Method of manufacturing thermal transfer print sheet and printing method

Abstract

A method of manufacturing a thermal transfer print sheet includes forming a color image layer on a transfer base material by a color image layer forming apparatus and forming, on the color image layer, a transfer destination material adhesive layer having a thickness of 40 μm or more and 120 μm or less in one printing operation by a transfer destination material adhesive layer forming apparatus using an electrophotographic procedure. The transfer destination material adhesive layer forming apparatus includes a plurality of developing devices. Among the plurality of developing devices, two or more developing devices include a white toner for forming the transfer destination material adhesive layer. The white toner includes a polyester resin, a polyurethane resin, and a release agent.

Description

[DESCRIPTION][Title of Invention]METHOD OF MANUFACTURING THERMAL TRANSFER PRINT SHEET ANDPRINTING METHOD[Technical Field]

[0001] The present disclosure relates to a method of manufacturing a thermal transfer print sheet and a printing method.[Background Art]

[0002] In an electrophotographic method of developing an electrostatic latent image by using a developer to form a visible image, an electrostatic latent image is formed on an electrostatic latent image bearer containing a photoconductive material, the electrostatic latent image is developed by using a developer containing a toner to form a toner image, and the toner image is transferred onto a transfer material such as paper. Afterwards, the toner image is fixed by applying heat and pressure to form a fixed image.To form a full-color image by an electrophotographic method, a toner set is generally used in which a black toner is combined with toners of three process colors including cyan, magenta, and yellow.

[0003] In recent years, as color image forming apparatuses employing electrophotographic methods are widely used, the applications of such apparatuses on printed items have also become more diverse. Particularly in the field of custom-made design consumer goods, there is a growing need for printing by electrophotographic methods on materials to which conventional electrophotographic toner intended for printing on paper media does not adhere and which therefore cannot be printed with conventional electrophotographic toner. Specifically, there is a growing need for printing on leather media and fabric media such as uniforms, shoes, and bags of sports teams.PTL 1 describes a clothing printing apparatus that uses an inkjet printer to directly print designs on products made of clothing materials such as T-shirts.PTL 2 describes an inkjet printing method and an apparatus therefor that use an inkjet printer to directly print desired image information on fabric, wood, a metal plate, and the like.PTL 3 describes a printing apparatus that uses a thermal transfer device to directly print on a fabric such as clothing.PTL 4 describes a method in which a thermal melt transfer ink ribbon and a color thermal printer are used to print patterns on three types of transfer media, the transfer media is closely contacted with a cotton fabric of a T-shirt and heated, and then, the transfer media is peeled off.PTL 5 describes a method in which two types of thermal transfer sheets are used, one of the sheets is copied to form a toner layer, and then, the two sheets are superimposed and heated to adhere to each other. Afterwards, the two sheets are peeled from each other to form a color layer and an adhesive layer on the toner layer. The obtained sheet is pressed against a T-shirt or the like to print the T-shirt by heat printing.PTL 6 also proposes a release sheet having a releasable surface, a print image that is formed on the release sheet and can be thermally transferred to a transfer destination medium, and a thermal transfer print sheet that can be transferred to a plain black T-shirt by transferring and fixing a special white toner layer onto the print image.[Citation List][Patent Literature]

[0004] [PTL 1]Japanese Unexamined Patent Application Publication No. 07-336466[PTL 2]Japanese Unexamined Patent Application Publication No. 08-207263[PTL 3]Japanese Unexamined Patent Application Publication No. 11-157139[PTL 4]Japanese Unexamined Patent Application Publication No. 05-077557[PTL 5]Japanese Unexamined Patent Application Publication No. 09-087980[PTL 6]Japanese Unexamined Patent Application Publication No. 2014-59486[Summary of Invention][Technical Problem]

[0005] The methods described in PTL 1 to PTL 3 are effective when manufacturing a large number of printed items having the same shape or when manufacturing a printed item having a large size. However, when the size of a piece of fabric or leather serving as a printing target object, is small, such as in the case of clothing, and items of different shapes are to be produced in small quantities and large varieties, a method of conveying the printing target object to a printer differs for each printing target object, and thus, manufacturing the printed items is time-consuming.Further, when printing on a dark-colored printing target object, it is necessary to use white ink. However, in a printing operation using an inkjet method, there may be problems such as precipitation of the white pigment and clogging of the head, so that the maintainability of the printing device greatly decreases. Moreover, when printing on a dark-colored printing targetobject, a thick white concealing layer needs to be applied, which results in slower printing speeds than when printing on a white or light-colored printing target object.

[0006] Further, PTL 4 describes a method in which a pattern is printed on a transfer medium and then thermally transferred to a printing target object such as a T-shirt. This method does not have the problem of a limited choice in the shape of the printing target object, which is observed in the above-described method. However, the size of the transfer medium is a standard size (for example, in many cases, A4 or A3), and thus, the shape to be transferred to the printing target object needs to be prepared separately.

[0007] In the method of PTL 5, two thermal transfer sheets are used to create a shape and then, the shape is thermally printed onto a printing target object such as a T-shirt. Therefore, this method solves the above-mentioned problems. However, this method requires a large amount of work, as it is necessary to use two thermal transfer sheets and perform the thermal printing operation twice. Further, the temperature and the pressure to be applied in the thermal printing operation actually differ for each sample to be prepared, and thus, the work requires skill.

[0008] The printing method of PTL 6 solves the above-described problem. However, the productivity of white toner is low, it is not possible to conceal dark-colored transfer destination materials, and the white color concealing properties are insufficient. Therefore, the transfer destination material is exposed and the color saturation and the brightness of the color image decrease. Further, when repeatedly printing in an attempt to apply a thick white concealing layer to obtain sufficient concealing properties, the productivity decreases due to the plurality of printing operations. Moreover, with an increasing number of printing operations, the transfer base material is more likely to curl, and thus, conveyance problems and positional deviation occur within the device, so that it is difficult to achieve reproducible printing.

[0009] An object of the present disclosure is to provide a method of manufacturing a thermal transfer print sheet, by which it is possible to print a toner image with high print reproducibility, in which the color saturation of the toner image does not decrease on a dark-colored transfer destination material, the toner image is sufficiently fixed to a flexible transfer destination material having strong irregularities, and the toner image has sufficient flexibility and strength.[Solution to Problem]

[0010] To solve the above-described problem, one embodiment of the present disclosure provides a method of manufacturing a thermal transfer print sheet. The method includes: forming acolor image layer on a transfer base material by a color image layer forming apparatus; and forming, on the color image layer, a transfer destination material adhesive layer having a thickness of 40 pm or more and 120 pm or less in one printing operation by a transfer destination material adhesive layer forming apparatus using an electrophotographic procedure. The transfer destination material adhesive layer forming apparatus includes a plurality of developing devices, and among the plurality of developing devices, two or more developing devices include a white toner for forming the transfer destination material adhesive layer. The white toner includes a polyester resin, a polyurethane resin, and a release agent.[Advantageous Effects of Invention]

[0011] According to one embodiment of the present disclosure, a method of manufacturing a thermal transfer print sheet is provided, by which it is possible to print a toner image with high print reproducibility, in which the color saturation of the toner image does not decrease on a dark-colored transfer destination material, the toner image is sufficiently fixed to a flexible transfer destination material having strong irregularities, and the toner image has sufficient flexibility and strength.[Brief Description of Drawings]

[0012] A more complete appreciation of embodiments of the present disclosure and many of the attendant advantages and features thereof can be readily obtained and understood from the following detailed description with reference to the accompanying drawings.[FIG. 1]FIG. 1 is a schematic view of a transfer destination material adhesive layer forming apparatus, used in a method of manufacturing a thermal transfer print sheet according to an embodiment of the present disclosure.[FIG. 2]FIG. 2 is a schematic view of a transfer destination material adhesive layer forming apparatus, used in a method of manufacturing a thermal transfer print sheet according to an embodiment of the present disclosure.[FIG. 3]FIG. 3 is a schematic view of a transfer destination material adhesive layer forming apparatus, used in the method of manufacturing a thermal transfer print sheet according to an embodiment of the present disclosure.[FIG. 4]FIG. 4 is a partial enlarged view of the transfer destination material adhesive layer forming apparatus of FIG. 3.[FIG. 5]FIG. 5 is a schematic view of a process cartridge in a transfer destination material adhesive layer forming apparatus used in a method of manufacturing a thermal transfer print sheet according to an embodiment of the present disclosure.The accompanying drawings are intended to depict embodiments of the present disclosure and should not be interpreted to limit the scope thereof. The accompanying drawings are not to be considered as drawn to scale unless explicitly noted. Also, identical or similar reference numerals designate identical or similar components throughout the several views. [Description of Embodiments]

[0013] In describing embodiments illustrated in the drawings, specific terminology is employed for the sake of clarity. However, the disclosure of this specification is not intended to be limited to the specific terminology so selected and it is to be understood that each specific element includes all technical equivalents that have a similar function, operate in a similar manner, and achieve a similar result.Referring now to the drawings, embodiments of the present disclosure are described below. As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.Embodiments of the present disclosure will be described in detail below.

[0014] (Method of Manufacturing Thermal Transfer Print Sheet)A method of manufacturing a thermal transfer print sheet of the present embodiment includes: forming a color image layer on a transfer base material by a color image layer forming apparatus; and forming, on the color image layer, a transfer destination material adhesive layer having a thickness of 40 pm or more and 120 pm or less in one printing operation by a transfer destination material adhesive layer forming apparatus using an electrophotographic procedure. Tthe transfer destination material adhesive layer forming apparatus includes a plurality of developing devices, and among the plurality of developing devices, two or more developing devices include a white toner for forming the transfer destination material adhesive layer. The white toner includes a polyester resin, a polyurethane resin, and a release agent.According to the present embodiment, a method of manufacturing a thermal transfer print sheet can be provided, by which it is possible to print a toner image with high print reproducibility, in which the color saturation of the toner image does not decrease on a darkcolored transfer destination material, the toner image is sufficiently fixed to a flexible transfer destination material having strong irregularities, and the toner image has sufficient flexibility and strength.

[0015] <Transfer Base Material>The transfer base material used in the method of manufacturing a thermal transfer print sheet of the present embodiment is not particularly limited, as long as the transfer base material is a sheet-like base material that is peelable and can transfer the color image layer and the transfer destination material adhesive layer to a transfer destination material by heat and pressure. However, preferable example of the transfer base material include, but are not limited to, paper, a transfer sheet having a transfer layer, a peeling sheet peeling film having a peeling layer, and a heat-resistant plastic film sheet.The transfer base material preferably includes a layer containing a thermoplastic resin and / or a higher fatty acid. In a case where the transfer base material includes a layer containing a thermoplastic resin and / or a higher fatty acid, when the thermoplastic resin thermally transfers an image to the transfer destination material, a layer containing the thermoplastic resin and the higher fatty acid is formed as a peeling layer on a topmost layer of the image. Therefore, the durability of the image on the transfer destination material can be improved. Further, in a case where the transfer base material includes a higher fatty acid, when an image is thermally transferred to the transfer destination material, the higher fatty acid melts and diffuses into a color image layer and a transfer destination material adhesive layer that are simultaneously formed. Thus, the flexibility of the image thermally transferred to the transfer destination material is further improved.

[0016] <Color Image Layer Forming Step and Color Image Layer Forming Apparatus >The color image layer is formed by the color image layer forming apparatus in the color image layer forming step.The color image layer is preferably formed directly on the transfer base material.An image of the color image layer to be formed is preferably a mirror image obtained by leftright inverting the original image. The color image layer is formed as a mirror image, so that, when the image formed on the thermal transfer print sheet is thermally transferred to the transfer destination material, the image is again left-right inverted, and thus, the image can be formed on the transfer destination material in the original orientation.The color image layer may also be formed by using a PC or the like to prepare in advance mirror image information that is left-right inverted and outputting the mirror image information by the color image layer forming apparatus.In the case of a color image layer forming apparatus including a scanner function, the original image may be scanned and then, an inverted image may be output to form a color image layer. Alternatively, an already left-right inverted mirror image may be scanned and then, output to form a color image layer.

[0017] The color image layer forming apparatus is not particularly limited, as long as the color image layer forming apparatus can form a color image layer as a reverse image on a transfer base material, but is preferably an electrophotographic printer or an inkjet printer, more preferablyan electrophotographic printer, and particularly preferably an electrophotographic printer using a color toner containing a polyester resin.By using an electrophotographic printer, the adhesion between the color image layer and the transfer destination material adhesive layer is improved, and it is possible to obtain a printed item having higher durability.

[0018] The color image layer to be formed on the transfer destination material may be formed by on- demand printing using an electrophotographic procedure or an inkjet procedure, and further, by offset printing, letterpress printing, gravure printing, flexographic printing, screen printing, and the like.

[0019] The color image layer forming apparatus includes at least an electrostatic latent image forming means and a developing means, and may further include other means, if desired. The color image layer forming step includes at least an electrostatic latent image forming step and a developing step, and may further include other steps, if desired.The electrostatic latent image forming step can be suitably implemented by the electrostatic latent image forming means, the developing step can be suitably implemented by the developing means, and the other steps can be suitably implemented by the other means.

[0020] << Electro static Latent Image Forming Step and Electrostatic Latent Image Forming Means >> The electrostatic latent image forming step in the color image layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the electrostatic latent image forming step is a step of forming an electrostatic latent image on an electrostatic latent image bearer of the color image layer forming apparatus. For example, the surface of the electrostatic latent image bearer may be charged and then, exposed to light in the form of an image, and the electrostatic latent image forming means may be used in the electrostatic latent image forming step.The electrostatic latent image forming means in the color image layer forming apparatus is not particularly limited and may be appropriately selected according to a purpose, as long as the electrostatic latent image forming means is a means used for forming an electrostatic latent image on an electrostatic latent image bearer. Examples of the electrostatic latent image forming means include, but are not limited to, a means including at least a charging member that charges the surface of the electrostatic latent image bearer, and an exposure member that exposes the surface of the electrostatic latent image bearer to light in the form of an image.

[0021] - Electrostatic Latent Image Bearer -The material, the structure, and the size of the electrostatic latent image bearer in the color image layer forming apparatus are not particularly limited and can be appropriately selectedfrom known electrostatic latent image bearers. Examples of the material include, but are not limited to, inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine.Examples of the organic photoconductor include, but are not limited to, a laminated photoconductor and a single-layer photoconductor. The laminated photoconductor has a laminated structure in which a layer in which a charge generation material such as metal-free phthalocyanine or titanyl phthalocyanine is dispersed in a binder resin (charge generation layer) and a layer in which a charge transport material is dispersed in a binder resin (charge transport layer), are stacked on a support body such as an aluminum drum. The single-layer photoconductor includes a photosensitive layer having a single layer structure in which both a charge generation material and a charge transport material are dispersed in a binder resin on a support body.In the case of the single-layer photoconductor, a hole transport agent and an electron transport agent may be added to the photosensitive layer as charge transport materials.Further, an undercoat layer may be provided between the support body and the charge generation layer in the laminated photoconductor or between the support body and the photosensitive layer in the single-layer photoconductor.

[0022] - Charging Member and Charging Process -The charging member in the color image layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose. Examples of the charging member include, but are not limited to, a known contact charging device including a conductive or semiconductive roller, a brush, a film, a rubber blade, or the like, and a non-contact charging device utilizing corona discharge such as a corotron and a scorotron.The charging process in the color image layer forming apparatus can be implemented, for example, by using the charging member to apply a voltage to the surface of the electrostatic latent image bearer.The shape of the charging member may be any shape, such as a roller, a magnetic brush, and a fur brush, and can be selected according to the specifications and aspects of the color image layer forming apparatus.The charging member in the color image layer forming apparatus is not limited to the contacttype charging member. However, it is preferable to use a contact-type charging member, because in this case, it is possible to obtain an image forming apparatus in which the amount of ozone generated from the charging member is reduced.

[0023] - Exposure Member and Exposure Process -The exposure member in the color image layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose, as long as the exposure member can expose, in the form of the image to be formed, the surface of the electrostatic latent imagebearer charged by the charging member. Examples of the exposure member include, but are not limited to, various types of exposure members such as copying optical systems, rod lens array systems, laser optical systems, and liquid crystal shutter optical systems.The light source used in the exposure member of the color image layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose. Examples of the light source include, but are not limited to, general light-emitting devices such as fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, lightemitting diodes (LED), semiconductor lasers (LD), and electroluminescence (EL) sources. To emit only light in a desired wavelength region, various types of filters can be used, such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter.The exposure process in the color image layer forming apparatus can be implemented, for example, by using an exposure member to expose the surface of the electrostatic latent image bearer in the form of an image.In the color image layer forming apparatus, a back-light method may be adopted in which the electrostatic latent image bearer is exposed to light in the form of an image from the back side.

[0024] <<Dev eloping Step and Developing Means >>The developing step in the color image layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the developing step is a step of developing the electrostatic latent image formed on the electrostatic latent image bearer of the color image layer forming apparatus by using a color toner to form a visible image. The developing step can be implemented by a developing means of the color image layer forming apparatus.The developing means in the color image layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose, as long as the developing means is a developing means that includes a color toner and develops the electrostatic latent image formed on the electrostatic latent image bearer to form a color image layer.An example of the developing means in the color image layer forming apparatus includes, but is not limited to, a developing device. Such a developing device includes at least a developer storage that stores color toner, and preferably includes a stirrer that frictionally stirs the color toner to charge the color toner, and a rotatable developer bearer including a magnetic field generating means fixed inside the developer bearer and carrying a developer containing the color toner on a surface.For example, in the developing means of the color image layer forming apparatus, the color toner and the carrier are mixed and stirred, and at this time, the color toner is charged by friction, and is maintained in an upright state on the surface of a rotating magnet roller, to form a magnetic brush. The magnet roller is arranged in the vicinity of the electrostatic latentimage bearer. Therefore, a part of the color toner forming the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image bearer by electric attraction. As a result, the electrostatic latent image is developed by the color toner, and a visible image is formed by the color toner on the surface of the electrostatic latent image bearer.

[0025] <<Other Steps and Other Means>>Examples of other steps in the color image layer forming step include, but are not limited to, a transfer step, a fixing step, a cleaning step, a static elimination step, a recycling step, and a control step.Examples of other means in the color image layer forming apparatus include, but are not limited to, a transfer means, a fixing means, a cleaning means, a static elimination means, a recycling means, and a control means.

[0026] - Transfer Step and Transfer Means -The transfer step in the color image layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the transfer step is a step of transferring a color image layer. However, in a preferred aspect, an intermediate transfer body is used, the color image layer is primarily transferred onto the intermediate transfer body, and then, the color image layer is secondarily transferred onto a transfer base material. For example, the transfer step in the color image layer forming step may be performed by charging the color image layer and the electrostatic latent image bearer with a transfer charger. The transfer step may be implemented by the transfer means.The transfer means in the color image layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose, as long as the transfer means is a means used for transferring a color image layer. However, in a preferred aspect, the transfer means includes a primary transfer means that transfers the color image layer onto the intermediate transfer body to form a composite transfer image, and a secondary transfer means that transfers the color image layer onto a transfer base material.

[0027] The intermediate transfer body in the color image layer forming apparatus is not particularly limited and can be appropriately selected from known transfer bodies according to a purpose. Preferred examples of the intermediate transfer body include, but are not limited to, a transfer belt.The transfer means (the primary transfer means and the secondary transfer means) in the color image layer forming apparatus preferably includes at least a transfer device that peels the visible image formed on the electrostatic latent image bearer and charges the peeled visible image toward the recording medium. Examples of the transfer device include, but are notlimited to, a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

[0028] - Fixing Step and Fixing Means -The fixing step in the color image layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the fixing step is a step of fixing the color image layer onto a transfer base material. The fixing step can be performed simultaneously at once in a state where the layers of the color toner output from the developing means of each color are laminated on each other.The fixing means in the color image layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose, as long as the fixing means is a means used for fixing a color image layer onto a recording medium. However, the fixing means is preferably a known heating and pressing member. Examples of the heating and pressing member include, but are not limited to, a combination of a heating roller and a pressure roller, and a combination of a heating roller, a pressure roller, and an endless belt.The fixing step in the color image layer forming step may be implemented by the fixing means in the color image layer forming apparatus.Normally, the heating temperature in the heating and pressing member of the color image layer forming apparatus is preferably from 80°C to 200°C.Note that, in the color image layer forming apparatus, according to a purpose, a known optical fixing device may be used together with or instead of the fixing means of the color image layer forming apparatus, for example.The surface pressure in the fixing step is not particularly limited and can be appropriately selected according to a purpose, but is preferably from 10 N / cm2to 80 N / cm2.

[0029] - Cleaning Step and Cleaning Means -The cleaning step in the color image layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the cleaning step is a step by which it is possible to remove color toner remaining on the electrostatic latent image bearer. For example, the cleaning step may be performed by the cleaning means in the color image layer forming apparatus.The cleaning means in the color image layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose, as long as the cleaning means is a means that can remove color toner remaining on the electrostatic latent image bearer. Examples of the cleaning means include, but are not limited to, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.

[0030] - Static Elimination Step and Static Elimination Means -The static elimination step in the color image layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the static elimination step is a step of applying a static elimination bias to the electrostatic latent image bearer to destaticize the electrostatic latent image bearer. For example, the static elimination step may be performed by the static elimination means in the color image layer forming apparatus.The static elimination means in the color image layer forming apparatus is not particularly limited and may be appropriately selected according to a purpose, as long as the static elimination means is a means that applies a static elimination bias to the electrostatic latent image bearer to destaticize the electrostatic latent image bearer. Examples of the static elimination means include, but are not limited to, a static elimination lamp.

[0031] - Recycling Step and Recycling Means -The recycling step in the color image layer forming step is not particularly limited and may be appropriately selected according to a purpose, as long as the recycling step is a step of causing the developing device to recycle the color toner removed in the cleaning step. For example, the recycling step may be performed by the recycling means in the in the color image layer forming apparatus.The recycling means in the color image layer forming apparatus is not particularly limited and may be appropriately selected according to a purpose, as long as the recycling means is a means causing the developing device to recycle the color toner removed in the cleaning step. Examples of the recycling means include, but are not limited to, a known conveyance means.

[0032] - Control Step and Control Means -The control step in the color image layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the control step is a step by which it is possible to control an operation in each step in the color image layer forming step. For example, the control step may be performed by the control means in the color image layer forming apparatus.The control means in the color image layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose, as long as the control means is a means that can control an operation of each means in the color image layer forming apparatus. Examples of the control means include, but are not limited to, devices such as a sequencer and a computer.

[0033] <Color Image Layer>The color image layer is formed by using a color toner.

[0034] <<Color Toner>>The color toner contains a resin and a colorant, and may contain other constituent materials such as a release agent, a charge control agent, an external additive, a fluidity improver, and a cleanability improver.

[0035] - Resin -The resin used as the material of the color toner employed in the color image layer forming apparatus may be a resin known in the related art. Examples of the resin include, but are not limited to, styrene-based resins (homopolymers or copolymers containing styrene or a styrene substitute) such as styrene, poly-a-methylstyrene, styrene-chlorostyrene copolymer, styrenepropylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene- vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene- a-me thy 1 chloroacrylate copolymer, and styrene-acrylonitrile-acrylic acid ester copolymer, epoxy resins, vinyl chloride resins, rosin-modified maleic acid resins, phenolic resins, polyethylene resins, polypropylene resins, petroleum resins, polyurethane resins, polyester resins, ketone resins, ethylene-ethyl acrylate copolymer, xylene resins, and polyvinyl butyrate resins. A method of manufacturing these resins is not particularly limited, and examples thereof include bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization.

[0036] The resin used in the color toner preferably contains a polyester resin. If the color toner contains a polyester resin, the adhesion between the color toner and a toner for a transfer destination material adhesive layer is improved, and a printed item with higher durability can be obtained.Further, from the viewpoint of further improving the adhesion to the transfer destination material adhesive layer and the durability, it is preferable that the resin used in the color toner contains a polyester resin similar to the resin used in the toner for a transfer destination material adhesive layer.

[0037] The color toner preferably contains a polyurethane resin. If the color toner contains a polyurethane resin, it is possible to obtain a color image layer that has high durability and does not easily crack or peel off.Further, from the viewpoint of further improving the adhesion to the transfer destination material adhesive layer and the durability, it is preferable that the resin used in the color toner contains a polyurethane resin similar to the resin used in the toner for a transfer destination material adhesive layer.

[0038] - Colorant -The color toner is not particularly limited and a colorant that is appropriately selected from commonly used colorants can be used in the color toner. Examples of the color toner include, but are not limited to, black toner, cyan toner, magenta toner, yellow toner, red toner, green toner, blue toner, fluorescent pink toner, fluorescent blue toner, and fluorescent yellow toner.

[0039] The black toner is not particularly limited and a suitable colorant can be selected according to a purpose. However, preferred examples of the black toner include, but are not limited to, carbon black used alone or a mixture of carbon black as a main component with copper phthalocyanine and the like, in which the hue and the brightness are adjusted.

[0040] The cyan toner is not particularly limited and a suitable colorant can be selected according to a purpose. However, preferred examples of the cyan toner include, but are not limited to, copper phthalocyanine, which serves as Pigment Blue 15:3, or a mixture of the above- mentioned colorants and aluminum phthalocyanine.

[0041] The magenta toner is not particularly limited and a suitable colorant can be selected according to a purpose. However, Pigment Red 53: 1, Pigment Red 81, Pigment Red 122, and Pigment Red 269 can be used alone or in combination with each other.

[0042] The yellow toner is not particularly limited and a suitable colorant can be selected according to a purpose. However, Pigment Yellow 74, Pigment Yellow 155, Pigment Yellow 180, and Pigment Yellow 185 can be used alone or in combination with each other. Among these yellow colorants, it is preferable to use Pigment Yellow 185 alone or a mixture of Pigment Yellow 185 and Pigment Yellow 74 to obtain color saturation and storability.

[0043] The red toner is not particularly limited, and a suitable colorant can be selected according to a purpose. However, Pigment Red 254, Pigment Red 166, Pigment Red 144, and Pigment Red 48:2 can be used alone or in combination with each other.

[0044] The green toner is not particularly limited, and a suitable colorant can be selected according to a purpose. For example, Pigment Green 7 and the like can be used, but safety needs to be ensured.

[0045] The blue toner is not particularly limited, and a suitable colorant can be selected according to a purpose. Examples of the blue toner include, but are not limited to, Pigment Blue 15:1 and Pigment Violet 23.

[0046] - Release Agent -The color toner may contain a release agent.The type of the release agent that can be used in the color toner is not particularly limited and can be appropriately selected according to a purpose. One type of release agent may be used alone, or two or more types of release agents may be used in combination.The release agent that can be used in the color toner is not particularly limited and can be appropriately selected according to a purpose. Examples of the release agent include, but are not limited to, liquid paraffin, microcrystalline wax, natural paraffin, synthetic paraffin, polyolefin wax, and partial oxides of these compounds, or aliphatic hydrocarbons such as fluorides and chlorides, animal oils such as beef tallow and fish oil, vegetable oils such as palm oil, soybean oil, rapeseed oil, rice bran wax, and carnauba wax, higher aliphatic alcohols and higher fatty acids such as montan wax, fatty acid amides, fatty acid bisamides, metal soaps such as zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, zinc oleate, zinc palmitate, magnesium palmitate, zinc myristate, zinc laurate, and zinc behenate, fatty acid esters, and polyvinylidene fluoride. Among these release agents, it is preferable to use at least an ester wax such as a fatty acid ester.

[0047] In a case where the toner contains a maleic acid-modified polyolefin having a polypropylene block in the main chain, if the content of the maleic acid-modified polyolefin is high, it may not be possible to separate the toner from the fixing roller or the fixing belt during fixing, and thus, a waste sheet jam may occur. However, this problem can be resolved by adding an ester wax as the release agent. Further, the ester wax can be finely dispersed in the maleic acid- modified polyolefin having a polypropylene block in the main chain.

[0048] The content of the release agent in the color toner is not particularly limited and can be appropriately selected according to a purpose. However, the content is preferably from 0.1 to 8.0 mass%, and more preferably from 1.0 to 6.0 mass%. If the content of the release agent in the color toner is 0.1 mass% or more, the toner is easily separated from the fixing roller or the fixing belt during fixing, and thus, waste sheet jams can be prevented. Further, if the content of the release agent in the color toner is 8.0 mass% or less, the toner can be sufficiently fixed to a plastic film.

[0049] - Charge Control Agent -The color toner may contain a charge control agent.The charge control agent can be appropriately selected according to a purpose, as long as the charge control agent is white or colorless. Examples of the charge control agent include, but are not limited to, onium salts such as phosphonium salts and lake pigments thereof, triphenylmethane dyes and lake pigments thereof, metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, and dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate, and dicyclohexyltin borate, organic metal complexes, chelate compounds, monoazo metal complexes, acetylacetone metalcomplexes, aromatic hydroxycarboxylic acids, metal complexes of aromatic dicarboxylic acids, and quaternary ammonium salts. Other examples of the charge control agent include, but are not limited to, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol. These charge control agents may be used alone or in combination of two or more types.

[0050] When these charge control agents are added internally to the color toner, the content of the charge control agents is not particularly limited and can be appropriately set according to a purpose. However, the content of the charge control agent is preferably from 0.1 to 10 mass% with respect to the total amount of the resin.

[0051] - External Additives -In the color toner, inorganic fine particles and the like can be used as an external additive. The inorganic fine particles used as external additives in the color toner are not particularly limited and can be appropriately selected according to a purpose. Examples of the inorganic fine particles include, but are not limited to, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these inorganic fine particles, silica, alumina, and titanium oxide are preferred.

[0052] The inorganic fine particles used in the color toner may be subjected to a surface treatment using a hydrophobicity treatment agent. The hydrophobicity treatment agent is not particularly limited and can be appropriately selected according to a purpose. However, preferred examples of surface treatment agents include, but are not limited to, silane coupling agents, silylation agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, and aluminum coupling agents. Further, it is possible to obtain a sufficient effect by using silicone oil as a hydrophobicity treatment agent.

[0053] The average diameter of primary particles of the inorganic fine particles used in the color toner is not particularly limited and may be appropriately selected according to a purpose, but is preferably from 5 to 500 nm, and more preferably from 5 to 200 nm. If the average diameter is 5 nm or more, the inorganic fine particles are prevented from aggregating, and the inorganic fine particles can be uniformly dispersed in the color toner. If the average diameter is 500 nm or less, the heat-resistant storage stability can be improved by a filler effect. Here, the average diameter of the primary particles of the inorganic fine particles refers to a value obtained by directly determining the particle diameter from an image obtained by atransmission electron microscope. It is preferable to observe at least 100 or more inorganic fine particles and use the average value of the major axes of the inorganic fine particles.

[0054] - Fluidity Improver -The color toner may contain a fluidity improver as an additive. The fluidity improver is not particularly limited and can be appropriately selected according to a purpose, as long as the fluidity improver can be used to perform a surface treatment to increase the hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under conditions including high humidity. Examples of the fluidity improver include, but are not limited to, silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum-based coupling agents, silicone oil, and modified silicone oil.When silica or titanium oxide is used as the external additive, it is preferable to perform a surface treatment with such a fluidity improver and use the silica or the titanium oxide as hydrophobic silica or hydrophobic titanium oxide.

[0055] - Cleanability Improver -The color toner may contain a cleanability improver as an additive. The cleanability improver is not particularly limited and can be appropriately selected according to a purpose, as long as the cleanability improver can be added to the color toner to remove color toner remaining on the electrostatic latent image bearer or the primary transfer medium after transfer. Examples of the cleanability improver include, but are not limited to, fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, and polymer fine particles prepared by soap-free emulsion polymerization such as polymethyl methacrylate fine particles, and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and preferably have a volume average particle diameter of 0.01 pm or more and 1 pm or less.

[0056] It is preferable that, in the release agent, the charge control agent, the external additive, the fluidity improver, and the cleanability improver used in the color toner, similar materials are used as those in the toner for a transfer destination material adhesive layer, to improve the adhesion between the color toner and the toner for a transfer destination material adhesive layer and to obtain a printed item having higher durability.

[0057] <<Developer>>The color toner may be used as a one-component developer or a two-component developer. However, when used in a high-speed printer and the like responding to the increased information processing speed in recent years, a two-component developer is preferred, because such a developer provides a longer service life.When the color toner is used as a one-component developer, and even if the toner is being consumed and resupplied, the particle diameter of the toner varies little, there is little filming of the toner on the developing roller, and the toner hardly fuses with components such as a blade used to obtain a thin layer of the toner. Therefore, it is possible to obtain good and stable developing properties and images, even when the color toner is stirred during a long period of time in the developing device.When the color toner is mixed with a carrier and used as a two-component developer, the particle diameter of the toner varies little, even when the toner is being consumed and resupplied over a long period of time. Therefore, good and stable developing properties and images can be obtained, even when the color toner is stirred during a long period of time in the developing device.The color toner can be mixed with a carrier to form a two-component developer, which can be used in an electrophotographic image forming method using a two-component developing procedure.A magnetic carrier can be used as the carrier.

[0058] As a developing procedure, a premix developing procedure may be adopted in which a premix developer is supplied, which is obtained by mixing a toner and a carrier in advance. In the premix developing procedure, an amount of carrier by which the carrier in the developing device increases is discharged as excess developer. This gradually renews the developer in the developing device. Therefore, it is possible to prolong the replacement cycle caused by deterioration of the developer, and to reduce the burden of replacing the developer.

[0059] - Magnetic Carrier -When a two-component developing procedure is used, the material of the magnetic fine particles used in the magnetic carrier is not particularly limited and can be appropriately selected according to a purpose. Examples of the material include, but are not limited to, iron powder, magnetite, spinel ferrite such as gamma iron oxide, spinel ferrite containing one or more metals other than iron (such as Mn, Ni, Zn, Mg, and Cu), magnetoplumbite-type ferrite such as barium ferrite, and iron or alloy particles having an oxide layer on the surface.Further, to ensure chemical stability, it is preferable to use magnetite, spinel ferrite containing gamma iron oxide, and magnetoplumbite-type ferrite such as barium ferrite, as the material of the magnetic fine particles. Specifically, preferred examples of the material include, but are not limited to, MFL-35S, MFE-35HS (manufactured by Powder Tech Co., Etd.), DFC-400M, DFC-410M, and SM-350NV (manufactured by Dowa IP Creation Co., Etd.).Among these materials, white materials are preferred in terms of color tone.The shape of the magnetic fine particles may be any shape among granular, spherical, and needle-like shapes. In particular, when it is desired to strongly magnetize the magnetic carrier, it is preferable to use ferromagnetic fine particles such as iron fine particles.

[0060] By selecting the type and the content of the magnetic fine particles, it is possible to use a magnetic carrier having a desired magnetic charge.The magnetic properties of the magnetic carrier are preferably such that the strength of the magnetic charge at 1,000 oersted is from 30 to 150 emu / g.

[0061] The chargeability of the magnetic carrier can be controlled by fixing positively or negatively charged fine particles or conductive fine particles to the surface of the magnetic fine particles, or by coating the surface of the magnetic fine particles with a resin.Examples of the resin that can serve as coating material for the surface of the magnetic fine particles include, but are not limited to, silicone resins, acrylic resins, epoxy resins, and fluorine-based resins. Among these resins, silicone resins and acrylic resins are preferred. The surface of the magnetic fine particles may be further coated with positively or negatively charged fine particles or with conductive fine particles.The magnetic carrier may be manufactured by spraying a molten and melt-kneaded mixture of magnetic fine particles and an insulating binder resin using a spray dryer. Alternatively, a monomer or a prepolymer may be reacted and cured in an aqueous medium in which the magnetic fine particles are present, to prepare the magnetic carrier as a resin carrier in which the magnetic fine particles are dispersed in a condensation-type binder.

[0062] In the two-component developer, the mass ratio of the carrier in the developer stored in the developing device is preferably 85 mass% or more and less than 98 mass%.When the mass ratio of the carrier in the developer is 85 mass% or more, the toner is unlikely to scatter from the developing device, and it is possible to reduce the occurrence of defective images.When the mass ratio of the carrier in the developer is less than 98 mass%, it is possible to suppress an excessive increase in the charge amount of the color toner and a shortage in the supply amount of the color toner, and thus, it is possible to reduce the occurrence of defective images due to a decrease in image density.

[0063] <Transfer Destination Material Adhesive Layer Forming Step and Transfer Destination Material Adhesive Layer Forming Apparatus>In the transfer destination material adhesive layer forming step, the transfer destination material adhesive layer forming apparatus forms, in one printing operation, a transfer destination material adhesive layer having a thickness of 40 pm or more and 120 pm or less. The transfer destination material adhesive layer forming apparatus uses an electrophotographic procedure. By employing an electrophotographic procedure, even if a white pigment is used in the toner for a transfer destination material adhesive layer, unlikeink, the white pigment does not precipitate or aggregate, and thus, the maintainability of the transfer destination material adhesive layer forming apparatus does not decrease.

[0064] The transfer destination material adhesive layer forming step is preferably performed after the color image layer forming step.It is preferable that, after the color image layer is formed on the transfer base material in the color image layer forming step, the transfer destination material adhesive layer is formed on the color image layer in the transfer destination material adhesive layer forming step.It is more preferable to form a transparent transfer destination material adhesive layer on the color image layer, and to form a white transfer destination material adhesive layer on the transparent transfer destination material adhesive layer.By forming the transparent transfer destination material adhesive layer on the color image layer, it is possible to obtain vivid print quality in which the color saturation and the brightness do not decrease, even if the color image layer is embedded in the transfer destination material adhesive layer during thermal transfer to the transfer destination material. Herein, "white toner for a transfer destination material adhesive layer" refers to a toner for a transfer destination material adhesive layer containing a white pigment, and "white transfer destination material adhesive layer" refers to a transfer destination material adhesive layer formed by the "white toner for a transfer destination material adhesive layer".Further, "transparent toner for a transfer destination material adhesive layer" refers to a toner for a transfer destination material adhesive layer not containing a coloring material, and "transparent transfer destination material adhesive layer" refers to a transfer destination material adhesive layer formed by the "transparent toner for a transfer destination material adhesive layer".

[0065] The transfer destination material adhesive layer is superimposed and formed on the color image layer. Therefore, when the image of the color image layer is a mirror image obtained by left-right inverting the original image, the transfer destination material adhesive layer is also formed based on the mirror image obtained by left-right inverting the original image, similarly to the color image layer.The transfer destination material adhesive layer may be formed by preparing mirror image information of a color image that is left-right inverted in advance by using a PC or the like, and using the transfer destination material adhesive layer forming apparatus to output the mirror image information.In the case of a transfer destination material adhesive layer forming apparatus including a scanner function, the original image may be scanned and then, an inverted image may be output to form the transfer destination material adhesive layer. Alternatively, a mirror image that is already left-right inverted may be scanned and then output to form the transfer destination material adhesive layer.

[0066] The thickness of the transfer destination material adhesive layer formed by the transfer destination material adhesive layer forming apparatus in one printing operation is 40 pm or more and 120 pm or less, preferably 50 pm or more and 120 pm or less, and more preferably 60 pm or more and 120 pm or less.If the thickness of the transfer destination material adhesive layer formed by the transfer destination material adhesive layer forming apparatus in one printing operation is less than 40 pm, the color saturation of the color image layer decreases when an image is formed on a dark-colored transfer destination material, and thus, it is difficult to obtain a vivid image. If the thickness is more than 120 pm, it is difficult to set fixing conditions by which hot offset and cold offset is suppressed, and thus, it is difficult to obtain stable quality.If the thickness of the transfer destination material adhesive layer formed by the transfer destination material adhesive layer forming apparatus in one printing operation is 50 pm or more and 120 pm or less, a more vivid color image layer can be obtained.If the transfer destination material adhesive layer includes a white transfer destination material adhesive layer and a transparent transfer destination material adhesive layer, the white transfer destination material adhesive layer is preferably 40 pm or more and 100 pm or less.

[0067] The transfer destination material adhesive layer forming apparatus includes at least an electrostatic latent image forming means and a developing means, and may further include other means, if desired.The transfer destination material adhesive layer forming step includes at least an electrostatic latent image forming step and a developing step, and may further include other steps, if desired.In the transfer destination material adhesive layer forming step, the electrostatic latent image forming step can be suitably implemented by the electrostatic latent image forming means, the developing step can be suitably implemented by the developing means, and the other steps can be suitably implemented by the other means.

[0068] << Electro static Latent Image Forming Step and Electrostatic Latent Image Forming Means >> The electrostatic latent image forming step in the transfer destination material adhesive layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the electrostatic latent image forming step is a step of forming an electrostatic latent image on an electrostatic latent image bearer. For example, the surface of the electrostatic latent image bearer may be charged and then exposed to light in the form of an image, and the electrostatic latent image forming means may be used in the electrostatic latent image forming step.The electrostatic latent image forming means in the transfer destination material adhesive layer forming apparatus is not particularly limited and may be appropriately selected according to a purpose, as long as the electrostatic latent image forming means is a means used for forming an electrostatic latent image on the electrostatic latent image bearer. Examples of the electrostatic latent image forming means include, but are not limited to, a means including at least a charging member that charges the surface of the electrostatic latent image bearer, and an exposure member that exposes the surface of the electrostatic latent image bearer to light in the form of an image.

[0069] - Electrostatic Latent Image Bearer -The material, the structure, and the size of the electrostatic latent image bearer in the transfer destination material adhesive layer forming apparatus are not particularly limited and can be appropriately selected from known electrostatic latent image bearers. Examples of the material include, but are not limited to, inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. Examples of the organic photoconductor include, but are not limited to, a laminated photoconductor and a single-layer photoconductor. The laminated photoconductor has a laminated structure in which, on a support body such as an aluminum drum, a layer in which a charge generation material such as metal-free phthalocyanine or titanyl phthalocyanine is dispersed in a binder resin (charge generation layer), and a layer in which a charge transport material is dispersed in a binder resin (charge transport layer) are stacked. The single-layer photoconductor includes a photosensitive layer having a single layer structure in which both a charge generation material and a charge transport material are dispersed in a binder resin on a support body.In the case of the single-layer photoconductor, a hole transport agent and an electron transport agent may be added to the photosensitive layer as charge transport materials.Further, an undercoat layer may be provided between the support body and the charge generation layer in the laminated photoconductor or between the support body and the photosensitive layer in the single-layer photoconductor.

[0070] - Charging Member and Charging Process -The charging member in the transfer destination material adhesive layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose. Examples of the charging member include, but are not limited to, a known contact charging device including a conductive or semiconductive roller, a brush, a film, a rubber blade, or the like, and a non-contact charging device utilizing corona discharge such as a corotron and a scorotron.The charging process in the transfer destination material adhesive layer forming apparatus can be implemented, for example, by using the charging member to apply a voltage to the surface of the electrostatic latent image bearer.The shape of the charging member may be any shape, such as a roller, a magnetic brush, and a fur brush, and can be selected according to the specifications and aspects of the transfer destination material adhesive layer forming apparatus.The charging member is not limited to the contact-type charging member, but it is preferable to use a contact-type charging member, because in this case, it is possible to obtain a transfer destination material adhesive layer forming apparatus in which the amount of ozone generated from the charging member is reduced.

[0071] - Exposure Member and Exposure Process -The exposure member in the transfer destination material adhesive layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose, as long as the exposure member can expose, in the form of the image to be formed, the surface of the electrostatic latent image bearer charged by the charging member. Examples of the exposure member include, but are not limited to, various types of exposure members such as copying optical systems, rod lens array systems, laser optical systems, and liquid crystal shutter optical systems.The light source used in the exposure member is not particularly limited and can be appropriately selected according to a purpose. Examples of the light source include, but are not limited to, general light-emitting devices such as fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light-emitting diodes (LED), semiconductor lasers (LD), and electroluminescence (EL) sources.

[0072] To emit only light in a desired wavelength region, various types of filters can be used, such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter.The exposure process in the transfer destination material adhesive layer forming apparatus can be implemented, for example, by using an exposure member to expose the surface of the electrostatic latent image bearer in the form of an image.In the transfer destination material adhesive layer forming apparatus, a back-light procedure may be adopted in which the electrostatic latent image bearer is exposed to light in the form of an image from the back side.

[0073] <<Dev eloping Step and Developing Means >>The developing step in the transfer destination material adhesive layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the developing step is a step of developing the electrostatic latent image formed on theelectrostatic latent image bearer of the transfer destination material adhesive layer forming apparatus, by using the toner for a transfer destination material adhesive layer to form a visible image. The developing step can be implemented by the developing means of the transfer destination material adhesive layer forming apparatus.The developing means in the transfer destination material adhesive layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose, as long as the developing means is a developing means that includes a toner for a transfer destination material adhesive layer and develops the electrostatic latent image formed on the electrostatic latent image bearer to form a transfer destination material adhesive layer.An example of the developing means in the transfer destination material adhesive layer forming apparatus includes, but is not limited to, a developing device. Such a developing device includes at least a developer storage that stores a toner for a transfer destination material adhesive layer, and preferably includes a stirrer that frictionally stirs the toner for a transfer destination material adhesive layer to charge the toner for a transfer destination material adhesive layer, and a rotatable developer bearer including a magnetic field generating means fixed inside the developer bearer and carrying a developer containing the toner for a transfer destination material adhesive layer on a surface.

[0074] For example, in the developing means of the transfer destination material adhesive layer forming apparatus, the toner for a transfer destination material adhesive layer and the carrier are mixed and stirred, and at this time, the toner is charged by friction, and is maintained in an upright state on the surface of a rotating magnet roller, to form a magnetic brush. The magnet roller is arranged in the vicinity of the electrostatic latent image bearer. Therefore, a part of the toner for a transfer destination material adhesive layer that forms the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image bearer by electric attraction. As a result, the electrostatic latent image is developed by the toner, and a visible image is formed by the toner for a transfer destination material adhesive layer, on the surface of the electrostatic latent image bearer.

[0075] The transfer destination material adhesive layer forming apparatus includes a plurality of developing devices, and among the plurality of developing devices, two or more developing devices include a white toner for a transfer destination material adhesive layer, that is used to form the transfer destination material adhesive layer and contains a polyester resin, a polyurethane resin, and a release agent. The white toner forms a white transfer destination material adhesive layer.It is preferable that the transfer destination material adhesive layer forming apparatus further includes a developing device including a transparent toner that is used to form the transfer destination material adhesive layer and contains a polyester resin, a polyurethane resin, and arelease agent. The transparent toner for a transfer destination material adhesive layer forms a transparent transfer destination material adhesive layer.

[0076] Among the plurality of developing devices included in the transfer destination material adhesive layer forming apparatus, two or more developing devices include a white toner for a transfer destination material adhesive layer, which contains a polyester resin, a polyurethane resin, and a release agent, and form a transfer destination material adhesive layer in one printing operation. Thus, it is possible to prepare a thermal transfer print sheet in which the color image layer does not protrude to the outside from the transfer destination material adhesive layer.It is preferable that the transfer destination material adhesive layer forming apparatus further includes a developing device including a transparent toner for a transfer destination material adhesive layer, containing a polyester resin, a polyurethane resin, and a release agent, and thus, it is possible to form in one printing operation a transfer destination material adhesive layer including a white transfer destination material adhesive layer and a transparent transfer destination material adhesive layer.

[0077] The developing device containing the white toner for a transfer destination material adhesive layer and the developing device containing the transparent toner for a transfer destination material adhesive layer are arranged in the transfer destination material adhesive layer forming apparatus so that a transparent transfer destination material adhesive layer is formed on the color image layer formed on the transfer base material and a white transfer destination material adhesive layer is formed on the transparent transfer destination material adhesive layer. Therefore, it is possible to prepare a thermal transfer print sheet in which the toner layers are layered in the following order: transfer base material - color image layer - transparent transfer destination material adhesive layer - white transfer destination material adhesive layer.

[0078] The amount of toner for a transfer destination material adhesive layer output from each developing device of the transfer destination material adhesive layer forming apparatus is preferably 1.7 mg / cm2or more and 4.8 mg / cm2or less, more preferably 1.7 mg / cm2or more and 3.2 mg / cm2or less, and even more preferably 1.7 mg / cm2or more and 3.0 mg / cm2or less. If the amount of toner for a transfer destination material adhesive layer output from each developing device is 1.7 mg / cm2or more and 4.8 mg / cm2or less, when a thermal transfer print sheet in which a transfer destination material adhesive layer is formed on a transfer base material by using a plurality of developing devices, is thermally transferred to a transfer destination material, the image on the transfer destination material does not become stiff, and the underlayer of the transfer destination material can be sufficiently concealed by the white color.If the amount of the toner for a transfer destination material adhesive layer output from each developing device is 1.7 mg / cm2or more and 3.2 mg / cm2or less, it is possible to prevent the toner for a transfer destination material adhesive layer from remaining as residue after the transfer. If the amount of the toner for a transfer destination material adhesive layer is 1.7 mg / cm2or more and 3.0 mg / cm2or less, it is possible to further prevent the toner for a transfer destination material adhesive layer from remaining as residue after the transfer.

[0079] The thickness of the transfer destination material adhesive layer formed by the toner for a transfer destination material adhesive layer output from one developing device of the transfer destination material adhesive layer forming apparatus is preferably 20 pm or more and 30 pm or less.If the thickness of the transfer destination material adhesive layer formed by the toner for a transfer destination material adhesive layer output from one developing device is 20 pm or more and 30 pm or less, when a thermal transfer print sheet in which a transfer destination material adhesive layer is formed on a transfer base material by using a plurality of developing devices, is thermally transferred to a transfer destination material, the image on the transfer destination material does not become stiff, and the underlayer of the transfer destination material can be sufficiently concealed by the white color. Further, it is possible to prevent the toner for a transfer destination material adhesive layer from remaining as residue after the transfer.

[0080] <<Other Steps and Other Means>>Examples of other steps in the transfer destination material adhesive layer forming step include, but are not limited to, a transfer step, a fixing step, a cleaning step, a static elimination step, a recycling step, and a control step.Examples of other means in the transfer destination material adhesive layer forming apparatus include, but are not limited to, a transfer means, a fixing means, a cleaning means, a static elimination means, a recycling means, and a control means.

[0081] - Transfer Step and Transfer Means -The transfer step in the transfer destination material adhesive layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the transfer step is a step of transferring the transfer destination material adhesive layer onto the color image layer on the transfer base material. However, in a preferred aspect of the transfer step, an intermediate transfer body is used to primarily transfer the transfer destination material adhesive layer onto the intermediate transfer body, and then, the transfer destination material adhesive layer is secondarily transferred onto the color image layer on the transfer base material.The transfer means is not particularly limited and can be appropriately selected according to a purpose, as long as the transfer means is a means used for transferring the transfer destination material adhesive layer onto the color image layer. However, in a preferred aspect, the transfer means includes a primary transfer means that transfers an image of the transfer destination material adhesive layer onto an intermediate transfer body to form a composite transfer image, and a secondary transfer means that transfers the composite transfer image onto the color image layer.For example, the transfer step may be performed by charging the transfer destination material adhesive layer and the electrostatic latent image bearer of the transfer destination material adhesive layer forming apparatus with a transfer charger. The transfer step be implemented by the transfer means.

[0082] Here, when the image to be secondarily transferred onto the color image layer is a transfer destination material adhesive layer containing two types of toners for a transfer destination material adhesive layer, that is, transparent toner and white toner, a configuration may be such that the transfer means sequentially superimposes the toner for a transfer destination material adhesive layer on the intermediate transfer body to form a transfer destination material adhesive layer on the intermediate transfer body, and the intermediate transfer means secondarily transfers the transfer destination material adhesive layer on the intermediate transfer body onto the color image layer in one process.

[0083] The intermediate transfer body in the transfer destination material adhesive layer forming apparatus is not particularly limited and can be appropriately selected from known transfer bodies according to a purpose. Preferred examples of the intermediate transfer body include, but are not limited to, a transfer belt.The transfer means (the primary transfer means and the secondary transfer means) in the transfer destination material adhesive layer forming apparatus preferably includes at least a transfer device that peels the visible image formed on the electrostatic latent image bearer and charges the peeled visible image toward the recording medium. Examples of the transfer device include, but are not limited to, a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

[0084] - Fixing Step and Fixing Means -The fixing step in the transfer destination material adhesive layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the fixing step is a step of fixing the transfer destination material adhesive layer transferred onto the transfer base material. The fixing step may be performed simultaneously at once in a state where the layers of toner for a transfer destination material adhesive layer output from each of the plurality of developing means are laminated on each other.The fixing means in the transfer destination material adhesive layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose, as long as the fixing means is a means used for fixing the transfer destination material adhesive layer transferred onto the transfer base material. However, the fixing means is preferably a known heating and pressing member. Examples of the heating and pressing member in the transfer destination material adhesive layer forming apparatus include, but are not limited to, a combination of a heating roller and a pressure roller, and a combination of a heating roller, a pressure roller, and an endless belt.The fixing step may be implemented by the fixing means in the transfer destination material adhesive layer forming apparatus.Normally, the heating temperature in the heating and pressing member of the transfer destination material adhesive layer forming apparatus is preferably from 80°C to 200°C. Note that, in the transfer destination material adhesive layer forming apparatus, according to a purpose, a known optical fixing device may be used together with or instead of the fixing means, for example.The surface pressure in the fixing step is not particularly limited and can be appropriately selected according to a purpose, but is preferably from 10 N / cm2to 80 N / cm2.

[0085] - Cleaning Step and Cleaning Means -The cleaning step in the transfer destination material adhesive layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the cleaning step is a step by which it is possible to remove the toner for a transfer destination material adhesive layer remaining on the electrostatic latent image bearer of the transfer destination material adhesive layer forming apparatus. For example, the cleaning step may be performed by the cleaning means.The cleaning means in the transfer destination material adhesive layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose, as long as the cleaning means is a means that can remove the toner for a transfer destination material adhesive layer remaining on the electrostatic latent image bearer. Examples of the cleaning means include, but are not limited to, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.

[0086] - Static Elimination Step and Static Elimination Means -The static elimination step in the transfer destination material adhesive layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the static elimination step is a step of applying a static elimination bias to the electrostatic latent image bearer of the transfer destination material adhesive layer forming apparatus to destaticize the electrostatic latent image bearer. For example, the static elimination step may be performed by the static elimination means.The static elimination means in the transfer destination material adhesive layer forming apparatus is not particularly limited and may be appropriately selected according to a purpose, as long as the static elimination means is a means that applies a static elimination bias to the electrostatic latent image bearer to destaticize the electrostatic latent image bearer. Examples of the static elimination means include, but are not limited to, a static elimination lamp.

[0087] - Recycling Step and Recycling Means -The recycling step in the transfer destination material adhesive layer forming step is not particularly limited and may be appropriately selected according to a purpose, as long as the recycling step is a step of causing the developing device in the transfer destination material adhesive layer forming apparatus to recycle the toner for a transfer destination material adhesive layer removed in the cleaning step. For example, the recycling step may be performed by the recycling means.The recycling means in the transfer destination material adhesive layer forming apparatus is not particularly limited and may be appropriately selected according to a purpose, as long as the recycling means is a means causing the developing device to recycle the toner for a transfer destination material adhesive layer removed in the cleaning step. Examples of the recycling means include, but are not limited to, a known conveyance means.

[0088] - Control Step and Control Means -The control step in the transfer destination material adhesive layer forming step is not particularly limited and can be appropriately selected according to a purpose, as long as the control step is a step by which it is possible to control an operation in each step in the transfer destination material adhesive layer forming step. For example, the control step may be performed by the control means.The control means in the transfer destination material adhesive layer forming apparatus is not particularly limited and can be appropriately selected according to a purpose, as long as the control means is a means that can control an operation of each means in the transfer destination material adhesive layer forming apparatus. Examples of the control means include, but are not limited to, devices such as a sequencer and a computer.

[0089] <Transfer Destination Material Adhesive Layer>The transfer destination material adhesive layer is a layer that adheres to the transfer destination material when the thermal transfer print sheet is thermally transferred to the transfer destination material.The transfer destination material is not particularly limited, as long as the transfer destination material adheres to the transfer destination material adhesive layer, and may be a flexible transfer destination material that has flexibility, or a non-flexible transfer destination material that does not have flexibility.Examples of flexible transfer destination materials include, but are not limited to, cloth, leather, and plastic films.Examples of non-flexible transfer destination materials include, but are not limited to, tiles, pottery, and easels.The transfer destination material adhesive layer is formed by a toner for a transfer destination material adhesive layer.A white transfer destination material adhesive layer is formed by a white toner for a transfer destination material adhesive layer, and a transparent transfer destination material adhesive layer is formed by a transparent toner for a transfer destination material adhesive layer.The structure of the transfer destination material adhesive layer is not particularly limited, as long as the structure includes a white transfer destination material adhesive layer. However, it is preferable that the white transfer destination material adhesive layer is formed to contact the transfer destination material, and it is even more preferable that a transparent transfer destination material adhesive layer is formed on the white transfer destination material adhesive layer.

[0090] <<Toner for Transfer Destination Material Adhesive Layer>>The toner for a transfer destination material adhesive layer contains a polyester resin, a polyurethane resin, and a release agent.The white toner for a transfer destination material adhesive layer contains a white pigment, and the transparent toner for a transfer destination material adhesive layer does not contain a coloring material.The toner for a transfer destination material adhesive layer may contain, as other constituent materials, a charge control agent, an external additive, a fluidity improver, a cleanability improver, and the like.

[0091] - Polyester Resin -The polyester resin used in the toner for a transfer destination material adhesive layer is preferably obtained by condensation polymerization of an alcohol and a carboxylic acid. The alcohol used in the condensation polymerization is not particularly limited and can be appropriately selected according to a purpose. Examples of the alcohol include, but are not limited to, glycols such as ethylene glycol, diene glycol, triethylene glycol, and propylene glycol, etherified bisphenols such as l,4-bis(hydroxymeta)cyclohexane and bisphenol A, other dihydric alcohol monomers, and trihydric or higher poly hydric alcohol monomers.

[0092] The carboxylic acid is not particularly limited and can be appropriately selected according to a purpose. Examples of the carboxylic acid include, but are not limited to, divalent organic acid monomers such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid, and trivalent or higher polyvalent carboxylic acidmonomers such as 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4- cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, l,3-dicarboxyl-2-methylenecarboxypropane, and 1,2,7,8-octanetetracarboxylic acid.

[0093] - Polyurethane Resin - Polyurethane resins generally have excellent tensile strength (strength against pulling), wear resistance, elasticity, and oil resistance, and thus, can be suitably used in the toner for a transfer destination material adhesive layer. In the composition of the polyurethane resin, it is preferable to use polyurethane resins including, for example, 1,4-butanediol (1,6-hexanediol), adipic acid, and diphenylmethane diisocyanate. The specific product name of the polyurethane resin being used is not particularly limited and can be appropriately selected according to a purpose. Examples of the product name include, but are not limited to, HOT MELT POWDER ECOFREEN POWDER (manufactured by ECOFREEN Co., Ltd.), T8175N (manufactured by DIC Covestro Polymer Ltd.), and P22MBRNAT (manufactured by Nippon Miractran Co., Ltd.).The toner for a transfer destination material adhesive layer contains a polyurethane resin, and thus, the transfer destination material adhesive layer can have rubber elasticity, so that an image thermally transferred to the transfer destination material is less likely to crack even when the material is pulled, bent, washed, and the like.

[0094] The softening temperature and the glass transition temperature of the polyurethane resin are both preferably 45 °C or lower. If the softening temperature and the glass transition temperature of the polyurethane resin are both 45 °C or lower, the flexibility of the transfer destination material adhesive layer after fixing can be ensured.The softening temperature and the glass transition temperature of the polyester resin are both preferably 55°C or higher. If the softening temperature and the glass transition temperature of the polyester are both 55 °C or higher, the heat-resistant storage stability of the transfer destination material adhesive layer can be ensured.

[0095] The toner for a transfer destination material adhesive layer contains a polyester resin and a polyurethane resin.The polyester resin and the polyurethane resin are preferably incompatible. If a combination of a polyester resin and a polyurethane resin is used, it is possible to form a sea-island structure in which the polyester resin and the polyurethane resin are incompatible in the cross section of the toner for a transfer destination material adhesive layer.In the sea-island structure in the cross section of the toner, it is preferable that the domains forming the island portions contain a polyurethane resin, and the matrix forming the sea portion contains a polyester resin.

[0096] The weight average molecular weight of the polyurethane resin is preferably from 20,000 to 100,000, more preferably from 20,000 to 80,000, and even more preferably from 20,000 to 60,000. If the weight average molecular weight is 20,000 or more, the transfer destination material adhesive layer does not melt when being thermally transferred to the transfer destination material. If the weight average molecular weight is 100,000 or less, an adhesive can be easily melt-kneaded with other components of the toner when the toner is prepared.

[0097] The content of the polyurethane resin is not particularly limited and can be appropriately selected according to a purpose. When the toner for a transfer destination material adhesive layer contains a release agent, the content of the polyurethane resin is preferably in the range of 10 to 50 mass%, and more preferably in the range of 20 to 40 mass%, with respect to the total mass of the resin and the release agent. When the content of the polyurethane resin with respect to the total mass of the resin and the release agent is 10 mass% or more, the toner can be sufficiently fixed to a flexible transfer destination material such as a cloth, and the transfer destination material adhesive layer after fixing is flexible. When the content of the polyurethane resin is 50 mass% or less, the thermal storage stability of the toner does not deteriorate and the toner particles do not aggregate.

[0098] Further, any one of polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, polybutylene isophthalate, and styrene butadiene rubber, which have the same properties as the above-described polyurethane resin, can be used as a substitute for all or a part of the polyurethane resin.

[0099] - Release Agent -The type of release agent that can be used in the toner for a transfer destination material adhesive layer is not particularly limited and can be appropriately selected according to a purpose. One type of release agent may be used alone, or two or more types of release agents may be used in combination.

[0100] The release agent that can be used in the toner for a transfer destination material adhesive layer is not particularly limited and can be appropriately selected according to a purpose. Examples of the release agent include, but are not limited to, liquid paraffin, microcrystalline wax, natural paraffin, synthetic paraffin, polyolefin wax, and partial oxides of these compounds, or aliphatic hydrocarbons such as fluorides and chlorides, animal oils such as beef tallow and fish oil, vegetable oils such as palm oil, soybean oil, rapeseed oil, rice bran wax, and carnauba wax, higher aliphatic alcohols and higher fatty acids such as montan wax, fatty acid amides, fatty acid bisamides, metal soaps such as zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, zinc oleate, zinc palmitate, magnesium palmitate, zinc myristate, zinc laurate, and zinc behenate, fatty acid esters, and polyvinylidene fluoride.Among these release agents, it is preferable to use at least an ester wax such as a fatty acid ester.

[0101] In a case where the toner for a transfer destination material adhesive layer contains a maleic acid-modified polyolefin having a polypropylene block in the main chain, if the content of the maleic acid-modified polyolefin is high, it may not be possible to separate the toner from the fixing roller (or the fixing belt) during fixing, and thus, a waste sheet jam may occur. However, this problem can be resolved by adding an ester wax as the release agent. Further, the ester wax can be finely dispersed in the maleic acid-modified polyolefin having a polypropylene block in the main chain.

[0102] The content of the release agent in the toner for a transfer destination material adhesive layer is not particularly limited and can be appropriately selected according to a purpose. However, the content is preferably from 0.1 to 8.0 mass%, and more preferably from 1.0 to 6.0 mass%. When the content of the release agent is 0.1 mass% or more, the toner and the fixing roller (or the fixing belt) can be separated from each other during fixing, and thus, waste sheet jams can be prevented. When the content of the release agent is 8.0 mass% or less, the toner can be sufficiently fixed to a plastic film.

[0103] - White Pigment -The white pigment that may be contained in the toner for a transfer destination material adhesive layer is not particularly limited and can be appropriately selected according to a purpose. For example, titanium dioxide, white lead, talc, kaolin, zinc sulfide, barium sulfate, calcium carbonate, zinc oxide, and hollow silica can be used as the white pigment.Further, a material that is obtained by subjecting a white pigment to a surface treatment may also be used. For example, a material obtained by subjecting a white pigment to a surface treatment with silicon, zirconia, aluminum, or an organic substance such as polyol may be used. Specifically, a material obtained by subjecting titanium dioxide to a surface treatment with aluminum and an organic substance such as polyol is preferred. It is assumed that this surface treatment causes the release agent in the toner for a transfer destination material adhesive layer to wet with the white pigment, and thus, reduce the hardness of the transfer destination material adhesive layer and result in a white transfer destination material adhesive layer that does not easily crack.

[0104] - Charge Control Agent -The toner for a transfer destination material adhesive layer may contain a charge control agent.The charge control agent can be appropriately selected according to a purpose, as long as the charge control agent is white or colorless. Examples of the charge control agent include, butare not limited to, onium salts such as phosphonium salts and lake pigments thereof, triphenylmethane dyes and lake pigments thereof, metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, and dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate, and dicyclohexyltin borate, organic metal complexes, chelate compounds, monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, metal complexes of aromatic dicarboxylic acids, and quaternary ammonium salts. Other examples of the charge control agent include, but are not limited to, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol. These charge control agents may be used alone or in combination of two or more types.

[0105] When these charge control agents are added internally to the toner for a transfer destination material adhesive layer, the content of the charge control agent is not particularly limited and can be appropriately set according to a purpose. However, the content of the charge control agent is preferably from 0.1 to 10 mass% with respect to the total amount of the resin.

[0106] - External Additives -In the toner for a transfer destination material adhesive layer, inorganic fine particles and the like can be used as an external additive.The inorganic fine particles used as the external additive in the present embodiment are not particularly limited and can be appropriately selected according to a purpose. Examples of the inorganic fine particles include, but are not limited to, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these inorganic fine particles, silica, alumina, and titanium oxide are preferred.

[0107] The inorganic fine particles may be subjected to a surface treatment using a hydrophobicity treatment agent. The hydrophobicity treatment agent is not particularly limited and can be appropriately selected according to a purpose. However, preferred examples of surface treatment agents include, but are not limited to, silane coupling agents, silylation agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, and aluminum coupling agents. Further, it is also possible to obtain a sufficient effect by using silicone oil as a hydrophobicity treatment agent.

[0108] The average diameter of primary particles of the inorganic fine particles is not particularly limited and may be appropriately selected according to a purpose, but is preferably from 5 to 500 nm, and more preferably from 5 to 200 nm. If the average diameter is 5 nm or more, theinorganic fine particles are prevented from aggregating, and the inorganic fine particles can be uniformly dispersed in the toner. If the average diameter is 500 nm or less, the heat-resistant storage stability can be improved by a filler effect. Here, the average diameter of the primary particles of the inorganic fine particles refers to a value obtained by directly determining the particle diameter from an image obtained by a transmission electron microscope. It is preferable to observe at least 100 or more inorganic fine particles and use the average value of the major axes of the inorganic fine particles.

[0109] - Fluidity Improver -The toner for a transfer destination material adhesive layer may contain a fluidity improver as an additive. The fluidity improver is not particularly limited and can be appropriately selected according to a purpose, as long as the fluidity improver can be used to perform a surface treatment to increase the hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under conditions including high humidity. Examples of the fluidity improver include, but are not limited to, silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum-based coupling agents, silicone oil, and modified silicone oil. When silica or titanium oxide is used as the external additive, it is preferable to perform a surface treatment with such a fluidity improver and use the silica or the titanium oxide as hydrophobic silica or hydrophobic titanium oxide.

[0110] - Cleanability Improver -The toner for a transfer destination material adhesive layer may contain a cleanability improver as an additive. The cleanability improver is not particularly limited and can be appropriately selected according to a purpose, as long as the cleanability improver can be added to the toner for a transfer destination material adhesive layer to remove toner remaining on the electrostatic latent image bearer or the primary transfer medium after transfer. Examples of the cleanability improver include, but are not limited to, fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, and polymer fine particles prepared by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and preferably have a volume average particle diameter of 0.01 pm or more and 1 pm or less.

[0111] The toner for a transfer destination material adhesive layer preferably has a sea-island structure in the cross section of the toner.A "sea-island structure" is a structure in which, if the continuous phase of one component represents the "sea", other components different from the sea portion exist in the "sea" in the form of "islands" that are incompatible with the sea portion. The island portions in the crosssection of the toner are called "domains" and the sea portion is called "matrix". To obtain a transfer destination material adhesive layer after fixing that does not easily crack, it is preferable that the toner for a transfer destination material adhesive layer includes an average of three or more domains having an aspect ratio of 2 or more and an area of 0.1 pm2or more per 100 pm2of the cross section of the toner, and it is more preferable that the toner includes an average of five or more such domains.

[0112] The particle diameter distribution based on volume percentage of the toner for a transfer destination material adhesive layer is not particularly limited and can be appropriately selected according to a purpose. However, the particle diameter distribution preferably has a peak in the range of 5 to 30 pm, and more preferably has a peak in the range of 10 to 20 pm. Here, the "peak" in the particle diameter distribution means that the peak top in the particle diameter distribution is in the particle diameter range mentioned above.The volume average particle diameter of the toner for a transfer destination material adhesive layer is not particularly limited and can be appropriately selected according to a purpose, but is preferably 5 pm or more and 30 pm or less, and more preferably 10 pm or more and 20 pm or less.If the above-described toner for a transfer destination material adhesive layer is used, by increasing the particle diameter of the toner, the development capability increases, the amount of toner being developed in one development operation can be increased, the pile height of layers of the toner can be increased, and it is possible to easily fill in irregularities in the surface of a flexible transfer destination material such as cloth.Further, in consideration of balance with transferability, which is in a trade-off relationship with the particle diameter, the toner for a transfer destination material adhesive layer more preferably has a particle diameter distribution having a peak in the range of 10 to 20 pm in the particle diameter distribution based on volume percentage. For a similar reason, the toner for a transfer destination material adhesive layer more preferably has a volume average particle diameter of 10 pm or more and 20 pm or less.

[0113] It is preferable that, in the release agent, the charge control agent, the external additive, the fluidity improver, and the cleanability improver used in the toner for a transfer destination material adhesive layer, similar materials are used as those in the material used in a color toner, to improve the adhesion between the color toner and the toner for a transfer destination material adhesive layer and to obtain a printed item having higher durability.

[0114] [Observation of Incompatible Domains in Cross Section of Toner for Transfer Destination Material Adhesive Layer]The sea-island structure in the cross section of the toner for a transfer destination material adhesive layer and the size and the shape of the island portions (domains) can be confirmedby observing a backscattered electron image using a scanning electron microscope (SEM). The presence of the sea portion (matrix) and the island portions (domains) and the incompatibility between the sea portion and the island portions can be confirmed by the difference in color between the island portions (domains) and the sea portion (matrix) in the sea-island structure of the cross section of the toner for a transfer destination material adhesive layer. To provide contrast and facilitate the distinction between the island portions and the sea portion, staining with ruthenium tetroxide may be implemented, if desired.The following procedure and conditions are given as an example of observing a backscattered electron image by using a scanning electron microscope.

[0115] The sea-island structure of the present embodiment can be similarly observed in the particles of the toner for a transfer destination material adhesive layer and in a coarsely crushed product of the melted and kneaded components of the toner for a transfer destination material adhesive layer.The particles of the toner for a transfer destination material adhesive layer or the particles of the coarsely crushed product of the melted and kneaded components of the toner for a transfer destination material adhesive layer are embedded in an epoxy resin, and a cross section is cut out. Subsequently, the cross-section can be observed under the following conditions by using a scanning electron microscope (SU8230, manufactured by Hitachi Ltd.). At this time, unstained areas are observed as dark portions, and thus, can be distinguished from stained areas (light portions).- Acceleration voltage: 5 kV- Emission current: 10 pA- Probe current: Norm- Condenser lens 1: 5.0- W. D.: 8.0 mm- Observation mode: SE- Magnification: 2,000 or 5,000 times

[0116] [Aspect Ratio and Area of Domains in Cross Section of Toner for Transfer Destination Material Adhesive Layer]The aspect ratio of the domains is the ratio between the length of the longest side and the length of the shortest side of the island portions (domains) of the sea-island structure in an SEM image obtained by observing the cross section of the toner for a transfer destination material adhesive layer with a scanning electron microscope. If the aspect ratio of the domains is larger, the anisotropy is higher. Further, the area of the domains can be defined as the area of the island portions (domains) of the sea-island structure in an SEM image obtained by observing a cross section of the toner for a transfer destination material adhesive layer by using a scanning electron microscope.

[0117] [Average Number of Specific Domains per 100 pm2of Cross Section of Toner for Transfer Destination Material Adhesive Layer]An example of a method of determining the average number of domains having an aspect ratio of 2 or more and an area of 0.1 pm2or more per 100 pm2of the cross section of the toner for a transfer destination material adhesive layer will be described below.

[0118] At least 10 or more particles of the toner for a transfer destination material adhesive layer having a particle diameter of 10 to 20 pm are prepared, and an SEM image of the cross section the toner is captured at a position substantially halfway along the particle diameter of each toner particle. By determining the number of domains having an aspect ratio of 2 or more and an area of 0.1 pm2or more among the domains present in the SEM image of the cross section of the toner and the area of the cross section of the toner, it is possible to determine the number of domains having an aspect ratio of 2 or more and an area of 0.1 pm2or more per 100 pm2. By determining the total number of domains having an aspect ratio of 2 or more and an area of 0.1 pm2or more per 100 pm2of each particle of the toner and dividing the total number by the number of cross sections of the toner being used, it is possible to calculate the average number of domains having an aspect ratio of 2 or more and an area of 0.1 pm2or more per 100 pm2in the SEM image of the cross sections of the toner.

[0119] [Capturing SEM Image of Fixed Image of Toner for Transfer Destination Material Adhesive Layer]When capturing an SEM image of a fixed image of the toner for a transfer destination material adhesive layer, the image may be captured by the same method as mentioned above in [Observation of Incompatible Domains], except that the fixed image of the toner for a transfer destination material adhesive layer is used as a sample.

[0120] [Method of Measuring Particle Diameter and Particle Diameter Distribution based on Volume Percentage of Toner for Transfer Destination Material Adhesive Layer]The particle diameter and the particle diameter distribution based on volume percentage of the toner for a transfer destination material adhesive layer can be measured, for example, by using a particle size measuring device ("MULTISIZER III", manufactured by Beckman Coulter Inc.) at an aperture diameter of 100 pm, and can be analyzed by using analysis software (Beckman Coulter MULTISIZER 3 Version 3.51). An example of the measurement is described below.0.5 ml of a 10 mass% surfactant (alkylbenzene sulfonate, NEOGEN SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is filled into a 100 ml glass beaker, 0.5 g of each toner is added and stirred with a microspatula. Subsequently, 80 ml of ion-exchanged water is added to obtain a dispersion liquid. The obtained dispersion liquid is subjected to a dispersiontreatment for 10 minutes using an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.) to obtain a sample dispersion liquid of the toner for a transfer destination material adhesive layer. The sample dispersion liquid of the toner for a transfer destination material adhesive layer is measured by using the above-mentioned MULTISIZER III and using ISOTON III (manufactured by Beckman Coulter, Inc.) as the measurement solution. To ensure measurement reproducibility, the sample dispersion liquid of the toner is added dropwise to avoid errors in the particle diameter and obtain a concentration of 8 ± 2% indicated by the device, and the volume average particle diameter of the toner is measured.

[0121] [Confirmation of Presence and Quantification of Resin in Toner for Transfer Destination Material Adhesive Layer]The presence and the amount of the resin contained in the toner for a transfer destination material adhesive layer can be suitably confirmed and quantified by gas chromatography mass spectrometry (GC-MS) or nuclear magnetic resonance (NMR). Specifically, the presence and the amount of the resin may be confirmed by using the following procedure, apparatus, and conditions.

[0122] [Component Analysis using Gas Chromatography Mass Spectrometry (GC-MS)]- Sample Preparation -The toner for a transfer destination material adhesive layer is dispersed in chloroform, and the mixture is stirred during 24 hours to obtain a dispersion liquid.Next, the dispersion liquid is separated by centrifugation and the supernatant liquid is collected. The collected supernatant liquid is evaporated to dryness and the composition is analyzed by gas chromatography mass spectrometry (GC-MS). An example of the measurement conditions by GC-MS is described below. About 1 pL of a methylating agent (20% methanol solution of tetramethylammonium hydroxide: TMAH) is added dropwise to about 1 mg of the sample to prepare a mixture to be used as a sample.

[0123] - Measurement Conditions -- Pyrolysis-gas chromatography mass spectrometry (Py-GCMS) analysis device: QP2010 (manufactured by Shimadzu Corporation)- Heating furnace: Py2020D (manufactured by Frontier Laboratories, Ltd.)- Heating temperature: 320°C- Column: ULTRA ALLOY-5 (L = 30 m, I.D = 0.25 mm, fdm = 0.25 pm, manufactured by GL Sciences Inc.)- Column temperature: 50°C (holding time: 1 min) - temperature increase (10°C / min) - 340°C (holding time: 7 min)- Split ratio: 1: 100- Column flow rate: 1.0 ml / min- Ionization method: El method (70 eV)- Measurement mode: Scan mode- Search data: NIST 20 MASS SPECTRAL LIB.

[0124] [Component Analysis by NMR]- Sample Preparation -The toner for a transfer destination material adhesive layer is dispersed in chloroform, and the mixture is stirred during 24 hours to obtain a dispersion liquid. Next, the dispersion liquid is separated by centrifugation and the supernatant liquid is collected. The collected supernatant liquid is evaporated to dryness and used as a sample for1H-NMR and13C-NMR, to analyze the composition by NMR. Examples of a method of preparing a sample for ’ H-NMR, a method of preparing a sample for13C-NMR, and measurement conditions are described below.

[0125] (1) 1 mL of d8-toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) is added to 100 mg of a sample used in the method of preparing a sample for ’ H-NMR, and the mixture is heated with a dryer to dissolve the sample, to prepare a sample for ' H-NMR.(2) 1 mL of deuterated 1,2-dichlorotoluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) is added to 100 mg of a sample used in the method of preparing a sample for13C-NMR, and the mixture is heated with a dryer to dissolve the sample, to prepare a sample for13C-NMR.

[0126] - Measurement Conditions -- NMR device: ECX-500 (manufactured by JEOL Ltd.)- Measurement nuclei =!H (500 MHz), measurement pulse file = single pulse dec.jxp (XH), 45°C pulse, total 20,000 times, relaxation delay -4 seconds, data points 32K, offset 100 ppm, observation width = 250 ppm, measurement temperature 70°C- Measurement nuclei =13C (125 MHz), measurement pulse file = single pulsedec.jxp (13C), 45°C pulse, total 64 times, relaxation delay 5 seconds, data points 32K, observation width = 15 ppm, measurement temperature 65 °C

[0127] [Measurement of Weight Average Molecular Weight]The weight average molecular weight of the resin used in the toner for a transfer destination material adhesive layer can be obtained by measuring the molecular weight distribution of a fraction soluble in tetrahydrofuran (THF) by a gel permeation chromatography (GPC) measurement device. The GPC measurement device is not particularly limited and can be appropriately selected according to a purpose. For example, a device with the product name GPC-150C (manufactured by Waters Corporation) and the like can be used.

[0128] The column used for measuring the weight average molecular weight is not particularly limited and can be appropriately selected according to a purpose. Examples of the column include, but are not limited to, columns of the trade names KF801 (column for organic solvent SEC (GPC)), KF802 (column for organic solvent SEC (GPC)), KF8O3 (column for organic solvent SEC (GPC)), KF804 (column for organic solvent SEC (GPC)), KF805 (column for organic solvent SEC (GPC)), KF806 (column for organic solvent SEC (GPC)), and KF807 (column for organic solvent SEC (GPC)) (all manufactured by Showa Denko K.K.).

[0129] The method of measuring the weight average molecular weight of the resin used in the toner for a transfer destination material adhesive layer is not particularly limited and can be appropriately selected according to a purpose. For example, the weight average molecular weight of the resin may be measured by the following method. The column is stabilized in a heat chamber at 40°C, and THF is passed through the column as a solvent at a flow rate of 1 mL per minute. Subsequently, 0.05 g of the sample is sufficiently dissolved in 5 g of THF. Next, the mixture is filtered through a pretreatment filter (for example, product name: CHROMATODISC, pore size: 0.45 pm, manufactured by Kurabo Industries, Ltd.) and the final sample concentration is adjusted to 0.05% mass% to 0.6 mass%. The weight average molecular weight (Mw) of the THF-soluble fraction contained in the THF sample solution can be measured as follows. 50 pL to 200 pL of the THF sample solution obtained by adjusting the sample concentration, is injected into a column, and the THF-soluble fraction contained in the THF sample solution is separated. Next, the fraction is converted into molecular weight by using a detector (for example, a differential refractive index (RI) detector (device name: GPC-150C, manufactured by Waters Corporation)).

[0130] The weight average molecular weight Mw and the number average molecular weight Mn of the THF-soluble fraction contained in the sample are measured by calculating the molecular weight distribution of the sample from a relationship between the count number and the logarithmic value of a calibration curve obtained by using several monodispersed polystyrene standard samples.Examples of the polystyrene standard samples for preparing the calibration curve include, but are not limited to, polystyrene standard samples having molecular weights of 6*102, 2.1*102, 4*102, 1.75*104, 5.1*104, 1.1*105, 3.9*105, 8.6*105, 2*106, and 4.48*106, manufactured by Pressure Chemical Company or Toyo Soda Kogyo Co., Ltd., and it is preferable to use at least about 10 polystyrene standard samples.Further, the detector is preferably a refractive index (RI) detector.

[0131] [Method of Measuring Softening Temperature]The softening temperature (Tm) of the resin used in the toner for a transfer destination material adhesive layer can be measured, for example, by using a flow tester (CFT-500D,manufactured by Shimadzu Corporation). The temperature at which the sample starts to deform (= temperature at which the sample starts to deform as the sample changes from a solid state to a rubber-like state) can be determined as the softening temperature. For example, the flow tester is used to heat 1.0 g of the sample at a heating rate of 6°C / min while applying a load of 1.96 MPa by a plunger. The sample is extruded from a nozzle having a diameter of 1.0 mm and a length of 1.0 mm. The extent to which the plunger of the flow tester descends is plotted against the temperature to obtain an S-curve indicating temperature (°C) / stroke (mm). The maximum value of the stroke in the S-curve is defined as Si, the stroke value of the baseline on a low temperature side is defined as S2, and the temperature in the S-curve where the stroke value is (Si + Si) / 2 can be determined as the softening temperature (Tm).

[0132] [Method of Measuring Glass Transition Temperature]The glass transition temperature (Tg) of the resin used in the toner for a transfer destination material adhesive layer can be measured, for example, by using a differential scanning calorimeter (DSC210, manufactured by Seiko Instruments Inc.). Specifically, for example, in the differential scanning calorimeter, 0.01 to 0.02 g of the sample is weighed into an aluminum pan at room temperature, and cooled to -20°C at a temperature drop rate of 10°C / min. Afterwards, the sample is heated to 200°C at a heating rate of 10°C / min. The glass transition temperature (Tg) can be determined as the temperature at an intersection point of an extension line of the baseline and a tangent line indicating the maximum slope from a portion where the peak starts to rise to the top of the peak.

[0133] <<Developer>>The toner for a transfer destination material adhesive layer may be a one-component developer or a two-component developer. However, when used in a high-speed printer and the like responding to the increased information processing speed in recent years, a two- component developer is preferred, because such a developer provides a longer service life. When the toner for a transfer destination material adhesive layer is used as a one-component developer, and even if the toner is being consumed and resupplied, the particle diameter of the toner varies little, there is little filming of the toner on the developing roller, and the toner hardly fuses with components such as a blade used to obtain a thin layer of the toner. Therefore, it is possible to obtain good and stable developing properties and images, even when the developer is stirred during a long period of time in the developing device.When the toner for a transfer destination material adhesive layer is mixed with a carrier and used as a two-component developer, the particle diameter of the toner varies little, even when the toner is being consumed and resupplied over a long period of time. Therefore, good and stable developing properties and images can be obtained, even when the toner is stirred during a long period of time in the developing device.The toner for a transfer destination material adhesive layer can be mixed with a carrier to form a two-component developer, which can be used in an electrophotographic image forming method using a two-component developing procedure.A magnetic carrier can be used as the carrier. The magnetic carrier that can be used is similar to the magnetic carrier that can be used in the two-component developer of the color toner.

[0134] In the two-component developer of the toner for a transfer destination material adhesive layer, the mass ratio of the carrier in the developer stored in the developing device is preferably 85 mass% or more and less than 98 mass%.When the mass ratio of the carrier in the developer is 85 mass% or more, the toner is unlikely to scatter from the developing device, and it is possible to reduce the occurrence of defective images.When the mass ratio of the carrier in the developer is less than 98 mass%, it is possible to suppress an excessive increase in the charge amount of the toner for a transfer destination material adhesive layer and a shortage in the supply amount of the toner for a transfer destination material adhesive layer, and thus, it is possible to reduce the occurrence of defective images caused by a decrease in image density.

[0135] <<Method of Manufacturing Toner for Transfer Destination Material Adhesive Layer>>The method of manufacturing the toner for a transfer destination material adhesive layer is not particularly limited and can be appropriately selected according to a purpose. An example of the method of manufacturing the toner for a transfer destination material adhesive layer will be described below.A melt-kneading and pulverization method is preferred as a method of manufacturing a transfer destination material adhesive layer toner containing a white pigment and having a function of concealing an underlayer of a transfer destination material. This is because white pigments have a larger specific gravity than other toner constituent materials, and thus, are difficult to granulate by using chemical methods such as a dissolution suspension method. Therefore, in addition to forming domains having an aspect ratio of 2 or more in the cross section of the toner, it is desired to provide a step of cooling and rolling the melted and kneaded mixture of the toner components.

[0136] In contrast, chemical methods such as a dissolution suspension method can be used for the toner for a transfer destination material adhesive layer, in a case where a structure and a manufacturing process of the toner material are such that a white pigment can be internally dispersed and domains having an aspect ratio of 2 or more can be formed in the cross section of the toner.The shape and the size of the domains in the cross section of the toner are determined by the compatibility between the material of the domains and the material of the matrix and thestretching force applied when the molten and kneaded product is cooled and rolled.Therefore, a simple method of controlling the diameter and the shape of the domains includes employing incompatible materials, determining in advance the relationship between the size and the shape of the domains and the thickness after rolling, and then, reducing the thickness of the melted and kneaded product of the toner material to an appropriate thickness, preferably 1 mm or less. Thus, it is possible to obtain a toner having large domains of an aspect ratio of 2 or more.The compatibility between the material of the domains and the material of the matrix is determined by the molecular weight and the composition of each material.

[0137] In one embodiment, the method of manufacturing a toner for a transfer destination material adhesive layer can include a step of obtaining a mixture of a resin (mixing step), a step of obtaining a kneaded product of the mixture (melt-kneading step), a step of obtaining a solid product of the kneaded product (solidification step), a step of obtaining a pulverized product of the solid product (fine pulverization step), and a step of classifying and collecting the pulverized product (classification step).

[0138] - Step of Obtaining Mixture of Resin (Mixing Step) -First, a polyester resin, a polyurethane resin, a release agent, and, if desired, a charge control agent and the like are mixed in a mixer to obtain a mixture (mixing step).When preparing a white toner for a transfer destination material adhesive layer, a white pigment is added to the above-mentioned components to obtain a mixture.The above-mentioned mixer is not particularly limited and can be appropriately selected according to a purpose. Examples of the mixer include, but are not limited to, a Henschel mixer (product name: FM20B, manufactured by Nippon Coke and Engineering Co., Ltd.) and a SUPER MIXER (SMV-20Ba, manufactured by Kawata Mfg. Co., Ltd.).

[0139] - Step of Obtaining Kneaded Product of Mixture (Melt- Kneading Step) -Next, the obtained mixture is melt-kneaded by using a hot melt kneader to obtain a kneaded product (melt-kneading step).The hot melt kneader is not particularly limited and may be appropriately selected according to a purpose. Examples of the hot melt kneader include, but are not limited to, kneaders of trade names such as twin-screw extruder PCM series (manufactured by Ikegai Co., Ltd.), TEM-type extruder (manufactured by Shibaura Machine Co., Ltd.), twin-screw extruder PCM Co-kneader (manufactured by Buss Corporation), and open roll-type continuous kneader KNEADEX (manufactured by Nippon Coke and Engineering Co., Ltd.).

[0140] - Step of Obtaining Solid Product of Kneaded Product (Solidification Step) -Next, the obtained kneaded product is cooled and solidified to obtain a solid product (solidification step). A cooling method and a solidification method are not particularly limited, can be appropriately selected according to a purpose, and any appropriate method can be used.

[0141] - Step of Obtaining Pulverized Product of Solid Product (Fine Pulverization Step) - Next, the obtained solid product is finely pulverized to obtain a pulverized product (fine pulverization step). The solid product can be pulverized by using known pulverization methods including the following methods. For example, a jet mill method can be used in which toner is introduced into a high-speed air stream and the solid product is pulverized by the energy generated when the toner collides with a collision plate. Further, an inter-particle collision method can be used in which toner particles are collided with each other in an air stream. Moreover, a mechanical pulverization method can be used in which toner is supplied into a narrow gap with a rotor rotating at high speed and pulverized.

[0142] - Step of Classifying and Collecting Pulverized Product (Classification Step) - Subsequently, the pulverized product is classified to collect a pulverized product having a predetermined volume average particle diameter. Thus, a toner for a transfer destination material adhesive layer can be obtained (classification step). A classification method is not particularly limited, can be appropriately selected according to a purpose, and any appropriate method can be used.

[0143] The toner for a transfer destination material adhesive layer can be manufactured by a dissolution suspension method. When a toner is manufactured by using a dissolution suspension method, toner materials such as a polyester resin, a polyurethane resin, and a release agent, and if desired, a charge control agent, are dissolved or dispersed in an organic solvent to obtain an oil phase, and the oil phase is dispersed in an aqueous medium (aqueous phase) to cause a reaction of the resin. Thus, a dispersion liquid is obtained that contains a dispersed body (oil droplets) containing a prepolymer in which the toner materials are emulsified or dispersed. When preparing a white toner for a transfer destination material adhesive layer, a white pigment is added to the above-mentioned components and a similar operation is performed. Afterwards, the organic solvent is removed from the dispersion liquid, and the dispersion liquid is filtered, washed, and dried. If desired, the dispersion liquid may be further classified to manufacture base particles of the toner for a transfer destination material adhesive layer. The toner for a transfer destination material adhesive layer may be obtained by granulating the base particles obtained by the dissolution suspension method. The organic solvent used in the dissolution and suspension method is not particularly limited and can be appropriately selected according to a purpose. However, an organic solvent having a boiling point of less than 150°C is preferred to easily remove the organic solvent.

[0144] The organic solvent having a boiling point of less than 150°C is not particularly limited and can be appropriately selected according to a purpose. Examples thereof include, but are not limited to, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2- dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. These organic solvents may be used alone or in combination of two or more types. Among these organic solvents, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable, and ethyl acetate is more preferable.

[0145] The aqueous medium used in the dissolution and suspension method is not particularly limited, can be appropriately selected according to a purpose, and examples thereof include, but are not limited to, water, a solvent miscible with water, and a mixture thereof.These aqueous media may be used alone or in combination of two or more types. Among these aqueous media, water is preferred.The solvent miscible with water is not particularly limited and can be appropriately selected according to a purpose. Examples of the solvent miscible with water include, but are not limited to, alcohols, lower ketones, dimethylformamide, tetrahydrofuran, and CELLOSOLVE solvents.The alcohol is not particularly limited, can be appropriately selected according to a purpose, and examples thereof include, but are not limited to, methanol, isopropanol, and ethylene glycol.The lower ketones are not particularly limited, can be appropriately selected according to a purpose, and examples thereof include, but are not limited to, acetone and methyl ethyl ketone.

[0146] A method of removing the organic solvent from the dispersion liquid in the dissolution and suspension method is not particularly limited and can be appropriately selected according to a purpose. Examples of the method include, but are not limited to, a method of gradually increasing the temperature of the entire reaction system to evaporate the organic solvent in the oil droplets, and a method of spraying the dispersion liquid into a dry atmosphere to remove the organic solvent in the oil droplets.

[0147] In the classification in the dissolution and suspension method, a fine particle portion may be separated in a liquid by using a cyclone, a decanter, or centrifugal separation. Alternatively, a classification operation may be implemented after drying.

[0148] <<Process CartridgesA process cartridge that uses the toner for a transfer destination material adhesive layer is molded to be detachably attached to various types of transfer destination material adhesive layer forming apparatuses, and includes at least an electrostatic latent image bearer carrying an electrostatic latent image, and a developing means that develops the electrostatic latent image carried on the electrostatic latent image bearer with a developer of the toner for a transfer destination material adhesive layer to form a toner image. Note that the process cartridge may further include other means, if desired.The developing means in the process cartridge is a developing device including at least a developer storage that stores a developer of the toner for a transfer destination material adhesive layer, and a developer bearer that carries and conveys the stored developer. The developing means in the process cartridge may further include a regulating member and the like that regulates the thickness of the developer carried in the developing means.

[0149] Next, one embodiment of a method of forming a transfer destination material adhesive layer by the transfer destination material adhesive layer forming apparatus will be described with reference to FIG. 1. A transfer destination material adhesive layer forming apparatus 100A illustrated in FIG. 1 includes an electrostatic latent image bearer 10, a charging roller 20 as a charging means, an exposure device 30 as an exposure means, a developing device 40 as a developing means, an intermediate transfer body 50, a cleaning device 60 as a cleaning means having a cleaning blade, and a static elimination lamp 70 as a static elimination means.

[0150] The intermediate transfer body 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside the loop of the intermediate transfer body 50 and stretch the intermediate transfer body 50. A part of the three rollers 51 also function as transfer bias rollers that can apply a predetermined transfer bias (a primary transfer bias) to the intermediate transfer body 50. A cleaning device 90 including a cleaning blade is arranged in the vicinity of the intermediate transfer body 50. Further, in the vicinity of the intermediate transfer body 50, a transfer roller 80 is arranged facing the intermediate transfer body 50. The transfer roller 80 serves as a transfer means that can apply a transfer bias for transferring (secondarily transferring) the transfer destination material adhesive layer to a transfer base material 95 serving as a recording medium and on which a color image layer is formed. A corona charging device 58 for applying an electric charge to the toner image on the intermediate transfer body 50 is arranged in the periphery of the intermediate transfer body 50, between a contact portion between the electrostatic latent image bearer 10 and the intermediate transfer body 50 and a contact portion between the intermediate transfer body 50 and the transfer base material 95 on which the color image layer is formed, in a rotation direction of the intermediate transfer body 50.

[0151] The developing device 40 includes a developing belt 41 as the developer carrier, and a first developing device 45K, a second developing device 45Y, a third developing device 45M, and a fourth developing device 45C juxtaposed in the periphery of the developing belt 41. The first developing device 45K includes a developer storage 42K, a developer supply roller 43K, and a developing roller 44K. The second developing device 45Y includes a developer storage 42Y, a developer supply roller 43Y, and a developing roller 44Y. The third developing device 45M includes a developer storage 42M, a developer supply roller 43M, and a developing roller 44M. The fourth developing device 45C includes a developer storage 42C, a developer supply roller 43C, and a developing roller 44C. The developing belt 41 is an endless belt that is rotatably stretched over a plurality of belt rollers and a part of the developing belt 41 contacts the electrostatic latent image bearer 10.

[0152] FIG. 1 is a schematic view of a transfer destination material adhesive layer forming apparatus, used in a method of manufacturing a thermal transfer print sheet according to an embodiment of the present disclosure.In the transfer destination material adhesive layer forming apparatus 100A illustrated in FIG. 1, the charging roller 20 uniformly charges the electrostatic latent image bearer 10, for example. An exposure device 30 exposes the electrostatic latent image bearer 10 in the form of an image to form an electrostatic latent image. The electrostatic latent image formed on the electrostatic latent image bearer 10 is developed with toner for forming a transfer destination material adhesive layer supplied from the developing device 40, to form a transfer destination material adhesive layer. The transfer destination material adhesive layer is transferred (primarily transferred) onto the intermediate transfer body 50 by a voltage applied from the rollers 51, and is further transferred (secondarily transfer) onto the transfer base material 95 on which the color image layer is formed. As a result, a transfer destination material adhesive layer is formed on the transfer base material 95 on which the color image layer is formed. Note that toner for forming a transfer destination material adhesive layer remaining on the electrostatic latent image bearer 10 is removed by the cleaning device 60, and the electrostatic charge on the electrostatic latent image bearer 10 is temporarily removed by the static elimination lamp 70.

[0153] FIG. 2 is a schematic view of a transfer destination material adhesive layer forming apparatus, used in the method of manufacturing a thermal transfer print sheet according to an embodiment of the present disclosure.A transfer destination material adhesive layer forming apparatus 100B has a configuration similar to that of the transfer destination material adhesive layer forming apparatus 100A illustrated in FIG. 1, except that the transfer destination material adhesive layer forming apparatus 100B does not include the developing belt 41, and the first developing device 45K, the second developing device 45Y, the third developing device 45M, and the fourthdeveloping device 45C are arranged directly facing each other around the periphery of the electrostatic latent image bearer 10.

[0154] FIG. 3 is a schematic view of a transfer destination material adhesive layer forming apparatus, used in the method of manufacturing a thermal transfer print sheet according to an embodiment of the present disclosure.FIG. 4 is a partial enlarged view of the transfer destination material adhesive layer forming apparatus of FIG. 3.

[0155] The transfer destination material adhesive layer forming apparatus illustrated in FIG. 3 includes a copying device main body 150, a sheet feeding table 200, a scanner 300, and an automatic document feeder (ADF) 400.An intermediate transfer body 50 that is formed as an endless belt is provided in a center portion of the copying device main body 150.The intermediate transfer body 50 is stretched over support rollers 14, 15, and 16 and is rotatable clockwise in FIG. 3. An intermediate transfer body cleaning device 17 for removing toner remaining on the intermediate transfer body 50 is arranged in the vicinity of the support roller 15. A tandem developing device 120 is arranged facing the intermediate transfer body 50 that is stretched by the support roller 14 and the support roller 15. In the tandem developing device 120, four developing devices 18, that is, a first developing device, a second developing device, a third developing device, and a fourth developing device, are arranged side by side facing the intermediate transfer body 50along a conveyance direction of the intermediate transfer body 50. The toner for forming a transfer destination material adhesive layer is output in the order from the first developing device to the fourth developing device. An exposure device 21 serving as the exposure member, is arranged in the vicinity of the tandem developing device 120. A secondary transfer device 22 is arranged on the side of the intermediate transfer body 50 opposite to the side on which the tandem developing device 120 is arranged. In the secondary transfer device 22, a secondary transfer belt 24, which is formed as an endless belt, is stretched over a pair of rollers 23. The intermediate transfer body 50 can contact a transfer base material on which a color image layer is formed and that is conveyed on the secondary transfer belt 24. A fixing device 25 serving as the fixing means is arranged in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26, which is formed as an endless belt, and a pressure roller 27 arranged to be pressed against the fixing belt 26.

[0156] In the present embodiment, an elastic intermediate transfer belt can be used as the intermediate transfer body 50. Examples of the elastic intermediate transfer belt include, but are not limited to, an intermediate transfer belt in which a flexible elastic layer is laminated on a rigid base layer that provides a certain bendability.To prevent the intermediate transfer body 50 from meandering, a skew prevention guide member may be provided on the inner circumferential surface of the intermediate transfer body 50.

[0157] In FIG. 3, the intermediate transfer body cleaning device 17 is arranged to clean the outer circumferential surface of the intermediate transfer body 50, but an intermediate transfer body cleaning device that cleans the inner circumferential surface of the intermediate transfer body 50 may be provided separately.The cleaning means included in the intermediate transfer member cleaning device 17 may be in the form of a blade or a brush. Further, a collection means may be provided for receiving toner and the like removed by the cleaning means. As the collection means, a dish- shaped tray or the like can be used.

[0158] Note that, in the transfer destination material adhesive layer forming apparatus of FIG. 3, a sheet reversing device 28 is arranged in the vicinity of the secondary transfer device 22 and the fixing device 25, and the sheet reversing device 28 reverses the transfer base material to form an image on both sides of the transfer base material.

[0159] Next, the formation of a transfer destination material-adhered image by using the tandem developing device 120 will be described.First, a color image document is placed on a platen 130 of the automatic document feeder (ADF) 400. Alternatively, the automatic document feeder 400 is opened, a color image document is placed on a contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed.When a start switch is pressed and a color image document is set on the automatic document feeder 400, the document is conveyed and moved onto the contact glass 32, and then, the scanner 300 is driven. On the other hand, when a color image document is placed on the contact glass 32, the scanner 300 is immediately driven. Subsequently, a first traveling body 33 and a second traveling body 34 start traveling.At this time, light from a light source is emitted by the first traveling body 33, and reflected light from the surface of the color image document is reflected by a mirror in the second traveling body 34, and is received by a reading sensor 36 via an image forming lens 35. Thus, image information of the color image document is read and converted into image information of colors including black, yellow, magenta, and cyan, and further, converted into solid image information in which all colors are uniformly deposited.

[0160] Subsequently, the solid image information is transmitted to each of the developing devices (the first developing device, the second developing device, the third developing device, and the fourth developing device) in the tandem developing device 120. In each developingdevice, an image that is uniform in all of the developing devices is formed by each of the developing devices. That is, as illustrated in FIG. 4, each of the developing devices 18 (the first developing device, the second developing device, the third developing device, and the fourth developing device) in the tandem type developing device 120 includes the electrostatic latent image bearer 10 (an electrostatic latent image bearer 10K for a first transfer destination material adhesive layer, an electrostatic latent image bearer 10Y for a second transfer destination material adhesive layer, an electrostatic latent image bearer 10M for a third transfer destination material adhesive layer, and an electrostatic latent image bearer 10C for a fourth transfer destination material adhesive layer), a charging device 160 serving as charging means that uniformly charges the electrostatic latent image bearer 10, an exposure device that exposes, based on the solid image information, the electrostatic latent image bearer to light (L in FIG. 4) in the form of an image corresponding to the solid image, to form an electrostatic latent image corresponding to the solid image information on the electrostatic latent image bearer, a developing device 61 serving as a developing means that develops the electrostatic latent image by using toner for forming a transfer destination material adhesive layer (a white toner for a transfer destination material adhesive layer and a transparent toner for a transfer destination material adhesive layer) and forms a transfer destination material adhesive layer with each toner for a transfer destination material adhesive layer, a transfer charging device 62 that transfers the toner image onto the intermediate transfer body 50, a cleaning device 63, and a static elimination device 64. Each developing device 18 forms a monochrome transfer destination material adhesive layer (a first transfer destination material adhesive layer, a second transfer destination material adhesive layer, a third transfer destination material adhesive layer, and a fourth transfer destination material adhesive layer), based on the image information of each color. The first transfer destination material adhesive layer, the second transfer destination material adhesive layer, the third transfer destination material adhesive layer, and the fourth transfer destination material adhesive layer formed in this manner, that is, the first transfer destination material adhesive layer formed on the electrostatic latent image bearer 10K for the first transfer destination material adhesive layer, the second transfer destination material adhesive layer formed on the electrostatic latent image bearer 10Y for the second transfer destination material adhesive layer, the third transfer destination material adhesive layer formed on the electrostatic latent image bearer 10M for the third transfer destination material adhesive layer, and the fourth transfer destination material adhesive layer formed on the electrostatic latent image bearer 10C for the fourth transfer destination material adhesive layer, are sequentially transferred (primarily transferred) onto the intermediate transfer body 50 which is rotatably moved by the support rollers 14, 15, and 16. The first transfer destination material adhesive layer, the second transfer destination material adhesive layer, the third transfer destination material adhesive layer, and the fourth transfer destination material adhesive layer are superimposed on the intermediate transfer body 50 to form a composite transfer destination material adhesive layer.

[0161] On the other hand, in the sheet feeding table 200, one of sheet feeding rollers 142 is selectively rotated to feed a sheet of a transfer base material on which a color image layer is formed from one of paper feed cassettes 144 provided in several stages in a paper bank 143. The sheets are separated one by one by separation rollers 145 and fed to a sheet feeding path 146, conveyed by conveyance rollers 147 and guided to a sheet feeding path 148 inside the copying device main body 150, where the sheets abut against and are stopped by registration rollers 49. Alternatively, the sheet feeding rollers 142 are rotated to feed sheets from a manual feed tray 54. The sheets are separated one by one by separation rollers 52 and fed into a manual feed path 53, and similarly abut against and are stopped by the registration rollers 49. The registration rollers 49 are generally grounded to be used, but may be used with a bias applied thereto to remove paper dust and the like from the sheet. The registration rollers 49 are rotated at a timing adjusted with a timing when the composite transfer destination material adhesive layer on the intermediate transfer body 50 is transferred onto the color image layer on the transfer base material. The sheet of the transfer base material on which the color image layer is formed is fed between the intermediate transfer body 50 and the secondary transfer device 22. Further, the secondary transfer device 22 transfers (secondarily transfers) the transfer destination material adhesive layer onto the transfer base material on which the color image layer is formed. Thus, the transfer destination material adhesive layer is transferred onto the transfer base material on which the color image layer is formed, and the transfer destination material adhesive layer is formed on the color image layer. After the transfer destination material adhesive layer is transferred, toner for forming the transfer destination material adhesive layer remaining on the intermediate transfer body 50 is cleaned by the intermediate transfer body cleaning device 17.

[0162] The transfer destination material adhesive layer is transferred and the sheet of transfer base material with the color image layer formed thereon on which the transfer destination material adhesive layer is formed is conveyed by the secondary transfer device 22 and transported to the fixing device 25. In the fixing device 25, the transfer destination material adhesive layer is fixed onto the sheet by heat and pressure. Subsequently, a switching claw 55 switches the sheet to ejection the sheet by ejection rollers 56 and the sheets are stacked on a sheet ejection tray 57. Alternatively, the sheet is switched by the switching claw 55, reversed by the sheet reversing device 28, and guided again to the transfer position. After the transfer destination material adhesive layer is also recorded on the back side of the sheet, the sheet is ejected by the ejection rollers 56 and the sheets are stacked on the sheet ejection tray 57.

[0163] The fourth developing device in the tandem developing device 120 is a developing device that finally outputs and develops, on the intermediate transfer body 50, the toner for a transfer destination material adhesive layer, and forms the transfer destination material adhesive layeras a first layer contacting the color image layer on the transfer base material. Therefore, it is preferable that the fourth developing device includes a transparent toner for a transfer destination material adhesive layer. When the fourth developing device includes a transparent toner for a transfer destination material adhesive layer, the transparent transfer destination material adhesive layer directly contacts the color image layer. When the fourth transfer destination material adhesive layer contacting the color image layer is a transparent transfer destination material adhesive layer and the color image layer and the transfer destination material adhesive layer laminated on the thermal transfer print sheet are thermally transferred to the transfer destination material, it is possible to prevent a decrease in color saturation of the color image layer that occurs when part of the color image layer is embedded in the transfer destination material adhesive layer. Therefore, it is possible to form a more vivid image with higher reproducibility.

[0164] FIG. 5 is a schematic view of a process cartridge in a transfer destination material adhesive layer forming apparatus used in a method of manufacturing a thermal transfer print sheet according to an embodiment of the present embodiment.A process cartridge 110 includes an electrostatic latent image bearer 10, a corona charging device 58, a developing device 40, a transfer roller 80, and a cleaning device 90.

[0165] (Printing Method)One embodiment of the present disclosure provides a printing method of printing a thermal transfer print sheet manufactured by the above-described method of manufacturing a thermal transfer print sheet, onto a flexible transfer destination material by using a thermal transfer device.The flexible transfer destination material is not particularly limited, as long as an image of the thermal transfer print sheet can be transferred thereto by using a thermal transfer device. However, preferred examples of the flexible transfer destination material include, but are not limited to, cloth, leather, and a plastic film.

[0166] <Thermal Transfer Device>A thermal transfer device is a device that thermally transfers a thermal transfer print sheet onto a transfer destination material such as cloth or leather, and can apply heat for a constant period of time and uniform pressure onto a press surface. Specific examples of the thermal transfer device include, but are not limited to, an iron press, a heat press, and a thermal press. However, it is preferable to use a thermal press because in this case, it is possible to apply heat uniformly and with a constant pressure. Further, thermal transfer may be performed by using a commercially available iron or the like.The thermal transfer device used in the printing method of the present embodiment may be a generally available thermal transfer device. Specific examples thereof include, but are notlimited to, GFH-380, GHP-300 (both manufactured by SystemGraphi Co., Ltd.), HPT234PS1, HSP-5400, HP-4536A-12, HP-54A, HP-84A, HSP-1513PV-AT, HSP-1010 (all manufactured by HASHIMA), TS-ONE (Sister), TP630M, and TP700A (Horizon).

[0167] It is preferable that the area of the press surface of the thermal transfer device is larger than the area of the transfer destination material, because in this case, it is possible to uniformly apply heat and pressure to the entire surface of the transfer destination material, and obtain an image after thermal transfer in which the transfer destination material does not have any press marks. The same applies to a case where a transfer destination material such as a T-shirt is subjected to thermal transfer by using a thermal transfer print sheet on which a color image layer and a transfer destination material adhesive layer are formed.The temperature in the thermal transfer varies depending on the material and the thickness of the transfer destination material. However, the temperature is preferably higher than the softening point Ts of the toner for a transfer destination material adhesive layer and lower than the heat resistance temperature Th of the transfer destination material, that is, Th - 20°C or lower.The pressure in the thermal transfer is preferably a low pressure, as long as transfer is possible, and is preferably 1000 g / cm2or less, more preferably 600 g / cm2or less, and even more preferably 300 g / cm2or less.[Examples]

[0168] The present embodiment will be described in more detail below with reference to examples and comparative examples, but the present embodiment is not limited to these examples and comparative examples.

[0169] (Preparation of Toner for Transfer Destination Material Adhesive Layer) [Manufacturing Example of Toner 1 for Transfer Destination Material Adhesive Layer]- Raw Materials of Toner 1 for Transfer Destination Material Adhesive Layer -- 30 parts by weight of polyurethane resin ECOFREEN POWDER (manufactured by ECOFREEN, softening point 120°C, glass transition temperature -29°C)- 60 parts by weight of polyester resin RN-306SF (manufactured by Kao Corporation, softening temperature 100°C, glass transition temperature 60°C)- 5 parts by weight of wax dispersant (EXD-001, manufactured by Sanyo Chemical Industries, Ltd.)- 5 parts by mass of ester wax (LW-13, manufactured by Sanyo Chemical Industries, Ltd.)- 80 parts by weight of titanium oxide white pigment PF-739 (manufactured by Ishihara Sangyo Kaisha, Ltd.)

[0170] The raw materials of the above-mentioned toner 1 for a transfer destination material adhesive layer were premixed by using a Henschel mixer (FM20B, manufactured by Nippon Coke and Engineering Co., Ltd.), and then melted and kneaded at a temperature of 100 to 130°C by using a single-axis kneader (manufactured by Buss, co-kneader kneading device, BUSS cokneader "MDK46-1 ID"). The obtained kneaded product was cooled and rolled with a rolling mill roll to a thickness of 1 mm or less, and then coarsely crushed to 200 to 300 pm with a ROTOPLEX (manufactured by Toa Machine Industry Co., Ltd.). In the coarse pulverization step, a coarsely pulverized product of a molten and kneaded product of the toner components is obtained.Next, a COUNTER JET MILL (100AFG, manufactured by Hosokawa Micron Group) was used to finely pulverize the coarsely pulverized product, while appropriately adjusting the pulverization air pressure to obtain a volume average particle diameter of 10 to 15 pm. Afterwards, an air classifier (EJ-LABO, manufactured by Matsubo Corp.) was used to classify the particles while appropriately adjusting the louver opening so that the volume average particle diameter was 11.0 ± 0.5 pm, to obtain toner base particles 1 for a transfer destination material adhesive layer.Next, toner 1 for a transfer destination material adhesive layer was prepared by using a Henschel mixer to stir and mix 1.0 part by mass of additive 1 (HDK-2000, manufactured by Clariant AG, substance name: silica) and 1.0 part by mass of additive 2 (H05TD, manufactured by Clariant AG, substance name: silica) with respect to 100 parts by mass of the obtained toner base particles for a transfer destination material adhesive layer.

[0171] [Manufacturing Example of Toner 2 for Transfer Destination Material Adhesive Layer]- Raw Materials of Toner 2 for Transfer Destination Material Adhesive Layer -- 40 parts by mass of polyurethane resin E780M128 (manufactured by Nippon Miractran, softening point 148°C, glass transition temperature -24°C)- 50 parts by mass of polyester resin RN-306SF (manufactured by Kao Corporation, softening temperature 100°C, glass transition temperature 60°C)- 5 parts by mass of wax dispersant (EXD-001, manufactured by Sanyo Chemical Industries, Ltd.)- 5 parts by mass of ester wax (LW-13, manufactured by Sanyo Chemical Industries, Ltd.)- 65 parts by mass of titanium oxide white pigment PF-739 (manufactured by Ishihara Sangyo Kaisha, Ltd.)Toner 2 for a transfer destination material adhesive layer was manufactured similarly to the toner 1 for a transfer destination material adhesive layer, except that the above-mentioned raw materials of the toner 2 for a transfer destination material adhesive layer were used.

[0172] [Manufacturing Example of Toner 3 for Transfer Destination Material Adhesive Layer]- Raw Materials of Toner 3 for Transfer Destination Material Adhesive Layer -- 40 parts by mass of polyurethane resin ECOFREEN POWDER (manufactured by ECOFREEN, softening point 120°C, glass transition temperature -29°C)- 40 parts by mass of polyester resin RN-306- 5 parts by mass of wax dispersant (EXD-001, manufactured by Sanyo Chemical Industries, Ltd.)- 5 parts by mass of ester wax (LW-13, manufactured by Sanyo Chemical Industries, Ltd.) Toner 3 for a transfer destination material adhesive layer was manufactured similarly to the toner 1 for a transfer destination material adhesive layer, except that the above-mentioned raw materials of the toner 3 for a transfer destination material adhesive layer were used.

[0173] [Manufacturing Example of Toner 4 for Transfer Destination Material Adhesive Layer]- Raw Materials of Toner 4 for Transfer Destination Material Adhesive Layer -- 60 parts by mass of polyester resin RN-306SF (manufactured by Kao Corporation, softening temperature 100°C, glass transition temperature 60°C)- 30 parts by mass of polyester resin RN-290 (manufactured by Kao Corporation, softening temperature 146°C, glass transition temperature 60°C)- 5 parts by mass of wax dispersant (EXD-001, manufactured by Sanyo Chemical Industries, Ltd.)- 5 parts by mass of ester wax (LW-13, manufactured by Sanyo Chemical Industries, Ltd.)- 80 parts by mass of titanium oxide white pigment PF-739 (manufactured by Ishihara Sangyo Kaisha, Ltd.)Toner 4 for a transfer destination material adhesive layer was manufactured similarly to the toner 1 for a transfer destination material adhesive layer, except that the above-mentioned raw materials of the toner 4 for a transfer destination material adhesive layer were used.

[0174] [Manufacturing Example of Toner 5 for Transfer Destination Material Adhesive Layer] Toner 5 for a transfer destination material adhesive layer was manufactured similarly to the toner 1 for a transfer destination material adhesive layer, except that the volume average particle diameter of the toner 1 for a transfer destination material adhesive layer after air flow classification was set to 15 pm.

[0175] Preparation of Carrier 1>- Raw materials of Carrier -- 710 parts by mass of IP solvent- 220 parts by mass of aluminum oxide, tin oxide, and mixed fine particles of phosphorus pentoxide (ECF-800, manufactured by Titan Kogyo Ltd.)- 40 parts by mass of silicone-acrylic resin-toluene solution (R5T, Toray Dow Coating Co., Ltd.)- 400 parts by mass of polyalkenylsiloxane / toluene solution (RCF-2130, Toray Dow Coating Co., Ltd.)- 45 parts by mass of titanium isopropoxybis(ethyl acetate) (CTC-754, manufactured by Matsumoto Fine Chemical Co., Ltd.)- 5 parts by mass of r-(2-aminoethyl)aminopropyltrimethoxysilane (RSH-602, manufactured by Toray Dow Corning Co., Ltd.)

[0176] The above-mentioned raw materials of carrier 1 were dispersed in a homomixer for 20 minutes to prepare a resin layer coating liquid. A fluidized bed-type coating device was used to apply the resin layer coating liquid to the surface of 7,200 parts by mass of spherical manganese-magnesium ferrite having an average particle diameter of 50 pm to prepare the carrier 1.

[0177] (Manufacturing of Developer for Transfer Destination Material Adhesive Layer)5 parts by mass of the toner 1 for a transfer destination material adhesive layer and 95 parts by mass of the carrier 1 were mixed in a ball mill to prepare a developer 1 for a transfer destination material adhesive layer.The toners 2 to 5 for a transfer destination material adhesive layer were each mixed with the carrier 1 similarly to the developer 1 for a transfer destination material adhesive layer, to prepare developers 2 to 5 for a transfer destination material adhesive layer.Next, a transfer print sheet was manufactured by using each of the prepared developers for a transfer destination material adhesive layer.

[0178] <Formation of Color Image Layer>The production printer RICOH Pro C7200S manufactured by Ricoh was used as a color image layer forming apparatus to output and print color toner on transfer base materials 1 and 2 described later, using mirror image information in which a color chart of CMYRGB gradation print patches was left-right inverted, to form a color image layer. The reference adhesion amount of each toner was set to 0.45 mg / cm2.Note that the toner (RICOH Pro toner C7200 series) used in the production printer RICOH Pro C7200S manufactured by Ricoh is a toner that contains a polyester resin, a thermoplastic elastomer, and a wax.As the transfer base materials, a transfer base material 1 (WoW LIGHT 8.0 A3 sheet manufactured by Piotec Co.) and a transfer base material 2 (CRV-4 A3 sheet manufactured by Kowa Technoa Ltd.) were used.

[0179] <Formation of Transfer Destination Material Adhesive Layer>A RICOH MFP IM C6000 (Ricoh Co., Ltd.), in which four developing devices can be mounted, was used as a transfer destination material adhesive layer forming apparatus. Ineach of five pieces of the transfer base materials 1 and 2 on which a color image layer was formed, a transfer destination material adhesive layer was formed on the color image layer under the following output conditions 1 to 12, so that a shape and a position of the transfer destination material adhesive layer were the same as a shape and a position of the color image layer, to manufacture a thermal transfer print sheet.In the thermal transfer print sheet, the transfer destination material adhesive layer was formed so that an edge of the transfer destination material adhesive layer protruded outward by 0.68 mm from an edge of the color image layer.

[0180] (Output Condition 1)All four developing devices that can be mounted in the transfer destination material adhesive layer forming apparatus (a first developing device - a second developing device - a third developing device - and a fourth developing device, in the order in which the developing devices output the developer to the intermediate transfer body) were provided with the developer 1 for a transfer destination material adhesive layer, and printing was performed by using all four developing devices to form the transfer destination material adhesive layer in one printing operation.The maximum amount of development from each developing device was 3.2 mg / cm2, and the thickness of a white transfer destination material adhesive layer that is output from and formed by the four developing devices was 80 pm.

[0181] (Output Condition 2)All four developing devices that can be mounted in the transfer destination material adhesive layer forming apparatus were provided with the developer 2 for a transfer destination material adhesive layer, and printing was performed by using all four developing devices to form a transfer destination material adhesive layer in one printing operation.The maximum amount of development from each developing device was 3.2 mg / cm2, and the thickness of a white transfer destination material adhesive layer that is output from and formed by the four developing devices was 80 pm.

[0182] (Output Condition 3)All four developing devices that can be mounted in the transfer destination material adhesive layer forming apparatus were provided with the developer 5 for a transfer destination material adhesive layer, and printing was performed by using all four developing devices to form a transfer destination material adhesive layer in one printing operation.The maximum amount of development from each developing device was 4.8 mg / cm2, and the thickness of a white transfer destination material adhesive layer that is output from and formed by the four developing devices was 120 pm.

[0183] (Output Condition 4)All of the four developing devices that can be mounted in the transfer destination material adhesive layer forming apparatus were provided with the developer 2 for a transfer destination material adhesive layer.In the transfer destination material adhesive layer forming apparatus, printing was performed by using three of the developing devices, that is, the first developing device - the second developing device - and the third developing device, at a development voltage of 800 V, which is the development condition in which no carrier adhesion occurs and the amount of toner being developed is maximized, and a transfer destination material adhesive layer was formed in one printing operation. The formed white transfer destination material adhesive layer was 60 pm thick.

[0184] (Output Condition 5)All of the four developing devices that can be mounted in the transfer destination material adhesive layer forming apparatus were provided with the developer 2 for a transfer destination material adhesive layer.In the transfer destination material adhesive layer forming apparatus, printing was performed by using two of the developing devices, that is, the first developing device - and the second developing device, at a development voltage of 800 V, which is the development condition in which no carrier adhesion occurs and the amount of toner being developed is maximized, and a transfer destination material adhesive layer was formed in one printing operation. The formed white transfer destination material adhesive layer was 40 pm thick.

[0185] (Output Condition 6)Among the four developing devices that can be mounted in the transfer destination material adhesive layer forming apparatus, three developing devices, that is, the first developing device - the second developing device - and the third developing device, were provided with the developer 1 for a transfer destination material adhesive layer, and the fourth developing device was provided with the developer 3 for a transfer destination material adhesive layer. Printing was performed by using all four developing devices to form a transfer destination material adhesive layer in one printing operation.The maximum amount of development by the first developing device was 2.7 mg / cm2, and the thickness of a transparent transfer destination material adhesive layer output from and formed by the first developing device alone was 20 pm.The total thickness of the transfer destination material adhesive layer output by using all of the developing devices was 80 pm, the thickness of the transparent transfer destination material adhesive layer was 20 pm, and the thickness of the white transfer destination material adhesive layer was 60 pm.

[0186] (Output Condition 7)All four developing devices that can be mounted in the transfer destination material adhesive layer forming apparatus were provided with the developer 4 for a transfer destination material adhesive layer, and printing was performed by using all four developing devices to form a transfer destination material adhesive layer in one printing operation.The maximum amount of development from each developing device was 3.2 mg / cm2, and the thickness of a white transfer destination material adhesive layer that is output from and formed by the four developing devices was 80 pm.

[0187] (Output Condition 8)All of the four developing devices that can be mounted in the transfer destination material adhesive layer forming apparatus were provided with the developer 4 for a transfer destination material adhesive layer.In the transfer destination material adhesive layer forming apparatus, printing was performed by using two of the developing devices, that is, the first developing device - and the second developing device, at a development voltage of 800 V, which is the development condition in which no carrier adhesion occurs and the amount of toner being developed is maximized, and a transfer destination material adhesive layer was formed in one printing operation. The formed white transfer destination material adhesive layer was 40 pm thick.

[0188] (Output Condition 9)All of the four developing devices that can be mounted in the transfer destination material adhesive layer forming apparatus were provided with the developer 2 for a transfer destination material adhesive layer.In the transfer destination material adhesive layer forming apparatus, printing was performed by using only one of the developing devices, that is, the first developing device, at a development voltage of 800 V, which is the development condition in which no carrier adhesion occurs and the amount of toner being developed is maximized, and a transfer destination material adhesive layer was formed in one printing operation. The formed white transfer destination material adhesive layer was 20 pm thick.

[0189] (Output Condition 10)All of the four developing devices that can be mounted in the transfer destination material adhesive layer forming apparatus were provided with the developer 2 for a transfer destination material adhesive layer.The amount of development from each developing device was set to 2.4 mg / cm2, and printing was performed by using two of the developing devices, that is, the first developing device - and the second developing device, to form a transfer destination material adhesive layer in one printing operation.The formed white transfer destination material adhesive layer was 30 m thick.

[0190] (Output Condition 11)All of the four developing devices that can be mounted in the transfer destination material adhesive layer forming apparatus were provided with the developer 1 for a transfer destination material adhesive layer.In the transfer destination material adhesive layer forming apparatus, a transfer destination material adhesive layer was formed by printing using only the first developing device at a development voltage of 800 V, which is a development condition in which no carrier adhesion occurs and the amount of toner being developed is maximized. Subsequently, the printed thermal transfer print sheet was set again in the transfer destination material adhesive layer forming apparatus and printed in a similar manner, and this process was repeated for a total of four printing operations.However, in the second printing operation, a positional deviation occurred in which the color image layer protruded from the range where the transfer destination material adhesive layer was to be formed. Also in the third printing operation, a large positional deviation occurred. In the fourth printing operation, a sheet jam occurred, and thus, output was stopped.

[0191] (Output Condition 12)All of the four developing devices that can be mounted in the transfer destination material adhesive layer forming apparatus were provided with the developer 1 for a transfer destination material adhesive layer.The amount of development from each developing device was set to 1.6 mg / cm2, and a transfer destination material adhesive layer was formed by printing using only two developing devices, that is, the first developing device and the second developing device. Subsequently, the printed thermal transfer print sheet was set again in the transfer destination material adhesive layer forming apparatus and printed in a similar manner, and this process was repeated for a total of three printing operations.However, in the second printing operation, a positional deviation occurred in which the color image layer protruded from the range where the transfer destination material adhesive layer was to be formed. Also in the third printing operation, a large positional deviation occurred. Further, in a portion where the three layers overlapped to form the transfer destination material adhesive layer, offset occurred during fixing.

[0192] Note that, under each output condition, five thermal transfer print sheets using the transfer base material 1 were printed consecutively, and then, five thermal transfer print sheets using the transfer base material 2 were printed consecutively.

[0193] For each transfer base material and each output condition, two sheets were randomly selected from the five thermal transfer print sheets obtained under output conditions 1 to 12. Each thermal transfer print sheet was placed at a randomly selected position on a black T-shirt (4.7 oz. dry silky touch T-shirt, low color bleeding, manufactured by United Athle) serving as the transfer destination material, so that the transfer destination material adhesive layer was in contact with the surface of the T-shirt. The black T-shirt was then set in a heat press machine (Model HTP234PS1, manufactured by Piotec Co.) and heat and pressure were applied at a temperature of 130°C for 20 seconds and a pressure of 300 g / cm2. Afterwards, the transfer base material was peeled off, and the color image layer and the transfer destination material adhesive layer were thermally transferred onto the black T-shirt and fixed on the black T- shirt.Further, a release paper was placed on the color image layer, and heat and pressure were again applied at a temperature of 130°C for 20 seconds and a pressure of 300 g / cm2, and then, the release paper was peeled off to complete the printed T-shirt.Examples 1 to 6 were obtained by subjecting a black T-shirt to thermal transfer using the thermal transfer print sheets prepared under output conditions 1 to 6. Comparative Examples 1 to 6 were obtained by subjecting a black T-shirt to thermal transfer using the thermal transfer print sheets prepared under output conditions 7 to 12.

[0194] [Evaluation]< Print Reproducibility >The positional misalignment between the color image layer and the transfer destination material adhesive layer was visually evaluated in five thermal transfer print sheets obtained by using the transfer base material 1 and five thermal transfer print sheets obtained by using the transfer base material 2, which were output under output conditions 1 to 12. The positional misalignment was evaluated according to the following evaluation criteria and the results are illustrated in Table 1.(Evaluation Criteria)In all sheets among the ten thermal transfer print sheets, the color image layer is entirely included in a printing range of the transfer destination material adhesive layer: A (good) In one or more sheets among the ten thermal transfer print sheets, the color image layer protrudes outside the transfer destination material adhesive layer: B (unacceptable)

[0195] <Fixability>The color loss and the peeling of the color image layer of printed T-shirts on which two thermal transfer print sheets using the transfer base material 1 and two thermal transfer print sheets using the transfer base material 2 were thermally transferred and fixed were evaluated. The color loss and the peeling were evaluated according to the following evaluation criteria and the results are illustrated in Table 1.(Evaluation Criteria)The color image layer did not lose color or peel off in any of the printed T-shirts: A (good) The color image layer did lose color or peel off in some of the printed T-shirts: B (unacceptable)

[0196] <Color Saturation>To evaluate the color saturation of the color image layer of printed T-shirts on which two thermal transfer print sheets using the transfer base material 1 and two thermal transfer print sheets using the transfer base material 2 were thermally transferred and fixed, the color saturation of the R solid patch in a color chart having 100% C and 100% M was measured by using an X-rite eXact™ (manufactured by X-Rite, Incorporated) under conditions including mO, UV komi / ISO 13655:2017. The color saturation was evaluated according to the following evaluation criteria and the results are illustrated in Table 1.(Evaluation Criteria)The color saturation *C of the color image layer in all printed T-shirts is 60 or more: A (excellent)The color saturation *C of the color image layer in all printed T-shirts is 50 or more and less than 60: B (good)The color saturation *C of the color image layer in all printed T-shirts is 45 or more and less than 50: C (acceptable)The color saturation*C of the color image layer in all printed T-shirts is less than 45: D (unacceptable)

[0197] <Method of Evaluating Laundering Fastness>The printed T-shirts manufactured in Examples 1 to 6 and Comparative Examples 1 to 6 were subjected to a laundering fastness test by using the test method of JIS 0844:2011 and evaluated according to the following evaluation criteria. The results are illustrated in Table 1. (Evaluation Criteria)In all printed T-shirts, the color image layer achieved rank 5 on the JIS 0844 discoloration gray scale, and no cracks were observed in the color image layer or the transfer destination material adhesive layer even after 10 repetitions of laundering: A (excellent)In all printed T-shirts, the color image layer achieved rank 5 on the JIS 0844 discoloration gray scale, and cracks were observed in the color image layer or the transfer destination material adhesive layer of some of the T-shirts after 10 repetitions of laundering: B (good) In all printed T-shirts, the color image layer achieved rank 4 or 3 on the JIS 0844 discoloration gray scale: C (acceptable)In all printed T-shirts, the color image layer achieved rank 2 or 1 on the JIS 0844 discoloration gray scale: D (unacceptable)

[0198] [Table 1]

[0199] Printed T-shirts in which the evaluation results of the print reproducibility and the fixability were A and the evaluation results of the color saturation and the laundering fastness were A to C, were determined as applicable to the present embodiment and were determined as "passed". All other printed T-shirts were determined as "failed".

[0200] In all of Examples 1 to 6, the evaluation results of the print reproducibility and the fixability were A and the evaluation results of the color saturation and the laundering fastness were A to C. Therefore, Examples 1 to 6 were applicable to the present embodiment and were determined as "passed".

[0201] In Comparative Examples 1 and 2, the toner for a transfer destination material adhesive layer did not contain a polyurethane resin. Thus, the color image layer on the printed T-shirts was likely to undergo discoloration and had poor fixability and laundering fastness. Therefore, Comparative Examples 1 and 2 were determined as "failed" in the present embodiment.

[0202] In Comparative Examples 3 and 4, the thickness of the transfer destination material adhesive layer was less than 40 pm, and the color saturation of the color image layer on the printed T- shirts was low. Therefore, Comparative Examples 3 and 4 were determined as "failed" in the present embodiment.

[0203] In Comparative Examples 5 and 6, the transfer destination material adhesive layer was formed by performing printing a plurality of times, and thus, the print reproducibility was poor.Further, in Comparative Example 5, a sheet jam occurred in the fourth printing operation, and thus, it was not possible to evaluate the fixability. In Comparative Example 6, offset occurred during fixing, so that the fixability was poor. Therefore, Comparative Examples 5 and 6 were determined as "failed" in the present embodiment.

[0204] Embodiments have been described above. However, the above-described embodiments are presented as examples, and the present embodiment is not limited to the above-described embodiments. The above-described embodiments can be implemented in various other forms, and can be modified, such as by adding, modifying, and omitting components, within the scope conceivable by a person skilled in the art. As long as the operation and effects of the present embodiment are achieved in any one of the modified embodiments, the modified embodiment is considered to be within the scope of the present embodiment.Further, various combinations, omissions, substitutions, modifications, and the like are possible without departing from the spirit of the present embodiment. The obtained embodiments and variations thereof are included in the scope and the spirit of the present embodiment, and are included in the scope of the present embodiment described in the claims and in equivalents thereof.

[0205] From the above, it can be understood that the method of manufacturing a thermal transfer print sheet of the present embodiment is a method of manufacturing a thermal transfer print sheet, by which it is possible to print a toner image with high print reproducibility, in which the color saturation of the toner image does not decrease on a dark-colored transfer destination material, the toner image is sufficiently fixed to a flexible transfer destination material having strong irregularities, and the toner image has sufficient flexibility and strength.

[0206] Aspects of the present disclosure are as follows, for example.According to a first aspect, a method of manufacturing a thermal transfer print sheet includes: forming a color image layer on a transfer base material by a color image layer forming apparatus: and forming, on the color image layer, a transfer destination material adhesive layer having a thickness of 40 pm or more and 120 pm or less in one printing operation by a transfer destination material adhesive layer forming apparatus using an electrophotographic procedure, in which the transfer destination material adhesive layer forming apparatus includes a plurality of developing devices, andamong the plurality of developing devices, two or more developing devices include a white toner for forming the transfer destination material adhesive layer, the white toner including a polyester resin, a polyurethane resin, and a release agent.According to a second aspect, in the method according to the first aspect, the plurality of developing devices further include a developing device including a transparent toner for forming the transfer destination material adhesive layer, the transparent toner including a polyester resin, a polyurethane resin, and a release agent.According to a third aspect, in the method according to the first aspect or the second aspect, the transfer destination material adhesive layer includes a white layer having a thickness of 40 pm or more.According to a fourth aspect, in the according to any one of the first aspect to the third aspect, the forming the transfer destination material adhesive layer is implemented after the forming the color image layer.According to a fifth aspect, in the method according to the fourth aspect, the forming the transfer destination material adhesive layer includes forming a transparent transfer destination material adhesive layer on the color image layer, and forming a white transfer destination material adhesive layer on the transparent transfer destination material adhesive layer. According to a sixth aspect, in the method according to any one of the first aspect to the fifth aspect, the white toner and the transparent toner for forming the transfer destination material adhesive layer have a volume average particle diameter of 10 pm or more and 20 pm or less. According to a seventh aspect, a printing method includes printing a thermal transfer print sheet manufactured by the method according to any one of the first aspect to the sixth aspect, onto a flexible transfer destination material by using a thermal transfer device.According to an eighth aspect, in the printing method according to the seventh aspect, the flexible transfer destination material includes cloth, leather, or a plastic film.

[0207] According to the method of manufacturing a thermal transfer print sheet described above in any one of the first aspect to the sixth aspect and the printing method described above in the seventh aspect or the eighth aspect, it is possible to solve the above-described conventional problems and achieve the object of the present embodiment.

[0208] The above-described embodiments are illustrative and do not limit the present invention. Thus, numerous additional modifications and variations are possible in light of the above teachings. For example, elements and / or features of different illustrative embodiments may be combined with each other and / or substituted for each other within the scope of the present invention. Any one of the above-described operations may be performed in various other ways, for example, in an order different from the one described above.

[0209] This patent application is based on and claims priority to Japanese Patent Application No. 2023-197691, filed on November 21, 2023, in the Japan Patent Office, the entire disclosure of which is hereby incorporated by reference herein.[Reference Signs List]

[0210] 45K First developing device45Y Second developing device45M Third developing device45C Fourth developing device61 Developing device95 Transfer base material on which color image layer is formed100A Transfer destination material adhesive layer forming apparatus100B Transfer destination material adhesive layer forming apparatus

Claims

[CLAIMS]

1. A method of manufacturing a thermal transfer print sheet, the method comprising: forming a color image layer on a transfer base material by a color image layer forming apparatus; and forming, on the color image layer, a transfer destination material adhesive layer having a thickness of 40 pm or more and 120 pm or less in one printing operation by a transfer destination material adhesive layer forming apparatus using an electrophotographic procedure, wherein the transfer destination material adhesive layer forming apparatus includes a plurality of developing devices, and among the plurality of developing devices, two or more developing devices include a white toner for forming the transfer destination material adhesive layer, the white toner including a polyester resin, a polyurethane resin, and a release agent.

2. The method according to claim 1, wherein the plurality of developing devices further include a developing device including a transparent toner for forming the transfer destination material adhesive layer, the transparent toner including a polyester resin, a polyurethane resin, and a release agent.

3. The method according to claim 1 or 2, wherein the transfer destination material adhesive layer includes a white layer having a thickness of 40 pm or more.

4. The method according to any one of claims 1 to 3, wherein the forming the transfer destination material adhesive layer is implemented after the forming the color image layer.

5. The method according to claim 4, wherein the forming the transfer destination material adhesive layer includes: forming a transparent transfer destination material adhesive layer on the color image layer; and forming a white transfer destination material adhesive layer on the transparent transfer destination material adhesive layer.

6. The method according to any one of claims 1 to 5, wherein the white toner and the transparent toner for forming the transfer destination material adhesive layer have a volume average particle diameter of 10 pm or more and 20 pm or less.

7. A printing method comprising:printing a thermal transfer print sheet manufactured by the method according to any one of claims 1 to 6, onto a flexible transfer destination material by using a thermal transfer device.

8. The printing method according to claim 7, wherein the flexible transfer destination material includes cloth, leather, or a plastic film.

Images