AU627182B2 - Electrostatic method for multicolor imaging from a single toner bath - Google Patents

Description

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OPI DATE 16/10/89 WORI AOJP DATE 09/11/89 APPLN. ID 35306 89 r s r i 4 PCr PCT NUMBER PCT/US89/01227 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PC'I) (51) International Patent Classification 4: (11) International Publication Number: WO 89/ 09433 G03G 13/01, 9/08 Al (43) International Publication Date: 5 October 1989 (05.10.89) (21) International Application Number: PCT/US89/01227 30 Mansfield Drive, Northford, CT 06032 (US).

(22) International Filing Date: 22 March 1989 (22.03.89) (74) Agents: CARLSON, Dale, Lynn et al.; Olin Corporation, 350 Knotter Drive, P.O. Box 586, Cheshire, CT (31) Priority Application Numbers: 171,614 06410-0586 (US).

274,542 308,713 (81) Designated States: AT (European patent), AU, BB, BE (European patent), BF (OAPI patent), BG, BJ (OAPI (32) Priority Dates: 23 March 1988 (23.03.88) patent), BR, CF (OAPI patent), CG (OAPI patent), 21 November 1988 (21.11.88) CH (European patent), CM (OAPI patent), DE (Eu- February 1989 (10.02.89) ropean patent), DK, FI, FR (European patent), GA (OAPI patent), GB (European patent), HU, IT (Euro- (33) Priority Country: US pean patent), JP, KP, KR, LK, LU (European patent), MC, MG, ML (OAPI patent), MR (OAPI pa- (71) Applicant: OLIN CORPORATION [US/US]; 350 tent), MW, NL (European patent), NO, RO, SD, SE Knother Drive, P.O. Box 586, Cheshire, CT (European patent), SN (OAPI patent), SU, TD (OAPI 06410-0586 patent), TG (OAF; patent).

(72) Inventors: WING, Feagin, Jr. 20 Terrie Road, Far- Published mington, CT 06032 DAY, Roger, W. 503 Wild With international search report.

Oak Court, Louisville, KY 40222 BURT, Willard, F. 46 Concord Street, Bristol, CT 06010 (US).

GROSSO, Paul, V. 19 Farmstead Lane, West Hartford, CT 06117 MORGAN, Michael, J. (54) Title: ELECTROSTATIC METHOD FOR MULTICOLOR IMAGING FROM A SINGLE TONER BATH (57) Abstract An electrostatic method is disclosed for providing multicolor imaging from a single toner bath. The toner bath is a blend of individual toners, each of which contains a color precursor different from the others. This invention also relates to electrostatic imaging systems, and, more particularly, color-self-developing toner particles and processes for the fabrication and use thereof. A blend of these toner paiticles is useful in multicolor electrostatic imaging using a single dry or liquid toner bath. Potential applications include full-color xerographic copying, full-color printing, full-color computer-gen-.

erated imaging, and the like.

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i b-i L~ WO 89/09433 PCT/US89/01227 -1- ELECTROSTATIC METHOD FOR MULTICOLOR IMAGING FROM A SINGLE TONER BATH" This invention relates generally to electrostatic imaging systems and, more particularly, to a method for providing multicolor imaging from a single toner medium using microencapsulated toner.

Conventional multicolor electrostatic imaging systems utilize a separate toner bath to develop each desired color. This use of separate toner baths is relatively expensive from the standpoint of equipment complexity, cost, maintenance, and processing time expended. It also requires multiple mechanical registrations to produce the multicolor image--a requirement fraught with the potential for error.

As an alternative to the use of toners and electrostatic imaging, a recent development in the industry utilizes an imaging sheet of paper completely coated on one side with microencapsulated color precursors. A portion of the microcapsules on the sheet is selectively hardened by exposure to light. The microcapsules having the desired color precursor in the image areas have liquid cores which remain unhardened.

These unhardened microcapsules are then ruptured to release liquid color precursor. The thus-released color precursor is contacted with a color developer to provide the color image, generally by transfer to a developer sheet via pressure contact of the imaging sheet with the developer sheet. Alternately, the color precursori.

WO 89/09433 PCT/US89/01227 w -2containing capsules are coated directly on a layer of developer material, which itself had previously been coated on a paper support.

By way of illustration, such a transfer imaging system containing microencapsulated color precursors is disclosed in U.S. Patent 4,554,235, assigned to Mead Corporation. In a variation of this type of system, U.S. Patent 4,501,809, assigned to Mitsubishi Paper Company, discloses a recording sheet containing two different types of photo- and pressure-sensitive microcapsules--one set containing color precursors and the other set containing color developer. Upon rupture of unhardened microcapsules on the recording sheet after selective exposure of the recording sheet to light in imagewise registration with an image to be copied, a color image is formed on the recording sheet.

The color imaging systems illustrated by the above-cited patents possess a common disadvantage. Both systems utilize an imaging or developer sheet containing microcapsules across a full surface of the sheet. Since in many color imaging applications the desired color image rarely occupies the full sheet, and, indeed, often occupies less than half of the full sheet, there is ao significant amount of waste attributable to the unused microcapsules and associated color precursor or developer contained on the non-imaged areas of the sheet. In addition, there is a substantial time and energy waste attributable to the need for photohardening the "unused" waste microcapsules using, for example, a scanning laser.

In view of the above, a new system for multicolor imaging utilizing microcapsules which does not result in such substantial waste of microcapsules and the i i j ;i c i i i -s WO 89/09433 PCr/US89/01227 Is~I a j :i

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-3associated colorant materials, plus wasted time and energy due to the need for photohardening of the waste microcapsules, would be highly desired by the color imaging community.

In one aspect, the present invention relates to a color imaging method which comprises the steps of: forming a latent image on a photoreceptor substrate, in any of a variety of known manners, for example by depositing a charge on a photoconductor and imagewise discharging, or imagewise depositing a charge on a dielectric material, electrostatically depositing a blended toner composition onto a charged or uncharged surface of said substrate to form a toned image which is a positive or reverse image as compared to said latent image, said blended toner composition comprising at least two different toners, each of said toners comprising a different color precursor contained in photo-sensitive toner particles, selectively photohardening or photosoftening at least a portion of said toner particles by imagewise exposure to appropriate wavelengths of radiation to provide harder toner particles and softer, rupturable toner particles, transferring said harder toner particles and said rupturable toner particles to a copy surface, ii i:91 d i;:t :14 8 P' i; ii:; i' L i- WO 89/09433 PCT/US89/01227 -4rupturing at least a portion of said rupturable toner particles on said copy surface to release color precursor(s) from said rupturable toner particles, and contacting said released color precursor(s) on said copy surface with a developer to form a color image on said copy surface.

In another aspect, step of the above method is effected before carrying out step Carrying out step before step is also within the scope of this invention, as are other orders for the steps.

In yet another aspect, the present invention relates to a developer-bearing microcapsular toner particle comprising a shell and a core, said shell being fabricated of a polymer, and said core comprising as a color precursor a colorless, chromogenic material, and additionally containing a radiation-sensitive material, said chromogenic material being capable of becoming colored upon contact with a developer, said shell possessing a charge characteristic to render said toner particle electrostatically depositable, said shell having.

a developer on the outer surface thereof, the shell of said microcapsule being rupturable to release said chromogenic material, thereby contacting and reacting said released chromogenic material with said developer to form a colored image.

In yet another aspect, the present invention relates to a blend of the above developer-bearing microcapsular toner particles, said blend comprising at least two, but more usually three or four, types of toner particles, each of said types containing a different i i .i i ij'lj a-s diJ ii' ii ii I_:I I_ 1 c i WO 89/09433 PCT/US89/01227 color precursor (preferably selected from the group consisting of cyan, yellow, magenta, and optionally additionally black), each of said types of particle additionally containing a photosensitive composition that is light-sensitive at wavelengths distinct from the wavelengths of light-sensitivity of the photosensitive composition contained in each of the other types of particles in the blend.

In yet another aspect, the present invention comprises a process for making the above developerbearing microcapsular toner particle which comprises coating a microcapsular toner particle with a color developer, by contacting a microcapsular toner particle with an.acidic or complexing developer.

In yet another aspect, the present invention relates to a color imaging method which comprises the steps of: forming a latent image on a photoconductive or dielectric substrate, in any of a variety of known manners, for example, by depositing a charge on a photoconductor and imagewise discharging,or imagewise depositing a charge on a dielectric material, electrostatically depositing a blended toner composition onto a charged or uncharged surface of said substrate to form a toned image which is a positive or reverse image as compared to said latent image, said blended toner composition comprising at least two different toners, each of said toners comprising a olor L 1 II WO 89/09433 PCT/US89/01227 v -6precursor contained in photo-sensitive toner particles, said toner particles containing a developer on the surface thereof, selectively photohardening or photosoftening at least a portion of said toner particles by imagewise exposure to appropriate wavelengths of radiation to provide harder toner particles and softer, rupturable toner particles, transferring said harder toner particles and said rupturable toner particles to a copy surface, and rupturing at least a portion of said toner particles on said copy surface to release color precursor(s) from said rupturable toner particles, thereby contacting and reacting said developer with said released color precursor(s) to form a color image on said copy surface.

In yet another aspect, the present invention relates to a color imaging method which comprises.the steps of: forming a latent image on a photoconductive or dielectric substrate, in any of a variety of known manners, for example, by depositing a charge on a photoconductor and imagewise discharging, or imagewise depositing a charge on a dielectric material, electrostatically depositing a blended toner composition onto a charged or uncharged surface of said substrate to C i I g~ WO 89/09433 PCT/US89/01227 -7form a toned image which is a positive or reverse image as compared to said latent image, said blended toner composition comprising at least two different toners, each of said toners comprising a color precursor contained in photo-sensitive toner particles, said toner particles containing a developer on the surface thereof, selectively photohardening or photos.ftening at least a portion of said toner particles by imagewise exposure to appropriate wavelengths of radiation to provide harder toner particles and softer, rupturable toner particles, rupturing at least a portion of said toner particles on said substrate to release color precursor(s) from said rupturable toner particles, thereby contacting and reacting said developer with said released color precursor(s) to form a color image on said substrate, and transferring said color image to a copy surface.

In yet another aspect, the present invention a color imaging method which comprises the forming a latent image on a photoconductive or dielectric substrate, in any of a variety of known manners, for example, by depositing a charge on a photoconductor and imagewise discharging, or imagewise depositing a charge on a dielectric material, relates to steps of: WO 89/09433 PCT/US9/01227 i -8-i electrostatically depositing a blended toner composition onto a charged or uncharged surface of said substrate to form a toned image which is a positive or reverse image as compared to said latent image, said blended toner composition comprising at least two different toners, each of said toners comprising a color precursor contained in photo-sensitive io toner particles, said toner particles containing a developer on the surface thereof, transferring said toned image to a copy surface, selectively photohardening or photosoftening at least a portion of said toner particles by imagewise exposure to appropriate wavelengths of radiation to provide harder toner particles and softer, rupturable toner particles, and rupturing at least a portion of said toner particles on said copy surface to release color precursor(s) from said i rupturable toner particles, thereby contacting and reacting said developer with said released color precursor(s) to form a color image on said copy surface.

In accordance with the present invention, it has now been surprisingly found that multicolor images can be formed using a single toner medium. The toner medium is a blend of 2, 3, 4, or more types of colorforming toner particles that are also photo-sensitive.

The relative simplicity and economy of this technique is

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WO 89/09433 PCT/US89/01227 -9expected by the present inventors to make it of significant benefit to the color imaging systems community. Key advantages of this invention include the ability to: utilize a single toner bath for multicolor imaging selectively limit the use of toner on the imaging or developer sheet to areas on the sheet where an image is desired, and avoid the need for multiple mechanical registrations for multicolor imaging.

The toner composition useful in the method of the present invention is a toner blend. This blend contains at least two different types of toner particles in order to provide at least two (preferably at least three or four) different color precursors. As used herein, the term "toner particle" is intended to designate any of a variety of particle forms which can be used to contain or carry and isolate color precursors.

Typical examples of particle forms are microcapsules, microsponges, softenable solid particles, and emulsion micelles. A "toner blend" or "blended toner" designates a mixture of different color-forming toner particles or toners which enables multicolor imaging using a single toner blend. If full-color imaging capability is desired, three or four (cyan, yellow, magenta, and optionally black) color precursors are typically utilized, each toner particle preferably containing one color precursor. Other color precursors red, green, or blue) can be used as desired. Either a liquid or a dry toner blend can be used.

The method of the present invention provides the above-described advantageous result using a multi-step method of color imaging. In the first two steps, a latent image and then an uncolored, toned image ri

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WO 89/09433 PCT/US89/01227 1 0are formed in typical electrostatic fashion on a support, typically a drum, web, or sheet. In the subsequent steps, the desired color is developed by taking advantage of the photosensitivity differences of the toner particles containing the individual color precursors.

These photosensitivity differences are suitably produced by using a different photoinitiator for each separate color precursor employed in the toner blend.

In a typical electrostatic method, the latent image is formed by known means. First, a blanket positive or negative charge is typically applied to a surface photoreceptor substrate, suitably a photoconductive drum, web, or sheet, by means of a corona. Portions of the surface of the photoreceptor are then selectively discharged. This selective discharge is suitably effected using light (desirably using a laser light source). The surface of the selectively-discharged photoconductor contains a latent image on either the charged portions of the surface (for positive development) or on the uncharged portions of the surface (for reversal development). (An alternate method for forming the latent image typically uses an ion-generating if cartridge or a charging head ("stylus") to deposit charges on a dielectric substrate to provide charged and uncharged portions of the substrate, as is well-known in S the art.) Once the latent image has been formed on the photoreceptor, a toner blend having a charge characteristic either opposite from (for positive development) or the same as (for reversal development) the charge on the selectively-discharged photoreceptor is then applied onto the surface of the photoreceptor. f Typically, the toner blend is applied to the photoconductive surface from a liquid toner bath, or in the case of a dry toner by means of a magnetic brush. A WO 89/09433 PCT/US89/01227 -11variety of development methods is usable and known to practione's of the art. The photo-sensitive toned image on the photoreceptor is then selectively hardened photopolymerized) (or in some embodiments softened, i.e., photodepolymerized) by exposure to radiation of a specified wavelength. This photopolymerization or photodepolymerization is carried out to cause only toner particles containing desired color precursors to be rupturable for releasing color precursors. For example, if a yellow image is desired, the toned image will be exposed to wavelengths of light which will cause the toner particles containing the cyan, magenta, and black color precursors to be hardened. Likewise if a green image is desired, the toned image will be exposed to wavelengths of light which cause the toner particles containing the magenta and black color precursors to selectively harden. All known colors can be likewise caused to form by exposure of toner particles to the appropriate wavelengths of light and then completing the imaging process. Additionally, the deliberate creation of partially hardened toner particles will give rise to intensity variations of the color produced. The toned image, composed of both hardened (or harder) and rupturable (or softer) toner particles,-is then transferred to a copy sheet by known procedures.

For example, this transfer is suitably effected by passing the substrate to be printed, such as a copy sheet of paper or a transparent film, between the photoreceptor and a transfer corona, thereby causing the toner particles to transfer from the photoreceptor to the copy sheet.

Once on the copy sheet, the rupturable toner particles of those making up the toned image are WO 89/09433 PCT/US89/01227 -12ruptured, typically by radiation, heat, pressure or a combination of these procedures (preferably by pressure) to release the desired color precursors. These desired color precursors are then developed by contact with a developer.

In a preferred aspect, the toner particle of the present invention is "color-self-developing". The term "color-self-developing", as used herein, is intended to designate a microcapsular toner particle that will form a color upon rupture of the toner particle without the need for any external additives. To form a color image, the microcapsular toner particle is ruptured by any of several means, such as, for example, pressure, onto a surface of a substrate such as a piece of paper, thereby causing release of core material from the toner particle to cause contact between the core material and the developer contained on the external surface of the shell of the particle. Upon contact of this developer with the chromogenic material contained in the core of I the toner particle, such as an electron-donating leuco dye, color is formed in the area of the ruptured particle. A desired color image is formed by the I selective rupture of a plurality of such toner particles in an appropriate combination to produce the desired color.

The color precursors useful in the present invention are preferably oil soluble color formers which will produce a color upon reaction with a developer material in the presence of a carrier oil. Substantially any of the precursors conventionally used in carbonless paper can be used in the present invention. In general, these materials are colorless electron-donating type compounds. Representative examples of such color formers ,4

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WO 89/09433 PCT/US8901227 -13include substantially colorless compounds having in their partial skeleton a lactone, a lactam, a sultone, a spiropyran, an ester or an amido structure.

Specifically, there are triarylmethane compounds, bisphenylmethane compounds, xanthene compounds, thiazine compounds, spiropyran compounds and the like. Mixtures of the respective color precursors can be used if desired.

Some representative leuco dye color precursors which give yellow, cyan, and magenta images are shown below.

Yellow color precursors:

OCH

2

CH

0 H3C OCH3 r" r Cyan color precursors:

(CH

3 2

N

-Ny(CH3) 2 (CH 3 CH 2 )2Nb( 2 .(CH CH3) 2 32 I j i 1W WO 89/09433 PCT/US89/01227 -14- (CH CH 2 3 CH NCH 2

H)

C H

NH

Cl (CH 3 CH 2 2Nl,,rbOiIlN

N(CH

2

CH

3 2 CH 2C).

Magenta color precursors: (CH 3 CH 2 2 N 0 N (CH 3 CH 2 2

(CH

2 cH 3 2 (CH 3 CH 2 0 WO 89/09433 PCT/US89/01227 The color precursors used in the present invention must be non-absorbing with respect to the exposure radiations relied upon to cure the photosensitive encapsulate since the color precursors are either present in the encapsulate or the exposure radiation must pass through the color precursor to expose the encapsulate. Hence, colorless electrondonating type compounds are preferred for use in the present invention. Of course, a completely colorless color precursor is difficult to obtain and a small degree of coloration may be tolerated in the color precursor as long as it does not interfere with exposure.

Developer materials useful in the present invention include those conventionally employed in carbonless paper technology and are well known.

Illustrative specific examples are clay minerals such as acid clay, active clay, attapulgite, etc.; organic acids such as tannic acid, gallic acid, propyl gallate, etc.; acid polymers such as phenol-formaldehyde resins, phenol actylene condensation resins, condensates between an organic carboxylic acid having at least one hydroxy group and formaldehyde, etc.; metal salts of aromatic carboxylic acids such as zinc salicylate, tin salicylate, zinc 2-hydroxy naphthoate, zinc 3,5 di-tert butyl salicylate; oil-soluble metal salts of phenol-formaldehyde novolak resins see U.S.

Patent Nos. 3,672,935; 3,732,120; and 3,737,410) such as zinc-modified oil soluble phenol-formaldehyde resin; and mixtures thereof.

The location of the developer is not narrowly critical and can vary over a wide range as long as the i WO 89/09433 PCT/US89/01227 -16developer is separate from the color precursor until release of the color precursor. For example, the developer can be maintained on a separate developer sheet, or otherwise external to the toner particles.

Alternately, the developer can be contained inside the toner particles in separate minimicrocapsules to maintain separation from the color precursor. In yet another alternative, the developer material may be coated on individual toner particles, giving rise to self-developing particles.

The toner particles, comprising what is referred to herein as "a toner blend" or "blended toner", in one preferred embodiment typically have a shell and a core. The core preferably contains the color precursor and the photosensitive composition. The shell is generally positively or negatively charged and can be made of various materials known in the art.

Typical shell materials include, for example, melamine resins, urethanes, or urea-formaldehyde. The average size of the particles is generally between about 0.1 and about 100 microns, preferably between 0.5 and microns. For liquid toners, an average toner particle size is suitably between about 0.1 and about 10 microns whereas a particularly suitable particle size for dry toners is between about 1 and about 20 microns. i In a preferred embodiment, a developer is 1 adsorbed to, coated on, or otherwise bound to the outer surface of the shell of the toner particle.

In order to fabricate the developer-bearing toner particles of the present invention, an aqueous dispersion of minute, microcapsular toner particles is typically combined with an acidic developer or a complexing developer. In a preferred method of

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WO 89/09433 PCT/US89/01227 -17fabricating the developer-bearing toner particles, an aqueous solution of citric acid is added to an aqueous dispersion of microcapsular toner particles. The concentration of the toner particles in the aqueous dispersion is generally between about 5 and about percent by weight, preferably between about 5 and about percent by weight, and most preferably between about and about 20 percent by weight. The citric acid is suitably added to provide a citric acid concentration of between about 1 and about 10 percent by weight, preferably between about 3 and about 7 percent by weight, most preferably about 5 percent by weight based upon the total weight of the aqueous dispersion plus the citric acid. The toner particle dispersion is then suitably spray-dried. The product obtained is a dry, free-flowing powder of toner particles wherein each toner particle is coated with citric acid which functions as an acidic developer.

If desired, the dry toner particles produced as described above and containing the developer on the individual microcapsules can be dispersed in a non-polar organic solvent, such as ISOPAR(R) G or ISOPAR(R) H, products of Exxon Corporation, preferably in conjunction with other toner additives such as dispersants and/or charge-directing agents, as is known in the art, to 1 provide a liquid reprographic toner composition. When using such a liquid composition, it is preferred that the dispersed particles be in a non-polar organic medium having a low dielectric constant of 3.5 or less and a high electrical resistance of l09 Ohms-centimeters or more. Suitable organic media include the n-paraffin hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, and WO 89/09433 PCT/US89/01227 -18preferably, isoparaffin hydrocarbons, such as the above-mentioned ISOPAR(R) compounds.

In an alternate embodiment, a dry powder of microcapsular toner particles is suitably coated with a developer as follows. First, dry toner particles are suspended in an organic medium such as tetrahydrofuran (also referred to as "THF") to provide particle concentration of up to about 50 weight percent based upon the total amount of particles plus tetrahydrofuran. A developer, such as citric acid, is then added to the resulting suspension in an amount of between about 0.1 and about 3 percent, preferably about 1 percent, based upon the suspension plus citric acid.

The tetrahydrofuran is then removed by evaporation or under vacuum to provide toner particles having a developer on the surface of each particle.

Typically, the core of the toner particles contains photohardenable, photosensitive composition(s). The viscosity of the core of the toner particles is increased substantially upon exposure to the appropriate wavelengths of radiation through mechanisms such as crosslinking or polymerization. When the toner particles are ruptured, the photosensitive j composition which polymerized upon exposure to radiation will flow very little, if at all, the unexposed or weakly exposed photosensitive composition can flow relatively freely. As a direct result, the chromogenic material the color precursor) reacts with the developer according to the inverse of the degree of exposure to the appropriate wavelength of radiation to form the desired color in the desired image area.

In an alternative embodiment, the photosensitive composition can be a high-viscosity 1 WO89/09433 PCT/US89/01227 -19- Scomposition which undergoes a substantial decrease in viscosity upon exposure to actinic radiation of the appropriate wavelength. In that case, the chromogenic material located in or on the exposed toner particles, is therefore made accessible to the developer upon rupture of the particles.

The photosensitive composition includes a material which undergoes a change in viscosity upon exposure to light, either alone or in conjunction with a photoinitiator. The photosensitive composition may be photohardenable, such as a monomer, dimer, or oligomer which is polymerized to a higher-molecular-weight compound or it may be a polymer which is polymerized further, by crosslinking. Alternatively, it may be a composition which is depolymerized or otherwise made less viscous upon exposure to light. Suitable radiation-curable materials include materials curable by free radical-initiated, chain-propagated, addition polymerization or ionic polymerization.

Representative photosensitive compositions are ethylenically unsaturated organic compounds. These compounds contain at least one ethylenic group per molecule. Typically they are liquid at room temperature and can also double as a carrier oil for the chromogenic material in the toner core. A preferred group of radiation-curable materials is ethylenically unsaturated compounds having two or more ethylenic groups per molecule. Representative examples of these compounds include ethylenically unsaturated acid esters of polyhydric alcohols such as trimethylol propane triacrylate or trimethacrylate, acrylate prepolymers derived from the partial reaction of pentaerythritol with acrylic or methacrylic acid or acrylic or A. AI 1 1 1 1 j I WO 89/09433 PCT/US89/01227 1 methacrylic acid esters; isocyanate modified acrylate, methacrylic and itaconic acid esters of polyhydric alcohols, etc.

Some typical examples of photosoftenable materials useful in other embodiments are photolysable compounds such as certain diazonium compounds, poly(3-oximino-2-butanone methacrylate) which undergoes main chain scission upon UV exposure, poly(4'-alkyl acylo-phenones), and certain resins having a quinone diazide residue.

Photoinitiators are optionally used in accordance with the method of the present invention to selectively photoharden or photosoften the toner particles as desired. The photoinitiator is typically responsive to a specific wavelength and/or amount of actinic radiation. These, alone or in conjunction with a sensitizer, are compounds which absorb the exposure radiation and generate a free radical with or without the aid of co-initiator. If a system which relies upon ionic polymerization is used, the photoinitiator may be the anion- or cation-generating type, depending on the nature of the polymerization. Suitable photoinitiators include alkoxy phenyl ketones, Michler's ketone, -:i acylated oximinoketones, polycyclic quinones, benzophenones, substituted benzophenones, xanthones, thioxanthones, halogenated compounds such as chlorosulfonyl and chloromethyl polynuclear aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethyl benzophenones and fluorenones, haloalkanes, halo-phenylacetophenones; photoreducible dye/reducing agent redox couples, halogenated paraffins brominated or chlorinated paraffin) and benzoin alkyl ethers.

L WO 89/09433 PCT/US89/01227 -21- If used, the amount of photoinitiator employed in the photosensitive composition to initiate polymerization photoharden) or depolymerization photosoften) of the photosensitive composition in the toner particles will depend upon the particular photosensitive composition selected, the particular photoinitiator selected, and the photohardening or photosoftening speed desired. The photoinitiator is preferably employed in an amount of between about 0.1 and about 30 (preferably between about 1 and about weight percent based upon the total weight of the toner particles.

Other additives can be employed in the toner particles such as carrier oils, deodorized kerosene or alkylated biphenyls. Curing agents can also be used. These are free-radical generators such as thermal initiators, which upon reacting with the photosensitive composition cause it to polymerize or crosslink. After selectively exposing the composition to actinic radiation, and rupturing the particles in the present of a developer material, the chromogenic material and the developer react to produce color in the form of an image, the curing agent then reacts with the released photosensitive composition and hardens it, thereby preventing image diffusion or degradation. In Sthe case of certain curing agents, it may be desirable to heat the image to accelerate the cure. A curing agent is preferably selected which is relatively inactive at room temperature (for good shelf life) and which is readily activated by heating to temperatures in excess of room temperature.

A particularly useful class of thermal initiators reactive with ethylenically unsaturated WO 89/09433 PCT/US89/01227 -22compounds are organic peroxides. Suitable peroxides include diacyl peroxides, ketone peroxides, peroxydicarbonates, alkyl peroxides, allyl hydroperoxides and sulfonyl peroxides. Also useful as thermal initiators are bisazides, perborates and diazo compounds.

The method of the present invention is expected to have commercial application in making full-color prints, transparencies and slides, as well as full-color computer-generated images and full-color xerographic copies.

The following examples are intended to illustrate, but in no way limit the scope of, the present invention.

ful-coor ompuer-enerted mags an ful-coor WO 89/09433 PCT/US89/01227 -23- SEXAMPLE 1 Preparation of Individual Toners, Followed by Toner Blend Preparation and Multicolor Imaging Using the Toner Blend Aqueous Preparation of Blue-Color-Forming Toner Particles Blue-color-forming toner particles, which were photosensitive to near-ultraviolet radiation, were prepared in water in the following manner. A solution was prepared by dissolving 5.0 g of ethylene-maleic anhydride copolymer (1:1 mole ratio; 80,000 MW) and 1.0 g of sodium hydroxide in 45.0 g of water with stirring and heating at 90 0 C for two hours. Then 100 g of water was added and the solution cooled to 55°C. The pH was adjusted from 4.3 to 4.00 with 10 percent sulfuric acid and the temperature was maintained at 55 C until the solution was used. The toner core solution was prepared by first mixing 60.14 g of trimethylolpropane triacrylate (TMPTA) and 16.55 g of methyl methacrylate (MMA). To this was added 4.52 g of COPIKEM(R) IX (a product of Hilton-Davis), a blue-dye precursor, which was dissolved by heating to 750C and strirring. After the dye precursor was dissolved, this solution was allowed to cool to room temperature. Then 5.20 g of Michler's ketone, a UV-sensitive photoinitiator, was added with stirring that was continued until the photoinitiator dissolved. 37.53 g of CYMEL(R) 385 (a modified melamine-formaldehyde resin, a product of American Cyanamid) was warmed to about The solution of ethylene-maleic anhydride copolymer was added to a jacketed blender which was heated to 55°C by means of circulated water. The WO 89/09433 PCT/US89/01227 -24blender power setting was controlled to 40 volts by means of a variable transformer. Next, the core solution was added and the blender power setting was increased to volts for 45 seconds to disperse the core liquid into small droplets. The blender power was reduced to volts and the CYMEL(R) 385 (a modified melamine-formaldehyde resin, a product of American Cyanamid) was added to the blender. Stirring and heating at 55°C were then continued for two hours.

The blue-color-forming toner particles were later isolated as a dry powder by spray drying.

Agueous Preparation of Magenta-Color- Forming Toner Particles Magenta-color-forming toner particles, which were photosensitive to blue light, were prepared in water in the following manner. A solution was prepared by dissolving 5.0 g of ethylene-maleic anhydride copolymer and 1.0 g of sodium hydroxide in 45.0 g of water by stirring and heating at 85 C for two hours. To this was added 100 g of water and the temperature was adjusted to 55 0 C. The pH was adjusted from 4.27 to 4.00 with percent sulfuric acid and the temperature was maintained at 55°C until the solution was used. The toner core solution was prepared by first mi~ring 60.11 g of trimethylolpropane triacrylate and 16.56 g of methyl methacrylate. To this was added 4.52 g of COPIKEMR) XX (a product of Hilton-Davis), a magenta dye precursor, which was dissolved by heating to 75°C and stirring.

After the dye precursor dissolved, the mixture was cooled to room temperature a:;d 2.64 g of camphorquinone and 2.37 g of triethanolamine were added. Stirring was continued until the photoinitiator and hydrogen doner dissolved.

A WO 89/09433 PCT/US89/01227 ite solution prepared from the ethylenemaleic anhydride copolymer was added to a jacketed blender which was heated and maintained at 55 C by means of circulated water. The blender power setting was controlled to 40 volts by means of a variable transformer. Next, the core solution was added and the blender power setting was increased to 90 volts for seconds to disperse the core liquid into small droplets.

The blender power was reduced to 40 volts and 37.4 g of CYMEL(R) 385 (a modified melamine-formaldehyde resin, a product of American Cyanamid), which had been preheated to about 50 0 C, was added to the blender. Stirring and heating at 55°C were then continued for two hours.

The magenta-color-forming toner particles were later isolated as a dry powder by spray drying.

Preparation of the Toner Blend and Electrostatic Photoselective Formation of a Multicolored Image A liquid blended toner was prepared by combining 2.0 g of the dry, blue-color-forming toner powder prepared as in Section 2.0 g of the dry, magenta-color-forming toner powder prepared as in Section and 196 g of a liquid hydrocarbon having a low dielectric contant, ISOPARG(R) (a product of Exxon Chemical Company). This mixture was first stirred in a beaker and then transferred to a jar and shaken.

A charged latent image was formed on a sheet of electrostatic paper (a product of Versatec Inc.) by means of a steel piece, 1-1/2 inches wide by 3 inches long, which was connected to a DC power supply set at 750 volts. The electrostatic paper was laid on a flat i^ril.i_-l.i-.IIl I i ii .iii I i WO: 89/09433 PCT/US89101227 -26aluminum ground plate and the steel piece, which was connected to the positive lead from the power supply, was held in contact with the paper surface for 60 seconds with the power on. The paper was then dipped into the liquid blended toner. Upon removal of the paper, a non-colored toned image was visible which exactly corresponded in area and location to the place of contact by the charged, steel piece. The toned image on the sheet was allowed to dry at room temperature.

Color-imagewise exposure of the non-colored, toned image was carried out in the following manner (see TABLE I below). The area upon which the toner had been deposited was covered by a contact mask (Mask A) which was subdivided into four areas with Areas 1 and 4 being opaque and Areas 2 and 3 being transparent. The mask was then covered with a glass, band-pass filter (Filter A) (Model No. 51800, a product of Oriel Corporation) which i! only passed light having wavelengths between 225 and 400 nm The toned image area was then irradiated i through Filter A and Mask A with a mercury lamp. Thus, Areas 2 and 3 were exposed to light of 225-400 nm and Areas 1 and 4 were not. Filter A and Mask A were then removed and the toned image area was then covered by a 1 mask (Mask Mask B had four areas corresponding to !i Areas 1-4 of Mask A except that in Mask B, Areas 1 and 3 were opaque and Areas 2 and 4 were transparent. This mask was then covered with a glass, long-pass filter (Filter B) (Model No. 51482, a product of Oriel Corporation) which only passed light with wavelengths greater than 420 nm. The toned image area was then irradiated through Filter B and Mask B with the same mercury lamp as before. Thus, Areas 2 and 4 were exposed to light of wavelengths greater than 420 nm and Areas 1 and 3 were not. Filter B and Mask B were then removed.

iY" j L 1 L. C i I r i k WO 89/09433 PCT/US89/01227 -27- In the areas exposed to the UV light (225-400 nm through Filter the blue-color-forming toner particles were hardened because they contained a photoinitiator sensitive to the UV light. In the areas exposed to the light of wavelength greater than 420 nm, the magenta-color-forming toner particles were hardened because they contained a photoinitiator sensitive to blue light.

The toned image area was then placed in contact with a developer sheet (20 white, NCR paper (TM) supplied by Appleton Papers, Inc.) and pressure was then applied to rupture the toner particles that had not been hardened. This resulted in an image that had purple (subtractive combination of blue and magenta), white, magenta, and blue areas. The purple color was produced in Area 1, which was not irradiated in either exposure.

Thus, neither type of toner particle was hardened. The white region was produced in Area 2 which was irradiated by both exposures, thus hardening both types of toner particles. The magenta color was produced in Area 3, I which was irradiated during only the first exposure, thus causing only the blue-color-forming toner particles to be hardened. The blue color was produced in Area 4, which was irradiated during only the second exposure, thus causing only the magenta-color-forming toner particles to be hardened.

The results in terms of the color produced for each of the various areas of the image are summarized in TABLE I.below.

n i-i -1 WO 89/043 PCT/US89/01227 -28- TABLE I First Exposure Filter A Area Mask A nm Second Exposure Filter B Mask B nm Color- Former Hardened Color Produced 1 opaque 2 transparent 3 transparent 4 opaque 300-400 300-400 opaque transparent opaque transparent none both purple white 420 blue magenta 420 magenta blue Note that the resulting colors included purple, magenta, and blue, as well as a portion of the image having the white coloration of the paper.

EXAMPLE 2 Proposed Example for Multicolor Imaging Using a Toner Blend Containing Microencapsulated Precursors for Three Different Colors In an analogous manner as described above, multicolor images are formed using a single toner bath comprised of a mixture of three different encapsulated toners, each containing either a cyan, magenta or yellow dye precursor. All three toners are co-deposited from a toner blend during the electrostatic imaging. Each color-producing toner in the blend contains a specific photoinitiator (or photoinitiator-sensitizer system) sensitive to a given wavelength distinct from the other (generally two or more) photoinitiator(s) contained in the other color toner particles in the blend. Thtee or -ir -29- more different lasers, each with a wavelength corresponding to that causing reaction of one of the photoinitiators are then used to selectively harden toner particles within the toned image. The toned and exposed image is then developed as described in the preceding examples to provide a multicolor image. Thus,for example, in a given region laser irradiation producing photohardening of the cyan-producing toner particles only would yield the color red in the final image by the release of yellow and magenta, while yellow would be produced by a region in which both the cyan-producing toner particles and the magenta-producing toner particles were hardened by the appropriate laser exposures. A lamp and filters could also be used in place of the lasers if desired. Imaging could also occur by transmitted or reflected light. A toner producing black could also be included in the toner blend and utilized in the same manner if desired.

EXAMPLE 3 Aqueous Preparation of Blue-Color-Forming Toner Particles Blue-color-forming toner particles, which were photosensitive to near-ultraviolet radiation, were prepared in water in the following manner. A solution was prepared by dissolving 5.0 g of ethylene-maleic anhydride copolymer (1:1 mole ratio; 80,000 MW) and 1.0 g of sodium hydroxide in 45.0 g of water with stirring and heating at 90 C for two hours. Then 100 g of water was added and the solution cooled to 55 0 C. The pH was adjusted from 4.3 to 4.00 with 10 percent sulfuric acid and the temperature was maintained at 55 C until the solution was used. The toner core solution was prepared iae sthndeelpd sdecibd nth reein WO 89/09433 PCT/US89/01227 by first mixing 60.14 g of trimethylolpropane triacrylate (TMPTA) and 16.55 g of methyl methacrylate (MMA). To this was added 4.52 g of COPIKEM(R) IX (a product of Hilton-Davis), a blue-dye precursor, which was dissolved by heating to 75°C and strirring. After the dye precursor was dissolved, this solution was allowed to cool to room temperature. Then 5.20 g of Michler's ketone, a UV-sensitive photoinitiator, was added with stirring that was continued until the photoinitiator dissolved. 37.53 g of CYMEL(R) 385 (a modified melamine-formaldehyde resin, a product of American Cyanamid) was warmed to about 50 0

C.

The solution of ethylene-maleic anhydride copolymer was added to a jacketed blender which washeated to 550C by means of circulated water. The blender power setting was controlled to 40 volts by means of a variable transformer. Next, the core solution was added and the blender power setting was increased to 90 volts for 45 seconds to disperse the core liquid into small droplets. The blender power was reduced to 40 volts and the CYMEL(R) 385 was added to the blender. Stirring and heating at 55 C were then continued for two hours.

The blue-color-forming toner particles were later isolated as a dry powder by spray drying.

EXAMPLE 4 Spray Drying an Aqueous Suspension of Toner Particles Treated With Citric Acid and Demonstration of Color-Self-Developing Using These Particles 20 ml of an aqueous suspension of magenta-color-forming toner particles containing in~rr-c-- 7 WO 89/09433 PCT/US89/01227 -31approximately 20 percent solids was diluted by 50 percent with water. To this was added 1.0 g of anhydrous citric acid. The mixture was stirred for 15 minutes at room temperature to dissolve the citric acid. Next the solution was spray dried and the solids, slightly pink particles, were collected. Scraping or crushing the particles against a sheet of plain paper caused the development of a deep magenta color.

EXAMPLE Preparation of Color-Self-Developing Toner Particles in a Non-Aqueous Medium and Color Development Therewith Another approach to produce color-selfdeveloping toner particles was to dissolve the citric acid in THF (tetrahydrofuran) and add this to the particles along with a dispersant. The system was then diluted with ISOPAR(R G, an isoparaffinic liquid, and the THF was removed by rotary evaporation. A batch of these particles was prepared by treating 0.1 g of particles with five drops of a 1 percent solution of citric acid in THF (1.8 mg citric acid). 0.05 g ZELEC) UN (an acidic phosphate ester, a product of E.

I. du Pont de Nemours Co.) was also added as a dispersant. The mixture was then diluted with 10 g of ISOPAR(R) and the THF was removed. These toner particles were applied to plain paper. After evaporation of the ISOPAR(R), a weighing paper was placed on top of this sheet and pen pressure was applied. This resulted in magenta-colored lines developing on tne plain paper.

L AA WO89/09433 PCT/US89/01227 i -32- EXAMPLE 6 Preparation of a Color-Self-Developing Toner Blend and Electrostatic, Photoselective Formation of A Multi-Colored Image Magenta-forming, color-self-developing toner particles and yellow-forming, color-self-developing toner particles were isolated as a powder by spray-drying as in Example 1 or 2. A mixture of spray-dried, color-self-developing toner particles, made up of one part magenta-forming particles and one part yellow-forming particles, was prepared. 3.0 g of a percent ISOPAR(R) H solution of SOLSPERSE(R) 21000 (a dispersant manufactured by ICI) were added to 1.17 g of the toner particle mixture. 60 g of ISOPAR(R) H were added and the entire mixture sonicated to form a dispersion of toner particles, 0.2 g of ZELEC(R) UN in mL of ISOPAR(R) H isoparaffinic liquid were added, followed by further sonication. The resulting toner particle dispersion was utilized as a toner blend to produce images electrostatically.

A latent image was formed on a piece of dielectric paper (4008-F T electrographic paper, a product of Versatec, Inc.) using a corona-charging technique. A sheet of MYLAR(R) having the letter "0"11 cut into it was laid on the dielectric paper. A corona connected to a +9000 V power supply was passed over the cut-out region several times, resulting in the formation of a charged area of the paper in the shape of the cut-out The dielectric paper was immersed in the above toner blend for several seconds. The paper, 1 ar L I b;r ~jur~u~ ~i; WO 89/09433 PCT/US89/01227 -33bearing a toned, colorless image was then dried to remove ISOPAR(R) H isoparaffinic liquid by briefly placing it in an oven at a temperature of A portion of the toned image was covered by an opaque mask and the paper was exposed to the output of a 100 W BLAK-RAY(R) lamp (manufactured by Ultra-Violet Products) for two minutes at a distance of 5 inches. The light was filtered using a long-pass filter that allowed only wavelengths longer than 420 nm to pass (Oriel Corporation, Model #51482). The yellow-forming, self-developing toner particles, containing camphoroquinone (a photoinitiator sensitive to 480 nm light) were hardened in the irradiated regions. The magenta-forming, self-developing toner particles were not hardened in either the irradiated or masked regions of the toned image, since these magenta-forming particles contained Michler's ketone as a photoinitiator to make these particles sensitive to 350 40 nm light.

The selectively hardened toned image on the paper was run through a nip roll, after covering the toned image with a piece of weighing paper to prevent toner particles sticking to the rolls during pressure development. The final electrostatically produced image was red where it had been shielded from the light (the subtractive combination of magenta and yellow) and magenta where the yellow-forming, self-color-developing toner particles had been hardened by irradiation.

I'

-U _Ci: L i P.

Claims (37)

1. A color imaging method characterized by forming a latent image on a photoconductive or dielectric substrate, electrostatically depositing a blended toner composition onto a charged or uncharged surface of said substrate to form a toned image which is a positive or reverse image as compared to said latent image, said blended toner composition comprising at least two different toners, each of said toners comprising a color precursGr contained in photo-sensitive toner particles, selectively photohardening or photosoftening at least a portion of said toner particles by imagewise exposure to appropriate wavelengths of radiation to provide harder toner particles and softer, rupturable toner particles, transferring said harder toner particles and said rupturable toner particles to a copy surface, rupturing at least a portion of said toner particles on said copy surface to release color precursor(s) from said rupturable toner particles, and contacting said released color precursor(s) on said copy surface with a developer, thereby causing said released iji ii,:i i: i :i an i, I iS I~ 1 35 color precursor(s) and said color developer to react to form a color image on said copy surface.

2. A method according to claim 1 wherein said blended toner composition comprises at least three types of toner particles, each of said types containing a different color precursor, and each of said types additionally containing a radiation-sensitive composition.

3. A method according to claim 2 wherein each of said types of toner particles contains a different color precursor selected from the group consisting of cyan, yellow, magenta, and optionally additionally black.

4. A method according to claim 2 or 3 wherein said radiation-sensitive material is a photohardenable or S: photosoftenable material and includes a photoinitiator for each of said types of toner particles, said photoinitiator .O being sensitive to a given wavelength of light distinct from the light sensitivity of each other photoinitiator contained in each other of said types of toner particles.

5. A method according to claim 4 wherein said radiation-sensitive composition is photohardenable and consists essentially of a photoinitiator and a polymerizable or crosslinkable material.

6. A method according to claim 4 wherein said radiation-sensitive material is photosoftenable and consists essentially of a depolymerizable material. WDN 4 V II I~ 7: WO 89/09433 PCT/US89/01227 ;t i i:B E S .i i; -36- ot corA ro TO i t-'e'4

7. T4e method .4 claim 6 rcha ra -redA in thAa said radiation-sensitive material additionally contains a photoinitiator. the steps of

8. A color imaging method characterized by forming a latent image on a photoconductive or dielectric substrate, electrostatically depositing a blended toner composition onto a charged or uncharged surface of said substrate to form a toned image which is a positive or reverse image as compared to said latent image, said blended toner composition comprising at least two different toners, each of said toners comprising a color precursor contained in photo-sensitive toner particles, selectively photohardening or photosoftening at least a portion of said toner particles by imagewise exposure to appropriate wavelengths of radiation to provide harder toner particles and softer, rupturable toner particles, rupturing at least a portion of said toner particles on said substrate to release color precursor(s) from said rupturable toner particles, transferring said released color precursor to a copy surface, and contacting said released color precursor(s) on said copy surface with a developer, thereby causing said released i- 1 I- 37 color precursor(s) and said color developer to react to form a color image on said copy surface.

9. A method according to claim 8 wherein said blended toner composition comprises at least three types of toner particles, each of said types containing a different color precursor, and each of said types additionally containing a radiation-sensitive composition.

A method according to claim 9 wherein each of said types of toner particles contains a different color precursor selected from the group consisting of cyan, yellow, magenta, and optionally aditionally black.

11. A method according to claim 9 or 10 wherein said radiation-sensitive material is a photohardenable or photosoftenable material and includes a photoinitiator for oo. each of said types of toner particles, said photoinitiator 2Q0 being sensitive to a given wavelength of light distinct from the light sensitivity of each othe photoinitiator contained *0 in each other of said types of toner particles.

12. A method according to claim 11 wherein said radiation-sensitive composition is photohardenable and consists essentially of a photoinitiator and a polymerizable or crosslinkable material.

13. A method according to claim 11 wherein said radiation-sensitive material is photosoftenable and consists essentially of a depolymerizable material. 39 r WDN WO 89/09433 PCT/US89/01227 -38-

14. Thkimethod e4lclaim 13Characterizd in that said radiation-sensitive material additionally contains a photoinitiator.

A color imaging method characterized by the steps of: forming a latent image on a photoconductive or dielectric substrate, electrostatically depositing a blended toner composition onto a charged or uncharged surface of said substrate to form a toned image which is a positive or reverse image as compared to said latent image, said blended toner composition comprising at least two different toners, each of said toners comprising a color precursor contained in photo-sensitive toner particles, transferring said toned image to a copy surface, selectively photohardening or photosoftening at least a portion of said toner particles by imagewise exposure to appropriate wavelengths of radiation to provide harder toner particles and softer, rupturable toner particles, rupturing at least a portion of said toner particles on said copy surface to release color precursor(s) from said rupturable toner particles, and contacting said released color A precursor(s) on said copy surface with a rs~ i 39 developer, thereby causing said released color precursor(s) and said color developer to react to form a color image on said copy surface.

16. A method according to claim 15 wherein said blended toner composition comprises at least three types of toner particles, each of said types containing a different color precursor, and each of said types additionally containing a radiation-sensitive composition.

17. A method according to claim 16 wherein each of said types of toner particles contains a different color precursor selected from the group consisting of cyan, yellow, magenta, and optionally additionally black.

18. A method according to claim 16 or 17 S wherein said radiation-sensitive material is a photohardenable or photosoftenable material and includes a photoinitiator for each of said types of toner particles, J said photoinitiator being sensitive to a given wavelength of S light distinct from the light sensitivity of each other S* photoinitiator contained in each other of said types of toner particles. i

19. A method according to claim 18 wherein said radiation-sensitive composition is photohardenable and consists essentially of a photoinitiator and a polymerizable or crosslinkable material. i SO

20. A method according to claim 18 wherein said radiation-sensitive material is photosoftenable and consists essentially of a depolymerizable material. WD39 WD s \i r:iAA 4- -40- S- 40

21. A method according to claim 20 wherein said radiation-sensitive material additionally contains a photoinitiator.

22. A method according to any one of the preceding claims wherein said blended toner composition is comprised of particle forms selected from the group consisting of microcapsules, microsponges, softenable solid particles, emulsion micelles, and combinations thereof.

23. A developer-bearing, color-self- developing, electrostatically-depositable, microcapsular toner particle comprising a shell and a core, said shell being fabricated of a polymer, and said core comprising as a color precursor a colorless, chromogenic material, and additionally containing a radiation-sensitive material, said chromogenic material being capable of becoming colored upon contact 'with a developer, said shell possessing a charge o0oo characteristic to render said toner particle electrostatically-depositable, said shell having a devloper on the outer surface thereof, the shell of said toner particle being rupturable to release said chromogenic material, thereby contacting and reacting said released chromogenic material with said developer to form a colored image.

24. A microcapsular toner particle according to 0@ *o claim 23 wherein said developer is an acidic developer or a complexing developer. ere S

25. A microcapsular toner particle according to claim 23 or 24 wherein said developer is an acidic developer S selected from the group consisting of citric n err i 3 r i ,r I kCI i ~i ii 41 acid, oxalic acid, maleic acid, gluconic acid, acrylic acid, methacrylic acid, and malonic acid.

26. A microcapsular toner particle according to claim 23 or 24 wherein said developer is a complexing developer selected from the group consisting of zinc, cobalt, and nickel salts of organic acids.

27. A blend of the microcapsular toner particles according to any one of claims 23 to 26 wherein said blend comprises at least two types of toner particles, each of said types containing a different color precursor, each of said types of toner particles additionally containing a photosensitive composition that is light-sensitive at wavelengths distinct from the wavelengths of light-sensitivity of the photosensitive composition contained in each of the other types of particles in the blend. 0

28. A blend according to claim 27, wherein at .2Q least three types of toner particles, each of said types contianing a different color precursor selected from the group consisting of cyan, yellow, magenta, and black.

29. A process for making the developer-bearing microcapsular toner particle according to claim 23 comprising coating a microcapsular toner particle with a color developer S by contacting the microcapsular toner particle with an acidic or complexing developer. .0

30. A process according to claim 2f wherein said contacting is conducted in an aqueous medium, followed by spray-drying to provide dry, developer-bearing microcapsular toner particles. S. 39 WDN I 42

31. A process according to claim2-q wherein said contacting is conducted in an organic medium, followed by removal of the organic medium to provide dry, developer-bearing microcapsular toner particles.

32. A process according to claim 31 which additionally comprises dispersing said dry, developer-bearing microcapsular toner particle in a nonpolar organic solvent.

33. A color imaging method characterized by the steps of: forming a latent image on a photoconductive or dielectric substrate, electrostatically depositing a blended toner composition onto a charged or uncharged surface of said substrate to form a toned image which is a positive or reverse image as compared to said latent image, said blended toner composition comprising at least two different toners, each of said toners comprising a color precursor contained in photosensitive toner particles, said toner particles bearing a developer on the surface thereof, selectively photohardening or photosoftening at least a portion of said #0 toner particles by imagewise exposure to appropriate wavelengths of radiation to provide harder toner particles and softer, rupturable toner particles, 4 C: WDN j 1 flu. WO 89/09433 PCT/US89/01227 -43- transferring said harder toner particles and said rupturable toner particles to a copy surface, and rupturing at least a portion of said toner particles on said copy surface to release color precursor(s) from said rupturable toner particles, thereby contacting and reacting said developer with said released color precursor(s) to form a color image on said copy surface.

34. the steps of: A color imaging method characterized by forming a latent image on a photoconductive or dielectric substrate, electrostatically depositing a blended toner composition onto a charged or uncharged surface of said substrate to form a toned image which is a positive or reverse image as compared to said latent image, said blended toner composition comprising at least two different toners, each of said toners comprising a color precursor contained in photosensitive toner particles, said toner particles bearing a developer on the surface thereof, selectively photohardening or photosoftening at least a portion of said toner particles by imagewise exposure to appropriate wavelengths of radiation to provide harder toner particles and softer, rupturable toner particles, L WO 89/09433 PCT/US89/01227 4 -44- rupturing at least a portion of said toner particles on said substrate to release color precursor(s) from said rupturable toner particles, thereby contacting and reacting said developer with said released color precursor(s) to form a color image on said substrate, and transferring said color image to a copy surface.

A color imaging method characterized by the steps of: forming a latent image on a photoconductive or dielectric substrate, electrostatically depositing a blended toner composition onto a charged or uncharged surface of said substrate to form a toned image which is a positive i or reverse image as compared to said latent image, said blended toner composition comprising at least two different toners, each of said toners comprising a color precursor contained i in photo-sensitive toner particles, said toner particles containing a developer on the surface thereof, transferring said toned image to a copy surface, selectively photohardening or photosoftening at least a portion of said toner particles by imagewise exposure to appropriate wavelengths of 45 radiation to provide harder toner particles and softer, rupturable toner particles, and rupturing at least a portion of said toner particles on said copy surface to release color precursor(s) from said rupturable toner particles, thereby contacting and reacting said developer with said released color precursor(s) to form a color image on said copy surface.

36. A method, according to any one of claims 1, 8 or 15 and 33 to 35 substantially as hereinbefore described with reference to any one of the examples.

37. A microcapsular toner particle, according to claim 23 substantially as hereinbefore described with reference to any one of the examples. *28*s DATED: 7 April, 1992 PHILLIPS ORMONDE FITZPATRICK Attorneys for: OLIN CORPORATION i f 9142N 0 39 WDN '1; .cI r i u 1l'i F7 i INTERNATIONAL SEARCH REPORT International Aoplication No. PCT/US89/01227 I. CLASSIFICATION OF SUBJECT MATTER (it several classification symools aooly, inacate all) 6 According to International Patent Classification (IPC) or to both National Classification ana IPC IPC(4): G03G 13/01, 9/08 U.S. CL: 430/42, 45, 47, 106, 138 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classification Symbols US 430/42, 45, 47, 106, 138 Documentation Searched other than Minimum Documentation to the Extent that such Documents are Includyd in the Fields Searched ill. DOCUMENTS CONSIDERED TO BE RELEVANT Category 1 Citation ol Document. tt with indication, where appropriate. of the relevant passages 12 Relevant to Claim No. t A US, A, 3,854,942 (AKMAN) 17 DECEMBER 1974 1-35 SEE DOCUMENT GENERALLY A US, A, 4,551,407 (SANDERS) 05 NOVEMBER 1985 1-35 SEE DOCUMENT GENERALLY A US, A, 4,554,235 (ADAIR ET AL) 19 NOVEMBER 1-35 1985 "SEE-DOCUMENT GENERALLY A GB, A, 2,133,899 (SANDERS) 12 FEBRUARY 1986 1-35 SEE DOCUMENT GENERALLY A US,A, 4,801,949 (MISONO ET AL) 31 JANUARY 1-35 1989 SEE DOCUMENT GENERALLY A CHEMICAL AND ENGINEERING NEWS, "NEW COLOR 1-35 TECHNOLOGY USING MICROCAPSULES, 11 JANUARY 1988, P. 23 SEE GENERALLY A CHEMICAL WEEK, "MEAD BRINGS COLOR TO BUSINESS 1-35 13 DECEMBER 1987, pp. 32-33. SEE GENERALLY Special categories of cited documents: to later document published after the international ling date or priority date and not in confict with the application but document defining the general state of the art which is not cited to understand the principle or theory underlying the considered to be of particular relevance invention earlier document but published on or after the international document of particular relevance: the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed Invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document i combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but docment member of the same patent family later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the Internatonal Search Date of Mailing of this international Search Report MAY 1989 2 6JUN 1989 International Searching Authority Slgnu rid Ofcer ISA/US. JEFFREY A. LINDEMAN Form PCTAIS2tO (mIod se (Rev.1147) I