, wherein the changeable colour colorant is a peacock green, the agent of ultraviolet ray transfer absorbed is Irgacure 184 (being the 1-hydroxycyclohexylphenylketone), and the molecule occlusion body is a beta-schardinger dextrin-.

Fig. 2 is the structural drawing of a ultraviolet transfer absorbed agent/changeable colour colorant/molecule occlusion body compound, wherein the changeable colour colorant is Victoria's pure blue B O (Blue 7), the agent of ultraviolet ray transfer absorbed is Irgacure 184 (being the 1-hydroxycyclohexylphenylketone), and the molecule occlusion body is a beta-schardinger dextrin-.

Fig. 3 represents is that the wavelength that are arranged in parallel into four row are the exciter lamp of 222 nanometers, and wherein the measurement of irradiation intensity is carried out from the distance that the distance exciter lamp is about 5.5 centimetres in 12 positions of 12 digitized representations of institute's target to these positions.

What Fig. 4 represented is that the parallel wavelength of lining up four row is the exciter lamp of 222 nanometers, and wherein the measurement of irradiation intensity is carried out from the distance that the distance exciter lamp is about 5.5 centimetres in 9 positions of 9 digitized representations of institute's target to these positions.

What Fig. 5 represented is that the parallel wavelength of lining up four row is the exciter lamp of 222 nanometers, wherein in the position shown in the numeral " 1 ", by increasing the distance between this position and the exciter lamp, its irradiation intensity is carried out measuring for 10 times (measurement result and list in table 7 apart from the distance of lamp).

Detailed description of the present invention

On the whole, the present invention relates to a kind of colorant (or pigment) system that is subjected to the irradiation changeable colour.The present invention relates to be included in this light transfer absorbed agent of composition that there is down colorant that can variable color in the agent of light transfer absorbed can the absorbing light radiation and make it that change color take place with colorant generation effect.

More particularly, composition of the present invention comprises colorant and ultraviolet transfer absorbed agent.In the presence of ultraviolet transfer absorbed agent, through this colorant of ultraviolet irradiation change color can take place.This ultraviolet ray transfer absorbed agent can absorb ultraviolet irradiation and make it that irreversible change color take place with colorant generation effect.Here said " composition " and derivative mean colorant and ultraviolet transfer absorbed agent as " colored composition ".When mentioning the colored composition that is suitable for special applications, as when being used for the toner of electrophotographic image forming process, " based on composition " is as a rhetoric speech, refer to a kind of material, for example a kind of toner, it comprises colorant and ultraviolet transfer absorbed agent, and also can comprise the molecule occlusion body.

Here said " colorant " can unrestrictedly comprise arbitrary material that can change its color in the presence of ultraviolet transfer absorbed agent, through ultraviolet irradiation.This colorant is generally a kind of organism, as a kind of organic dyestuff or pigment, comprises toner and color lake.This colorant is transparent to the ultraviolet ray of its suffered irradiation preferably, not that is to say with ultraviolet ray significant effect to take place." colorant " can be a kind of material, also can be the potpourri of two or more material.

As example, organic dyestuff comprises: the triaryl methyl dyestuff, as peacock green carbinol base { 4-(dimethylamino)-α-(4-(dimethylamino) phenyl)-α-phenyl benzene-methyl alcohol }, peacock green methoxide hydrochlorate { N-4-((4-(dimethylamino) phenyl)-phenylmethylene)-2,5-cyclohexadiene-1-subunit)-N-methyl chlorination first ammonium or two (right-(dimethylamino) phenyl) benzyl chloride }, with peacock green oxalates { N-4-((4-(dimethylamino) phenyl) phenylmethylene)-2,5-cyclohexadiene-1-subunit)-N-methyl chlorination first ammonium or two (right-(dimethylamino) phenyl) benzyl oxalates }; Monoazo dyes,, chrysoidine (alkaline orange 2 black as cyanine; 4-(phenylazo)-1,3-phenylenediamine mono-hydrochloric salts) and orange beta-naphthol; Thiazine dye, as methylene green, zine chloride double salt (3, two (the dimethylamino)-6-nitrophenols thiazines of 7--5-chlorine closes zine chloride double salt); Oxazine dye is as photopigment (Lumichrome) (7, the 8-lumichrome); The naphthalimide dyestuff is as fluorescein CH{6-amino-2-((hydrazino carbonyl) amino)-2,3-dihydro-1,3-dioxo-1H-benzisoquinoline-5,8-disulfonic acid dilithium salt }; Azine dye is as Janus green B { 3-(diethylamino salt)-7-((4-(dimethylamino) phenyl) azo)-5-phenyl azophenlyene chloride }; Cyanine dye, green { Ka Diou is green or Fox is green as the indigo cyanine; 2-(7-(1,3-dihydro-1,1-dimethyl-3-(4-sulphur butyl)-2H-benz-2-subunit)-1,3,5-heptan three rare base)-1,1-dimethyl 3-(4-sulphur butyl)-1H-benz base hydroxide inner salt sodium salt }; Bipseudoindoxyl dye is as indigo { indigo or vat blue 1; 2-(1,3-dihydro-3-oxo-2H-indoles-2-subunit)-1,2-dihydro-3H-indoles-3-ketone }; Coumarine dye is as 7-hydroxy-4-methylcoumarin (4-methylumbelliferone); The benzimidazole dyestuff is as Hoechst33258 (two benzimides or 2-(4-hydroxy phenyl)-5-(4-methyl isophthalic acid-piperazinyl)-2, the inferior hydrate of 5-pair-1H-benzo imidazole tri hydrochloride; The paraquinones dyestuff is as haematine { natural black 1; 7,11-dihydrobenzo (b) indeno (1,2-d) pyrans-3,4,6a, 9,10 (6H) king alcohol }; Fluorescein(e) dye is as fluorescein amine (the amino fluorescein of 5-); Diazo colours, as the red RC of diazonium (azo diazonium 10 or fast red RC salt; 2-methoxyl-5-chlorobenzene diazonium chloride closes zine chloride double salt); The azo diazo colours are as fast blue BB salt (azo diazonium 20; 4-stupid formamido-2,5-diethoxybenzene diazonium chloride closes zine chloride double salt); The phenylenediamine dyestuff is as disperse yellow 9 (N-(2, the 4-dinitrophenyl)-1,4-phenylenediamine or solvent orange 53); Diazo colours are as disperse orange 13 (solvent orange 52; 1-phenylazo-4-(4-hydroxy phenyl azo) naphthalene); Anthraquinone dye is as disperse blue 3 (Celliton fast blue FFR; 1-methylamino-4-(2-hydroxyethylamino)-9, the 10-anthraquinone), disperse blue 14 (Celliton fast blue B; 1,4-two (methylamino)-9,10-anthraquinone) and alizarin blue black B (mordant dyeing black 13); Trisazo dyes is as direct blue 71 { the light blue BRR of benzo light blue FFL or Sirius; 3-((4-((4-((6-amino-1-hydroxyl-3-sulfo group-2-naphthyl) azo)-6-sulfo group--1-naphthyl) azo)-1-naphthyl) azo)-1,5-naphthalene diacid tetrasodium salt }; Xanthene dye, as 2, the 7-dichlorofluorescein; The proflavine sulfate dyestuff is as proflavine (proflavine sulfate); The sulfonephthalein dyestuff is as cresol red (o-cresolsulfon-phthalein); Phthalocyanine dye is as copper phthalocyanine { pigment blue 15; (SP-4-1)-(29H, 31H-phthalocyanine acyl (2-)-N ²⁹, N ³⁰, N ³¹, N ³²) copper; The carotenoid dyestuff is as Trans-Beta-Carotene (food orange 5); Carmine acid dyestuff, as famille rose, aluminium or calcium aluminium cochinilin color lake (7-a-D-glucopyranosyl-9,10-dihydro-3,5,6,8-tetrahydroxy-1-methyl 9,10-dioxo-2-anthroic acid); Azure dyes, as reddish black A (3-amino-7-(dimethylamino) phenothiazine-5-base chloride or 7-(dimethylamino)-3-imino group-3H-phenothiazine hydrochloride }; And acridine dye, as acridine orange (Basic Orange 14; 3, two (dimethylamino) acridinium salt hydrochlorates of 8-close zine chloride double salt) and acriflavine (acriflavine neutral; 3,6-diaminostilbene 0-methylacridine hydrochloric acid and 3, the potpourri of 6-acridine diamines).

" changeable colour " speech relevant with colorant, its meaning is in the presence of ultraviolet transfer absorbed agent, through ultraviolet irradiation, the absorption maximum in the visible-range of electromagnetic wave spectrum of colorant can change.Usually, just passable through the front and back of ultraviolet irradiation as long as maximum absorption wavelength has taken place to change, and also this variation is irreversible.New maximum absorption wavelength is not necessarily just in the visible-range of electromagnetic wave spectrum.In other words, colorant can be changed into other color or colourless.When colorant is used for colored composition and is used for electrophotographic image forming as toner, becoming colorless, it is comparatively desirable that yes, because when reusing electrophotographic image forming copy substrates thing, at first be that colored composition is become colorless, form new image then thereon.

Here said " irreversible " is meant that the colorant that has changed color will can not recover its original color no longer after ultraviolet radiation.The colorant of this variable color should be stable, promptly no longer is subjected to the influence of ambient radiation, as nature or artificial light rays and thermal-radiating influence.The colorant that has become colorless preferably can keep its colourless state indefinitely.

" the ultraviolet transfer absorbed agent " of herein using is meant can absorb ultraviolet ray and have an effect with colorant and makes it produce the arbitrary substance of change color.In some embodiment, ultraviolet transfer absorbed agent can be an organic compound." compound " speech here both can be an one matter, also can be the potpourri that two or more material is formed.If two or more material, it is consistent that the ultraviolet wavelength that they absorbed needs not to be.

The present invention comprises can absorb the ultraviolet special compound of narrow range of wavelengths.These compounds synthesize by wavelength being selected sensitive agent and light reaction thinner.This light reaction agent can not absorb energy-rich radiation usually well.When selecting after sensitive agent combines with wavelength, the compound that obtains is the single-minded compound of a wavelength, can absorb the radiation in the very narrow wavelength coverage effectively.The example of ultraviolet ray transfer absorbed agent is seen embodiment 5 and embodiment 9.

The reaction mechanism of ultraviolet ray transfer absorbed agent and colorant also do not understand fully fully, can believe that they react by number of ways.For example, ultraviolet transfer absorbed agent can be converted into one or more free radicals and reacts with colorant then after having absorbed ultraviolet ray.These compounds that produce free radical are generally steric hindrance ketone, for example benzil dimethanol ketal (trade names Irgacure ^651, Ciba-Geigy company, Hawthornc, New York); 1-hydroxycyclohexylphenylketone (Irgacure ^500); 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholino-third-1-ketone (Irgacure ^907); 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone (Irgacure ^369) and 1-hydroxycyclohexylphenylketone (Irgacure ^184), also have other ketone, be not limited to this.

UV radiation can cause between ultraviolet transfer absorbed agent and the colorant and carry out electronics or redox reaction.Ultraviolet transfer absorbed agent this moment can be (but being not limited thereto) Michler ketone (two (to dimethylamino phenyl) ketone) or trimethyl stannic acid benzyl ester.The reaction of positive ion mechanism also may take place, and ultraviolet transfer absorbed agent this moment can be two hexafluorophosphate (the trade names Degacure of two (4-(diphenyl sulphur) phenyl) sulfide ^KI85, Ciba-Geigy company, Hawthorn, New York), Cyracure ^UVI-6990 (Ciba-Geigy company), a kind of potpourri of forming by two (4-(diphenyl sulphur) phenyl) sulfide two (hexafluorophosphate) and corresponding single sulfo group hexafluoro acid; And 5-2,4-cyclopentadienyl group (1,2,3,4,5,6-(Methylethyl) benzene)-iron (II) hexafluorophosphate (Irgacure ^261).

" ultraviolet ray " used herein be meant wavelength coverage about 4 to the electromagnetic radiation between about 400 nanometers.Its wavelength coverage of ultraviolet ray among the present invention is preferably between about 100 to 375 nanometers.So it comprises usually said ultraviolet region and vacuum ultraviolet.The wavelength coverage in these two zones be respectively about 180 to about 400 nanometers and about 100 to about 180 nanometers.

In some embodiment, the mol ratio of ultraviolet transfer absorbed agent and colorant is equal to or greater than 0.5.Usually, ultraviolet transfer absorbed agent absorbs ultraviolet ray and promptly shifts the energy that is absorbed with the colorant effect and makes its ability that irreversible change color takes place strong more, and the numerical value of this mol ratio is just low more.According to modern molecular photochemistry theory, the lower bound of this mol ratio should be 0.5, produces two free radicals because a photon can excite.But in actual conditions, require this mol ratio to surpass 1 through regular meeting, may be also can be up to about 10, the present invention is not limited to any specific molar ratio range.Important principle is that the amount of transfer absorbed agent should be enough to make colorant generation change color.

For ease of practical operation, colorant and ultraviolet transfer absorbed agent are preferably solid matter, but do not get rid of wherein arbitrary or all be liquid substance.At a colored composition is in the embodiment of solid, and when colorant mixes with ultraviolet transfer absorbed agent when thorough, the effect of ultraviolet transfer absorbed agent can obviously improve.Therefore, mixing fully between both and also presumable other component wishes.This kind mixing can realize by arbitrary method that those of ordinary skills know.When comprising polymkeric substance in the colour cell compound, colorant dissolves in the polymkeric substance softening or fusing with ultraviolet transfer absorbed agent to small part will help mixing of they.In such cases, temper machine production said composition easily with a pair of roller.In addition, when one or more components were liquid, colored composition can also be a liquid substance.

In some applications, colored composition of the present invention will use with graininess.In other was used, composition grain must be very little.During for example as the toner in the electrophotographic image forming process, the particle of colored composition generally is made up of the particle of mean diameter 7-15 micron, though also can use thinner or thicker particle.The very important point is that it is even that the size of particle should keep as much as possible.The method of making this particle is for well known to those of ordinary skill in the art.

Photochemistry comprises molecule such as ultraviolet transfer absorbed agent molecule absorbing light quantum, or claims photon, produces to have the electronic laser attitude of high reaction activity.Unless the energy of light quantum (with the wavelength proportion relation of radiated wave) and nonexcitation state (ground state) are complementary with the energy difference of excited state, otherwise the energy that molecule can not the absorbing light quantum.Though the ultraviolet wavelength coverage to irradiation that colored composition makes does not directly limit, and has at least the wavelength of a part of radiation can provide enough energy that ultraviolet transfer absorbed agent is energized into upper state, thereby can react with colorant.

Therefore, the desirable maximum absorption wavelength of ultraviolet transfer absorbed agent should be complementary with the ultraviolet wavelength of institute irradiation, can improve the efficient that makes colorants change color like this.If ultraviolet wavelength coverage is concentrated relatively and the maximum absorption wavelength of ultraviolet transfer absorbed agent also in this scope, then also can improve the efficient that makes colorants change color.For these reasons, comparatively suitable ultraviolet range is about 100 to 375 nanometers.The noncontinuity that the ultraviolet ray that is positioned at this scope is preferably produced by a dielectric field discharge excitation lamp, the pulsed ultraviolet ray.

" discrete, pulsed is ultraviolet " is meant the radiant rays that is produced by dielectric field discharge excite state atomic lamp (to call " excite state atomic lamp " in the following text).This lamp is for example at " Silentdischarge for the generation of ultraviolet and vacuum ultravioletexcimer radiation " (U.Kogelschatz, pure and applied chemistry, 62 is rolled up, the 9th phase, the 1667-1674 page or leaf, nineteen ninety) and " UV Excimer Radiationfrom Dielectric-Barrier Discharges, " (E.Eliasson and U.Kogelschatz, applied physics B, 46 volumes, 299-303 page or leaf, 1988).Develop the excite state atomic lamp by ABBInfocom Ltd (Lenzburg, Switzerland) the earliest, developed this technology by HarausNoblelight AG (Hanau, Germany) afterwards.

The ray that the excite state atomic lamp produces has very narrow spectral bandwidth, and the one half width approximately is the 5-15 nanometer.The ray that produces is the discrete pulses formulas, and pulsed frequency is relevant with the frequency of AC power, and is general in about scope of 20 to about 300KHZ.The excite state atomic lamp generally is to be sign with its beam wavelength that produces maximum intensity, among the present invention also along this tradition is arranged.Produce the commercial uviol lamp difference of covers entire ultraviolet district even visible region ray with other, the ray that the excite state atomic lamp produces is monochromatic basically.

Excited state molecule is unsettled molecular complex, only exists under extreme condition, as instantaneous existence in the gas discharge of some special shapes.Typical example is as between two rare-gas atoms or the molecule combination between rare-gas atom and the halogen atom.Exciplex decomposed in the time less than a microsecond, in decomposable process, discharged their binding energy with ultraviolet form.It is about 125 rays to about 360 nanometers that known excited state molecule generally produces wavelength coverage, and this kind with the gaseous mixture that is stimulated is relevant.

Though the colorant of front and ultraviolet transfer absorbed agent are described respectively, they can be the different pieces with a part.For example, can be directly between them or by a relatively little molecule or sept indirectly covalency be connected together.In addition, colorant and ultraviolet transfer absorbed agent can be jointly link to each other with a big molecule such as oligomer or polymkeric substance covalency, particularly when solid coloured complex of the present invention during as the toner in the electrophotographic image forming process.Colorant and ultraviolet transfer absorbed agent also can be connected by Van der Waals force, hydrogen bond and other acting force and a big molecule.Other connected mode is clearly to the people with this professional general knowledge.

For example, in an embodiment of the present composition, composition is also comprising the molecule occlusion body.Herein " molecule occlusion body " is meant the arbitrary substance with the chemical constitution that is limited to a rare cavity.That is to say that this molecule occlusion body is a structure that contains cavity." cavity " herein is meant that being large enough to hold on the size is one or two the arbitrary perforate or the space of certain part in colorant and the ultraviolet transfer absorbed agent at least.Molecule occlusion body cavity can be tunnel shape or concave shaped space.Cavity can isolate, and also can be interconnective between a plurality of.

The molecule occlusion body can be inorganic or organic.In the embodiment of some, the chemical constitution of molecule occlusion body is suitable for forming molecule and comprises complex.As example, some molecule occlusion bodies be cage type or embedded type material, zeolites and cyclodextrin material.The example of cyclodextrin material includes, but is not limited to alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin, HP-, hydroxyethyl-, sulphation beta-schardinger dextrin-, sulphation gamma-cyclodextrin (American Maize-ProductsCompany, Hammod, the Indiana).In some embodiment, the molecule occlusion body is a cyclodextrin, particularly alpha-cyclodextrin.In other embodiments, the molecule occlusion body is a beta-schardinger dextrin-.Though be not limited to following theory, can believe that the distance of transfer absorbed agent and colorant is near more on the molecule occlusion body, having an effect between them, it is also just big more to make colorant produce the effect of variable color.Therefore not only containing can be with the reaction of transfer absorbed agent molecule and with the functional group of its binding but also contain can the molecule occlusion body of the functional group of agent molecule be better molecule occlusion body near linking changeable colour.

Colorant and ultraviolet transfer absorbed agent and molecule occlusion body are connected." binding " speech is meant that from wide view colorant and ultraviolet transfer absorbed agent are at least nearly near the molecule occlusion body.For example, colorant and/or ultraviolet transfer absorbed agent can be passed through hydrogen bond, Van der Waals force or other similar effect power and the molecule occlusion body keeps approaching nearly.In addition, one of them or both of colorant and ultraviolet transfer absorbed agent can link to each other with molecule occlusion body covalency.In certain embodiments, colorant and molecule occlusion body link to each other by hydrogen bond and/or Van der Waals force or other similar effect power, and ultraviolet transfer absorbed agent links to each other with covalent bond with the molecule occlusion body.In the other embodiment, colorant is comprised in the cavity of molecule occlusion body at least in part, and ultraviolet transfer absorbed agent then is positioned at outside the cavity of molecule occlusion body.

In the embodiment that colorant and ultraviolet transfer absorbed agent and molecule occlusion body are connected, colorant is a crystal violet, and ultraviolet transfer absorbed agent is dehydration phthalyl glycine-2959, and the molecule occlusion body is a beta-schardinger dextrin-.In the embodiment that another colorant and ultraviolet transfer absorbed agent and molecule occlusion body are connected, colorant is a crystal violet, and ultraviolet transfer absorbed agent is 4-(4-hydroxy phenyl)-Ding-2-ketone-2959 (chlorine replaces), and the molecule occlusion body is a beta-schardinger dextrin-.

In the embodiment that another colorant and ultraviolet transfer absorbed agent and molecule occlusion body are connected, colorant is a peacock green, and ultraviolet transfer absorbed agent is Irgacure184, and the molecule occlusion body is a beta-schardinger dextrin-, as shown in Figure 1.In the embodiment that another colorant and ultraviolet transfer absorbed agent and molecule occlusion body are connected, colorant is Victoria's pure blue B O, and ultraviolet transfer absorbed agent is Irgacure 184, and the molecule occlusion body is a beta-schardinger dextrin-, as shown in Figure 2.

Embodiment 5 to 9 has provided the preparation method of these colorants and ultraviolet transfer absorbed agent and the method that they and beta-schardinger dextrin-are connected.These methods only are preparation and a kind of means that link these compositions, also can adopt the known method of other many chemists.In the present invention, in case selected special component, prepare and link them or will be known by personnel with this professional general knowledge with the method that other composition that may use is connected.

For making things convenient for practical operation, colorant, ultraviolet transfer absorbed agent and molecule occlusion body preferably all are solid matter.But these materials wherein arbitrary or all also can be liquid.When wherein one or more components are liquid, or when the molecule occlusion body be organism when having adopted solvent, colored composition is liquid.Suitable solvent comprises (being not limited to): acid amides such as N, dinethylformamide; Sulfoxide such as dimethyl sulfoxide; Ketone such as acetone, fourth copper and methyl butyl ketone; Aliphatic hydrocarbon and aromatic hydrocarbon such as hexane, octane, benzene, toluene and dimethylbenzene; Ester class such as ethyl acetate; Water and other.When the molecule occlusion body was cyclodextrin, most preferred was amide-type and sulfoxide kind solvent.

The invention still further relates to a kind of method that changes the color of colorant in its composition.In brief, this method is exactly the composition that comprises changeable colour colorant and ultraviolet transfer absorbed agent with the ultraviolet irradiation of the dosage that is enough to make colorants change color.As mentioned above, composition also comprises the molecule occlusion body in one embodiment.In another embodiment, composition had been applied on the substrate in the past through ultraviolet irradiation.

The dosage of the suffered ultraviolet irradiation of colorant of the present invention what generally are to make colorant produce the necessary amounts of variable color.This necessary ultraviolet dosage of colorant generation variable color that makes can be determined with normal experiment by the professional.Energy density is what a physical quantity of the electromagnetic radiation of being passed on the unit of measurement area, often with every square centimeter of what watt (W/cm ²) represent for unit.The horizontal extent of used energy density is at approximate 5mw/cm ²To 15mw/cm ², be preferably in 8 to 10mw/cm ²The dosage of the suffered irradiation of colored composition is again the function of exposure time and radiation source intensity or flux usually.The latter is subjected to the influence of the distance between composition and the light source, and according to ultraviolet wavelength difference, also is subjected to the influence of atmosphere between the composition light source.Therefore, in some cases, composition is in a specific atmosphere or accept ultraviolet irradiation in the vacuum, yet does not wish to adopt above-mentioned two kinds of methods generally speaking.

For example, in one embodiment, colorant of the present invention produces variable color under the irradiation of 222 nanometer excite state atomic lamps.Especially, the crystal violet colorant produces variable color under the irradiation of 222 nanometer excite state atoms.More particularly, the crystal violet colorant produces variable color under the irradiation of 222 nanometer excite state atomic lamps of about 5 to 6 centimeters apart from it, and as shown in Figure 3 and Figure 4, these lamp banks become parallel four lines, about 30 centimeter length.It is to be noted that this arrangement is not to be vital to the present invention.One or more lamps can be arranged arbitrarily also can carry out UV radiation to colorant so that it produces variable color from any distance.Those of ordinary skills can decide which kind of spread geometry and which distance to be fit to conventional method.Know that also different excite state atomic lamps should be used for different ultraviolet transfer absorbed agent.The excite state atomic lamp that is used to make the colorant that links to each other with ultraviolet transfer absorbed agent to produce variable color should produce the ultraviolet ray that wavelength can be absorbed by ultraviolet transfer absorbed agent.

Colored composition of the present invention can be used on any substrate or within.If composition is used within the substrate, this substrate must be fully transparent to the ultraviolet ray that makes colorants change color.That is, ultraviolet ray is not with substrate generation effect or be absorbed.From practical operation, composition is generally all on substrate, and the most frequently used substrate is a paper.But also can use other substrate, comprise weaving and non-cloth or fabric, film and other analog of spinning.

Another aspect of the present invention is at the substrate that has the image that is formed by the present composition thereon.Though the present invention relates to anyly can fix the substrate of a colored image thereon, best this substrate is a paper, is good with copy paper and facsimile transmission paper especially, but also can is other type paper.

The present composition can join in the toner that is applicable to the electrophotographic image forming process.This toner includes colorant, ultraviolet transfer absorbed agent and carrier.This carrier can be a polymkeric substance, and toner also can include charge carrier.Briefly, the electrophotographic image forming process is exactly at first imaging on the photoreceptor surface, then toner is added to the toner image that duplicate with formation on the photoreceptor surface, again toner image is transferred on the substrate, at last toner image is fixed on the substrate.After toner was fixed on the substrate, the ultraviolet irradiation by with sufficient dosage made the color of the colorant in the composition that irreversible variation take place.In certain embodiments, the used ultraviolet wavelength that makes colorants change color is about 100 to about 375 nanometers.In other embodiments, used ultraviolet ray is the discrete pulsed ultraviolet ray that is produced by dielectric field discharge excite state atomic lamp.In another embodiment, also include the molecule occlusion body in the toner.

When the colour cell compound is used for the electrophotographic image forming process as toner, also include carrier in the said composition, the character of this carrier is known by this area professional.In many application, this carrier is a polymkeric substance, typically is thermosetting or thermoplastic polymer, and the latter is more more general.

The example of thermoplastic polymer has (but being not limited to): the polyacetals class of end-blocking, and as polyoxymethylene or polyoxymethylene, parachloral, poly-valeraldehyde, metacetaldehyde, poly-propionic aldehyde and other; The acrylic acid base polymer, as polyacrylamide, polyacrylic acid, polymethylacrylic acid, polyacrylic acid second fat, polymethylmethacrylate and other; Fluorocarbon polymer, as teflon, perfluorinate ethylene-propylene copolymer, ethylene tetrafluoroethylene copolymer, poly-three fluoro-vinyl chloride, ethene-three fluoro-vinyl chloride copolymer, Kynoar, polyvinyl fluoride and other; Epoxy resin is as the condensed polymer of chloropropylene oxide and bisphenol-A; Polyamide-based, as poly-(6-aminocaprolc acid) or polycaprolactam, polyhexamethylene adipamide, polyhexamethylene decanedioyl diamines, poly-(11-aminoundecanoic acid) and other; The Nomex class is as poly-(imino group-1,3-phenylene imines isophthaloyl) or poly-(-phenylene isophthaloyl diamines) and other; The parylene class, as poly-p-xylylene, polychlorostyrene is for terephthalylidene and other; The polyarylether class, poly-(oxygen-2,6-dimethyl-1,4-phenylene) or poly-to benzene oxygen and other; The polyarylsufone class, as poly-(oxygen-1, the inferior benzene sulfonyl-1 of 4-, the inferior benzene oxygen-1 of 4-, the inferior benzene isopropylidene-1 of 4-, 4-phenylene), poly-(sulphonyl-1, the inferior benzene oxygen-1 of 4-, the inferior benzene sulfonyl-4 of 4-, the two phenylenes of 4-) and other; Polycarbonate-based, as poly bisphenol or poly-(phosphinylidyne dioxy-1, the inferior benzene isopropylidene-1 of 4-, the inferior stupid base of 4-) and other; Polyesters, as polyethylene terephthalate, poly terephthalic acid butylidene ester, poly terephthalic acid 1,4-cyclohexyl diformazan alcohol ester or poly-(oxygen methylene-1,4-cyclohexylmethylene oxygen paraphenylene terephthalamide) and other; The polyarylphosphorus ethers is as polyphenylene sulfide or poly-sulphur-1,4-phenylene) and other; Polyimide is as poly-(benzene four acid imides-1,4-phenylene) and other; Polyolefins, as tygon, polypropylene, poly-1-butylene, poly-2-butylene, poly-1-amylene, poly-2-amylene, poly-(3-Methyl-1-pentene), poly-(4-methyl-1-pentene) 1,2-gathers 1,3-butadiene, 1,4-gathers-1,3-butadiene, polyisoprene, neoprene, polyacrylonitrile, polyvinyl acetate (PVA), Vingon, polystyrene and other; And aforementioned various multipolymer, as acrylonitrile-butadiene-styrene (ABS) (ABS) multipolymer, styrene-n-BMA multipolymer, ethylene-vinyl acetate copolymer and other.

Some thermoplastic polymers commonly used comprise styrene-n-BMA multipolymer, polystyrene, the positive butyl ester multipolymer of styrene-propene acid, Styrene-Butadiene, polycarbonate, polymethylmethacrylate, Kynoar, polyamide (PA-12), tygon, polypropylene, ethylene-vinyl acetate copolymer and epoxy resin.

The example of thermosetting polymer comprises (but being not limited to): alkyd resin, and as phthalic anhydride-maleic resin, maleic acid-maleic resin, hexane diacid-maleic resin and phthalic anhydride-pentaerythritol resin; Allyl resin, in this resinoid as phthalic acid di-allyl ester, m-phthalic acid di-allyl ester, diallyl maleate and these monomers of chlorine mattress diallyl phthalate as the non-volatile crosslinking chemical of polyester thing; Amino resins, as aniline-formaldehyde resin, ethylene urea urea formaldehyde, dicyandiamide-formaldehyde resin, melamine-formaldehyde resin, sulfanilamide (SN)-formaldehyde resin and Lauxite; Epoxy resin is as crosslinked chloropropylene oxide-bisphenol a resin; Phenolics as phenol formaldehyde resin, comprises line style phenolic aldehyde and thermosetting phenolic; And heat cured polyester, silicon rubber and polyurethane etc.

Except colorant, ultraviolet transfer absorbed agent and presumable carrier, colored composition of the present invention can also comprise other composition according to its purposes.During for example as the toner of electrophotographic image forming, composition also may comprise charge carrier, thermal oxidation resistance stabilizing agent, viscoelasticity improver, crosslinking chemical, plastifier and other.Further, a kind of present composition as toner in the electrophotographic image forming may include electric charge adjusting additive such as quaternary ammonium salt; Mobile adjuvant such as hydrophobic silica gel, zinc stearate, calcium stearate, lithium stearate, polyvinyl stearate and the polyethylene powders regulated; The adjuvant that filler such as lime carbonate, clay and talcum and other those of ordinary skills use always.In some applications, charge carrier is the principal ingredient of toner.Charge carrier is well known to those of ordinary skill in the art, normally the metallic particles of coated polymer.Those of ordinary skills know the kind and the quantity of these adjuvants in the colored composition.As mentioned above, also can comprise the molecule occlusion body in the toner of the present invention.

When the colour cell compound is used as toner in the electrophotographic image forming, may have several its variants, and these variants also belong to scope of the present invention.For example, on a body paper, formed first image by toner based on composition.As described herein, the colorant in the composition is wherein become colorless, so just can reclaim this paper of winning victory again with this paper of ultraviolet irradiation.On this paper, can form second image.This second image can be formed by the known toner of standard, or by forming with the identical or different toner based on composition of first image.

Each steel plate be of a size of 3 * 5 inches (7.6cm * 12.7cm), steel plate is Q-Panel Company, Cleveland, Ohio provides.Become the thickness estimation of film to be about the 10-20 micron on the steel plate.

In each situation of present embodiment, colorant is that (Milwaukee Wisconsin), followingly for simplicity represents with colorant A (Colorant A) the peacock green oxalates for AldrichChemical Company, Inc..Ultraviolet ray transfer absorbed agent (UVRT) is made up of in following one or more: Irgacure ^500 (" UVRT A "), Irgacure ^651 (" UVRT B ") and Irgacure ^907 (" UVRT C ") all introduce in front, are Ciba-Geigy Corporation, Hawthorne, the product of New York.Polymkeric substance be selected from following one of them: chloropropylene oxide-bisphenol A epoxide resin (" polymer A "), Epon ^1004F (Shell Oil Company, Houston, Texas); Weight-average molecular weight is about 8000 polyglycol (" polymer B "), Carbowax8000 (Aldrich Chemical Company); Be about 4,600 polyglycol (" polymkeric substance C "), Carbowax 4600 (Aldrich ChemicalCompany) with weight-average molecular weight.The film of a contrast usefulness only contains colorant and polymkeric substance.The composition of various films is listed in table 1.

Table 1

Contain colorant and the agent of ultraviolet transfer absorbed

The composition of the broad film of (" UVRT ")

See toner UVRT thin polymer film kind umber kind umber kind umber A A 1 A 6 A 90

C????????4?B????????????A???????1????????A????????12??????A???????90

C????????8?C????????????A???????1????????A????????18??????A???????90

C????????12?D????????????A???????1????????A????????6???????A???????90

B????????4?E????????????A???????1????????B????????30??????A???????70?F????????????A???????1????????--???????--??????A???????100?G????????????A???????1????????A????????6???????B???????90

C????????4?H????????????A???????1????????B????????10??????C???????90

Each film is subjected to ultraviolet irradiation on steel plate.The every block plate that has film sample on the surface is placed on the travelling belt of a variable speed controllable.Use three kinds of different uv radiation sources.Lamp A is that wavelength is the excite state atomic lamp of 222 nanometers, and lamp B is that wavelength is the excite state atomic lamp of 308 nanometers, introduces in front.Lamp C is molten lamp (fusionlamp) system, have one " D " type bulb (Fusion system Corporation, Rockville, Maryland).A plurality of excite state atomic lamps are arranged in the cylindrical light group that four lines is about 30cm, and its orientation is vertical with the direction of motion of travelling belt.These lamps are cooled off by the recirculated water of flow through its center or internal pipeline, and its working temperature is in a relatively low level, promptly about 50 ℃.The energy density of the outside surface of these lamps generally about 4 to about 20 joules of every square metre of (J/m ²) scope in.

But only having reflected present excite state atomic lamp, this scope can provide the amount of capacity of energy; In the future may provide higher energy density.For lamp A and lamp B, the distance of lamp and membrane sample is 4.5cm, and line speed is decided to be 20ft/min (0.1m/sec).For lamp C, line speed is 14ft/min (0.07m/sec), and the distance of lamp and sample is 10cm.Table 2 has been listed the result that different film samples are subjected to ultraviolet irradiation.Except film F, the numeral that writes down in the table is the number of times of required this lamp of process when film is become colorless under a certain light irradiation.For film F, what write down in the table is the number of times of test, and film still keeps primary colors after each test, without any variation.

Table 2

Contain colorant and ultraviolet transfer absorbed agent (UVRT) film through the ultraviolet wire spoke

According to the result.

Excite state atomic lamp film lamp A lamp B melts lamp A 33 15 B 23 10 C 13 10 D 11 10 E, 111 F, 55 10 G 3--10 H 3--10

Embodiment 2

The present embodiment narration is used for the preparation of the solid colored composition of electrophotographic image forming process toner.Under each situation, toner comprises as the colorant A among the embodiment 1; A kind of polymkeric substance, DER667 is chloropropylene oxide-bisphenol A epoxide resin (polymkeric substance D), Epon ^1004 F (Dow chemical company, Midland, Michigan); With a kind of charge carrier, carrier A, form by very thin coated polymer metal.The agent of ultraviolet ray transfer absorbed is made up of following one or more: the UVRTB in the example example 1, Irgacure ^369 (UVRT D) and Irgacure ^184 (UVRTE); Both introduced the back in front, were the product of Ciba-Geigy company (Hawthorne, New York).In certain situation, comprise another kind of polymkeric substance, styrene-acrylate 1221, the styrene-propene acid copolymer (Hercules Incorporated, Willmington, Delaware).

Be the preparation toner, is 3VV 800E with colorant, ultraviolet transfer absorbed agent and polymkeric substance in model, size is 3 inches * 7 inches, and ((Farrel Corporatron, Ansonia dissolve blend on Connetticut) with mills in two rollers researchs of 7.6cm * 17.8cm).The molten mixed thing that obtains is having 0.010 inch herringbone sieve (R.D.Kleinfeldt, Cincinnati, grinding on Mikropul hammer-mill Ohio) is then at Sturtvant, be filtered to suitable dimensions on 2 inches comminutors of air blast (R.D.Kleinfeldt), make preceding toner.In preceding toner, add charge carrier and mixing fully.Table 3 has been listed the composition of various preceding toners, and table 4 has been listed the composition of various toners.

Table 3

The composition of preceding toner

Toner A (g) kind gram kind gram A 1 D 20 D 80 B 1 B 20 D 80 C 1 B 10 D 80 before the colorant UVRT polymkeric substance

D???????10???D??????????1?????????B???????6.9??????D?????40

D???????6.6??????E?????40

F???????6.6

Table 4

Toner is formed

Preceding color toner agent kind g charge carrier (g) A A 8.4 210 B B 8.4 210 C C 8.4 210 D D 8.4 210

Every kind of toner all is coated in toner reel (model: Sharp ModelZT-50 TD1) respectively, and to be installed in model be Sharp Model Z-76 or SharpModel Z-77 Xerox (Sharp Electronics Corporation, Mahwah, New Jersey) on.With conventional method image is become on copy paper (Neenah Bond).The copy paper that will have image is with carrying out ultraviolet irradiation as the lamp B among the embodiment 1.In each situation, it is colourless just image to be become through irradiation.

Embodiment 3

What present embodiment was told about is the preparation of beta-schardinger dextrin-molecule occlusion body, and wherein (1) ultraviolet transfer absorbed agent links to each other with the cyclodextrin covalency in the cavity outside of cyclodextrin, and (2) colorant links to each other with cyclodextrin by hydrogen bond and/or Van der Waals force.

A. the Fridel-Crafts acylation reaction of transfer absorbed agent

On three mouthfuls of round-bottomed flasks of 250ml, assemble condenser pipe, isobaric tap funnel and ammonia conduit, and in bottle, add the stirring bar magnet.At logical N ₂The time, in bottle, add 10g (0.05mol) 1-hydroxycyclohexylphenylketone (Irgacure ^184, Ciba-Geigy Corporation, Hawthorne, New York), the 100ml anhydrous tetrahydro furan (Aldrich Chemical Company, Milwaukee, Wisconsin) and 5g (0.05mol) succinic anhydride (Aldrich).Under agitation add 6.7g anhydrous Aluminum chloride (Aldrich) then.Reaction mixture is kept about 1 hour of reaction in 0 ℃ of ice bath, be heated to room temperature then, keep reaction 2 hours.Reaction mixture is poured in the potpourri of 500ml frozen water and 100ml ether then.Add small amount of sodium chloride to promote phase-splitting at aqueous phase.Then ether is told mutually, used anhydrous magnesium sulfate drying.Remove ether under reduced pressure, obtain 12.7g (87%) white crystalline powder.Through nuclear magnetic resonance spectroscopy, products therefrom is 1-hydroxy-cyclohexyl 4-(2-carboxy ethyl) carbonyl phenyl ketone.

B. the preparation of the transfer absorbed agent acyl chlorides of acidylate

In being housed, the 250ml round-bottomed flask of condenser pipe adds 12.0g 1-hydroxy-cyclohexyl 4-(2-carboxyl hexyl) carbonyl phenyl ketone (0.04mol), 5.95g (0.05mol) thionyl chloride (Aldrich) and 50ml ether.The reaction mixture that obtains removes solvent under reduced pressure then 30 ℃ of following stirring reactions 30 minutes.Remaining white solid distills 30 minutes to remove residual solvent and excessive thionyl chloride under 0.01 Torr pressure, obtain 1-hydroxy-cyclohexyl 4-(2-chloroformyl ethyl) the carbonyl phenyl ketone of 12.1g (94%).

C. the transfer absorbed agent of acidylate combines with common Jie of cyclodextrin

At logical N ₂Situation under, in three mouthfuls of round-bottomed flasks of the 250ml of the isobaric tap funnel that magnetic stirring rod condenser pipe, thermometer, band nitrogen ingress pipe are housed, add 10g (9.8mmol) beta-schardinger dextrin-(American Maize-Products Company, Hammod, Indiana), 31.6g (98mmol) 1-hydroxy-cyclohexyl 4-(2-chloroformyl ethyl) carbonyl phenyl ketone and 100ml N, dinethylformamide.Reaction mixture is heated to 50 ℃ and add the triethylamine of 0.5ml.Potpourri reacted 1 hour down at 50 ℃ then, was cooled to room temperature.Behind current preparation feedback, product is not separated.Product is the beta-schardinger dextrin-(for simplicity, being called beta-schardinger dextrin--transfer absorbed agent later on) that links to each other with ultraviolet transfer absorbed agent covalency.

Repeat aforementioned program and product is separated.Finish the back in reaction and reaction mixture is concentrated to the about 10% of original volume, pour into then in the frozen water, add sodium chloride and saltout product is precipitated out from solution with Rotary Evaporators.Filter and use the ether washing precipitate.Obtain the 24.8g white powder after the vacuum drying.In preparation feedback for the third time, the concentrate behind the rotary evaporation is placed on the long upper end that contains the pillar of 15g silica gel of about 7.5cm, use N, dinethylformamide carries out wash-out, eluent usefulness chromatographic sheet (Whatman ^Flexible-Backed TLC Plates; Accession number No.05-713-161, Fisher Scientific, Pittsburgh, Pennsylvania).The eluting solvent evaporation can be obtained eluted product.The structure of product is analyzed with nuclear magnetic resonance analyser.

D. the preparation of the binding-colored composition of colorant and cyclodextrin-transfer absorbed agent

Pack in the 250ml round-bottomed flask and be dissolved in 150ml N, the solution of the 10g of dinethylformamide (about 3.6mmol) beta-schardinger dextrin--transfer absorbed agent, under the room temperature to the peacock green oxalates that wherein adds 1.2g (3.6mmol) (Aldrich Chemical Company, Inc., Milwankee, Wisconsin; Hereinafter referred to as colorant A).Potpourri room temperature reaction 1 hour under magnetic stirs.Remove most solvent then on Rotary Evaporators, residue carries out wash-out as previously mentioned on silicagel column.Beta-schardinger dextrin--transfer absorbed agent and colorant A comprise compound wash-out at first, can separate fully with colorant and beta-schardinger dextrin--transfer absorbed agent.The eluent that will contain compound is collected, and rotary evaporation removes and desolvates, and decompression distillation obtains the blue-green powder-product to remove residual solvent under 0.01Torr pressure then.

E. the variable color of colored composition

Ultraviolet irradiation beta cyclodextrin-transfer absorbed agent of sending with two kinds of different lamps-lamp A and lamp B-and colorant A comprise compound.Lamp A lines up the cylindricality lamp cohort that four row are about 30cm, and wavelength is 222 nanometers.These lamps are by the recirculated water cooling of the pipeline of flow through its center or inside, and its working temperature is relatively low, about 50 ℃.The energy density of the outside surface of these lamps is about 4 to 20 joules of every square metre of (J/m ²) scope in.This scope has in fact only reflected the amount of capacity of present excite state energy that atomic lamp provides, and in the future, may contain the energy density that provides higher.The distance of lamp and institute's irradiation sample is 4.5cm.Lamp B is 500 watts of Hanovia medium pressure mercury lamps (Hanovia Lamp Co., Newark, New Jersey), and the distance of lamp B and institute's irradiation sample is about 15cm.

With the N that comprises compound of several beta-schardinger dextrin-s-transfer absorbed agent and colorant A, the dinethylformamide drips of solution is in skim chromatosheet (TLC plate) and little weighing pan of tygon.These two samples under lamp A irradiation, all fade within second (state becomes colorless) at 15-20.With lamp B irradiation at 30 seconds with the interior similar results that also obtains.

By the N of colorant A and beta-schardinger dextrin-, the comparative sample 1 that dinethylformamide solution forms is faded not producing under lamp A irradiation.By the N of colorant A and 1-hydroxycyclohexylphenylketone, the comparative sample 2 that the dinethylformamide solvent forms is faded in 60 seconds through lamp A irradiation.But within one hour after radiation no longer, its color occurs again.

Be of the influence of research solvent, the compound that comprises of 50mg beta-schardinger dextrin--transfer absorbed agent and colorant A is dissolved in the 1ml solvent fading.Gained solution places on the cover glass and uses lamp A irradiation 1 minute.The speed of fading, even the time that sample becomes colorless is directly related with the dissolubility of compound in solvent, see the following form:

Solvent solubility fades the time

N, dinethylformamide slightly soluble 1 minute

Dimethyl sulfoxide is solvable＜and 10 seconds

Acetone is solvable＜and 10 seconds

Hexane is insoluble--

Ethyl acetate slightly soluble 1 minute

The compound that comprises of 10mg beta-schardinger dextrin--transfer absorbed agent and colorant A is placed on the cover glass and with pestle and pushes.The gained powder is used lamp A irradiation 10 seconds.Powder becomes colorless.Can obtain similar result with lamp B irradiation, just speed more slowly.

Embodiment 4

In the preparation of embodiment 3 colored compositions, owing to exist the transfer absorbed agent acyl chlorides of acidylate to occupy the possibility of cyclodextrin cavity at least in part, colorant partly or entirely is left out, need to adopt a kind of improved preparation method.Therefore present embodiment has been narrated a kind of preparation method of beta-schardinger dextrin-molecule occlusion body, and wherein (1) colorant is included in to small part within the cavity of cyclodextrin and with hydrogen bond and/or Van der Waals force and is attached thereto; (2) ultraviolet transfer absorbed agent links to each other with the cyclodextrin covalency outside cyclodextrin cavity.

A. the binding of colorant and cyclodextrin

At the 150ml N that contains 10.0g (9.8mmol) beta-schardinger dextrin-, add the colorant A of 3.24g (9.6mmol) in the dinethylformamide solution.Stirring at room reaction 1 hour.Reaction solution is evaporated to about original volume 1/10 with Rotary Evaporators.Then as described in the C part among the embodiment 1, with residue through the silicagel column wash-out.Solvent in the eluent is removed with the Rotary Evaporators decompression, obtains 12.4g blue-green powder, and A comprises compound for the beta-schardinger dextrin-colorant.

B. agent of acidylate transfer absorbed and cyclodextrin colorant comprise the preparation of the covalent bond-colored composition of compound

Under the condition of continuously logical nitrogen, add 10g (9.6mmol) beta-schardinger dextrin-colorant A in three mouthfuls of round-bottomed flasks of 250ml of isobaric tap funnel of nitrogen conduit and comprise compound magnetic stirring bar, thermometer, condenser pipe being housed and being furnished with, 13.6g (98mmol) 1-hydroxy-cyclohexyl 4-(2-chloroformyl ethyl) carbonyl phenyl ketone (partly preparing) and 150ml N as B among the embodiment 1, dinethylformamide.With mixture heated to 50 ℃ and add the 0.5ml triethylamine.Reaction was cooled to room temperature after 1 hour under 50 ℃.Reaction mixture obtains the compound that comprises of 14.2g beta-schardinger dextrin--transfer absorbed agent and colorant A through processing as described in top (A portion), is the blue-green powder.

C. the variable color of colored composition

The compound that comprises of beta-schardinger dextrin--transfer absorbed agent that B is partly obtained and colorant A repeats the described step of E part among the embodiment 1, can obtain similar result.

Embodiment 5

That present embodiment is narrated is a kind of preparation method who is called the ultraviolet transfer absorbed agent of phthalyl glycine-2959.

Dean ﹠amp is being housed; Add in three mouthfuls of round-bottomed flasks of the 250ml of Stark water trap and condenser pipe and two glass plugs: 20.5g (0.1mol) wavelength is selected sensitive agent, phthalyl glycine (Aldrich); 24.6g (0.1mol) light reaction agent, and DARCUR2959 (Ciba-Geigy, Hawthorne, NY); 100ml benzene (Aldrich) and 0.4g p-toluenesulfonic acid (Aldrich).Heating reflux reaction 3 hours is collected 1.8ml water in the water trap.Removal of solvent under reduced pressure obtains the 43.1g white powder.With the hexane that contains 30% ethyl acetate (Fisher) recrystallization, obtain 40.2g (93%) white crystalline powder, fusing point is 153-4 ℃.Reaction equation is as follows:

Products therefrom is called phthalyl glycine-2959, and its spectral signature is: IR[Nujol Muu]] v _Max3440,1760,1740,1680,1600cm ^-1 ¹HNMR[CDCL ₃] ppm 1.64[s], 4.25[m], 4.49[m], 6.92[m] and, 7.25[m], 7.86[m] and, 7.98[m], 8.06[m] and ppm

Embodiment 6

What present embodiment was narrated is the dewatering of phthalyl glycine among the embodiment 5-2959.

One Dean ﹠amp is housed; The 250ml round-bottomed flask of Stark water trap and condenser pipe adds 21.6g (0.05mol) phthalyl glycine-2959; 100ml anhydrous benzene (Aldrich) and 0.1g p-toluenesulfonic acid (Aldrich).Back flow reaction 3 hours.After water trap was collected 0.7ml water, reaction dissolvent was removed in decompression, obtains 20.1g (97%) white solid.Should fixing not need further purification can be directly used in the next step.Reaction equation is as follows:

The spectral signature of gained reaction product:

Infrared; γ _Max1617cm ^-1(C=C=0)

Embodiment 7

That present embodiment is narrated is the preparation method that covalency is connected with the beta-schardinger dextrin-of dehydration phthalyl glycine-2959 group among the embodiment 6.

In-100ml round-bottomed bottle, add 5.0g (4mmol) beta-schardinger dextrin-(American Maize Product Company, Hammod, Indiana; Below claim β-CD) in the reaction; 8.3g (20mmol) dehydration phthalyl glycine-2959; 50ml dry DMF (being N, dinethylformamide); 20ml benzene and 0.01g paratoluensulfonyl chloride (Aldrich).Reaction mixture is put into cryosel and was bathed stirring reaction 24 hours.After the reaction mixed liquor is poured in the 150ml dilute sodium bicarbonate solution, and with 50ml extracted with diethyl ether three times.The water filtration is obtained the 9.4g white solid, wherein contain the beta-schardinger dextrin-that is connected with phthalyl glycine 2959 groups.Inverse thin layer chromatography is analyzed (with the developping agent of 50: 50 DMF and acetonitrile mixed liquor) and is shown, occurs a new peak different with initiation material in the product.

Certainly, several firsts and seconds alcohol groups that can react with phthalyl glycine-2959 are arranged in the cyclodextrin molecular.Last figure is the explanation reaction, has only expressed phthalyl glycine-2959 molecule.

Embodiment 8

Present embodiment narration be the method for the molecule occlusion body beta-schardinger dextrin-that its valency is connected to ultraviolet transfer absorbed agent phthalyl glycine-2959 described in colorant and ultraviolet transfer absorbed agent and molecule the occlusion body method, especially the crystal violet colorant that are connected and the embodiment 7-be connected.

In the 100ml beaker, add beta-schardinger dextrin-and the 50ml water that 4.0g is connected to dehydration phthalyl glycine-2959 group.Be heated to 70 ℃, solution becomes is limpid.Add in the solution then 0.9g (2.4mmol) crystal violet (Aldrich ChemicalCompany, Milwaukee, WI) and stirred 20 minutes.Filter, leach thing and wash with filtrate, dry in 84 ℃ of vacuum drying ovens then.Obtain 4.1g (92%) hyacinthine powder.The spectral signature of product is:

Ultraviolet (DMF), absorption maximum γ _Max610nm (cf cv λ _Max604nm)

Embodiment 9

That present embodiment is narrated is ultraviolet transfer absorbed agent 4 (4-hydroxy phenyl) fourth-2-ketone-2959 preparation method of (chlorine replaces).

Add in the 250ml round-bottomed bottle of condenser pipe and magnetic stirring bar is housed: 17.6g (0.1mol) wavelength is selected sensitive agent, and 4-(hydroxy phenyl) fourth-2-ketone (AldrichChemical Company, Milwaukee, WI); 26.4g (0.1mol) light reaction agent, chloro DARCUR2959 (Ciba-Geigy Corporation New York); 1.0ml pyridine (Aldrich) and 100ml anhydrous tetrahydro furan (Aldrich).After the back flow reaction 3 hours, partial solvent (60%) is removed in decompression.Reaction mixture is poured in the frozen water also with branch extracting twice such as 50ml ether then.Desolvate remaining 39.1g white solvent with removing behind the anhydrous magnesium sulfate drying.With the hexane solvent recrystallization that contains 30% ethyl acetate, can obtain the white crystalline powder of 36.7g (91%), fusing point is 142-3 ℃.Reaction equation is as follows:

IR[Nujol Muu] v _Max3460,1760,1700,1620,1600cm ^-1 ¹H[CDCL ₃] ppm 1.62[s], 4.2[m], 4.5[m], 6.9[m] and ppm

The ultraviolet transfer absorbed agent that present embodiment makes, 4-(4-hydroxy phenyl) fourth-2-ketone-2959 (chloro), can be connected with beta-schardinger dextrin-and colorant such as crystal violet, method adopts the method for embodiment 6-8 narration, wherein uses the dehydration phthalyl glycine-2959 among 4-(4-hydroxy phenyl) fourth-2-ketone-2959 (chloro) replacement embodiment 6-8.

Embodiment 10

The 222 nanometer excite state atomic lamps that the present embodiment explanation is shown in Figure 3, to be enough to the making colorant of the present composition contained on the substrate surface produce the amount of variable color, at distance lamp 5.5cm, be arranged on the surface of substrate of the digital institute of figure mark position, the reading of the energy that is produced is identical.Lamp 10 is made up of a lampshade 15 and four parallel arranged, the excite state atomic lamp 20 that is about 30cm.These excite state atomic lamps are cooled off by the recirculated water of flow through its center or internal pipeline (not marking in the drawings), make it a relatively low temperature, promptly about 50 ℃ of work down.The energy density of excite state atomic lamp outside surface is generally at every square metre of (J/m of about 4-20 joule ²) scope in.

Table 5 is enumerated is the reading of the energy intensity surveyed by the gauging table that is positioned at the substrate surface.Among Fig. 31,4, the distance of 7 and 10 4 positions and left end is 7.0 centimetres approximately.Among Fig. 33,6, the distance of 9 and 12 4 positions and right-hand member is 5.5 centimetres approximately.Among Fig. 32,5,8 and 11 4 positions are placed in the middle, with the distance at two ends be 17.5 centimetres approximately.

Table 5

Background (μ W)	Reading (mW/cm ²)
Background (μ W)	Reading (mW/cm ²)	????24.57 ????19.56- ????22.67 ????19.62 ????17.90 ????19.60 ????21.41 ????17.91 ????23.49 ????19.15 ????17.12 ????21.44	????9.63 ????9.35 ????9.39 ????9.33 ????9.30 ????9.30 ????9.32 ????9.30 ????9.30 ????9.36 ????9.35 ????9.37

Embodiment 11

The 222 nanometer excite state atomic lamps that the present embodiment explanation is shown in Figure 4, to be enough to make the colorant in the present composition contained on the substrate surface to produce the amount of variable color, at distance lamp 5.5cm, be arranged on the surface of substrate of the digital institute of figure mark position, the reading of the energy intensity that is produced is identical.Lamp 10 is made up of a lampshade 15 and four parallel arranged, the excite state atomic lamp 20 that is about 30cm.These excite state atomic lamps are cooled off by the recirculated water of flow through its center or internal pipeline (not marking in the drawings), make it a relatively low humidity, promptly about 50 ℃ of work down.The energy density of excite state atomic lamp outside surface is generally at every square metre of (J/m of about 4-20 joule ²) scope in.

Table 6 is enumerated is the reading of the energy intensity surveyed by the gauging table that is positioned at the substrate surface.1,4 and 7 three position among Fig. 4 and the distance of left end are 7.0 centimetres approximately.3,6 and 9 three positions among Fig. 4 and the distance of right-hand member are 5.5 centimetres approximately.Among Fig. 42,5,8 three positions are placed in the middle, with the distance at two ends be 17.5 centimetres approximately.

Table 6

Background (μ W)	Reading (mW/cm ²)
Background (μ W)	Reading (mW/cm ²)	????23.46 ????16.12 ????17.39 ????20.19 ????16.45 ????20.42 ????18.33 ????15.50 ????20.90	????9.32 ????9.31 ????9.32 ????9.31 ????9.29 ????9.31 ????9.32 ????9.30 ????9.34

Embodiment 12

What present embodiment illustrated is 222 nanometer excite state atomic lamps shown in Figure 5, and the light intensity that is produced on a substrate surface is the function of the distance of substrate and lamp.These light intensities are enough to make the generation of the colorant in institute's present composition variable color on the substrate surface.Excite state atomic lamp 10 is made up of lampshade 15 and four parallel arranged, the excite state atomic lamp 20 that is about 30cm.These excite state atomic lamps are cooled off by the recirculated water of flow through its center or internal pipeline (not marking in the drawings), make it a relatively low temperature, promptly about 50 ℃ of work down.The energy density of excite state atomic lamp outside surface is generally at every square metre of (J/m of about 4-20 joule ²) scope in.

What table 7 was enumerated is on position shown in Figure 61, is positioned at the intensity reading that the gauging table on substrate surface is surveyed.In Fig. 5, position 1 is positioned at the center, and the distance at itself and two ends is about 17cm.

Table 7

Distance (cm)	Background (μ W)	Reading (mW/cm ²)
Distance (cm)	Background (μ W)	Reading (mW/cm ²)	????5.5 ????6.0 ????10 ????15 ????20 ????25 ????30 ????35 ????40 ????50	????18.85 ????15.78 ????18.60 ????20.90 ????21.67 ????19.86 ????22.50 ????26.28 ????24.71 ????26.95	????9.30 ????9.32 ????9.32 ????9.38 ????9.48 ????9.69 ????11.14 ????9.10 ????7.58 ????5.20

The present invention is after above explanation, and those are conspicuous relevant changes and improvements for those of ordinary skills, all within the spirit and scope of the present invention.

Claims

1. colored composition that contains changeable colour colorant and ultraviolet transfer absorbed agent.

2. the colored composition of claim 1, it also contains the molecule occlusion body.

3. the colored composition of claim 2, wherein said molecule occlusion body is selected from clathrate compound, zeolite and cyclodextrin.

4. the colored composition of claim 2, wherein changeable colour colorant and ultraviolet transfer absorbed agent are connected with the molecule occlusion body.

5. the colored composition of claim 4, wherein colorant is at least partially contained within the cavity of molecule occlusion body.

6. the colored composition of claim 4, its middle-ultraviolet lamp transfer absorbed agent is connected with the molecule occlusion body outside cavity.

7. the colored composition of claim 6, its middle-ultraviolet lamp transfer absorbed agent links to each other with covalent bond with the molecule occlusion body.

8. method that makes the colored composition variable color, wherein colored composition contains changeable colour colorant and ultraviolet transfer absorbed agent, and this method comprises with being enough to make colorant to produce the step of ultraviolet irradiation colored composition of the dosage of irreversible change color,

9. the method for claim 8, wherein colored composition also contains the molecule occlusion body.

10. the method for claim 9, wherein colorant links to each other with the molecule occlusion body with ultraviolet transfer absorbed agent.

11. the method for claim 8, also be included in colored composition be subjected to ultraviolet irradiation before, colored composition is applied to the step of substrate.

12. the method for claim 11, wherein the colorant of variable color has stability.

13. the method for claim 10 also is included in before colored composition is subjected to ultraviolet irradiation, colored composition is applied to the step of substrate.

14. the method for claim 13, wherein the colorant of variable color has stability.

15. a toner that is used for the electrophotographic image forming process, it contains: changeable colour colorant, the carrier of ultraviolet transfer absorbed agent and colorant and ultraviolet transfer absorbed agent.

16. the toner in the claim 15, wherein carrier comprises polymkeric substance.

17. the toner of claim 15 wherein also contains charge carrier in the said composition.

18. the toner of claim 15, the ultraviolet wavelength that its middle-ultraviolet lamp transfer absorbed agent is absorbed are about 100 to about 375 nanometers.

The ultraviolet ray of discrete, the pulsed that 19. the solid colored composition of claim 18, its middle-ultraviolet lamp are dielectric field discharge excite state atomic lamp to be sent.

20. the toner of claim 15, it also contains the molecule occlusion body.

21. the toner of claim 20, wherein the changeable colour colorant links to each other with the molecule occlusion body with ultraviolet transfer absorbed agent.

22. the toner of claim 21, wherein the changeable colour colorant is at least partially contained within the cavity of molecule occlusion body.

23. the toner of claim 21, its middle-ultraviolet lamp transfer absorbed agent is that covalency links to each other with the molecule occlusion body.

24. an electrophotographic image forming method, its step comprises:

On the photoreceptor surface, generate image;

Toner is applied to the photoreceptor surface, forms the toner image of original image duplicate, contain changeable colour colorant, ultraviolet transfer absorbed agent and carrier in this toner;

Toner image is transferred on the substrate; And

Toner image is fixed on the substrate.

25. the electrophotographic image forming method of claim 24, wherein carrier comprises polymkeric substance.

26. the electrophotographic image forming method of claim 24 wherein also contains charge carrier in the composition.

27. the electrophotographic image forming method of claim 24, the ultraviolet wavelength that its middle-ultraviolet lamp transfer absorbed agent is absorbed are about 100 to about 375 nanometers.

The ultraviolet ray of discrete, the pulsed that 28. the electrophotographic image forming method of claim 27, its middle-ultraviolet lamp are dielectric field discharge excite state atomic lamp to be produced.

29. the electrophotographic image forming method of claim 24, wherein this toner also contains the molecule occlusion body.

30. the electrophotographic image forming method of claim 29, wherein the changeable colour colorant links to each other with the molecule occlusion body with ultraviolet transfer absorbed agent.

31. the electrophotographic image forming method of claim 30, wherein the changeable colour colorant is at least partially contained within the cavity of molecule occlusion body.

32. the electrophotographic image forming method of claim 30, its middle-ultraviolet lamp transfer absorbed agent is that covalency links to each other with the molecule occlusion body.

33. an electrophotographic image forming method, it comprises:

1) provide the substrate that first image that is formed by first toner is arranged thereon,

First toner comprises:

The changeable colour colorant;

The agent of ultraviolet ray transfer absorbed; With

The carrier of colorant and ultraviolet transfer absorbed agent;

2) enough to make colorant produce first image on the ultraviolet irradiation substrate of dosage of irreversible variable color;

3) on the photoreceptor surface, form second image;

4) on the photoreceptor surface, form the toner image of the second copying image product with second toner;

5) second toner image of second image is transferred on the substrate; And

6) second toner image is fixed on the substrate.

34. the electrophotographic image forming method of claim 33, wherein said carrier are polymkeric substance.

35. the electrophotographic image forming method of claim 33, wherein first toner also contains charge carrier.

36. the electrophotographic image forming method of claim 33, wherein first toner also contains the molecule occlusion body.

37. it is about 100 to about 375 nanometers that the electrophotographic image forming method of claim 33, its middle-ultraviolet lamp transfer absorbed agent absorb ultraviolet wavelength.

38. the electrophotographic image forming method of claim 37, its middle-ultraviolet lamp is the ultraviolet ray of discrete, the pulsed that produced by dielectric field discharge excite state atomic lamp.

39. the electrophotographic image forming method of claim 33, wherein second toner contains:

The second changeable colour colorant;

The second ultraviolet transfer absorbed agent; With

Second carrier of second colorant and the second ultraviolet transfer absorbed agent.

40. the electrophotographic image forming method of claim 39, wherein said second carrier is a polymkeric substance.

41. the electrophotographic image forming method of claim 39, wherein second toner contains charge carrier.

42. the electrophotographic image forming method of claim 39, wherein second toner also contains the molecule occlusion body.

43. the electrophotographic image forming method of claim 39, wherein ultraviolet wavelength are about 100 to about 375 nanometers.

44. the electrophotographic image forming method of claim 43, the ultraviolet wavelength that its middle-ultraviolet lamp transfer absorbed agent is absorbed are about 100 to about 375 nanometers.

45. a substrate that has on it by the formed image of colored composition, this colored composition contains changeable colour colorant and ultraviolet transfer absorbed agent.

46. the substrate of claim 45, wherein said colored composition also contains the molecule occlusion body.

47. the substrate of claim 46, wherein said molecule occlusion body is selected from clathrate compound, zeolite and cyclodextrin.

48. the substrate of claim 46, wherein changeable colour colorant and ultraviolet transfer absorbed agent are connected with the molecule occlusion body.

49. a substrate that has on it by the formed image of electrophotographic image forming toner, this electrophotographic image forming toner contains the carrier of changeable colour colorant, ultraviolet transfer absorbed agent and changeable colour colorant and ultraviolet transfer absorbed agent.

50. the substrate of claim 49, wherein said carrier includes polymkeric substance.

51. the substrate of claim 49, wherein said toner also contains charge carrier.

52. the substrate of claim 49, wherein this toner also contains the molecule occlusion body.

53. the substrate of claim 52, wherein said molecule occlusion body is selected from clathrate compound, zeolite and cyclodextrin.

54. the substrate of claim 52, wherein changeable colour colorant and ultraviolet transfer absorbed agent are connected with the molecule occlusion body.

55. a ultraviolet transfer absorbed agent, it contains the wavelength that combines and selects sensitive agent and light reaction agent.

56. the ultraviolet transfer absorbed agent of claim 55, its medium wavelength select sensitive agent to link to each other with light reaction agent covalency.

57. the ultraviolet transfer absorbed agent of claim 55, the ultraviolet wavelength that its medium wavelength selects sensitive agent to absorb are about 100 to about 375 nanometers.

58. the ultraviolet transfer absorbed agent of claim 57, its middle-ultraviolet lamp be by dielectric field discharge excite state atomic lamp produced discrete, pulsed is ultraviolet.

59. the ultraviolet transfer absorbed agent of claim 55, wherein said wavelength select sensitive agent to be selected from phthalyl glycine and 4-(4-oxygen phenyl)-2-butanone.

60. the ultraviolet transfer absorbed agent of claim 55, wherein the light reaction agent is selected from (4-(2 hydroxyl-oxethyl) phenyl)-2-hydroxy-2-methyl third-1-ketone and cyclohexyl phenyl ketone ester.

61. the ultraviolet transfer absorbed agent of claim 55, wherein said transfer absorbed agent are phthalyl glycyl-1-(4-(2-hydroxyl-oxethyl) phenyl)-2-hydroxy-2-methyl third-1-ketone.

62. the ultraviolet transfer absorbed agent of claim 55, wherein said transfer absorbed agent are phthalyl glycyl-cyclohexyl-phenyl ketone ester.

63. the ultraviolet transfer absorbed agent of claim 55, wherein said transfer absorbed agent are 4-(4-oxygen phenyl)-2-butanone-1-(4-(2-oxygen ethyl) phenyl)-2-hydroxy-2-methyl-third-1-ketone ester.

64. the ultraviolet transfer absorbed agent of claim 55, wherein said transfer absorbed agent are 4-(4-oxygen phenyl)-2-butanone-1-cyclohexyl--phenyl ketone ester.