Recording System Having a Coating Device for Coating Recording Medium or Photosensitive Medium With Developer Material Reacting With Color Precursor

1. Field of the Invention

The present invention relates to a recording system or an image transfer system which includes an exposing device for image-wise exposing a pressure-sensitive photosensitive medium having a layer of a chromogenic material or color precursor, so as to form latent images corresponding to desired source image information, and a developing device for applying a pressure to the image-wise exposed photosensitive medium so as to cause a chemical reaction with a developer material provided on the photosensitive medium or on a separate recording medium, so that the latent images are developed into visible images.

2. Discussion of the Prior Art

In a known recording system of the type indicated above, a chromogenic material or color precursor capable of reacting with a developer material so as to produce a color image is contained in each of a multiplicity of microcapsules which constitute a microcapsule layer on a pressure-sensitive photosensitive medium. In one form of this type of photosensitive medium, the microcapsules further contain a resin which supports the chromogenic material and whose mechanical strength is varied upon exposure to a radiation. In another form of the photosensitive medium, the mechanical strength of the microcapsules containing the chromogenic material is varied upon exposure to a radiation. In either case, the microcapsules whose mechanical strength after exposure to a radiation is comparatively low are ruptured, to permit the chromogenic material to come out from the ruptured microcapsules, whereby the chromogenic material chemically reacts with the developer material, so as to produce a color image.

The developer material is provided either as a developer layer formed on the substrate of a photosensitive medium, or alternatively as a separate developer sheet which is superposed on the photosensitive medium when the latent images on the photosensitive medium are developed into the visible images on the developer sheet. In the former case, the visible images are formed on the photosensitive medium having the developer layer. This type of photosensitive medium is a so-called "self-activated" type. In the latter case, the photosensitive medium is used as a transfer sheet while the developer sheet is used as a recording medium on which the visible images are eventually formed. This latter arrangement is referred to as a "separate" type.

An example of the self-activated type of photosensitive medium is disclosed in U.S. Pat. No. 4,440,846, while an example of the separate type is disclosed in U.S. Pat. No. 4,399,209.

In both cases indicated above, the photosensitive medium having a microcapsule layer is image-wise exposed in a suitable manner. For example, the photosensitive medium is exposed to a radiation which is reflected by an original bearing desired source image information, or which is transmitted through the original. In the former case, the photosensitive medium and the original may be held in close contact with each other. The developing device for pressing the image-wise exposed photosensitive medium may use suitable pressing means such as presser rollers, impact head, or rotating balls.

As indicated above, the known recording system of the type described uses either a self-activated photosensitive recording medium, or a combination of a photosensitive medium without a developer layer and a separate recording medium with a developer layer. In either case, therefore, the user of the recording system has to use the exclusively designed photosensitive recording medium or developer sheet, on which desired images are eventually formed. In other words, the user cannot copy desired images on a desired recording medium such as commercially available ordinary papers, postcards, fabrics, plastic films or sheets, or other planar members made of other materials. If the user wishes to have the desired images formed on a desired recording medium, the images must be first formed on a self-activated photosensitive medium or a developer sheet, and the imaged medium or sheet must then be bonded to the surface of the desired medium such as a postcard. This procedure is time-consuming, and results in the finally obtained medium having an increased thickness.

It is therefore an object of the present invention to provide a recording system which permits desired images to be easily formed on a desired recording medium, by using a pressure-sensitive photosensitive medium having a chromogenic material which reacts with a developer material.

The above object may be attained according to the principle of the present invention, which provides a recording system including an exposing device for image-wise exposing a pressure-sensitive photosensitive medium according to source image information, so as to form thereon latent images, and a developing device for applying a pressure to the image-wise exposed photosensitive medium so as to cause a chemical reaction with a developer material, to thereby develop the latent images into visible images on a recording medium, wherein a coating device is provided for applying the developer material to the recording medium.

In the recording system of the present invention constructed as described above, a desired recording medium such as a postcard or plastic film is coated with a layer of the developer material, by the coating device, and the developer material chemically reacts with the chromogenic material or color precursor of the photosensitive medium which has been image-wise exposed by the exposing device. Therefore, the images corresponding to the source image information may be formed on the desired recording medium, when the image-wise exposed photosensitive medium is subjected to a developing process which involves the pressure application to cause the chemical reaction between the chromogenic material and the developer material. Thus, the instant recording system permits desired images to be formed on a desired recording medium.

In one form of the recording system of the invention, the developing device includes a device for superposing the recording medium on the photosensitive medium after the latent images are formed on the photosensitive medium by the exposing device, and for pressing the superposed recording medium and photosensitive medium, to thereby transfer the latent images from the photosensitive medium to the recording medium. In this case, the developing device includes the coating device, which is adapted to apply the developer material to the recording medium to which the latent images have been transferred from the photosensitive medium. In other words, the developer material is applied to the recording medium after the chromogenic material is image-wise transferred from the photosensitive medium to the recording medium. The developer material applied to the recording medium chemically reacts with the chromogenic material already transferred to the recording medium, whereby the latent images are developed into the visible images on the desired recording medium. According to the instant recording system, a desired number of copies of an original may be produced on a desired copy sheet or recording medium. If the coating device and the mechanism to feed the photosensitive medium are constructed as compact cartridge units, the required maintenance procedure can be simplified.

In another form of the instant recording system, the developing device also includes a device for superposing the desired recording medium on the photosensitive medium after the latent images are formed on the photosensitive medium by the exposing device, and for pressing the superposed recording medium and photosensitive medium, to thereby develop the latent images into the visible images. In this case, the developing device includes the coating device, which is adapted to apply the developer material to the recording medium before the recording medium is superposed on the photosensitive medium. Namely, the coating device incorporated in the recording system as a part of the developing device may be considered as a device for preparing a developer sheet on which the developer layer is formed and on which desired images are eventually formed.

In a further form of the present recording system, the pressure-sensitive photosensitive medium functions as the recording medium, and the coating device is adapted to apply the developer material to the photosensitive medium on which the images are eventually formed. In this instance, the photosensitive medium is considered as a desired recording medium which is commercially available. Since the photosensitive medium is processed into a self-activated photosensitive medium only after the medium is used on the recording system, there is no possibility of an otherwise possible chemical reaction between the developer material and the chromogenic material, which would occur on the conventional self-activated photosensitive medium.

In the above form of the invention, the developing device may further include a device for forming a layer of microcapsules on the substrate of the photosensitive medium. Each microcapsule contains the chromogenic material or color precursor. The microcapsules are sensitive to a radiation such that their mechanical strength is changed depending upon an amount of radiation to which the microcapsules are exposed.

In a still further form of the present invention, the photosensitive medium is sensitive to different wavelengths of radiation, and the exposing device image-wise exposes the photosensitive medium to the different wavelengths of radiation, to produce color images when the latent images are developed by the developing device.

The developer material applied to the recording medium by the coating device may be contained in a liquid, or take the form of a powder. The coating device may uses a a removable reservoir for accommodating the developer material.

In still another form of the instant recording system, the coating device is adapted to act on a developer sheet which includes a developer layer containing the developer material and a substrate supporting the developer layer. The coating device includes transfer means for transferring the developer layer from the developer sheet to the desired recording medium, by forcing the developer layer against the recording medium. According to this arrangement, the desired recording medium coated with the developer layer is superposed on the image-wise exposed photosensitive medium, and the latent images on the exposed photosensitive medium are developed into the visible images on the recording medium when the superposed media are pressed by the developing device. In this arrangement, too, desired images may be directly formed on a desired recording medium such as a postcard or an ordinary cut sheet, without bonding a separately prepared imaged sheet to the desired recording medium.

In the above form of the invention, the coating device may include one or more presser rollers forcing the developer sheet against the recording medium while heating the developer sheet and the recording medium. For facilitating the transfer of the developer layer from the developer sheet to the recording medium, at least one of the developer sheet and the recording medium may be humidified as with a water vapor by a suitable humidifying device. The developer layer may be formed from a liquid which is cast on a surface of the substrate, the liquid containing the developer material in the form of a developer agent capable of reacting with a color precursor on the recording medium, and further containing a binder.

It is another object of the present invention to provide a toner for forming a developer medium having a developer layer, which developer medium is used as a recording medium.

This second object may be achieved according to another aspect of the present invention, which provides a toner for forming a developer medium, containing as major components a developer material capable of reacting with a chromogenic material to produce a color image, and a thermoplastic resin. The toner may be applied to a desired substrate or recording medium in a suitable manner, preferably by an electrostatic or electromagnetic method, either after or before latent imges are developed into visible images by a developing device. Preferably, the toner applied to the substrate or recording medium is heated for fixation.

The developer material may consists of at least one material selected from the group consisting of (a) electron acceptor compounds selected from the group which includes (i) inorganic acid substances selected from the group including acid earth, active clay, zeolite and bentonite, (ii) compounds of phenolic resins selected from the group including substituted phenolic compounds selected from the group including p-cresol, p-octylphenol, p-cyclohexylphenol, p-phenylphenol, .alpha.-naphthylphenol, cumylphenol and p-chlorophenol, (iii) compounds of phenolic resins selected from the group including phenol-formalin condensation products, and substituted phenol-formalin condensation products; (iv) compounds of phenolic resins modified by high-valence metals selected from the group including zinc and nickel; (v) compounds of aromatic carboxylic acids selected from the group including p-butyl benzoic acid, p-hydroxybenzoic acid, 2,5-dihydroxybenzoic acid, salicylic acid, 5-tert-butyl salicylic acid, 3,5-di-tert-butyl salicylic acid, and 3.5-di(.alpha.-methylbenzyl) salicylic acid, and (vi) metal salts of aromatic carboxylic acid compounds, consisting of high-valence metals such as zinc and nickel; (b) ligands selected from the group including 8-quinolinol, gallic acid, dodecyl gallate, 1,10-phenanthroline, o-phenylenediamine diphenylthiourea, guanidine, hydroxynaphthoic acid, dipivaloylmethane, and trifluoroacetylacetone; and (c) metal compounds selected from the group including iron (III) stearate, magnesium stearate, zinc stearate, and zinc N-phenyl-N-ethyldithiocarbamate.

The thermoplastic resin of the instant toner may consist of at least one material selected from the group consisting of: (a) a homopolymer obtained by polymerizing a monomer of (i) styrenes selected from the group including .alpha.-methylstyrene, and p-chlorostyrene, (ii) vinyl esters selected from the group inlcuding vinyl chloride, vinyl bromide, vinyl propionate, vinyl fluoride, vinyl acetate, vinyl benzoic acid, and vinyl butyrate, (iii) esters of .alpha.-methylene aliphatic monocarboxylic acid selected from the group including methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, phenylacrylic acid, methyl(.alpha.-chloro) acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate, (iv) acrylonitrile, (v) methacrylonitrile, (vi) acrylic amide, (vii) vinyl ethers such as vinylmethyl ether, vinylisobutyl ether, and vinylethyl ether, (viii) vinyl ketones selected from the group including vinylmethyl ketone, vinylhexyl ketone, and vinylisopropenyl ketone, or (ix) N-vinyl compounds selected from the group including N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; (b) a copolymer obtained by copolymerizing a plurality of monomers selected from (a); (c) a mixture of a homopolymer and a copolymer selected from (a) and (b), respectively; (d) a non-vinyl resin selected from non-vinyl thermoplastic resins selected from the group including rosin-modified phenol-formalin resins, oil-modified epoxy resins, polyurethane resins, and cellulose resins; or (e) a mixture of at least one vinyl resin selected from (a), (b) and (c) and at least one non-vinyl resin selected from (d).

It is a third object of the present invention to provide a toner for forming a developer medium which is capable of sufficiently reacting with a chromogenic material so as to produce a highly visible dye image and which is easily electrostatically transferred to an ordinary or photosensitive recording medium.

The above object may be achieved according to a further aspect of the present invention, which provides a toner for forming a developer medium capable of reacting with a chromogenic material to produce a visible dye image, the toner comprising developer particles and thermoplastic resin particles having a smaller grain size than the developer particles. Each developer particle includes a developer mataerial capable of reacting with the chromognic material, and carries a multiplicity of the thermoplastic resin particles deposited on its surface.

The instant developer toner excellently performs two different functions which are conventionally considered incompatible. Namely, the particles of a thermopolastic resin such as polymethacrylate deposited on the surface of each developer particle function to hold the developer particle electrostatically fixed on the surface of an ordinary or photosensitive recording medium. On the other hand, the developer material contained in each developer particle is highly capable of reacting with a chromogenic material, since the developer material does not have to contain a large amount of thermoplastic resin. Further, the thermoplastic resin particles permit an easy flow of the chromogenic material to the developer particles. In other words, the resin particles do not disturb the reaction of the developer material with the chromogenic material to produce a visible dye image.

Preferably, the sizes of the developer and resin particles are determined such that the ratio of the average grain size of the resin particles to that of the developer particles is held within a range between 1/5 and 1/50.

The above and optional objects, features and advantages of the present invention will be better understood by reading the following detailed description of presently preferred embodiments of the invention, when considered in connection with the accompanying drawings, in which:

FIG. 1 is a schematic elevational view of one embodiment of a recording system of the present invention;

FIG. 2 is an elevational view of a part of the recording system of FIG. 1;

FIG. 3 is a fragmentary view of another embodiment of the invention;

FIGS. 4 and 5 are schematic elevational views of further embodiments of the invention, respectively;

FIG. 6 is a schematic elevational view showing a modification of the embodiments of FIGS. 4 and 5;

FIG. 7 is a schematic elevational view of a still further embodiment of the recording system of the present invention;

FIG. 8 is an enlarged fragmentary elevational view in cross section showing a part of the system of FIG. 7, in which hot presser rollers are provided to transfer a developer layer to a recording medium such as a post card;

FIG. 9 is a schematic elevational view in cross section of a yet further embodiment of the present invention; and

FIG. 10 is an illustration of one of developer particles of a toner according to a further embodiment of the invention for forming a developer medium, the developer particle carrying multiple thermoplastic particles deposited thereon.

Referring first to FIG. 1, the recording system is generally indicated at R. The recording system R includes an exposing device which has a halogen lamp 4 for irradiating a color-image original 3, and a lens 5 for converging a radiation reflected from the original 3, so as to image-wise expose a pressure-sensitive photosensitive medium 1 to the reflected radiation, so that latent images are formed on the photosensitive medium 1, according to source image information represented by the images on the color-image original 3.

The photosensitive medium 1 has a layer of radiation-curable microcapsules R, G, B which are sensitive to different wavelengths of light. The exposing device includes a filter device 12 which has three color filters which transmit the rays of light having the different wavelengths to which the three kinds of microcapsules R, G and B are sensitive. Therefore, the photosensitive medium 1 is exposed three times to the reflected radiation from the original 3, with the different color filters of the filter device 12 selectively placed in their operated position.

The microcapsules in the exposed areas of the photosensitive medium 1 are radiation-cured, while the microcapsules in the non-exposed areas remain uncured. Thus, the latent images are formed on the photosensitive medium 1. A suitable recording medium 2 is fed through guide rollers 13, 13, such that the image-wise exposed photosensitive medium 1 is superposed on the recording medium 2 in close contact with each other. The superposed photosensitive medium 1 and recording medium 2 are passed through a pressure nip between developing rollers in the form of presser rollers 6, 6. As a result, the non-cured microcapsules are ruptured, whereby a chromogenic material or color precursor 11 comes out of the ruptured microcapsules and adheres to the surface of the recording medium 2, as shown in FIG. 2.

Thus, the latent images are transferred from the photosensitive medium 1 to the recording medium 2, such that the chromogenic material 11 is transferred to local areas of the recording medium 2 which correspond to the non-cured microcapsules on the photosensitive medium 1.

The presser rollers 6 constitute a part of a developing device for developing the latent images which have been formed on the photosensitive medium 1 by the exposing device 4, 5, 12. The developing device further includes a coating device 8 as shown in FIG. 2. The coating device has a coating roller 7 adapted to apply a developer material 10 to the surface of the recording medium 2 to which the latent images have been transferred from the photosensitive medium 1.

As described later in greater detail, the developer material 10 may be a clay mineral, an inorganic acid polymer, a metal salt, an aromatic carboxylic acid, or a mixture of two or more of these substances.

Referring to FIG. 2, the coating device 8 has a reservoir 8b for storing a liquid which contains the developer material 10 dispersed in water. The liquid is fed to the surface of the coating roller 7, through an elastic member 8a made of a sponge, asbestos, cotton or similar material. With the coating roller 7 rotated in rolling contact with the recording medium 2, the developer material 10 is applied to the surface of the medium 2.

As a result, the developer material 10 chemically react with a pattern of the chromogenic material 11 forming the latent images on the recording medium 2, whereby the latent images are eventually developed into the visible color images, as the medium 2 is fed past the coating roller 7.

The recording medium 2 with the visible images formed thereon is then passed through a nip of heat rollers 9, 9, so that the imaged surface of the medium 2 is lustered or glossed.

Referring further to FIG. 3, there is illustrated a second embodiment of the invention, wherein the developing material 10 is provided in the form of a powder or toner. In this embodiment, the powdered developer material 10 is delivered onto the surface of the recording medium 2, directly from the reservoir 8b of the coating device. The medium 2 is then passed through the nip of the heat rollers 9, 9, for improving the glossiness of the imaged surface of the medium 2.

Referring next to FIG. 4, there is generally shown at A a third embodiment of the recording system of this invention. The recording system A includes an exposing device B, a coating device C, and an developing device D. The exposing device B includes a support 101 for supporting an original in the form of a sheet 102, a light source 105, and a color filter device 106. The coating device C includes a reservoir 109 for storing a developer material, a feed roller 110, a metering roller 111, a coating roller 112, and a drying furnace 113. The developing device D includes a pair of presser rollers 114, 114, and a heater 117.

The original sheet 102 bears desired source image information as in the form of photographs, or films having images, characters and graphical representations. The form of the original sheet 102 is more or less limited, depending upon the manner in which the original sheet is irradiated by the exposing device B. The support 101 consists of a colorless transparent sheet which has a thickness not exceeding 100 microns, and which is made of a resin such as polyester, or a glass material. The light source 105 may be a tungsten or halogen lamp, or a similar lamp, which produces a visible spectrum of light having a wavelength range between 400 nm and 700 nm. The color filter device 106 has three filters corresponding to red, green and blue bands of the visible spectrum. With the filter device 106 rotated, the three filters are selectively brought into their operative position right below the light source 105.

A stack of recording media 108 is accommodated in a storage cassette 107. The type of the recording media 108 that can be used on the instant recording system A is not limited to an ordinary cut sheet used for general copying applications. The reservoir 109 stores a developer liquid in the form of a solution or a dispersion which contains at least a developer material and a binder. The developer material that can be used in the present system may be selected from known materials which are used for pressure-sensitive papers suitable for non-carbon duplication. The binder may be a commonly used type such as gelatin or polyvinyl alcohol.

The feed roller 110 of the coating device C is adapted to receive the developer liquid and transfer the liquid to the coating roller 112, and the coating roller 112 is adapted to apply the received liquid to the surface of the recording medium 108 fed from the cassette 107. The metering roller 111 is provided to control the rate of supply of the liquid from the reservoir 109 to the recording medium 108 via the feed and coating rollers 110, 112. Each of the rollers 110, 111, 112 is provided with a cleaning scraper 110a, 111a, 112a, and a receiver for accommodating the liquid removed from the rollers by the scrapers 110a, 111a, 112a.

The drying furnace 113 is provided to dry the developer liquid applied on the recording medium 108. The temperature within the furnace 113 is maintained within a range of 60.degree.-200.degree. C., by a heater and a fan.

The presser rollers 114 of the developing device D are provided to develop latent images formed on a pressure-sensitive photosensitive medium 104. More specifically, the non-cured microcapsules on the photosensitive medium 104 image-wise exposed by the exposing device B are ruptured while the photosensitive medium 104 is passed through the nip of the presser rollers 114, 114, together with the recording medium 108 superposed on the photosensitive medium 104. As described below in detail, the chromogenic material or color precursor flowing from the ruptured microcapsules chemically reacts with the developer material covering the surface of the recording medium 108, whereby visible color images corresponding to the latent images on the photosentive medium 104 are formed on the recording medium 108. The pressure at the nip of the rollers 114 is set to 10 kg/cm or higher. The heater 117 is provided to fix the visible images formed on the recording medium, by applying heat to the recording medium 108. The heating temperature is controlled within a range of 50.degree.-200.degree. C. The heater 117 is adapted to be held in contact with the surface of the recording medium 108 opposite to the imaged surface.

An image transfer operation of the recording system A of the present embodiment will be described.

The operation is started with the original sheet 102 set on the support 101. The photosensitive medium 104 is fed from a supply roll 103, so as to pass below the support 101 on which the original sheet 102 is placed. Simultaneously, a radiation emitted from the light source 105 is transmitted through the red color filter of the filter device 106, so that the photosensitive medium 104 is exposed to the rays of light in the red band of the visible spectrum, through the original sheet 102 and the support 101. Thus, the microcapsules corresponding to the red images on the original sheet 102 are exposed. Similarly, the microcapsules corresponding to the blue and green images on the original sheet 102 are exposed to the radiation from the light source 105 through the corresponding blue and green color filters. In the meantime, the recording medium 108 is fed from the cassette 107, and is coated with a 20-micron thick layer of the developer liquid which is supplied from the reservoir 109 via the feed roller 110 and the coating rollers 112. The developer layer applied on the recording medium 108 is dried while being passed through the drying furnace 113 whose operating temperature is set at about 80.degree. C.

The image-wise exposed photosensitive medium 104 and the dried recording medium 108 are superposed on each other such that the exposed surface of the medium 104 and the developer layer of the recording medium 108 are held face to face. The superposed media 108, 104 are then passed through the nip of the presser rollers 114, 114, whereby the latent images on the medium 104 are developed into visible color images on the recording medium 108. After the development, the photosensitive medium 104 and the recording medium 108 are separated from each other by a separator 115. The photosensitive medium 104 is wound on a take-up roll 116, while the recording medium 108 is passed under the heater 117, so that the visible images are fixed and the imaged-surface is glossed. Then, the recording medium 108 is delivered out of the recording system A. Thus, the images are transferred from the original sheet 102 to the recording medium 108, such that the imaged surface of the recording medium 108 has substantially the same glossiness as the imaged surface of the original sheet 102.

Referring next to FIG. 5, there is shown a fourth embodiment of the present invention. The same reference numerals as used in FIG. 4 will be used in FIG. 5 to identify the corresponding components.

The present embodiment is charcterized in that a pressure-sensitive photosensitive medium 119 having a layer of radiation-sensitive microcapsules is coated with a developer layer, and is used as a recording medium on which visible images are eventually formed.

In the instant recording system A, the photosensitive medium 119 in the form of cut sheets is fed from a cassette 118 upon commencement of an image transfer operation with the original sheet 102 set on the support 101. The photosensitive medium 119 fed from the cassette 118 is coated with the developer layer by the coating device C which includes the reservoir 109 and the feed, metering and coating rollers 110, 111, 112 as described above with respect to the third embodiment. The applied developer layer is dried by the drying furnace 113. Thus, the photosensitive medium 119 is processed into a photosensitive recording medium with the developer layer having a thickness of 21 microns. The photosensitive recording medium 119 which has been fed from the furnace 113 is then passed under the support 101, so that the medium 119 is exposed to a radiation from the light source 105 through the original sheet 102 and the support 101, in the same manner as described above in connection with the preceding embodiment. The recording medium 119 is then developed by the presser rollers 114, 114 of the developing device D, whereby visible images corresponding to the images on the original sheet 102 are formed on the recording medium 119. The developed medium 119 is then heated by the heater 117, for fixation of the formed visible images and improved glossiness of the imaged surface. The glossiness of the imaged surface of the medium 119 is substantially the same as that of the imaged surface of the original sheet 102.

While the illustrated embodiments of FIGS. 1-5 use the photosensitive medium 1, 104, 119 whose microcapsules increase their mechanical strength due to curing upon exposure to a radiation, it is possible to use a photosensitive medium of the type in which the microcapsules are softened and their mechanical strength is reduced, upon exposure to a radiation.

A modification of the embodiment of FIG. 5 is shown as a fifth embodiment in FIG. 6. This fifth embodiment incorporates a microcapsule coating device E, as well as the coating device C. Described more specifically, the present recording system uses an ordinary cut sheet 129 which is first coated with a developer layer by the coating device C as described above, and then coated with a layer of microcapsules by the microcapsule coating device E which has substantially the same arrangement as the coating device C. Accordingly, the ordinary cut sheet 129 is processed into a pressure-sensitive photosensitive medium 130 which functions as a recording medium on which visible images are eventually formed. In this photosensitive medium 130, the microcapsule layer is formed on the developer layer, as distinguished from the recording medium 119 of FIG. 5 in which the developer layer is formed on the microcapsule layer.

A still further embodiment of the present invention will be described, by reference to FIGS. 7 and 8, wherein an image transfer or copying system is generally indicated at 216.

A recording medium 205 such as an ordinary cut sheet, or a postcard or handkerchief, on which the user desires to form images according to source image information, is fed through an inlet 216a of the copying system 216, by feed rollers 218. Initially, the recording medium 205 is humidified by a ultrasonic humidifying device 220, so that the 0.5 gram of water vapor is evenly distributed over a unit area of 100 cm.sup.2 of the recording medium 205. The humidified medium 205 is then brought into contact with a developer sheet 201, and the thus superposed medium 205 and sheet 201 are passed through a nip of heated presser rollers 204a, 204b, while the medium and sheet 205, 201 are fed together. As illustrated in FIG. 8, the developer sheet 201 consists of a substrate 202 and a developer layer 203 which contains a suitable developer material as described above and as described later in greater detail. While the recording medium 205 and the developer sheet 201 are passed through the nip of the presser rollers 204a, 204b, the developer layer 203 is transferred onto the contacting surface of the recording medium 205, under a pressure exerted by the rollers 204a, 204b. In the present arrangement, the presser rollers 204a, 204b are heated to 80.degree. C. and provide a squeezing pressure of 8 kg/cm.sup.2. Since the recording medium 205 is pre-humidified, the developer layer 203 is readily transferred to the surface of the medium 205.

The substrate 202 of the developer sheet 201 may be a sheet of paper or PET (polyethylene terephthalate). The developer material contained in the developer layer 203 includes, for example, a clay mineral, organic acid, acid polymer, metal salt, or aromatic carboxylic acid, which is dispersed or dissolved in a solvent, and further includes a binder, a viscosity adjusting agent, and other suitable additives. To form the developer layer 203, the developer material is cast on the substrate 202, by a coating roller, spray, or doctor blade, or other suitable means.

In the meantime, a pressure-sensitive photosensitive medium 209 having a microcapsule layer is fed in a direction indicated by arrow in FIG. 7 from a supply roll 215, such that the medium 209 is passed under an exposing device 210, 212, and through the nip of presser rollers 213, 213. The medium 209 is finally wound on a take-up roll 214. The microcapsule layer consists of a multiplicity of microcapsules each of which contains a chromogenic material or color precursor capable of reacting with the developer material of the developer layer 203, and a radiation-sensitive material whose mechanical strength is varied upon exposure to a radiation. In operation, a radiation produced by a light source 210 is reflected by the surface of an original 211, and the reflected radiation is converged on the surface of the photosensitive medium 209 by a lens 212. The microcapsules which are exposed to a comparatively large amount of radiation are cured, and their mechanical strength is increased.

After the photosensitive medium 209 is image-wise exposed, the recording medium 205 having the developer layer 203 is transferred onto an exposed length of the medium 209 by a suitable feeding device, such that the developer layer 203 is in contact with the exposed surface of the medium 209. Then, the superposed media 205, 209 are passed through the pressure nip between the presser rollers 213, 213, whereby the microcapsules whose mechanical strength is comparatively small are ruptured. As a result, the chromogenic material flowing from the ruptured microcapsules chemically reacts with the developing material contained in the developer layer 203. Thus, latent images formed on the exposed medium 209 according to the source image information on the original 211 are developed into visible images on the recording medium 205.

Although the illustrated embodiments are adapted to image-wise expose a photosensitive medium to a radiation which is reflected by or transmitted through an original, it is possible that the photosensitive medium is exposed by optical signals fed from a suitable controller according to source image information. In this case, too, the recording medium is superposed on the thus exposed photosensitive medium, and the superposed media are pressed by a suitable developing device. Further, the ultrasonic type humidifying device 220 for applying a water vapor to the recording medium 205 may be replaced by other humidifying means. The humidifying device may be adapted to humidify the developer sheet 201, rather than the recording medium 205. In this case, too, the developer layer 203 may be readily transferred to the recording medium 205.

While the developer layer 203 is transferred from the prepared developer sheet 201 to the desired kind of recording medium 205 in the above embodiment, it is possible to apply a suitable toner directly to a desired recording medium, so as to form a developer medium having a developer layer consisting of the toner, before or after the photosensitive medium is image-wise exposed. Further, the toner may be applied to a photosensitive medium before or after the photosensitive medium is image-wise exposed. For example, the toner may be used in place of the developer material 10 used in the embodiment of FIG. 3 in which the developer material is applied to the recording medium 2 to which the chromogenic material has been transferred from the exposed and pressed photosensitive medium 201.

Further, the toner containing a developer material may be used to coat an ordinary recording medium with the developer material in the form of a developer layer, so that the developer material of the developer layer reacts with the chromogenic material on an image-wise exposed surface of a photosensitive medium. A recording system having a developer coating device to practice this recording method is illustrated in FIG. 9.

In the figure, reference numeral 211 denotes a frame of the recording system. A side wall of the frame 211 has a tray 212 attached thereto to receive cut sheets on which images have been recorded by the instant system. The frame 1 has an original support member 213 on its top wall. The support member 213 is adapted to support an original which bears an image to be reproduced. The instant recording system uses a photosensitive web 216 supplied from a supply roll 214, and a recording medium also in the form of a web 218 supplied from a supply roll 217. The rollers 214 and 217 are rotatably supported within the frame 211. Like the photosensitive medium 1 used in the embodiment of FIG. 1, the photosensitive medium 216 has a layer of radiation-curable microcapsules containing a chromogenic material. As described below, the image on the original supported on the support member 213 is reproduced on the recording web 218, and the web 218 is cut into cut sheets which are received by the tray 212.

The photosensitive web 216 is fed so as to pass an exposing station indicated at 215, so that a length of the web 216 is image-wise exposed by a suitable exposing device as used in the embodiment of FIG. 1, while the web 216 is fed past the exposing station 215. The image-wise exposed length of the photosensitive web 216 is passed through a pressure nip between a pair of presser rolls 228 of a developing device 227 disposed below the exposing station 215. As described below, the recording web 218 is superposed on the exposed length of the photosensitive web 216 before the superposed webs 216, 218 are passed through the pressure nip of the presser rolls 228. Downstream of the developing device 227, there is disposed a fixing device 229 for fixing the image formed on the web 218.

The recording medium in the form of the recording web 218 supplied from the roll 217 is fed into a developer coating device generally indicated at 230. This coating device 230 includes a toner container 219 for accommodating a mass of a toner 220 which will be described for illustrative purpose only. The toner 220 is electrostatically deposited on the surface of the recording web 218, in the manner described below. The recording web 218 coated with the toner or developer layer is passed through a heating unit 224 which includes a heater 225 and an auxiliary roll 226. The heating unit 224 is disposed between the coating device 230 and the developing device 227. Between the fixing device 229 following the developing device 227 and the tray 212, there is provided a cutter 231 for cutting the recorded web 218 into cut sheets, as indicated above.

The toner 220 accommodated in the container 219 of the coating device 230 is adapted to be substantially melted at about 120.degree. C. The coating device 230 includes a coating roller 222 associated with the container 219, and an auxiliary roller 221 disposed at a lower position within the container 219. The auxiliary roller 221 cooperates with the coating roller 222 to electrostatically positively charge the adjacent mass of the toner 220 due to frictions between the toner particles, and transfer the electrostatically positively charged toner 220 to the recording web 218. Opposite to the coating roller 222, there is disposed a charging roller 223 which guides the recording web 218 from the supply roll 217, so as to pass between the rollers 222, 223. The charging roller 223 is electrically connected to a DC power source El, so that the surface of the roller 223 is electrostatically negatively charged, so that the electrostatically positively charged toner 220 transferred from the coating roller 222 is attracted on the surface of the recording web 218 on the charging roller 223.

Thus, the surface of the recording web 218 is coated with a developer medium in the form of a layer of the electrostatically positively charged toner 220 which is electrostatically attracted to the web surface due to the electrostatically negatively charged charging roller 223 disposed opposite to the coating roller 222.

The toner-coated length of the recording web 218 is heated by the heater 225 of the heating unit 224, on the side remote from the coated surface, to a temperature necessary to slightly melt the toner 220 on the web 218, for example. Thus, the toner layer is given a suitable adhesive force with respect to the surface of the recording web 218.

The auxiliary roll 226 is provided to effect a thermal adjustment of the toner layer, in order to avoid an excessive degree of melting of the toner material by the heater 225, which may lead to insufficient chemical reaction of the developer material of the toner 220 with the chromogenic material on the image-wise exposed surface of the photosensitive web 216, at the developing device 227. It is also desirable that the heater 225 is suitably controlled so as to avoid the above inconvenience.

The coated and heated portion of the recording web 218 is passed under the image-wise exposed portion of the photosensitive web 216, and these two webs 218, 216 are superposed on each other such that the exposed surface of the web 216 contacts the coated surface of the web 218, when the superposed webs 216, 218 are passed through the nip of the presser rolls 228 of the developing device 227. Thus, the latent image formed on the image-wise exposed surface of the photosensitive web 216 is developed into a visible image on the recording web 218, as a result of chemical reaction between the developer material of the toner 220 and the chromogenic material on the web 216.

Since the layer of the toner 220 securely adheres to the surface of the recording web 218, the toner layer will not be even partially or locally removed or separated from the web 218 during the transfer toward the developing device 227 or during the development by the developing device 227.

The developed image produced by the chemical reaction between the toner 220 and the chromogenic material of the microcapsules of the photosensitive web 216 is fixed by the fixing device 229, and the recording web 218 is cut into a sheet having a suitable length. The cut sheet is received by the tray 212.

The heater 225 may be a fan heater, untraviolet lamp or other radiation heating device.

The toner 220 includes a developer material and a resin material. The following materials capable of chemically reacting with the chromogenic material or color precursor within the microcapsules of a photosensitive medium, so as to produce a color image, may be used as the developer material contained in the instant toner: (a) electron acceptor compounds selected from the group which includes (i) inorganic acid substances such as acid earth, active clay, kaoline, zeolite and bentonite, (ii) compounds of phenolic resins including substituted phenolic compounds such as p-cresol, p-octylphenol, p-cyclohexylphenol, p-phenylphenol, .alpha.-naphthylphenol, cumylphenol and p-chlorophenol, (iii) compounds of phenolic resins such as phenol-formalin condensation products, and substituted phenol-formalin condensation products, (iv) compounds of phenolic resins modified by high-valence metals such as zinc and nickel, (v) compounds of aromatic carboxylic acids such as p-butyl benzoic acid, p-hydroxybenzoic acid, 2,5-dihydroxybenzoic acid, salicylic acid, 5-tert-butyl salicylic acid, 3,5-di-tert-butyl salicylic acid, and 3.5-di(.alpha.-methylbenzyl) salicylic acid, and (vi) metal salts of aromatic carboxylic acid compounds, consisting of high-valence metals such as zinc and nickel; (b) ligands such as 8-quinolinol, gallic acid, dodecyl gallate, 1,10-phenanthroline, o-phenylenediamine diphenylthiourea, guanidine, hydroxynaphthoic acid, dipivaloylmethane, and trifluoroacetylacetone; and (c) metal compounds such as iron (III) stearate, magnesium stearate, zinc stearate, and zinc N-phenyl-N-ethyldithiocarbamate. However, the developer agent that can be used according to the invention is not limited to the materials listed above. The selected developer agent should be included in the toner, in an amount sufficient to produce a color image as a result of reaction with the chromogenic material.

The resins that may be preferably contained in the toner of the invention may include thermoplastic resins which are: (a) homopolymers obtained by polymerizing monomers of (i) styrenes such as styrene, .alpha.-methylstyrene, and p-chlorostyrene, (ii) vinyl esters such as vinyl chloride, vinyl bromide, vinyl propionate, vinyl fluoride, vinyl acetate, vinyl benzoic acid, and vinyl butyrate, (iii) esters of .alpha.-methylene aliphatic monocarboxylic acid such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, phenylacrylic acid, methyl(.alpha.-chloro) acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate, (iv) acrylonitrile, (v) methacrylonitrile, (vi) acrylic amide, (vii) vinyl ethers such as vinylmethyl ether, vinylisobutyl ether, and vinylethyl ether, (viii) vinyl ketones such as vinylmethyl ketone, vinylhexyl ketone, and vinylisopropenyl ketone, and (ix) N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; (b) copolymers obtained by copolymerizing the above-indicated two or more monomers in combination; (c) mixtures of the above-indicated homopolymers and copolymers; (d) non-vinyl resins including non-vinyl thermoplastic resins such as rosin-modified phenol-formalin resins, oil-modified epoxy resins, polyurethane resins, and cellulose resins; and (e) mixtures of the above-indicated vinyl resins and non-vinyl resins.

80 parts by weight of copolymer resin of styrene/n-butylmethacrylate having a softening point of 115.degree.-125.degree. C., and 15 parts by weight of copolymer resin of ethylene/vinyl acetate having a softening point of 89.degree. C. were heated to prepare a molten mass. To the prepared molten mass, there was added 20 parts by weight of acid earth. The mixture was evenly kneaded, cooled and then ground. Thus, a toner having an average particle size of 12 microns was obtained.

The obtained toner was electrostatically applied to the surface of an ordinary paper, and then fixed to the paper surface by heat rollers at 120.degree. C. The thus prepared developer sheet and a pressure-sensitive photosensitive sheet having microcapsules containing a chromogenic material were superposed on each other, and the superposed sheets were passed through a nip of developing presser rollers. As a result, latent images formed on the photosensitive sheet were developed into sufficiently colored visible images on the developer sheet.

50 parts by weight of copolymer resins of styrene/n-butylmethacrylate having a softening point of 115.degree.-125.degree. C., and 45 parts by weight of epoxy resin having a softening point of 90.degree.-94.degree. C. were heated to prepare a molten mass. To the prepared molten mass, there was added 25 parts by weight of phenol-formalin condensation product. The mixture was evenly kneaded, cooled and then ground. Thus, a toner having an average particle size of 10.5 microns was obtained.

The obtained toner was electrostatically applied to the surface of an ordinary paper, and then fixed to the paper surface by heat rollers at 120.degree. C. The thus prepared developer sheet and a pressure-sensitive photosensitive sheet having microcapsules containing a chromogenic material were superposed on each other, and the superposed sheets were passed through a nip of developing presser rollers. As a result, latent images formed on the photosensitive sheet were developed into sufficiently colored visible images on the developer sheet.

It will be understood from the description of Examples 1 and 2 that the toner used in the recording systems illustrated above is a powdered mass consisting of particles each of which includes both a developer material capable of reacting with a chromogenic material or color former, and a thermoplastic resin which functions as a binder for coagulating the developer material into a particle and as a material for holding the developer material fixed on the surface of a suitable medium. This type of toner usually contains the thermoplastic resin in a comparatively small amount with respect to the developer material, preferably 10-30%, so that the developer material contained in each toner particle may sufficiently react with the chromogenic material, so as to form a highly visible dye image or dense color. On the other hand, there is a requirement that the toner particles easily adhere as a developer medium to an ordinary or photosensitive recording medium as indicated at 2, 108, 119, 129, 205, and 218 in FIGS. 1, 4, 5, 6, 7 and 8, by an electrostatic force between the thermoplastic resin and the medium, and/or an adhesive force of the resin. This requirement exists also where the toner is image-wise electrostatically transferred to image-wise exposed local portions of a photosensitive medium as indicated at 216 in FIG. 8. In this case, too, the toner forms a developer medium which reacts with the chromogenic material existing in the local image areas of the photosensitive medium. To satisfy this requirement, each particle should contain the thermoplastic resin in a relatively large amount.

In view of the above two requirements which are more or less incompatible on the toner described above, it is desirable to use a toner which consists of developer particles 301, and a multiplicity of thermoplastic resin particles 302 deposited on the surface of each developer particle 301, as indicated in FIG. 10. This type of toner is particularly suitable for use in the recording system of FIG. 8.

The developer particles 301 have an average grain size which is considerably larger than that of the thermoplastic resin particles 302. Each developer particle 301 includes a developer material capable of reacting with a chromogenic material or color precursor, and a binder for coagulating the developer material into a coherent mass. The binder also functions to produce an adhesive force for the thermoplastic resin particles 302 to adhere to the surface of the developer particles 301. The thermoplastic resin particles 302 are secured to the developer particles 301 due to partial embedment of the particles 302 in the particles 301. Further, the thermoplastic resin particles 302 more or less adhere to the developer particles 301 by means of an electrostatic force between the binder and the resin particles.

The developer material contained in the developer particles 301 comprises at least one material selected from the group consisting of: mineral clays such as acid earth, active clay and attapulgite; organic acids such as tannic acid and gallic acid; esters such as propyl gallic acid ester; acidic polymers such as phenol-formaldehyde resins, phenol-acetylene condensation polymer resins, condensation polymers of carboxylic acid having at least one hydroxy radical and formaldehyde; metal salts of aromatic carboxylic acids such as zinc salicylates, tin salicylates, zinc 2-hydroxynaphthoic acid, zinc 3,5-di-tert-butyl salicylic acid, and zinc .alpha.-methylbenzyl salicylic acid; oil-soluble metal salts of phenol-formaldehyde novlak resin modified by zinc; and zinc carbonate.

The binder contained in the developer particles 301 consists of at least one material selected from such materials that serve to coagulate the developer material into a coherent mass 301 and that serve to hold the thermoplastic resin particles 302 deposited or adhering to the surface of the developer particles 301. For instance, the binder comprises at lteast one material selected from the group consisting of: polystyrenes and/or copolymers thereof; polyesters and/or copolymers thereof; epoxy, acrylate, methacrylate, and/or copolymers thereof; silicone resins; polypropylenes and/or copolymers thereof; waxes; fluorine-contained resins; polyamides; polyvinyl alcohol; polyurethane; polyurea; and phenolic resins.

The materials indicated above for the binder are selected on different standards, depending upon whether the thermoplastic resin particles 302 are deposited on the surface of the developer particles 301 by means of electrostatic forces between the binder and the particles 302, or by means of both of the electrostatic forces and adhesive forces between the binder and the particles 302.

The thermoplastic particles 302 are preferably formed of polymethyl methacrylate. However, the particles 302 may be formed of other suitable thermoplastic resins such as ethylene, polyolefin, polyester, or wax. It is desirable that the particles 302 have an average grain size ranging from 0.05 to 5 microns, preferably 0.15 to 0.5 micron, and also desirable that the ratio of the average grain size of the particles 302 to that of the developer particles 301 be held within a range between 1/5 and 1/50. Namely, the grain size of the particles 302 should be less than one-fifth of that of the developer particle 301, so that the particles 302 may suitably surround the central developer particle 301. Further, the grain size of the particles 302 is smaller than 1/50 of that of the particle 301, the particles 302 tend to cohere with each other. The optimum ratio of the average grain size of the particles 302 to that of the particles 301 is considered to be in the neighborhood of 1/10.

30 parts by weight of a developer material, 3 parts by weight of PVA (polyvinyl alcohol) and 150 parts by weight of toluene as a medium are mixed so as to prepare a mixture in the form of a dispersion or solution wherein the developer material is dispersed or dissolved in the medium. A suitable additive is added to the dispersion or solution so that the viscosity of the dispersion or solution is held within a range between 500 cp and 2000 cp. The dispersion or solution is sprayed and dried by a spray drier, at an inlet temperature of 90.degree. C. and at a feed rate of 15 g/min., with a spraying pressure of 0.6 kg/cm.sup.2. Thus, A mass of the developer particles 301 having an average grain size of 10-15 microns is prepared. Then, 210 parts by weight of polymethyl methacrylate (PMMA) particles 302 are added to 50 parts by weight of the developer particles 301, and the particles 301, 302 are intimately mixed by a mixer for 10 minutes at 10000 r.p.m. Thus, a toner mass wherein each developer particle 301 carries the PMMA particles adhering to its surface is obtained.

30 parts by weight of a developer material, 3 parts by weight of PVA (polyvinyl alcohol) and 150 parts by weight of styrene-acrylic resin as a solvent are mixed so as to prepare a solution wherein the PVA is dissolved in the solvent. The developer material is dispersed or dissolved in the solution of the PVA. A suitable additive is added to the dispersion or solution so that the viscosity of the dispersion or solution is held within a range between 500 cp and 2000 cp. The dispersion or solution is sprayed and dried by a spray drier, at an inlet temperature of 90.degree. C. and at a feed rate of 15 g/min., with a spraying pressure of 0.6 kg/cm.sup.2. Thus, A mass of the developer particles 301 having an average grain size of 10-15 microns is prepared. Then, 210 parts by weight of polymethyl methacrylate (PMMA) particles 302 are added to 50 parts by weight of the developer particles 301, and the particles 301, 302 are intimately mixed by a mixer for 10 minutes at 10000 r.p.m. Thus, a toner mass wherein each developer particle 301 carries the PMMA particles adhering to its surface is obtained.

150 parts by weight of a developer material and 15 parts by weight of phenolic resin are heated into a molten mixture and kneaded for 10 minutes. The mixture is milled first by a coarse mill and then by a fine mill, so that a mass of the developer particles 301 having an average grain size of 10-15 microns is prepared. The developer particles 301 and the PMMA particles 302 are mixed in the same manner as in Example 3, whereby a toner mass is prepared.

The non-magnetic toner masses thus prepared according to Examples 3-5 are suitably used in the recording system of FIG. 8 described above. However, if these toner masses are used in a recording system wherein the developer toner is electrostatically transferred to image-areas of an image-wise exposed photosensitive medium, a suitable ferrous component is preferably added to the toner masses.

While the present invention has been described in its presently preferred embodiments with a certain degree of particularity, it is to be understood that the invention is not limited to the precise details of the illustrated embodiments, but may be embodied with various changes, modifications and improvements, which may occur to those skilled in the art, without departing from the scope of the invention defined in the following claims.